CN109810415B - Intumescent flame retardant taking pentaerythritol modified melamine formaldehyde resin/piperazine pyrophosphate compound as char forming agent - Google Patents
Intumescent flame retardant taking pentaerythritol modified melamine formaldehyde resin/piperazine pyrophosphate compound as char forming agent Download PDFInfo
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Abstract
The invention relates to an Intumescent Flame Retardant (IFR) prepared by mixing and compounding a pentaerythritol modified melamine formaldehyde resin/piperazine pyrophosphate compound serving as a charring agent, melamine cyanurate serving as a foaming agent and ammonium polyphosphate serving as a dehydrating agent. The IFR comprises the following components in percentage by mass: 70-80% of ammonium polyphosphate, 10-20% of pentaerythritol modified melamine formaldehyde resin, 2-5% of melamine cyanurate and 7-12% of piperazine pyrophosphate. The IFR has good flame retardant effect on polypropylene, and basically does not contain chlorine, so that the IFR is safer and more environment-friendly. In addition, the prepared flame-retardant polypropylene has better color.
Description
Technical Field
The invention relates to a novel intumescent flame retardant, in particular to an intumescent flame retardant taking a pentaerythritol modified melamine formaldehyde resin/piperazine pyrophosphate compound as a char forming agent, belonging to the field of chemical industry and high polymer material additives.
Background
The Intumescent Flame Retardant (IFR) is a composite flame retardant system consisting of an acid source (dehydrating agent), a carbon source (char-forming agent) and a gas source (foaming agent), has the advantages of high flame retardant efficiency, low smoke, low toxicity, less addition and the like, meets the requirements of the current flame retardant material on smoke suppression and low toxicity, and is considered to be a green flame retardant with great development potential (Thomson, Juniperus, Qianliemilitary. research progress of the intumescent flame retardant, China plastics, 2012, (8): 1-8). Nevertheless, the IFR currently used still has the problems of poor flame retardant effect, poor compatibility with the polymer, large influence on the physical properties of the polymer, and the like.
The carbon forming agent is the basis for forming an expanded carbonized layer and is one of key substances influencing the flame retardant effect of the IFR. Therefore, the development of new char-forming agents has been the focus of IFR research.
The most used char-forming agents were mainly polyols such as pentaerythritol, dipentaerythritol, starch, sorbitol, etc. The carbon forming agents have high water solubility, poor compatibility with materials, easy migration and precipitation, poor carbon forming performance and thermal stability and large addition amount, so that the mechanical properties and the like of the materials are seriously reduced. These problems have severely hampered the development of IFR. In order to solve the above problems, extensive research has been carried out on char-forming agents at home and abroad, and many novel char-forming agents have been developed, such as thermoplastic polyurethane char-forming agents (Bugajny M, Bras M L, Bourbigot S, et al. thermoplastic polyurethanes as carbonifying agents in organic blends part 1: Fire tar. of polypropylene/thermoplastic polyurethanes/ammonium polyolefin blends J Fire Sci,1999,17(6):494 513), thermoplastic phenolic resin char-forming agents (Zhang Y, Wu W, Wu R, scientific. the thermoplastic polyurethane blending means of the thermoplastic polyurethane resins of polyurethane resins as polyolefin resins, thermoplastic polyurethanes as copolymers of thermoplastic polyurethanes, polyamide resins, 2012,127(2), 1061-1068), etc. Although the defects of high water solubility, easy precipitation, poor thermal stability and the like of the traditional carbon forming agent are overcome, the carbon forming property is not ideal, so the carbon forming agent is not widely applied.
