CN112226057A - Natural mineral modified degradable high-molecular flame-retardant composite material and preparation method thereof - Google Patents
Natural mineral modified degradable high-molecular flame-retardant composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a natural mineral modified degradable high-molecular flame-retardant composite material, which comprises the following steps: putting the natural mineral micro powder and the coupling agent into mixing equipment for coupling reaction, and cooling after the reaction is finished to obtain modified mineral micro powder uniformly coated by the coupling agent; putting the modified mineral micro powder, the degradable polymer, the synergistic flame retardant A, the synergistic flame retardant B, the compatilizer, the antioxidant and the plasticizer into mixing equipment in proportion for melt blending, and cooling and granulating or directly granulating after mixing uniformly to obtain flame-retardant master batches; and uniformly stirring the functional master batches and the degradable polymers, and putting the functional master batches and the degradable polymers into melt blending equipment for melt blending to obtain the degradable polymer flame-retardant composite material. The invention promotes the modified mineral micro powder and the synergistic flame retardant to be uniformly dispersed in the degraded polymer matrix and to be highly stripped, forms a more perfect network structure and fully exerts the unique functions of synergistic flame retardance and reinforcement.
Description
Technical Field
The invention relates to a silicate mineral micro powder modified degradable high-molecular flame-retardant material, in particular to a natural mineral modified degradable high-molecular flame-retardant composite material with high strength, high toughness and excellent flame-retardant property and a preparation method thereof, belonging to the technical field of high-valued utilization of minerals.
Background
The application of the traditional non-degradable plastics in a large amount not only consumes a large amount of petroleum and resources, but also causes huge environmental pollution and ecological damage. Although part of the plastic is recycled and reused, most of the waste plastic is buried and incinerated, especially the plastic packaging waste in the household garbage. Traditional petroleum-based plastics are discarded to the environment after consumption, creating tremendous environmental pressure. In order to solve the global problem, the development of green polymer materials is urgently needed, and the research and development of degradable polymer materials draw extensive attention and attention.
The industrial and academic circles pay great attention to the production and research of degradable high polymer materials, and the successfully developed varieties reach dozens of varieties, mainly including polylactic acid (PLA), Polycaprolactone (PCL), polybutylene succinate (PBS), Polyhydroxyalkanoate (PHA), polyvinyl alcohol (PVA) and the like. However, some intrinsic property defects of degradable high polymer materials, such as poor flame retardant property, low fire resistance grade, etc., limit their wider application in decoration, structure, etc. The defects of the prior art are as follows: (1) environmental pollution pressure of petroleum-based traditional materials: the existing high molecular flame retardant material in the market is developed based on petroleum-based traditional non-degradable high molecular material, is difficult to recover due to the existence of complex flame retardant, cannot be degraded after being discarded, and causes huge pressure on the environment. (2) The high-efficiency flame-retardant composite material has high filling amount and is difficult to process: in order to achieve a high-efficiency flame-retardant effect of a flammable polymer material, a large amount of flame retardant is often required to be filled, so that the cost of the flame-retardant material is increased, the flame-retardant material is difficult to process, and the mechanical properties of the polymer material are often seriously damaged. (3) The filler dispersion effect in the conventional melt processing form is poor: the conventional one-step processing technology has poor dispersing effect on the introduced flame retardant, has great damage to production environment or processing equipment, and is difficult to ensure low-cost sustainable industrialized green production. Therefore, it is necessary to modify degradable polymers in a targeted manner to meet specific flame retardant requirements.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an environment-friendly route for quickly modifying mineral micro powder in order to meet the requirements of decoration, automobile and electronic industries on flame-retardant degradable high polymer materials, and uniformly introduces the mineral micro powder and a synergistic flame retardant into a degradable high polymer matrix, thereby realizing the synchronous improvement of the mechanical property and the flame retardant property of the degradable high polymer composite material.
In order to solve the technical problems, the preparation method of the natural mineral modified degradable high-molecular flame-retardant composite material provided by the invention comprises the following steps:
s1, preparing modified mineral micro powder: placing the natural mineral micro powder and the coupling agent into mixing equipment at the temperature of 60 ‒ 110 ℃, uniformly mixing, carrying out coupling reaction for 3 minutes ‒ 20 minutes, and cooling after the reaction is finished to obtain modified mineral micro powder uniformly coated by the coupling agent;
s2, preparing functional master batches: putting the modified mineral micro powder obtained in the step S1, the degradable polymer, the synergistic flame retardant A, the synergistic flame retardant B, the compatilizer, the antioxidant and the plasticizer into mixing equipment in proportion for melt blending, and cooling and granulating or directly granulating after mixing uniformly to obtain functional master batches;
s3, degradable high-molecular flame-retardant composite material: and (3) uniformly stirring the functional master batch obtained in the step S2 and the degradable polymer according to a certain proportion, and putting the mixture into a melt blending device for melt blending to obtain the degradable polymer flame-retardant composite material.
