CN108409916B - Preparation method of halogen-free low-smoke flame-retardant unsaturated polyester resin composite material - Google Patents
Preparation method of halogen-free low-smoke flame-retardant unsaturated polyester resin composite material Download PDFInfo
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- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
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- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
Abstract
The invention provides a preparation method of a halogen-free low-smoke flame-retardant unsaturated polyester resin composite material, which is prepared by adding organic modified inorganic particles, expandable graphite, magnesium gluconate, ammonium polyphosphate and the like into raw materials of maleic anhydride, phthalic anhydride and propylene glycol for preparing unsaturated polyester resin according to a specific process. Tests show that when the addition amount of the organic modified inorganic particles is about 4%, the composite material still can maintain excellent mechanical properties, can effectively reduce the heat release of the unsaturated polyester resin composite material in the combustion process, improves the high-temperature thermal stability and the carbon residue of the material, has higher oxygen index (the oxygen index is not lower than 24.5, and the horizontal and vertical combustion UL-94V-0 level), has the maximum smoke density of below 80 under the flameless condition, and can be widely applied to a plurality of fields of vehicles, building facilities, electronic and electrical appliances, chemical industries and the like.
Description
Technical Field
The invention relates to a preparation method of a halogen-free low-smoke flame-retardant unsaturated polyester resin composite material, belonging to the technical field of flame-retardant materials and the technical field of high polymer materials.
Background
The unsaturated polyester resin composite material is in a research and development stage before world war II, is firstly applied to military aviation during the world war II, and is popularized to civilian use after the war II. Since 1950, glass fiber reinforced plastic products have been the main use of unsaturated polyester resin materials, and have been widely used in paint coating, buttons, artificial marble, artificial agate, flooring, and the like. The unsaturated polyester resin is a linear polymer containing unsaturated double bonds and having a certain molecular weight, which is obtained by the polycondensation reaction of dibasic acid or anhydride and dihydric alcohol. The double bond on the molecular chain can be copolymerized with various olefins in the presence of an initiator to obtain the thermosetting resin. The unsaturated polyester resin has excellent comprehensive performance and good processing characteristics, can be cured and molded at room temperature and normal pressure, and has wide application in the fields of traffic, electronic appliances, buildings, articles for daily use and the like.
Due to the special chemical structure and flammability characteristics of the resin, the traditional unsaturated polyester resin has low Limiting Oxygen Index (LOI), low melting and dropping phenomena during combustion, and a large amount of black smoke and toxic gases are accompanied during combustion, so that the traditional unsaturated polyester resin is limited in many fields. Therefore, research on the combustion characteristics of unsaturated polyester resin materials and improvement of the flame retardancy of the materials are always the direction of intensive research by many researchers. At present, the preparation of the flame-retardant unsaturated polyester mainly comprises two methods, namely an additive method and an intrinsic method, wherein the additive method is used for physically mixing the flame-retardant filler with a polymer matrix. The method has good flame retardant effect, but the required filler addition amount is high, the interface bonding force between the filler and a matrix is poor, and other properties of the material are seriously influenced. The intrinsic type is to introduce a flame retardant into the unsaturated polyester resin structure, which has the advantages of improving the flame retardance of the material, reducing the fire hazard, having no great influence on the mechanical properties of the material and even improving the mechanical properties of partial materials. However, the method has high cost and insufficient improvement of the smoke suppression capability of the material. Therefore, the combination of the two methods can effectively solve the problems, so that the method can be widely applied.
Although the halogen flame retardant in the market has a high-efficiency flame retardant effect, the halogen-containing material can release a large amount of smoke and toxic gas during combustion, and the health and property safety of human beings are seriously harmed, so that the research on the halogen-free, low-smoke, low-toxicity and environment-friendly flame retardant is a hotspot of the current research. In the inorganic flame retardant, aluminum hydroxide, magnesium hydroxide, palygorskite, layered double hydroxide and the like have large decomposition and absorption heat, and the oxide generated after decomposition can cover the surface of a polymer, so that the effect of isolating air can be achieved, and meanwhile, water vapor generated by decomposition can dilute combustible gas to play a certain fire extinguishing effect.