In recent years, the successful use of macromolecular triazine char-forming agents has significantly improved the flame retardant effect of IFR. It has both carbonizing and foaming functions, and is insoluble in water and has high compatibility with polymer. IFR compounded by the IFR and APP not only has obviously improved flame retardant effect compared with the traditional IFR, but also has obviously improved water resistance and mechanical property (Feng C, Zhang Y, Liu S, et al. Synthesis of novel triazine harringting agent and its effect in organic flame-retardant polypropylene. J Appl M Sci,2012,123(6): 3208) 3216, Feng C, Liang M, J, et al. synthetic effect of a novel triazine harringting agent and ammonium phosphate on the flame-retardant polypropylene), thus widely appreciating the formation of triazine as a domestic and foreign flame-retardant composition. There are many reports on such char-forming agents. Nevertheless, such char-forming agents also have the following problems: 1) it is mainly prepared by using cyanuric chloride, monoamine (such as ethanolamine, butylamine and the like) and polyamine (such as ethylenediamine, piperazine) as raw materials through condensation and polycondensation. Because cyanuric chloride is not completely substituted, the product generally contains about 1.0 percent of chlorine, which can not completely meet the halogen-free requirement of users on the flame retardant and still has certain safety problem; 2) a large amount of waste water containing sodium chloride is generated in the production process and is difficult to treat. In addition, since a large amount of a low-boiling solvent (e.g., acetone) is used in the production process, the loss of the solvent is large, causing serious air pollution. Due to the problem of environmental pollution, the carbon forming agent is not produced in large scale at home, so that the popularization and the use of the carbon forming agent are influenced; 3) the flame retardant effect and the water resistance are still to be further improved, and the water resistance of the flame retardant material prepared by the flame retardant material can not meet the quality standards at home and abroad. Aiming at the problems, the patent designs and synthesizes a novel macromolecular triazine charring agent-pentaerythritol modified melamine formaldehyde resin (Tanglinsheng, Zhuxin, Yangxi Wei, and the like, pentaerythritol modified melamine formaldehyde resin and a preparation method thereof, and the patent application number is 201910072232.0,2019-01-25) according to the flame retardant mechanism of IFR, the structural characteristics of the triazine charring agent, and the like. The charring agent grafts pentaerythritol onto melamine formaldehyde resin through etherification, which not only successfully solves the problems of large water solubility of pentaerythritol, poor compatibility with polymers and the like, but also has charring and foaming functions because the charring agent contains pentaerythritol structural units and triazine ring structural units. However, the pentaerythritol modified melamine formaldehyde resin has slightly poor thermal stability and charring property, the thermal decomposition temperature of 2% weight loss is only about 210 ℃, the effect of the pentaerythritol modified melamine formaldehyde resin alone as a charring agent is not ideal, and the flame retardant product is easy to turn yellow.
Disclosure of Invention
In view of the above problems, the inventors of the present invention have conducted intensive studies on the formulation of IFR using pentaerythritol-modified melamine-formaldehyde resin as a char-forming agent and a preparation method thereof, and as a result, found that the disadvantages of pentaerythritol-modified melamine-formaldehyde resin as a char-forming agent can be essentially overcome by compounding piperazine pyrophosphate having good thermal stability and char-forming property, and that IFR having good flame retardant effect on polypropylene can be prepared by compounding a pentaerythritol-modified melamine-formaldehyde resin/piperazine pyrophosphate complex as a char-forming agent, melamine cyanurate as a foaming agent, and ammonium polyphosphate as a dehydrating agent.
The IFR comprises the following components in percentage by mass:
furthermore, the pentaerythritol modified melamine formaldehyde resin is prepared by taking melamine, paraformaldehyde and pentaerythritol as raw materials through three steps of reactions such as hydroxymethylation, polycondensation and etherification.
The IFR has good flame retardant effect on polypropylene, and basically does not contain chlorine, so that the IFR is safer and more environment-friendly. In addition, the prepared flame-retardant PP has good color.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
All percentages used in the present invention are mass percentages unless otherwise indicated.
The polypropylene (PP for short) used in the application is PP SP179 type co-polypropylene produced by Qilu division of China petrochemical company and PP H8020 homo-polypropylene produced by Lanzhou petrochemical company of China petroleum and natural gas, and the two are mixed according to the mass ratio w (PP SP179) that w (PP H8020) is 3:1 for use; ammonium polyphosphate (APP for short) and Melamine Cyanurate (MCA) are produced by Shouguangdong chemical company Limited; piperazine pyrophosphate is produced by Sichuan fine chemical research and design institute; the pentaerythritol modified melamine formaldehyde resin is self-made.
Preparation of flame-retardant PP sample: and extruding and uniformly mixing PP and IFR in a double-screw extruder (with the rotating speed of 20-30 rpm) at 190-200 ℃ according to a certain mass ratio, and granulating. And (3) performing compression molding on the dried granules at 200-210 ℃ by using a tablet press under the pressure of 5MPa, then performing cold pressing under the pressure of 5MPa, and cutting the granules into sample strips with required specifications for performance testing.
