CN113461966A - Flame-retardant unsaturated polyester resin and preparation method thereof - Google Patents
Flame-retardant unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN113461966A CN113461966A CN202110970448.6A CN202110970448A CN113461966A CN 113461966 A CN113461966 A CN 113461966A CN 202110970448 A CN202110970448 A CN 202110970448A CN 113461966 A CN113461966 A CN 113461966A
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Abstract
The invention discloses a flame-retardant unsaturated polyester resin and a preparation method thereof, wherein the preparation method comprises the following steps: putting vermiculite into a maleic anhydride solution for grinding modification to obtain modified vermiculite; mixing modified vermiculite, phthalic anhydride and propylene glycol to obtain a mixed material; reacting the mixed materials under the heating condition to prepare the flame-retardant unsaturated polyester resin; according to the preparation method, firstly, the vermiculite is modified by adopting the maleic anhydride, then the modified vermiculite is reacted with the phthalic anhydride and the propylene glycol to prepare the unsaturated polyester resin, and the unsaturated polyester resin prepared by introducing the vermiculite has excellent flame retardant property, impact resistance and elongation at break.
Description
Technical Field
The invention relates to the technical field of unsaturated polyester resin, in particular to flame-retardant unsaturated polyester resin and a preparation method thereof.
Background
The traditional unsaturated polyester resin is mostly prepared by polycondensation of rigid dibasic acid such as isophthalic acid, phthalic anhydride, terephthalic acid and the like, and dihydric alcohol such as maleic anhydride, propylene glycol, neopentyl glycol and the like, but the unsaturated polyester resin has poor tensile property, heat resistance and the like and has no flame retardance.
At present, in order to improve the performance of unsaturated polyester resin, different inorganic materials, curing agents, glass fibers and other high polymer materials which can be compounded, such as epoxy resin, polyurethane, polyethylene and the like, are used for compounding with the unsaturated polyester resin to prepare a modified unsaturated polyester resin material meeting the application requirement; however, there has been no report on an unsaturated polyester resin having flame retardant properties.
Disclosure of Invention
The invention aims to provide a flame-retardant unsaturated polyester resin and a preparation method thereof.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the first aspect of the present invention provides a method for preparing a flame-retardant unsaturated polyester resin, comprising the steps of:
(a) putting vermiculite into a maleic anhydride solution for grinding modification to obtain modified vermiculite;
(b) mixing modified vermiculite, phthalic anhydride and propylene glycol to obtain a mixed material;
(c) and (3) reacting the mixed materials under a heating condition to obtain the flame-retardant unsaturated polyester resin.
Preferably, the vermiculite is no greater than 6 μm in size; the ion exchange capacity is 0.95 to 1.00 mmol/g.
Preferably, the concentration of the maleic anhydride solution is 20-30 g/L.
Preferably, the vermiculite is the same mass as the maleic anhydride in the maleic anhydride solution.
Preferably, the grinding modification time is 2-5 h.
Preferably, the mass ratio of the modified vermiculite to the phthalic anhydride to the propylene glycol is (48.7-50) to (24.1-24.7) to (25.4-27.2).
Preferably, the reacting the mixture under heating specifically comprises:
heating the mixed materials to 75-85 ℃ within 15min, stirring and uniformly mixing, then heating to 150-170 ℃ within 42-48 min, heating to 190-200 ℃ within 45-60 min, and carrying out heat preservation reaction for 60-70 min.
The second aspect of the invention provides a flame-retardant unsaturated polyester resin prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that at least:
according to the preparation method, firstly, the vermiculite is modified by adopting the maleic anhydride, then the modified vermiculite is reacted with the phthalic anhydride and the propylene glycol to prepare the unsaturated polyester resin, and the unsaturated polyester resin prepared by introducing the vermiculite has excellent flame retardant property, impact resistance and elongation at break.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is a schematic diagram of vermiculite modification in an embodiment of the invention.
Detailed Description
The following describes embodiments of the present invention in detail with reference to the following embodiments. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
The following examples used the following starting materials:
vermiculite: the size is not more than 6 μm; the ion exchange capacity is 0.98mmol/g, and the ion exchange capacity is from Shanghai Michelin Biochemical technology, Inc.;
maleic anhydride: from abundant energy science and technology, ltd;
phthalic anhydride: from Shanghai Aladdin Biotechnology, Inc.;
propylene glycol: from Shanghai Aladdin Biotechnology Ltd
Example 1
The embodiment is a preparation method of flame-retardant unsaturated polyester resin, which comprises the following steps:
(a) firstly, dissolving 25g of maleic anhydride in 1L of deionized water to prepare 25g/L of maleic anhydride solution, then adding 25g of vermiculite into the maleic anhydride solution, grinding for 3 hours by using a ball mill, washing for multiple times by using the deionized water, and drying in vacuum to obtain modified vermiculite, wherein the modification principle of the vermiculite is shown in figure 1;
(b) sequentially adding the modified vermiculite, the phthalic anhydride and the propylene glycol into a reactor according to the mass ratio of 49: 24.5: 26 of the modified vermiculite, the phthalic anhydride and the propylene glycol, slowly heating and starting a condensation cycle;
(c) heating the mixed material to 80 ℃ for 15min, stirring and uniformly mixing, then heating to 160 ℃ for 45min, heating to 200 ℃ for 60min, and carrying out heat preservation reaction for 60min to obtain the flame-retardant unsaturated polyester resin.