Disclosure of Invention
The invention aims to provide a preparation method of a halogen-free low-smoke flame-retardant unsaturated polyester resin composite material aiming at the problems of the unsaturated polyester resin composite material in practical application.
Preparation of halogen-free low-smoke flame-retardant unsaturated polyester resin composite material
The invention discloses a method for preparing a halogen-free low-smoke flame-retardant unsaturated polyester resin composite material, which comprises the following steps:
(1) organic functionalization of inorganic microparticles
Adding the inorganic particles into an ethanol solution of organic acid, magnetically stirring for 6-10 hours at the temperature of 60-80 ℃, filtering, repeatedly washing with absolute ethanol, and drying in vacuum to obtain white powdery solid, namely the organic modified inorganic particles.
Wherein the inorganic particles are magnesium hydroxide, aluminum hydroxide, palygorskite, hydrotalcite or montmorillonite with the particle size of 400-600 nm;
the organic acid is itaconic acid, maleic acid, isophthalic acid and adipic acid; the mass ratio of the organic acid to the inorganic fine particles is 1:1 to 1: 6.
(2) Synthesis of unsaturated polyester resin
Mixing the organic modified inorganic particles obtained in the step (1) with maleic acid, phthalic anhydride and propylene glycol, adding a polymerization inhibitor hydroquinone, and reacting at about 190-210 ℃; stopping the reaction when the acid value of the system is reduced to 40 +/-2 mg KOH/g, reducing the temperature to 145-155 ℃, quickly adding hydroquinone serving as a polymerization inhibitor and styrene serving as a diluent into the system, and stirring for 2-3 hours to obtain the unsaturated polyester resin.
The molar ratio of the maleic acid to the phthalic anhydride to the propylene glycol is 1:1: 2.1-1: 3: 4.1; the addition amount of the organic functionalized inorganic particles is 0.5-6% of the total mass of the maleic acid, the phthalic anhydride and the propylene glycol.
The addition amount of the polymerization inhibitor hydroquinone is 1/10000-2/10000 of the total mass of the organic functionalized inorganic particles, the maleic acid, the phthalic anhydride and the propylene glycol.
The addition amount of the diluent styrene is 20-40% of the total mass of the inorganic particles, the maleic acid, the phthalic anhydride and the propylene glycol.
(3) Preparation of halogen-free low-smoke flame-retardant unsaturated polyester resin composite material
Adding a curing agent and an accelerator into the synthesized unsaturated polyester resin, stirring and uniformly mixing, pouring into a mold, curing at room temperature for 20-25 h, and curing at 60-120 ℃ for 3-5 h to obtain the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material. In order to further improve the flame retardant property of the material, expandable graphite, magnesium gluconate and ammonium polyphosphate can be added into the unsaturated polyester resin.
The accelerant is cobalt naphthenate, and the addition amount of the accelerant is 1-2% of the mass of the unsaturated polyester resin composite material.
The curing agent is methyl ethyl ketone peroxide, and the addition amount of the curing agent is 1-2% of the mass of the unsaturated polyester resin composite material.
The expandable graphite is used as a carbon source, so that the material can form a more compact carbon layer in the combustion process. The addition amount of the unsaturated polyester resin composite material is 2-12% of the mass of the unsaturated polyester resin composite material.
The addition amount of the magnesium gluconate is 1-6% of the mass of the unsaturated polyester resin composite material; the addition amount of the ammonium polyphosphate is 1-10% of the mass of the unsaturated polyester resin composite material. Magnesium gluconate and ammonium polyphosphate are used as a composite acid source to dilute the concentration of combustible gas so as to prevent further spread of fire and prevent heat from being transferred to the interior of the material.
