CN113462108B - Degradable organic-inorganic flame-retardant composite material based on core-shell structure - Google Patents
Degradable organic-inorganic flame-retardant composite material based on core-shell structure Download PDFInfo
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Abstract
The invention belongs to the technical field of degradable plastics, and discloses a degradable organic-inorganic flame-retardant composite material based on a core-shell structure. Dissolving a degradable polymer substrate in a solvent, adding inorganic flame-retardant particles and ammonia water, and stirring and mixing uniformly to obtain a mixed solution; heating the obtained mixed solution to 50-70 ℃, dropwise adding a silicate ester compound under the stirring condition for condensation reaction, and performing vacuum drying to remove the solvent to obtain SiO with inorganic flame-retardant particles as cores2Degradable organic-inorganic flame-retardant composite material with degradable polymer interpenetrating network as shell. The organic-inorganic flame-retardant composite material has good dispersion stability when being applied to flame-retardant degradable plastic functional master batches or flame-retardant degradable plastics, has obvious reinforcing effect on degradable plastic base materials, can obviously improve the mechanical property of the degradable plastics while having stable flame-retardant effect, and has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of degradable plastics, and particularly relates to a degradable organic-inorganic flame-retardant composite material based on a core-shell structure.
Background
The biodegradable plastic is also called biodegradable plastic, and is characterized in that the biodegradable plastic is degraded under the conditions of nature such as soil and/or sandy soil, and/or under specific conditions such as composting conditions or anaerobic digestion conditions or in aqueous culture solution, and is finally completely degraded into carbon dioxide (CO)2) Or-And methane (CH)4) Water (H)2O) and mineralized inorganic salts of the elements contained therein, and new plastics of biomass.
The main target markets of the biodegradable plastics are packaging films, agricultural films, special fiber materials, plastic bags, plastic tableware and the like. Compared with the traditional plastic material, the novel degradable material has slightly higher cost. However, with the enhancement of environmental awareness, people are willing to use a novel degradable material with a slightly higher price for protecting the environment, and the enhancement of environmental awareness brings huge development opportunities for the new biodegradable material industry.
However, the use performance of the existing biodegradable plastics still has obvious disadvantages, such as difficulty in reaching the use performance of the traditional plastic products in the aspect of mechanical properties. Particularly, when other functional additives such as inorganic flame retardants are introduced, the mechanical properties are greatly reduced, and even the additives are separated out in severe cases. If the particle size of the flame retardant powder is too large, the dispersion in the base material is not satisfactory, and if the amount of the flame retardant powder is too large, the use performance of the material is deteriorated. In order to disperse the flame retardant powder in the base material, it is necessary to make the particle diameter smaller and the particle diameter distribution narrower. Therefore, the flame retardant is miniaturized and even nanocrystallized, so that the contact surface between the flame retardant and the material can be increased to improve the compatibility, and the dosage of the flame retardant can be reduced. However, the commercial flame retardant powder in China often cannot meet the requirement of ultra-fining or nano-fining.