And (3) testing the flame retardant property: the Limiting Oxygen Index (LOI) is determined by adopting a JF-3 type oxygen index determinator (Jiangning district analytical instrument factory in Nanjing city) according to GB/T2046-1993, and the size of a test sample is 100mm multiplied by 6.5mm multiplied by 1.6 mm; the vertical burning test adopts an CZF-3 type horizontal vertical burning tester (Jiangning district analytical instrument factory in Nanjing) and refers to GB/T2408-1996 test, and the sample size is 100mm multiplied by 13mm multiplied by 1.6 mm.
Example 1
The preparation method of the pentaerythritol modified melamine formaldehyde resin comprises the following specific steps:
126g (1.0mol) of melamine, 225g (7.5mol) of paraformaldehyde and 1L of deionized water are added into a 2L three-neck flask provided with a reflux condenser tube, a stirrer and a thermometer, the pH of the material is adjusted to about 9 by using 10 mass percent sodium hydroxide solution, and then the temperature is increased to 75 ℃ for reaction for 1 h. Then the temperature of the material is reduced to 55 ℃, 613g (4.5mol) of pentaerythritol is added, hydrochloric acid with the mass fraction of 20% is used for adjusting the pH of the material to about 1.5, the material reacts for 2.5 hours at the temperature of 55 +/-5 ℃, and the temperature is increased to 80 +/-5 ℃ for continuous reaction for 2 hours. After the reaction is finished, the mixture is mixed with 10 percent sodium hydroxide solution by mass fractionAdjusting the pH of the materials to about 9, cooling to room temperature, filtering, washing a filter cake for 3 times by using 1L multiplied by 3 deionized water, and drying the obtained filter cake for 3 hours at 150 ℃ to obtain 292g of white powdery product. The yield of the product was 99.2%, the solubility of the product was 0.22g/100mL of water, and the temperature at which the product lost 2% (T)2wt％) 5% temperature (T)5wt％) 10% temperature (T)10wt％) And temperature at maximum rate of thermal weight loss (T)max) 213.1 deg.C, 235.4 deg.C, 256.0 deg.C and 357.0 deg.C, respectively.
Example 2
An intumescent flame retardant taking pentaerythritol modified melamine formaldehyde resin/piperazine pyrophosphate compound as a char forming agent comprises the following components in parts by mass: 750g of ammonium polyphosphate, 130g of pentaerythritol modified melamine formaldehyde resin, 30g of melamine cyanurate and 90g of piperazine pyrophosphate. The components are added into a conventional powder mixer or a high-speed mixer and mixed for 10-20 min to obtain IFR.
The above IFR was subjected to the flame retardancy evaluation test in the manner described above, and the results are shown in Table 1. The results in Table 1 show that the IFR prepared in this example has good flame retardant effect on PP, and when the addition amount is 28% of the total mass of the material, the vertical burning test passes V-0 grade, t1And t1Only 1.12s and 2.45s, respectively, and the flame retardant PP has no significant yellowing in color.
Example 3
An intumescent flame retardant taking pentaerythritol modified melamine formaldehyde resin/piperazine pyrophosphate compound as a char forming agent comprises the following components in parts by mass: 750g of ammonium polyphosphate, 110g of pentaerythritol modified melamine formaldehyde resin, 30g of melamine cyanurate and 110g of piperazine pyrophosphate. The components are added into a conventional powder mixer or a high-speed mixer and mixed for 10-20 min to obtain IFR.
The above IFR was subjected to the flame retardancy evaluation test in the manner described above, and the results are shown in Table 1. The results in Table 1 show that the IFR prepared in this example has good flame retardant effect on PP, but the flame retardant effect is slightly worse than that of example 1, when the addition amount accounts for 28% of the total mass of the material, the vertical burning test only passes V-1 grade,t1and t15.24s and 10.63s, respectively, but the flame retardant PP is whiter in color.