Characterization of halogen-free low-smoke flame-retardant unsaturated polyester resin composite material
The structure of the inorganic particle magnesium hydroxide after organic functionalization by maleic acid, the preparation of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material and the performance are explained below by taking the inorganic particle magnesium hydroxide as an example.
FIG. 1 is a plot of the infrared absorption spectrum of an organically functionalized inorganic particulate magnesium hydroxide. As can be seen in FIG. 1, 3695cm-1OH as magnesium hydroxide-Peak of stretching vibration of 3400cm-1The stretching vibration peak indicates that the product contains water of crystallization, 1578cm-1And 1313cm-1Is COO-Shows the-OH of the magnesium hydroxide after modification-The characteristic peaks are attenuated.
FIG. 2 is an electron microscope scanning of the organic functionalization of inorganic particulate magnesium hydroxide. As can be seen from FIG. 2, there is a difference in the morphology of magnesium hydroxide before modification (left) and after modification (right). Because the unmodified magnesium hydroxide surface has strong polarity and is easy to form agglomeration, and the modified magnesium hydroxide surface has certain dispersibility, the compatibility with a matrix is improved, and the flame retardant property of the polymer material is improved.
FIG. 3 is an analysis of the organic functionalized thermal stability of inorganic particulate magnesium hydroxide. As can be seen from FIG. 3, the thermal decomposition temperature of MA (maleic acid) is 150-200 ℃. MH (magnesium hydroxide) absorbs heat at high temperature (300-400 ℃) and decomposes into magnesium oxide and water vapor. The thermal decomposition of MA-MH (modified magnesium hydroxide) is divided into three stages: (1) the loss of water is mainly caused in the temperature range of 50-100 ℃, because the surface of MA-MH has hydrophilic groups (COOH) and the existence of bound water. (2) Thermal decomposition of MH in MA-MH results in a loss of quality. (3) The thermal degradation of organics in MA-MH results in mass loss.
The structural and morphological characteristics of figures 1, 2 and 3 show that maleic acid is successfully grafted to the surface of magnesium hydroxide, and the desired target product is obtained. Because the surface of the modified product has a large amount of carboxyl and magnesium hydroxide inorganic matters, the modified product can participate in the synthetic reaction of unsaturated polyester resin, the interface bonding strength of inorganic particles and the unsaturated polyester resin is enhanced, and the mechanical property and the flame retardant property of the composite material can be improved.
FIG. 4 is an infrared spectrum of the unsaturated polyester resin composite material. As can be seen from FIG. 4, the length of the groove is 1733cm-1A strong absorption band appears at the position, which is a stretching vibration peak of C = O; 1278cm-1And 1057cm-1There are 2 absorption peaks, namely, (C-O-C) symmetric stretching vibration and asymmetric stretching vibration, and the two peaks are both characteristic peaks of ester. 1642cm-1The absorption band is C = C stretching vibration peak; and 3695cm of modified magnesium hydroxide-1-OH-Peak sum 1578cm-1The COO-peak disappeared.
FIG. 5 is an electron microscope scan of the surface of the carbon layer after the burning of the unsaturated polyester resin. As can be seen from FIG. 5, the unsaturated polyester resin added with the flame retardant forms a carbon layer with a compact and continuous structure, can play a good physical barrier in the combustion process of the polyester resin, and also can play roles in heat insulation, oxygen insulation and smoke suppression, thereby not only effectively improving the flame retardance of the composite material, but also preventing the further degradation of the internal material.
Performance test of halogen-free low-smoke flame-retardant unsaturated polyester resin composite material
1. Flame retardant properties
The test method comprises the following steps: the test is carried out by adopting the GB/T2460-93 standard.
And (3) testing results: the oxygen index is not lower than 24.5, and the smoke density is not higher than 80.
2. Mechanical Properties
The test method comprises the following steps: the GB/T9341-88 standard test is adopted.