Example 2
The embodiment is a preparation method of flame-retardant unsaturated polyester resin, which comprises the following steps:
(a) firstly, dissolving 25g of maleic anhydride in 1L of deionized water to prepare 25g/L of maleic anhydride solution, then adding 25g of vermiculite into the maleic anhydride solution, grinding for 3 hours by using a ball mill, washing for multiple times by using the deionized water, and drying in vacuum to obtain modified vermiculite;
(b) sequentially adding the modified vermiculite, the phthalic anhydride and the propylene glycol into a reactor according to the mass ratio of 49: 24.5: 26 of the modified vermiculite, the phthalic anhydride and the propylene glycol, slowly heating and starting a condensation cycle;
(c) heating the mixed material to 85 ℃ for 10min, stirring and uniformly mixing, then heating to 170 ℃ for 48min, heating to 190 ℃ for 45min, and carrying out heat preservation reaction for 70min to obtain the flame-retardant unsaturated polyester resin.
Example 3
The embodiment is a preparation method of flame-retardant unsaturated polyester resin, which comprises the following steps:
(a) firstly, dissolving 25g of maleic anhydride in 1L of deionized water to prepare 25g/L of maleic anhydride solution, then adding 25g of vermiculite into the maleic anhydride solution, grinding for 3 hours by using a ball mill, washing for multiple times by using the deionized water, and drying in vacuum to obtain modified vermiculite;
(b) sequentially adding the modified vermiculite, the phthalic anhydride and the propylene glycol into a reactor according to the mass ratio of 49: 24.5: 26 of the modified vermiculite, the phthalic anhydride and the propylene glycol, slowly heating and starting a condensation cycle;
(c) heating the mixed material to 75 ℃ for 15min, stirring and uniformly mixing, then heating to 150 ℃ for 42min, heating to 200 ℃ for 60min, and carrying out heat preservation reaction for 65min to obtain the flame-retardant unsaturated polyester resin.
Example 4
The embodiment is a preparation method of flame-retardant unsaturated polyester resin, which comprises the following steps:
(a) firstly, dissolving 30g of maleic anhydride in 1L of deionized water to prepare 30g/L of maleic anhydride solution, then adding 30g of vermiculite into the maleic anhydride solution, grinding for 3 hours by using a ball mill, washing for multiple times by using the deionized water, and drying in vacuum to obtain modified vermiculite;
(b) sequentially adding the modified vermiculite, the phthalic anhydride and the propylene glycol into a reactor according to the mass ratio of 49: 24.5: 26 of the modified vermiculite, the phthalic anhydride and the propylene glycol, slowly heating and starting a condensation cycle;
(c) heating the mixed material to 80 ℃ for 15min, stirring and uniformly mixing, then heating to 160 ℃ for 45min, heating to 200 ℃ for 60min, and carrying out heat preservation reaction for 60min to obtain the flame-retardant unsaturated polyester resin.
Example 5
The embodiment is a preparation method of flame-retardant unsaturated polyester resin, which comprises the following steps:
(a) firstly, dissolving 20g of maleic anhydride in 1L of deionized water to prepare a 20g/L maleic anhydride solution, then adding 20g of vermiculite into the maleic anhydride solution, grinding for 3 hours by using a ball mill, washing for multiple times by using the deionized water, and drying in vacuum to obtain modified vermiculite;
(b) sequentially adding the modified vermiculite, the phthalic anhydride and the propylene glycol into a reactor according to the mass ratio of 49: 24.5: 26 of the modified vermiculite, the phthalic anhydride and the propylene glycol, slowly heating and starting a condensation cycle;
(c) heating the mixed material to 80 ℃ for 15min, stirring and uniformly mixing, then heating to 160 ℃ for 45min, heating to 200 ℃ for 60min, and carrying out heat preservation reaction for 60min to obtain the flame-retardant unsaturated polyester resin.
Example 6
The embodiment is a preparation method of flame-retardant unsaturated polyester resin, which comprises the following steps:
(a) firstly, dissolving 25g of maleic anhydride in 1L of deionized water to prepare 25g/L of maleic anhydride solution, then adding 25g of vermiculite into the maleic anhydride solution, grinding for 3 hours by using a ball mill, washing for multiple times by using the deionized water, and drying in vacuum to obtain modified vermiculite, wherein the modification principle of the vermiculite is shown in figure 1;
(b) sequentially adding the modified vermiculite, the phthalic anhydride and the propylene glycol into a reactor according to the mass ratio of 48.7: 24.7: 25.4 of the modified vermiculite, the phthalic anhydride and the propylene glycol, slowly heating and starting a condensation cycle;
(c) heating the mixed material to 80 ℃ for 15min, stirring and uniformly mixing, then heating to 160 ℃ for 45min, heating to 200 ℃ for 60min, and carrying out heat preservation reaction for 60min to obtain the flame-retardant unsaturated polyester resin.
