CN110396284B - Intumescent flame retardant, flame-retardant polylactic acid material and preparation method thereof - Google Patents
Intumescent flame retardant, flame-retardant polylactic acid material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an intumescent flame retardant, a flame-retardant polylactic acid material and a preparation method thereof. The intumescent flame retardant is prepared from the following components in mass ratio of 96-80: 4-20 parts of chitosan salt and ZIF-8@ GO, wherein the chitosan salt is prepared by reacting 2-carboxyethyl phenyl hypophosphorous acid with chitosan, and the ZIF-8@ GO is prepared by loading a zeolite imidazole ester framework material ZIF-8 on graphene oxide; adopting a solution blending method to mix a chloroform solution of polylactic acid and a chloroform dispersion liquid of the intumescent flame retardant according to a mass ratio of 95: 5, and coating to obtain the flame-retardant polylactic acid material. The flame-retardant polylactic acid material disclosed by the invention is simple in formula, halogen-free and environment-friendly, the mechanical property and the flame retardant property of polylactic acid are obviously improved, the molten drop phenomenon of the flame-retardant polylactic acid material is obviously weakened, a continuous and compact carbon layer is generated after combustion, and the heat insulation and oxygen isolation effects are achieved.
Description
Technical Field
The invention belongs to the technical field of polylactic acid materials, and relates to an intumescent flame retardant, a flame-retardant polylactic acid material and a preparation method thereof.
Background
The polylactic acid has the advantages of both environment and resources, and is a biodegradable high polymer material with potential and application value. Polylactic acid is widely used in various fields in life because of its excellent mechanical properties, easy processing and molding, and good biocompatibility. However, polylactic acid has the problems of flammability, serious molten drop and the like, has great potential safety hazard, and greatly limits the application of the polylactic acid in the fields of automobiles, electronic appliances and the like. Therefore, the preparation of flame retardant polylactic acid materials is an inevitable research trend.
Chitosan (CS) is a natural alkaline amino polysaccharide with polyhydroxy, and has wide application prospect in the aspects of biomedical materials, biodegradable packages, cosmetics, wastewater treatment and the like due to the characteristics of wide sources, low price, no toxicity, biodegradability and the like. The chitosan contains a large amount of C, N and is a good flame retardant, but the chitosan is a strong polar material and has poor compatibility with polymers, which inevitably causes the deterioration of the composite material performance, such as mechanical property, flame retardant property and the like. In order to solve this problem, it is necessary to treat chitosan to introduce hydrophobic groups into the chitosan to promote the compatibility of the chitosan with the polymer. Shi Xingxing et al (Shi X, et al Polymers Advanced Technologies, 2018, 29, 860-866) synthesize the flame retardant CS-P-Co, and then add the flame retardant CS-P-Co into polylactic acid to improve the flame retardant property of the polylactic acid, and the experimental result shows that the flame retardant CS-P-Co is well dispersed in the polylactic acid matrix but does not play a good flame retardant effect, and when 4wt% of CS-P-Co is added, the LOI value of the composite material is only 22.5%.
The zeolite imidazolate framework (ZIF-8) contains a large amount of N, Zn and is a very promising flame retardant. Zhang et al (Zhang M, et al, Journal of Materials Science, 2018, 53, 7083-.
Disclosure of Invention
Aiming at the problems of flammability, low limiting oxygen index, serious brittleness and the like of polylactic acid, the invention aims to provide an intumescent flame retardant, a flame-retardant polylactic acid material containing the intumescent flame retardant and a preparation method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
the intumescent flame retardant consists of chitosan salt and binary hybrid nanoparticles ZIF-8@ GO according to different mass ratios, wherein the chitosan salt is obtained by reacting 2-carboxyethyl phenyl hypophosphorous acid with chitosan.
Furthermore, the binary hybrid nano particle ZIF-8@ GO is prepared by loading a zeolite imidazole ester framework material ZIF-8 on graphene oxide through coordination, wherein the loading amount of the ZIF-8 is 16.1-18.0%.
Further, the mass ratio of chitosan salt to ZIF-8@ GO in the intumescent flame retardant is 96-80: 4 to 20.
The invention provides a preparation method of the intumescent flame retardant, which comprises the following specific steps:
firstly, heating in a water bath at 60-70 ℃, dissolving 2-carboxyethyl phenyl hypophosphorous acid in water, stirring to completely dissolve the 2-carboxyethyl phenyl hypophosphorous acid to prepare 2wt% of 2-carboxyethyl phenyl hypophosphorous acid aqueous solution for standby, adding chitosan into the 2-carboxyethyl phenyl hypophosphorous acid aqueous solution for a few times, stirring for 5-6 hours at 60-70 ℃, cooling reactants, separating out the reactants by ethanol to obtain a product which is a light yellow solid, and drying the reactants for standby to obtain chitosan salt.