And (3) testing results: flexural strength 20-38 MPa flexural modulus: 1700 to 2800 MPa.
Therefore, the unsaturated polyester resin is modified by a method combining the flame retardant and the intrinsic flame retardance, so that the flame retardant and the smoke suppressant are achieved, and the flame retardant and the smoke suppressant have good mechanical properties.
Drawings
FIG. 1 is a plot of the infrared absorption spectrum of an organically functionalized inorganic particulate magnesium hydroxide.
FIG. 2 is an electron microscope scanning of the organic functionalization of inorganic particulate magnesium hydroxide.
FIG. 3 is an analysis of the organic functionalized thermal stability of inorganic particulate magnesium hydroxide.
Fig. 4 is an infrared absorption spectrum curve of the unsaturated polyester resin composite material.
FIG. 5 is an electron microscope scan of the surface of the carbon layer after the burning of the unsaturated polyester resin.
Detailed Description
The preparation method and properties of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material of the invention are further explained by the following specific examples.
Example 1
(1) Organic functionalization of inorganic particle magnesium hydroxide: dissolving 9.98g of maleic acid in 500ml of absolute ethyl alcohol, adding 10g of magnesium hydroxide, magnetically stirring for 8 hours at 80 ℃, filtering, repeatedly washing with absolute ethyl alcohol, and drying in vacuum to obtain modified magnesium hydroxide.
(2) Synthesis of unsaturated polyester resin composite material: mixing 1.43g of modified magnesium hydroxide, 29.42g of maleic anhydride, 44.43g of phthalic anhydride, 47.94g of propylene glycol and 0.01g of hydroquinone, reacting at 180 ℃ for 2h, heating to 200 ℃, stopping the reaction when the acid value of the system is reduced to 40 +/-2 mg of KOH/g, cooling to 150 ℃, rapidly adding 0.01g of polymerization inhibitor hydroquinone and 66.35g of diluent styrene into the system, and rapidly stirring for 2-3 h to uniformly mix and dissolve the styrene and the polyester product to obtain the unsaturated polyester resin.
(3) The preparation of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material comprises the following steps: 166.05g of the synthesized unsaturated polyester resin is taken, 6.64g of expandable graphite, 4.28g of magnesium gluconate and 7.14g of ammonium polyphosphate are added into the unsaturated polyester resin, the mixture is stirred at a constant temperature for 1 to 3 hours, then 3.42g of methyl ethyl ketone peroxide and 3.51g of cobalt naphthenate are added, the mixture is stirred at a constant temperature and poured into a mold, the mixture is cured at room temperature for 24 hours, then cured at 60 ℃ for 3 hours and cured at 100 ℃ for 1 hour, and the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material is obtained.
(4) The halogen-free low-smoke flame-retardant unsaturated polyester resin composite material has the following properties: flame retardant property: oxygen index 24.5, smoke density 79. Mechanical properties: flexural strength 26.2MPa, flexural modulus 2132MPa, and impact strength 10.3KJ/M2。
Example 2
(1) Organic functionalization of inorganic particle palygorskite: dissolving 7.14g of isophthalic acid in 500ml of absolute ethyl alcohol, adding 12g of palygorskite, magnetically stirring for 8 hours at 80 ℃, filtering, repeatedly washing with absolute ethyl alcohol, and drying in vacuum to obtain the modified palygorskite.
(2) Synthesis of unsaturated polyester resin composite material: mixing 2.41g of modified palygorskite, 29.42g of maleic anhydride, 44.43g of phthalic anhydride, 47.94g of propylene glycol and 0.01g of hydroquinone at 180 ℃ for reaction for 2h, heating to 200 ℃, stopping the reaction when the acid value of the system is reduced to 40 +/-2 mg of KOH/g, cooling to 150 ℃, rapidly adding 0.01g of polymerization inhibitor hydroquinone and 66.88g of diluent styrene into the system, and rapidly stirring for 2-3 h to uniformly mix and dissolve the styrene and the polyester product, thereby obtaining the unsaturated polyester resin.