Example 4
An intumescent flame retardant taking pentaerythritol modified melamine formaldehyde resin/piperazine pyrophosphate compound as a char forming agent comprises the following components in parts by mass: 750g of ammonium polyphosphate, 130g of pentaerythritol modified melamine formaldehyde resin, 50g of melamine cyanurate and 70g of piperazine pyrophosphate. The components are added into a conventional powder mixer or a high-speed mixer and mixed for 10-20 min to obtain IFR.
The above IFR was subjected to the flame retardancy evaluation test in the manner described above, and the results are shown in Table 1. The results in Table 1 show that the IFR prepared in the example also has better flame retardant effect on PP, but the flame retardant effect is inferior to that of the IFR prepared in the example 1 and the IFR prepared in the example 2, when the IFR is added in 28 percent of the total mass of the materials, the IFR only passes V-2 grade in the vertical burning test, and t is t1And t1Only 7.74s and 17.58s, respectively, and drips upon combustion.
Comparative example 1
An intumescent flame retardant taking pentaerythritol modified melamine formaldehyde resin as a char forming agent comprises the following components by mass: 750g of ammonium polyphosphate, 220g of pentaerythritol modified melamine formaldehyde resin and 30g of melamine cyanurate. The components are added into a conventional powder mixer or a high-speed mixer and mixed for 10-20 min to obtain IFR.
The above IFR was subjected to the flame retardancy evaluation test in the manner described above, and the results are shown in Table 1. The results in Table 1 show that the IFR prepared in the example also has a good flame retardant effect on PP, but the flame retardant effect is obviously inferior to that of the example, when the addition amount of the IFR accounts for 30% of the total mass of the material, the IFR can pass the V-0 level in the vertical burning test, and the color of the flame retardant PP is slightly yellow.
TABLE 1 flame retardant Properties of flame retardant PP
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. An intumescent flame retardant is characterized in that a compound of pentaerythritol modified melamine formaldehyde resin and piperazine pyrophosphate is used as a char forming agent, melamine cyanurate is used as a foaming agent, ammonium polyphosphate is used as a dehydrating agent, and the intumescent flame retardant is prepared by mixing and compounding, wherein the mass fractions of the components are as follows: 70-80% of ammonium polyphosphate, 10-20% of pentaerythritol modified melamine formaldehyde resin, 2-5% of melamine cyanurate and 7-12% of piperazine pyrophosphate; the pentaerythritol modified melamine formaldehyde resin is prepared by taking melamine, paraformaldehyde and pentaerythritol as raw materials through hydroxymethylation, polycondensation and etherification, and comprises the following specific processes: adding 126g of melamine, 225g of paraformaldehyde and 1L of deionized water into a 2L three-neck flask provided with a reflux condenser, a stirrer and a thermometer, adjusting the pH of the materials to 9 by using a 10% sodium hydroxide solution by mass fraction, heating to 75 ℃ for reaction for 1h, then cooling the temperature of the materials to 55 ℃, adding 613g of pentaerythritol, adjusting the pH of the materials to 1.5 by using 20% hydrochloric acid by mass fraction, reacting at 55 +/-5 ℃ for 2.5h, heating to 80 +/-5 ℃ for further reaction for 2h, adjusting the pH of the materials to 9 by using a 10% sodium hydroxide solution by mass fraction after the reaction is finished, cooling to room temperature, filtering, washing the filter cake for 3 times by using 1L multiplied by 3 deionized water, and drying the obtained filter cake at 150 ℃ for 3h to obtain the product.
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| CN102304250A (en) * | 2011-09-07 | 2012-01-04 | 上海日之升新技术发展有限公司 | High-melt-index halogen-free flame-retarding polypropylene and preparation method thereof |
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| CN102304250A (en) * | 2011-09-07 | 2012-01-04 | 上海日之升新技术发展有限公司 | High-melt-index halogen-free flame-retarding polypropylene and preparation method thereof |
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| 哌嗪类磷酸盐的合成及其在阻燃聚丙烯中的应用研究;唐海珊;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20180715;B016-86 * |
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Effective date of registration: 20221214 Address after: 751500 agricultural products processing park, Yanchi County, Wuzhong City, Ningxia Hui Autonomous Region Patentee after: Ningxia Dayu New Material Technology Co.,Ltd. Address before: No. 53, Zhengzhou Road, North District, Qingdao, Shandong Patentee before: QINGDAO University OF SCIENCE AND TECHNOLOGY |