And secondly, preparing a methanol dispersion liquid of the graphene oxide by using the graphene oxide obtained by the Hummers method, and sequentially adding 2-methylimidazole and zinc nitrate hexahydrate into the methanol dispersion liquid of the graphene oxide to obtain ZIF-8@ GO.
And thirdly, mixing chitosan salt and ZIF-8@ GO according to a proportion to obtain the intumescent flame retardant.
Further, in the first step, the mass ratio of 2-carboxyethylphenylphosphinic acid to chitosan was 2.14: 4.5.
The invention provides an intumescent flame-retardant polylactic acid material, which is prepared from the following components in percentage by mass of 95: 5 and an intumescent flame retardant.
The invention provides a preparation method of the intumescent flame-retardant polylactic acid material, which comprises the following steps:
mixing the polylactic acid and the chloroform solution of the intumescent flame retardant according to a proportion, paving a film, volatilizing the solvent, and drying to obtain the flame-retardant polylactic acid material.
Compared with the prior art, the invention has the following advantages:
(1) 2-carboxyethyl phenyl hypophosphorous acid is used for modifying chitosan, and groups such as benzene rings in the 2-carboxyethyl phenyl hypophosphorous acid can promote the compatibility of the chitosan and a polylactic acid matrix; ZIF-8 is loaded on graphene oxide, and organic ligands in the ZIF-8 can promote the compatibility of the graphene oxide and a polylactic acid matrix.
(2) In the combustion process, chitosan salt and combustion products of ZIF-8@ GO, such as zinc oxide and pyrophosphoric acid, have high chemical activity, can catalyze polylactic acid, graphene oxide and chitosan to dehydrate and form carbon to form a cross-linked and compact carbon layer, and play a role in blocking, so that the flame retardant property of the polylactic acid is improved;
(3) zn in ZIF-8@ GO2+The polylactic acid contains open sites, and can form coordination bonds with ester groups on polylactic acid chains, so that a large number of polylactic acid chains are captured around the polylactic acid chains, and a local cross-linking structure is formed to enhance the mechanical property of the polylactic acid; in addition, the benzene ring group in the chitosan salt has a certain enhancement effect on the mechanical property of the polylactic acid;
(4) in the combustion process, the chitosan salt is heated and decomposed to generate PO. and HPO free radicals, so that combustible free radicals H and HO in the surrounding environment are easily captured; meanwhile, ZIF-8@ GO is heated and decomposed to generate NH3、N2The concentration of the combustible gas is diluted by non-combustible gas, and the combustion rate is slowed down, so that the flame retardant property of the polylactic acid is improved;
(5) the intumescent flame retardant disclosed by the invention is halogen-free and degradable, is a green flame retardant, and has small harm to the environment in the combustion process and combustion products.
Detailed Description
The present invention will be described in more detail with reference to examples.
According to the invention, 2-carboxyethyl phenyl hypophosphorous acid is utilized to improve the compatibility of chitosan and polylactic acid, ZIF-8 is utilized to improve the compatibility of graphene oxide and polylactic acid, a flame-retardant system is halogen-free, degradable, green and environment-friendly, and the mechanical property and flame retardant property of the polylactic acid material are improved. The chitosan salt is prepared from-POOH and-COOH groups at two ends of 2-carboxyethyl phenyl hypophosphorous acid and-NH in chitosan2The radicals reacting to form- [ NH ]3]+[POO]-And- [ NH ]3]+[COO]-Ionic bonding, and synthesizing chitosan salt.
The synthetic route is as follows:
example 1: preparation of intumescent flame retardant
(1) Heating in a water bath at 60-70 ℃, dissolving 2.14g of 2-carboxyethyl phenyl hypophosphorous acid in 98mL of deionized water, stirring to completely dissolve the 2-carboxyethyl phenyl hypophosphorous acid to prepare a 2wt% 2-carboxyethyl phenyl hypophosphorous acid aqueous solution for later use, adding 4.5g of chitosan into the 2-carboxyethyl phenyl hypophosphorous acid aqueous solution for a few times, stirring for 5-6 hours at 60-70 ℃, cooling the reactant, separating out the reactant by using ethanol to obtain a product which is a light yellow solid, and drying the reactant for later use to obtain the chitosan salt.