(3) The preparation of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material comprises the following steps: and (2) taking 166.05g of the synthesized unsaturated polyester resin, adding 13.28g of expandable graphite, 10.17g of magnesium gluconate and 12.45g of ammonium polyphosphate, stirring at a constant temperature for 1-3 h, adding 4.66g of methyl ethyl ketone peroxide and 4.32g of cobalt naphthenate, stirring at a constant temperature, pouring into a mold, curing at room temperature for 24h, curing at 60 ℃ for 3h, and curing at 100 ℃ for 1 ℃ to obtain the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material.
(4) The halogen-free low-smoke flame-retardant unsaturated polyester resin composite material has the following properties: flame retardant property: oxygen index 28, smoke density 55. Mechanical properties: bending strength of 20.2MPa, bending modulus of 1800MPa and impact strength of 10.1KJ/M2。
Example 3
(1) Organic functionalization of inorganic particle hydrotalcite: dissolving 5.03g of adipic acid in 500ml of absolute ethyl alcohol, adding 8g of hydrotalcite, magnetically stirring for 8 hours at 80 ℃, filtering, repeatedly washing with absolute ethyl alcohol, and drying in vacuum to obtain the modified hydrotalcite.
(2) Synthesis of unsaturated polyester resin composite material: 3.85g of modified hydrotalcite, 29.42g of maleic anhydride, 44.43g of phthalic anhydride, 47.94g of propylene glycol and 0.01g of hydroquinone are mixed and reacted at 180 ℃ for 2h, the temperature is raised to 200 ℃, the reaction is stopped when the acid value of the system is reduced to 40 +/-2 mg of KOH/g, the temperature is lowered to 150 ℃, 0.01g of polymerization inhibitor hydroquinone and 67.65g of diluent styrene are rapidly added into the system, and the mixture is rapidly stirred for 2-3 h, so that the styrene and the polyester product are uniformly mixed and dissolved, and the unsaturated polyester resin is obtained.
(3) The preparation of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material comprises the following steps: and (2) taking 166.05g of the synthesized unsaturated polyester resin, adding 19.93g of expandable graphite, 16.13g of magnesium gluconate and 14.44g of ammonium polyphosphate into the unsaturated polyester resin, stirring at a constant temperature for 1-3 h, adding 5.21g of methyl ethyl ketone peroxide and 4.89g of cobalt naphthenate, stirring at a constant temperature, pouring into a mold, curing at room temperature for 24h, curing at 60 ℃ for 3h, and curing at 100 ℃ for 1h to obtain the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material.
(4) The halogen-free low-smoke flame-retardant unsaturated polyester resin composite material has the following properties: the flame retardant property of the material is as follows: oxygen index 32, smoke density 47. Mechanical properties: bending strength of 20.3MPa, bending modulus of 1700MPa and impact strength of 10.2KJ/M2。
Claims (8)
1. A preparation method of a halogen-free low-smoke flame-retardant unsaturated polyester resin composite material comprises the following steps:
(1) organic modification of inorganic microparticles: adding inorganic particles into an ethanol solution of organic acid, magnetically stirring for 6-10 hours at the temperature of 60-80 ℃, filtering, repeatedly washing with absolute ethanol, and drying in vacuum to obtain white powdery solid, namely the organic modified inorganic particles; the inorganic particles are magnesium hydroxide, aluminum hydroxide, palygorskite, hydrotalcite or montmorillonite with the particle size of 400-600 nm;
(2) synthesis of unsaturated polyester resin: mixing the obtained organic modified inorganic particles with maleic acid, phthalic anhydride and propylene glycol, adding hydroquinone serving as a polymerization inhibitor, and reacting at 190-210 ℃; stopping the reaction when the acid value of the system is reduced to 40 +/-2 mgKOH/g, reducing the temperature to 145-155 ℃, quickly adding hydroquinone serving as a polymerization inhibitor and styrene serving as a diluent into the system, and stirring for 2-3 hours to obtain unsaturated polyester resin;
(3) the preparation of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material comprises the following steps: adding expandable graphite, magnesium gluconate, ammonium polyphosphate, a curing agent and an accelerator into the unsaturated polyester resin, stirring and uniformly mixing, pouring into a mold, curing at room temperature for 20-25 h, and curing at 60-120 ℃ for 3-5 h to obtain the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material.