Patent CN104910438A discloses a degradable flame-retardant plastic film, which comprises the following components in parts by mass: 10-18 parts of polylactic resin, 40-60 parts of thermoplastic starch, 8-16 parts of polyethylene wax, 6-12 parts of polyvinyl alcohol, 10-15 parts of polyol, 0.2-0.8 part of initiator, 0.2-0.5 part of antibacterial agent, 2-6 parts of flame retardant, 0.2-0.8 part of nano antioxidant and 1.2-2.4 parts of toughening agent. The flame retardant is one or more of decabromodiphenylethane, monoammonium phosphate and ammonium polyphosphate. Patent CN106496645A discloses a flame-retardant degradable starch-based composite material for injection molding, which comprises the following raw materials in parts by weight: 60-70 parts of thermoplastic starch, 40-60 parts of polyhydroxybutyrate, 25-40 parts of glycerol, 20-40 parts of talcum powder, 5-15 parts of cross-linking agent, 5-10 parts of compatilizer and 10-E of nano magnesium hydroxide20 parts of other additives and 1-2 parts of other additives. Patent CN112940424A discloses a flame retardant degradable plastic, which comprises: 45-70 parts of modified polyvinyl alcohol, 30-60 parts of starch, 3-8 parts of glycerol, 10-23 parts of hydroxypropyl cellulose and modified SiO217-34 parts of nano particles and 0.3-0.8 part of antioxidant; the modified polyvinyl alcohol is flame retardant modified polyvinyl alcohol, and the flame retardant is 2-hydroxy-5, 5-dimethyl-2, 2-oxo-1, 3, 2-dioxaphosphorite ethanolamine salt (PNOEA). The invention has the beneficial effects that (1) the polyvinyl alcohol is modified by adopting the novel flame retardant, and the prepared modified polyvinyl alcohol resin has better flame retardant effect and better mechanical property; (2) by using modified SiO2The nano particles are used as the filler, so that the dispersion performance of the degradable plastic is improved, and the prepared degradable plastic has better mechanical property. Although the above patent technologies can solve the problem of mechanical property reduction of degradable plastics to a certain extent, they all need to use specific components or nano-flame retardants, and thus the degree of commercialization is not high and the industrial application is limited.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a degradable organic-inorganic flame-retardant composite material based on a core-shell structure.
The invention also aims to provide the degradable organic-inorganic flame-retardant composite material based on the core-shell structure, which is prepared by the method.
The invention further aims to provide application of the degradable organic-inorganic flame-retardant composite material based on the core-shell structure in preparation of flame-retardant degradable plastic functional master batches or flame-retardant degradable plastics.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a degradable organic-inorganic flame-retardant composite material based on a core-shell structure comprises the following preparation steps:
(1) dissolving a degradable polymer substrate in a solvent, adding inorganic flame-retardant particles and ammonia water, and stirring and mixing uniformly to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 50 ℃Dripping silicate ester compound at 70 deg.C under stirring for condensation reaction, vacuum drying to remove solvent to obtain SiO with inorganic flame-retardant particles as core2Degradable organic-inorganic flame-retardant composite material with degradable polymer interpenetrating network as shell.
Further, in the step (1), the degradable polymer substrate is at least one of polyvinyl alcohol, polylactic acid, poly adipic acid/butylene terephthalate, cellulose, chitosan and polycaprolactone.
Further, the solvent in the step (1) is an organic solvent or a mixed solvent of an organic solvent and water.
Further, in the step (1), the inorganic flame-retardant particles are at least one of aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate and zinc borate.
Further, the particle size of the inorganic flame retardant particles in the step (1) is 20nm to 100 μm.
Further, the mass ratio of the degradable polymer base material to the inorganic flame-retardant particles in the step (1) is 1 (1-5).
Further, the silicate compound in the step (2) is at least one of methyl orthosilicate (TMOS), ethyl orthosilicate (TEOS), and isopropyl orthosilicate (TPOS).
Further, the mass ratio of the addition amount of the silicate compound to the inorganic flame-retardant particles in the step (2) is 1 (1-4).
Further, the temperature of the vacuum drying in the step (2) is 110-140 ℃.
A degradable organic-inorganic flame-retardant composite material based on a core-shell structure is prepared by the method.
Further, the particle size of the degradable organic-inorganic flame-retardant composite material based on the core-shell structure is 50 nm-150 μm.
The degradable organic-inorganic flame-retardant composite material based on the core-shell structure is applied to preparation of flame-retardant degradable plastic functional master batches or flame-retardant degradable plastics.
Further, the application process is as follows: mixing and granulating the degradable organic-inorganic flame-retardant composite material based on the core-shell structure and the degradable polymer base material to obtain the flame-retardant degradable plastic functional master batch or the flame-retardant degradable plastic.
Further, the mass percentage content of the degradable organic-inorganic flame-retardant composite material based on the core-shell structure in the flame-retardant degradable plastic functional master batch is 8-40%; the mass percentage content in the flame-retardant degradable plastic is 1-6%.