(2) Weighing 0.163g of graphene oxide, pouring the graphene oxide into 100ml of methanol solution, and performing ultrasonic treatment to uniformly disperse the graphene oxide by using a Hummers method; 1.602g of 2-methylimidazole and 1.487g of zinc nitrate hexahydrate are weighed and dissolved in 100ml of methanol respectively; and sequentially adding the graphene oxide into a methanol dispersion liquid of graphene oxide, stirring for 1-2 h at room temperature, centrifuging, washing with alcohol, and drying to obtain ZIF-8@ GO.
(3) Mixing chitosan salt and ZIF-8@ GO according to a mass ratio of 96: 4,92: 8,88: 12, 84: 16, 80: 20 are mixed in sequence, and the intumescent flame retardant obtained by mixing is named as CHZ-1, CHZ-2, CHZ-3, CHZ-4 and CHZ-5 in sequence.
Example 2
Weighing 9.5g of polylactic acid particles, adding the polylactic acid particles into 40ml of chloroform solution, and magnetically stirring for 2 hours to completely dissolve the polylactic acid particles; adding the intumescent flame retardant CHZ-1 into 20mL chloroform solution, performing ultrasonic treatment for 2h to uniformly disperse the intumescent flame retardant CHZ-1, pouring the mixture into the chloroform solution of polylactic acid, stirring for 4h, coating a film on a glass plate by using a film coating machine, standing at room temperature for 24h to volatilize the solvent, then demolding with warm water, putting into an oven, and standing at 50 ℃ for 72h, which is marked as PCHZ-1. The tensile strength is 47.5 +/-0.5 MPa, the limiting oxygen index is 24.2 percent and the vertical burning grade is V-2 grade according to the test method of GB/T2406-1993.
Example 3
Weighing 9.5g of polylactic acid particles, adding the polylactic acid particles into 40ml of chloroform solution, and magnetically stirring for 2 hours to completely dissolve the polylactic acid particles; adding the intumescent flame retardant CHZ-2 into 20mL of chloroform solution, performing ultrasonic treatment for 2 hours to uniformly disperse the intumescent flame retardant CHZ-2, pouring the mixture into the chloroform solution of polylactic acid, stirring for 4 hours, coating a film on a glass plate by using a film coating machine, standing at room temperature for 24 hours to volatilize the solvent, then demolding with warm water, putting into an oven, and standing at 50 ℃ for 72 hours, which is marked as PCHZ-2. The tensile strength is 50.7 +/-0.6 MPa, the limiting oxygen index is 24.5 percent and the vertical burning grade is V-2 grade according to the test method of GB/T2406-1993.
Example 4
Weighing 9.5g of polylactic acid particles, adding the polylactic acid particles into 40ml of chloroform solution, and magnetically stirring for 2 hours to completely dissolve the polylactic acid particles; adding the intumescent flame retardant CHZ-3 into 20mL of chloroform solution, performing ultrasonic treatment for 2 hours to uniformly disperse the intumescent flame retardant CHZ-3, pouring the mixture into the chloroform solution of polylactic acid, stirring for 4 hours, coating a film on a glass plate by using a film coating machine, standing at room temperature for 24 hours to volatilize the solvent, then demolding with warm water, putting into an oven, and standing at 50 ℃ for 72 hours, which is marked as PCHZ-3. The tensile strength is 56.5 +/-0.4 MPa, the limiting oxygen index is 25.2 percent and the vertical burning grade is V-2 grade according to the test method of GB/T2406-1993.
Example 5
Weighing 9.5g of polylactic acid particles, adding the polylactic acid particles into 40ml of chloroform solution, and magnetically stirring for 2 hours to completely dissolve the polylactic acid particles; adding the intumescent flame retardant CHZ-4 into 20mL of chloroform solution, performing ultrasonic treatment for 2 hours to uniformly disperse the intumescent flame retardant CHZ-4, pouring the mixture into the chloroform solution of polylactic acid, stirring for 4 hours, coating a film on a glass plate by using a film coating machine, standing at room temperature for 24 hours to volatilize the solvent, then demolding with warm water, putting into an oven, and standing at 50 ℃ for 72 hours, which is marked as PCHZ-4. The tensile strength is 61.5 +/-0.8 MPa, the limiting oxygen index is 26.0 percent and the vertical burning grade is V-2 grade according to the test method of GB/T2406-1993.