In the improvement, in step S1, the natural mineral micro powder is silicate, and is at least one of montmorillonite, attapulgite, kaolin, sepiolite, talcum powder, wollastonite, mica powder, diatom powder, vermiculite, bentonite and tourmaline, and the particle size is 1000 ‒ 20000 meshes.
In the improvement, in the step S1, the coupling agent is a silane coupling agent, and the mass ratio of the silane coupling agent to the natural mineral micro powder is 1:50-1: 5.
In step S1, the coupling agent is at least one of octadecylamine coupling agent, isocyanate coupling agent, aluminate coupling agent and titanate coupling agent, and the mass ratio of the coupling agent to the natural mineral micropowder is 1:100 ‒ 1: 1.
In the modification, the mixing device in the step S1 is at least one of a high-speed mixer, an open mill, an internal mixer, a Z-type kneader, a screw kneader, a vacuum kneader, and a horizontal twin-screw mixer.
As an improvement, the degradable polymer is at least one of polylactic acid (PLA), Polycaprolactone (PCL), polyvinyl alcohol (PVA), polybutylene succinate (PBS), Polyhydroxyalkanoate (PHA) and polybutylene adipate terephthalate (PBAT).
In the improvement, in the step S2, the mass fraction of the modified mineral micro powder in the functional master batch is 10% ‒ 60%.
In the improvement, in the step S2, the synergistic flame retardant a is ammonium polyphosphate or a derivative thereof, and the mass fraction in the functional master batch is 10% ‒ 30%.
In the improvement, in the step S2, the synergistic flame retardant B is melamine, and the mass fraction of the synergistic flame retardant B in the functional master batch is 8% ‒ 25%.
In the improvement, in step S2, the compatibilizer is at least one of maleic anhydride grafted polyolefin elastomer (MAH-g-POE), maleic anhydride grafted ethylene-methyl acrylate copolymer (MAH-g-EMA), maleic anhydride grafted ethylene-ethyl acrylate copolymer (MAH-g-EEA), maleic anhydride grafted ethylene-butyl acrylate copolymer (MAH-g-EBA), and glycidyl methacrylate, and the mass fraction in the functional masterbatch is 2% ‒ 5%.
In the improvement, in step S2, the compatibilizer is at least one of tetrabutyl titanate, a reactive polyepoxy compatibilizer and acetyl tri-n-butyl citrate, and the mass fraction of the compatibilizer in the functional masterbatch is 0.2% ‒ 1.5.5%.
As an improvement, in the step S2, the antioxidant is at least one of hindered amine antioxidant, hindered phenol antioxidant and phosphite antioxidant, and the mass fraction in the functional masterbatch is 0.3% ‒ 2%.
In the improvement, in step S2, the plasticizer is at least one of polysiloxane, erucamide, pentaerythritol, dipentaerythritol, tripentaerythritol, polyethylene glycol, epoxidized soybean oil, stearic acid, stearate, and polyethylene wax, and the mass fraction of the functional masterbatch is 1% ‒ 5%.
As an improvement, the mixing equipment in the step S2 is at least one of a high-speed mixer, an open mill, a turnover type internal mixer, a continuous type internal mixer, a reciprocating screw extruder, a twin-screw extruder, a single-screw extruder, a Z-type kneader, a screw kneader, a vacuum kneader and a horizontal twin-screw mixer, the mixing temperature is 100 ‒ 250 ℃, and the energy consumption per unit mass in the mixing process is 0.1 ‒ 5 kWh/kg.
In step S3, the mass ratio of the functional masterbatch to the degradable polymer is 1:9 ‒ 2: 3.
As a modification, the melt blending device in the step S3 is at least one of a turnover type internal mixer, a continuous type internal mixer, a reciprocating screw extruder, a twin-screw extruder and a single-screw extruder, and the melt blending temperature is 120 ‒ 250 ℃.