The principle of the invention is as follows: in the degradable polymer base material solution system, silicate ester compounds are hydrolyzed and condensed to form polysilicic acid with a net structure under the action of an ammonia water catalyst, and the silicate ester compounds are hydrolyzed in the polymer base material solution to form a polysilicic acid network, so polymer macromolecules inevitably exist in the polysilicic acid network, and an organic-inorganic interpenetrating network is formed. In the subsequent process of removing the solvent by vacuum drying, the polysilicic acid is solidified and formed into SiO on the surface of the inorganic flame-retardant particles2And polymer macromolecules are firmly embedded into SiO2In the network, the degradable polymer modification on the surface of the inorganic flame-retardant particle is realized.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts SiO2Surface modification of inorganic flame-retardant particles by an interpenetrating network shell structure of a degradable polymer, wherein SiO2Firmly combined with inorganic flame-retardant particles; meanwhile, an organic-inorganic interpenetrating network is formed by the sol-gel reaction of silicate ester compound and degradable polymer macromolecules, and the polymer macromolecules are firmly embedded into SiO2In the network, the obtained degradable organic-inorganic flame-retardant composite material based on the core-shell structure has good compatibility with a degradable polymer base material, can be conveniently added into a degradable plastic functional master batch or biodegradable plastic, has a stable flame-retardant effect, can remarkably improve the mechanical property of the degradable plastic, and has good industrial application prospect.
(2) The invention can realize the addition of the conventional commercial micron-sized flame retardant powder, does not reduce the mechanical property of the degradable plastic, and does not need to carry out ultra-fining or nano-fining on the flame retardant powder.
(3) The inorganic flame-retardant particles adopted by the invention have the advantages of high-efficiency flame retardance, environmental friendliness, small addition amount and low cost, and the SiO prepared by the invention2After the interpenetrating network shell structure of the degradable polymer is subjected to surface modification, the flame retardant effect is further improved.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The degradable organic-inorganic flame-retardant composite material based on the core-shell structure is prepared by the following method:
(1) adding 20 parts by mass of polyvinyl alcohol into 500 parts by mass of a mixed solvent of water and ethanol (the volume ratio of water to ethanol is 1:1), heating to 75 ℃, stirring and dissolving uniformly, then adding 100 parts by mass of an aluminum hydroxide flame retardant (D50 with the particle size of 12 mu m) and 10 parts by mass of ammonia water, stirring and mixing uniformly to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 55-60 ℃, dropwise adding 30 parts by mass of TEOS under the stirring condition for condensation reaction, and after the reaction is finished, performing spray drying at 120-140 ℃ to remove the solvent to obtain the SiO solid with the aluminum hydroxide flame retardant as the core2-degradable organic-inorganic flame-retardant composite material with polyvinyl alcohol interpenetrating network as shell.
The degradable organic-inorganic flame-retardant composite material obtained in the embodiment has a particle size of 17 μm as measured by an Euro-American Kerr LS-609 laser particle size distribution instrument D50.
Example 2
The degradable organic-inorganic flame-retardant composite material based on the core-shell structure is prepared by the following method:
(1) adding 30 parts by mass of polylactic acid into 500 parts by mass of dichloromethane solvent, heating to 70 ℃, stirring and dissolving uniformly, then adding 100 parts by mass of magnesium hydroxide flame retardant (D50 with the particle size of 26 mu m) and 20 parts by mass of ammonia water, stirring at high speed and mixing uniformly to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 60-65 ℃, and stirring at a high speedDripping 40 parts by mass of TMOS under the condition for condensation reaction, and after the reaction is finished, carrying out spray drying to remove the solvent to obtain the SiO solid with the magnesium hydroxide flame retardant as the core2-degradable organic-inorganic flame-retardant composite material with polylactic acid interpenetrating network as shell.
The degradable organic-inorganic flame-retardant composite material obtained in the embodiment has a D50 particle size of 39 μm measured by an Europe and America LS-609 laser particle size distribution instrument.