Example 7
The embodiment is a preparation method of flame-retardant unsaturated polyester resin, which comprises the following steps:
(a) firstly, dissolving 25g of maleic anhydride in 1L of deionized water to prepare 25g/L of maleic anhydride solution, then adding 25g of vermiculite into the maleic anhydride solution, grinding for 3 hours by using a ball mill, washing for multiple times by using the deionized water, and drying in vacuum to obtain modified vermiculite, wherein the modification principle of the vermiculite is shown in figure 1;
(b) sequentially adding the modified vermiculite, the phthalic anhydride and the propylene glycol into a reactor according to the mass ratio of 50: 24.1: 27.2 of the modified vermiculite, the phthalic anhydride and the propylene glycol, slowly heating and starting a condensation cycle;
(c) heating the mixed material to 80 ℃ for 15min, stirring and uniformly mixing, then heating to 160 ℃ for 45min, heating to 200 ℃ for 60min, and carrying out heat preservation reaction for 60min to obtain the flame-retardant unsaturated polyester resin.
Comparative example 1
The comparative example is a preparation method of flame-retardant unsaturated polyester resin, which comprises the following steps:
sequentially adding maleic anhydride, phthalic anhydride and propylene glycol into a reactor according to the mass ratio of the maleic anhydride to the propylene glycol of 49: 24.5: 26, starting to slowly heat and starting a condensation cycle, heating to 75 ℃ within 15 minutes, fully stirring, heating to 150 ℃ within 42 minutes, heating to 200 ℃ within 60 minutes, and carrying out heat preservation reaction for 65 minutes to obtain the flame-retardant unsaturated polyester resin.
Comparative example 2
The comparative example is a preparation method of flame-retardant unsaturated polyester resin, which comprises the following steps:
sequentially adding the vermiculite, the maleic anhydride, the phthalic anhydride and the propylene glycol into a reactor according to the mass ratio of the maleic anhydride to the vermiculite to the propylene glycol of 24.5: 26, starting to slowly heat and start a condensation cycle, heating to 75 ℃ within 15 minutes, fully stirring, heating to 150 ℃ within 42 minutes, heating to 200 ℃ within 60 minutes, and carrying out heat preservation reaction for 65 minutes to obtain the flame-retardant unsaturated polyester resin.
Examples of the experiments
Preparing flame-retardant unsaturated polyester resin according to the preparation methods of the examples 1 to 7 and the comparative examples 1 to 2 respectively; then, the mixture is poured into a mold with standard size respectively, cured for 30min at 120 ℃, then cured for 1h at 150 ℃, and demoulded after cooling to test each sample strip.
The flame retardancy test is carried out according to the vertical burning test in the test standard of the flame retardancy grade of American Standard UL94, the strength test is carried out according to the GB/T1039-1992 standard, and the test results are shown in Table 1:
TABLE 1 test results of different flame-retardant unsaturated polyester resins
As can be seen from Table 1:
according to the invention, the modified vermiculite is added, so that the prepared flame-retardant unsaturated polyester resin has flame retardant property, and the impact strength and the elongation at break of the prepared unsaturated polyester resin can be obviously improved; in addition, the comprehensive performance of the flame-retardant unsaturated polyester resin can be better improved by modifying maleic anhydride and vermiculite.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (8)
1. The preparation method of the flame-retardant unsaturated polyester resin is characterized by comprising the following steps of:
(a) putting vermiculite into a maleic anhydride solution for grinding modification to obtain modified vermiculite;
(b) mixing modified vermiculite, phthalic anhydride and propylene glycol to obtain a mixed material;
(c) and (3) reacting the mixed materials under a heating condition to obtain the flame-retardant unsaturated polyester resin.
2. The method of claim 1, wherein the vermiculite is no greater than 6 μm in size; the ion exchange capacity is 0.95 to 1.00 mmol/g.
3. The method according to claim 1, wherein the concentration of the maleic anhydride solution is 20 to 30 g/L.
4. The method according to claim 1, wherein the vermiculite is the same mass as the maleic anhydride in the maleic anhydride solution.
5. The preparation method of claim 1, wherein the grinding modification time is 2-5 h.
6. The preparation method according to claim 1, wherein the mass ratio of the modified vermiculite to the phthalic anhydride to the propylene glycol is (48.7-50) to (24.1-24.7) to (25.4-27.2).
7. The preparation method according to claim 1, wherein the reacting the mixture under heating specifically comprises:
heating the mixed materials to 75-85 ℃ within 15min, stirring and uniformly mixing, then heating to 150-170 ℃ within 42-48 min, heating to 190-200 ℃ within 45-60 min, and carrying out heat preservation reaction for 60-70 min.
8. The flame-retardant unsaturated polyester resin prepared by the preparation method of any one of claims 1 to 7.
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| US4013614A (en) * | 1975-01-29 | 1977-03-22 | H. H. Robertson Company | Method of preparing shaped articles from polymerizable compositions |
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