The invention also provides a natural mineral modified degradable high polymer flame-retardant composite material which consists of modified mineral micro powder, degradable high polymer, a synergistic flame retardant A, a synergistic flame retardant B, a compatilizer, a plasticizer and an antioxidant; the modified mineral micro powder is silicate mineral micro powder modified by a coupling agent; the degradable polymer is at least one of polylactic acid (PLA), Polycaprolactone (PCL), polyvinyl alcohol (PVA), polybutylene succinate (PBS), Polyhydroxyalkanoate (PHA) and polybutylene adipate terephthalate (PBAT); the synergistic flame retardant A is ammonium polyphosphate or a derivative thereof; the synergistic flame retardant B is melamine; the compatilizer is at least one of maleic anhydride grafted polyolefin elastomer (MAH-g-POE), maleic anhydride grafted ethylene-methyl acrylate copolymer (MAH-g-EMA), maleic anhydride grafted ethylene-ethyl acrylate copolymer (MAH-g-EEA), maleic anhydride grafted ethylene-butyl acrylate copolymer (MAH-g-EBA), glycidyl methacrylate (the mass fraction in the functional master batch is 2% ‒ 5%), tetrabutyl titanate, reactive polyepoxy compatibilizer or acetyl tributyl citrate; the plasticizer is at least one of polysiloxane, erucamide, pentaerythritol, dipentaerythritol, tripentaerythritol, polyethylene glycol, epoxidized soybean oil, stearic acid, stearate and polyethylene wax; the antioxidant is at least one of hindered amine antioxidant, hindered phenol antioxidant and phosphite antioxidant. The Limit Oxygen Index (LOI) of the composite material is more than 28 percent, and the UL-94 flame retardant rating is V-0.
The invention has the beneficial effects that: (1) through coupling reaction, a coupling agent modification layer is directly formed on the surface of the silicate natural mineral micro powder, so that the affinity to high polymer materials is improved, and the agglomeration among the mineral micro powder is inhibited. (2) The high shear rate melting compounding process effectively strips and uniformly disperses the modified mineral micro powder, the synergistic flame retardant and other processing aids in the degradable polymer to obtain the functional master batch containing the modified mineral micro powder and the synergistic flame retardant, and endows the master batch with good dispersibility and processability. (3) The modified mineral micro powder and the flame-retardant master batch thereof are prepared firstly, and then the composite material with high efficiency, flame retardance and high mechanical property, which is formed by directly melting and blending the master batch and the degradable high polymer material, is obtained. (4) The invention adopts a technical route combining a 'synergistic flame retardant technology' and a 'masterbatching processing technology', promotes the modified mineral micro powder and the synergistic flame retardant to be uniformly dispersed in a degraded polymer matrix and to obtain high peeling, forms a perfect network structure, and fully exerts unique functions of synergistic flame retardance and reinforcement. The production process adopted by the method is simple and convenient, is easy for large-scale production, and has low production cost, various product functions and wide application prospect.
Drawings
FIG. 1 is a flow chart of a preparation method of the natural mineral modified degradable high molecular flame retardant composite material of the invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
As shown in fig. 1, a preparation method of a natural mineral modified degradable high molecular flame retardant composite material comprises the following steps:
s11, preparing modified mineral micro powder: at 60 ℃, uniformly mixing 100 parts of montmorillonite micropowder (with the particle size of 1000 meshes) and 20 parts of silane coupling agent, carrying out coupling reaction for 20 minutes, and cooling after the reaction is finished to obtain modified mineral micropowder uniformly coated by the coupling agent;
s12, preparing functional master batches: stirring and mixing 60 parts of modified mineral micro powder obtained by S11, 11.7 parts of PBS, 10 parts of ammonium polyphosphate, 8 parts of melamine, 5 parts of MAH-g-EMA, 0.3 part of hindered amine antioxidant and 5 parts of plasticizer (comprising 3 parts of polysiloxane and 2 parts of erucamide) in a high-speed mixer at 100 ℃ for 10 minutes, carrying out melt blending in a turnover internal mixer (at the temperature of 250 ℃), cooling and granulating after the unit mass energy consumption reaches 5 kWh/kg, and obtaining the flame-retardant functional master batch;
s13, preparing the degradable high-molecular flame-retardant composite material: and (3) uniformly stirring 10 parts of the functional master batch obtained from S12 and 90 parts of PLA, and obtaining the degradable high-molecular flame-retardant composite material by a double-screw extruder (interval temperature 140 ‒ 230 ℃).