Example 3
The degradable organic-inorganic flame-retardant composite material based on the core-shell structure is prepared by the following method:
(1) adding 40 parts by mass of poly (butylene adipate)/terephthalate into 300 parts by mass of dichloromethane solvent, heating to 65 ℃, uniformly stirring and dissolving, then adding 100 parts by mass of zinc borate flame retardant (D50 with the particle size of 6 mu m) and 20 parts by mass of ammonia water, uniformly stirring and mixing at a high speed to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 65-70 ℃, dropwise adding 50 parts by mass of TPOS under the condition of high-speed stirring for condensation reaction, after the reaction is finished, carrying out vacuum stirring, drying to remove the solvent, grinding and crushing to obtain the SiO flame retardant with the zinc borate flame retardant as the core2-a degradable organic-inorganic flame-retardant composite material with a shell of poly (butylene adipate/terephthalate) interpenetrating network.
The degradable organic-inorganic flame-retardant composite material obtained in the embodiment has a D50 particle size of 18 μm measured by an Europe and America LS-609 laser particle size distribution instrument.
Example 4
The flame-retardant degradable PVA plastic functional master batch is prepared by the following method:
and (2) melting, mixing, extruding and granulating 30 parts by mass of the degradable organic-inorganic flame-retardant composite material obtained in the example 1 and 70 parts by mass of polyvinyl alcohol slice particles by using an extruder to obtain the flame-retardant degradable PVA plastic functional master batch.
Example 5
The flame-retardant degradable PLA plastic functional master batch is prepared by the following method:
and (3) melting, mixing, extruding and granulating 30 parts by mass of the degradable organic-inorganic flame-retardant composite material obtained in the example 2 and 70 parts by mass of polylactic acid sliced particles by using an extruder to obtain the flame-retardant degradable PLA plastic functional master batch.
Example 6
The flame-retardant degradable PBAT plastic functional master batch is prepared by the following method:
and (2) melting, mixing, extruding and granulating 30 parts by mass of the degradable organic-inorganic flame-retardant composite material obtained in the embodiment 3 and 70 parts by mass of polybutylene adipate/terephthalate slice particles by using an extruder to obtain the flame-retardant degradable PBAT plastic functional master batch.
Comparative example 1
The flame-retardant degradable PVA plastic functional master batch of the comparative example is prepared by the following method:
and (3) melting, mixing, extruding and granulating 30 parts by mass of an aluminum hydroxide flame retardant (D50 with the particle size of 12 mu m) and 70 parts by mass of polyvinyl alcohol slice particles by using an extruder to obtain the flame-retardant degradable PVA plastic functional master batch.
Comparative example 2
The flame-retardant degradable PLA plastic functional master batch of the comparative example is prepared by the following method:
and (3) melting, mixing, extruding and granulating 30 parts by mass of magnesium hydroxide flame retardant (D50 with the particle size of 26 mu m) and 70 parts by mass of polylactic acid sliced particles by using an extruder to obtain the flame-retardant degradable PLA plastic functional master batch.
Comparative example 3
The flame-retardant degradable PBAT plastic functional master batch of the comparative example is prepared by the following method:
and (3) melting, mixing, extruding and granulating 30 parts by mass of zinc borate flame retardant (D50 with the particle size of 6 microns) and 70 parts by mass of polybutylene adipate/terephthalate slice particles by using an extruder to obtain the flame-retardant degradable PBAT plastic functional master batch.
And (3) performing performance test on the plastic functional master batches obtained in the above examples 4-6 and comparative examples 1-3, and performing melt mixing on the plastic functional master batches and the corresponding degradable plastic base materials according to the mass ratio of 1:9 by an extruder (2% of polyethylene glycol plasticizer is added in the process), and injecting by an injection molding machine to obtain a standard sample. Testing the tensile strength and the elongation at break of the standard sample according to the national standard of ASTM-D638; the flame retardant properties of the standard specimens were tested according to UL94 (where the value after V-0 rating is the vertical burning time of the bars after 10s of burning). The test results are shown in table 1 below.