2. The preparation method of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material as claimed in claim 1, characterized in that: the organic acid in the step (1) is itaconic acid, maleic acid, isophthalic acid and adipic acid; the mass ratio of the organic acid to the inorganic fine particles is 1:1 to 1: 6.
3. The preparation method of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material as claimed in claim 1, characterized in that: in the step (2), the molar ratio of the maleic acid to the phthalic anhydride to the propylene glycol is 1:1: 2.1-1: 3: 4.1; the addition amount of the organic functionalized inorganic particles is 0.5-6% of the total mass of the maleic acid, the phthalic anhydride and the propylene glycol.
4. The preparation method of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material as claimed in claim 1, characterized in that: in the step (2), the addition amount of the polymerization inhibitor hydroquinone is 1/10000-2/10000 of the total mass of the organic functionalized inorganic particles, the maleic acid, the phthalic anhydride and the propylene glycol.
5. The preparation method of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material as claimed in claim 1, characterized in that: in the step (2), the addition amount of the diluent styrene is 20-40% of the total mass of the inorganic particles, the maleic acid, the phthalic anhydride and the propylene glycol.
6. The preparation method of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material as claimed in claim 1, characterized in that: in the step (3), the accelerant is cobalt naphthenate, and the addition amount of the accelerant is 1-2% of the mass of the unsaturated polyester resin composite material.
7. The preparation method of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material as claimed in claim 1, characterized in that: in the step (3), the curing agent is methyl ethyl ketone peroxide, and the adding amount of the curing agent is 1-2% of the mass of the unsaturated polyester resin composite material.
8. The preparation method of the halogen-free low-smoke flame-retardant unsaturated polyester resin composite material as claimed in claim 1, characterized in that: in the step (3), the addition amount of the expandable graphite is 2-12% of the mass of the unsaturated polyester resin composite material; the addition amount of the magnesium gluconate is 1-6% of the mass of the unsaturated polyester resin composite material; the addition amount of the ammonium polyphosphate is 1-10% of the mass of the unsaturated polyester resin composite material.
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| CN112920545A (en) * | 2019-12-05 | 2021-06-08 | 湖南三合汽车新材料有限公司 | Expandable graphite modified SMC material |
| CN112850678B (en) * | 2021-02-08 | 2022-10-18 | 西北师范大学 | Preparation of micromolecular phosphorus-magnesium flame retardant and application of micromolecular phosphorus-magnesium flame retardant in preparation of flame-retardant copolyester material |
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| CN101935439A (en) * | 2010-09-03 | 2011-01-05 | 吉林大学 | Method for preparing uniformly dispersed PET/nano-inorganic composite material |
| CN106749947A (en) * | 2016-12-03 | 2017-05-31 | 安徽富丽华化工有限公司 | A kind of resistant to elevated temperatures modified unsaturated polyester resin of high tenacity and preparation method thereof |
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| JP2000063844A (en) * | 1998-08-24 | 2000-02-29 | Nippon Chem Ind Co Ltd | Flame retardant composition and flame-retardant resin composition |
| CN101200575A (en) * | 2006-12-15 | 2008-06-18 | 上海杰事杰新材料股份有限公司 | Montmorillonite modified polyester and preparation method thereof |
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| CN101935439A (en) * | 2010-09-03 | 2011-01-05 | 吉林大学 | Method for preparing uniformly dispersed PET/nano-inorganic composite material |
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