Example 6
Weighing 9.5g of polylactic acid particles, adding the polylactic acid particles into 40ml of chloroform solution, and magnetically stirring for 2 hours to completely dissolve the polylactic acid particles; adding the intumescent flame retardant CHZ-5 into 20mL chloroform solution, performing ultrasonic treatment for 2h to uniformly disperse the intumescent flame retardant CHZ-5, pouring the mixture into the chloroform solution of polylactic acid, stirring for 4h, coating a film on a glass plate by using a film coating machine, standing at room temperature for 24h to volatilize the solvent, then demolding with warm water, putting into an oven, and standing at 50 ℃ for 72h, which is marked as PCHZ-5. The tensile strength is 56.6 +/-0.5 MPa, the limiting oxygen index is 25.0 percent and the vertical burning grade is V-2 grade according to the test method of GB/T2406-1993.
Comparative example 1
Weighing 10g of polylactic acid particles, adding 40ml of chloroform solution, magnetically stirring for 2h to completely dissolve the polylactic acid particles, coating a film on a glass plate by using a film coating machine, standing at room temperature for 24h to volatilize the solvent, then demoulding with warm water, placing in an oven, and standing at 50 ℃ for 72h, wherein the mark is PLA. The tensile strength is 35.8 +/-0.4 MPa and the limited oxygen index is 21.0 percent, which does not reach the grade of vertical burning, determined according to the GB/T2406-1993 standard test method.
Comparative example 2
9.5g of polylactic acid particles were weighed, 40ml of chloroform solution was added, and the mixture was magnetically stirred for 2 hours to be completely dissolved. 0.5g of intumescent flame retardant consisting of chitosan salt alone is weighed, added into 20mL of chloroform solution, ultrasonically treated for 2h to uniformly disperse the intumescent flame retardant, poured into the chloroform solution of polylactic acid, stirred for 4h, coated on a glass plate by a coating machine, placed at room temperature for 24h to volatilize the solvent, then demoulded by warm water, placed in an oven, and placed at 50 ℃ for 72h, which is marked as PCH. The tensile strength is 43.3 +/-0.7 MPa, the limiting oxygen index is 24.0 percent and the vertical burning grade is V-2 grade according to the test method of GB/T2406-1993.
Claims (6)
1. The intumescent flame retardant is characterized by consisting of chitosan salt and binary hybrid nanoparticles ZIF-8@ GO, wherein the chitosan salt is prepared by reacting 2-carboxyethyl phenyl hypophosphorous acid with chitosan;
in the intumescent flame retardant, the mass ratio of chitosan salt to ZIF-8@ GO is 96-80: 4 to 20.
2. The intumescent flame retardant of claim 1, wherein the binary hybrid nanoparticles ZIF-8@ GO are obtained by loading a zeolitic imidazolate framework material ZIF-8 on graphene oxide through coordination, wherein the loading of ZIF-8 is 16.1-18.0%.
3. A process for the preparation of an intumescent flame retardant as claimed in claim 1 or 2, characterized by the following specific steps:
firstly, heating in a water bath at 60-70 ℃, dissolving 2-carboxyethyl phenyl hypophosphorous acid in water, stirring to completely dissolve the 2-carboxyethyl phenyl hypophosphorous acid to obtain 2wt% of 2-carboxyethyl phenyl hypophosphorous acid aqueous solution, adding chitosan into the 2-carboxyethyl phenyl hypophosphorous acid aqueous solution in several times, stirring for 5-6 hours at 60-70 ℃, cooling, separating out and drying to obtain chitosan salt;
secondly, sequentially adding 2-methylimidazole and zinc nitrate hexahydrate into a methanol dispersion liquid of graphene oxide to prepare ZIF-8@ GO;
and thirdly, mixing chitosan salt and ZIF-8@ GO according to a proportion to obtain the intumescent flame retardant.
4. The method of claim 3, wherein in the first step, the mass ratio of 2-carboxyethylphenylphosphinic acid to chitosan is 2.14: 4.5.
5. An intumescent flame-retardant polylactic acid material is prepared from the following components in percentage by mass of 95: 5 and an intumescent flame retardant as claimed in claim 1 or 2.
6. A preparation method of an intumescent flame retardant polylactic acid material is characterized in that a solution blending method is adopted, and a chloroform solution of polylactic acid and a chloroform dispersion liquid of an intumescent flame retardant as claimed in claim 1 or 2 are mixed according to a mass ratio of 95: 5, and coating to obtain the flame-retardant polylactic acid material.
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