TABLE 1
As can be seen from the results in table 1, the conventional micron-sized inorganic flame retardant particles without any modification can significantly deteriorate the mechanical properties of the degradable plastic, which is caused by the reason that the particle size of the flame retardant powder is too large and is not uniformly dispersed in the base material and is unstable. The degradable organic-inorganic flame-retardant composite material with the core-shell structure can obviously improve the mechanical property of degradable plastics. The reason is that SiO of the shell layer2The polymer interpenetrating network wraps and fixes the inorganic flame-retardant particles and is firmly embedded into SiO2Polymer macromolecules in the network can be integrated with the degradable plastic base material, and the interpenetrating network can improve the dispersion stability of the inorganic flame-retardant particles and simultaneously can play a role in reinforcing the degradable plastic base material, so that the mechanical property of the interpenetrating network is obviously improved. In addition, it can be seen that the present invention uses SiO2After the surface of the inorganic flame-retardant particles is modified by the interpenetrating network shell structure of the degradable polymer, the flame-retardant effect is further improved, and the reason is that besides the improvement effect of the dispersion stability, the SiO2The interpenetrating network shell structure of the degradable polymer also plays a certain role.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of a degradable organic-inorganic flame-retardant composite material based on a core-shell structure is characterized by comprising the following preparation steps:
(1) dissolving a degradable polymer substrate in a solvent, adding inorganic flame-retardant particles and ammonia water, and stirring and mixing uniformly to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1) to 50-70 ℃, dropwise adding a silicate ester compound under the stirring condition for condensation reaction, and drying in vacuum to remove the solvent to obtain SiO particles with inorganic flame-retardant particles as cores2-degradable organic-inorganic flame retardant composites with an interpenetrating network of degradable polymers as shell;
in the step (1), the degradable polymer base material is at least one of polyvinyl alcohol, polylactic acid, poly adipic acid/butylene terephthalate, cellulose, chitosan and polycaprolactone; the solvent is an organic solvent or a mixed solvent of the organic solvent and water; the inorganic flame-retardant particles are at least one of aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate and zinc borate; the particle size of the inorganic flame-retardant particles is 20 nm-100 mu m.
2. The preparation method of the degradable organic-inorganic flame-retardant composite material based on the core-shell structure according to claim 1, characterized in that: the mass ratio of the degradable polymer base material to the inorganic flame-retardant particles in the step (1) is 1 (1-5).
3. The preparation method of the degradable organic-inorganic flame-retardant composite material based on the core-shell structure according to claim 1, characterized in that: in the step (2), the silicate compound is at least one of methyl orthosilicate, ethyl orthosilicate and isopropyl orthosilicate.
4. The preparation method of the degradable organic-inorganic flame-retardant composite material based on the core-shell structure according to claim 1, characterized in that: the mass ratio of the addition amount of the silicate ester compound to the inorganic flame-retardant particles in the step (2) is 1 (1-4); the temperature of the vacuum drying is 110-140 ℃.
5. A degradable organic-inorganic flame-retardant composite material based on a core-shell structure is characterized in that: prepared by the method of any one of claims 1 to 4; the particle size of the degradable organic-inorganic flame-retardant composite material based on the core-shell structure is 50 nm-150 microns.
6. The use of the degradable organic-inorganic flame retardant composite material based on the core-shell structure of claim 5 in the preparation of a flame retardant degradable plastic functional masterbatch or a flame retardant degradable plastic.
7. The application according to claim 6, characterized in that the application process comprises: mixing and granulating the degradable organic-inorganic flame-retardant composite material based on the core-shell structure and the degradable polymer base material to obtain the flame-retardant degradable plastic functional master batch or the flame-retardant degradable plastic.
8. Use according to claim 7, characterized in that: the mass percentage of the degradable organic-inorganic flame-retardant composite material based on the core-shell structure in the flame-retardant degradable plastic functional master batch is 8-40%; the mass percentage of the flame-retardant degradable plastic is 1-6%.
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