Example 2
A preparation method of a natural mineral modified degradable high-molecular flame-retardant composite material comprises the following steps:
s21, preparing modified mineral micro powder: uniformly mixing 100 parts of talcum powder (with the particle size of 20000 meshes) and 2 parts of silane coupling agent at 110 ℃ to perform coupling reaction for 3 minutes, and cooling after the reaction is finished to obtain modified mineral micro powder uniformly coated by the coupling agent;
s22, preparing functional master batches: carrying out melt blending on 10 parts of modified mineral micro powder obtained by S21, 10 parts of PBS, 20 parts of PBAT, 30 parts of microcapsule-coated ammonium polyphosphate taking phenolic resin as a capsule wall, 25 parts of melamine, 2 parts of MAH-g-EBA, 2 parts of hindered phenol antioxidant and 1 part of zinc stearate through a continuous internal mixer (at the temperature of 120 ‒ 220 ℃), and cooling and granulating after the unit mass energy consumption reaches 0.1 kWh/kg to obtain flame-retardant master batches;
s23, preparing the degradable high-molecular flame-retardant composite material: and (3) uniformly stirring 40 parts of the functional master batch obtained by S22, 30 parts of PHB and 30 parts of PCL, and obtaining the degradable high-molecular flame-retardant composite material by a double-screw extruder (the interval temperature is 120 ‒ 250 ℃).
Example 3
A preparation method of a natural mineral modified degradable high-molecular flame-retardant composite material comprises the following steps:
s31, preparing modified mineral micro powder: at 90 ℃, uniformly mixing 50 parts of talcum powder (with the average particle size of 20000 meshes), 50 parts of wollastonite (with the average particle size of 10000 meshes) and 1 part of aluminate coupling agent, carrying out coupling reaction for 10 minutes, and cooling after the reaction is finished to obtain modified mineral micro powder uniformly coated by the coupling agent;
s32, preparing functional master batches: carrying out melt blending on 30 parts of modified mineral micro powder obtained by S31, 20 parts of PLA, 13 parts of PVA and 15 parts of microcapsule-coated ammonium polyphosphate taking melamine formaldehyde resin as a capsule wall, 15 parts of melamine, 3 parts of MAH-g-EEA, 1 part of phosphite antioxidant, 2 parts of polyethylene glycol and 1 part of epoxy soybean oil through a reciprocating single-screw extruder (the temperature is 120-120 ‒ 210 ℃), and cooling and dicing after the unit mass energy consumption reaches 2 kWh/kg to obtain flame-retardant functional master batches;
s33, preparing the degradable high-molecular flame-retardant composite material: and (3) uniformly stirring 25 parts of the functional master batch obtained from S32, 40 parts of PCL and 35 parts of PVA, and extruding by using a single-screw extruder (interval temperature of 140 ‒ 220 ℃) to obtain the degradable high-molecular flame-retardant composite material.
Example 4
A preparation method of a natural mineral modified degradable high-molecular flame-retardant composite material comprises the following steps:
s41, preparing modified mineral micro powder: uniformly mixing 50 parts of mica powder (with an average particle size of 8000 meshes), 50 parts of tourmaline (with an average particle size of 5000 meshes) and 10 parts of isocyanate coupling agent at 90 ℃, carrying out coupling reaction for 15 minutes, and cooling after the reaction is finished to obtain modified mineral micro powder uniformly coated by the coupling agent;
s42, preparing functional master batches: carrying out melt blending on 20 parts of modified mineral micro powder obtained by S41, 10 parts of PBAT, 13 parts of PVA and 15 parts of microcapsule-coated ammonium polyphosphate taking melamine formaldehyde resin as a capsule wall, 15 parts of melamine, 3 parts of MAH-g-EEA, 1 part of phosphite antioxidant, 2 parts of pentaerythritol and 1 part of polyethylene wax by a turnover internal mixer (the temperature is 190 ‒ 200 ℃), and cooling and granulating after the unit mass energy consumption reaches 3 kWh/kg to obtain flame-retardant functional master batches;
s43, preparing the degradable high-molecular flame-retardant composite material: and (3) uniformly stirring 25 parts of the functional master batch obtained from S42, 40 parts of PCL and 35 parts of PLA, and extruding by using a single-screw extruder (the interval temperature is 150 ‒ 230 ℃) to obtain the degradable high-molecular flame-retardant composite material.
Example 5
A preparation method of a natural mineral modified degradable high-molecular flame-retardant composite material comprises the following steps:
s51, preparing modified mineral micro powder: uniformly mixing 50 parts of attapulgite (with the average particle size of 12000 meshes), 50 parts of sepiolite (with the average particle size of 15000 meshes) and 5 parts of titanate coupling agent at 80 ℃, carrying out coupling reaction for 8 minutes, and cooling after the reaction is finished to obtain modified mineral micro powder uniformly coated by the coupling agent;
s52, preparing functional master batches: carrying out melt blending on 30 parts of modified mineral micropowder obtained in S51, 20 parts of PBS, 9.5 parts of PHA and 20 parts of microcapsule-coated ammonium polyphosphate taking melamine resin as a capsule wall, 10 parts of melamine, 4 parts of MAH-g-EBA, 1.5 parts of hindered phenol antioxidant, 3 parts of polyethylene glycol and 2 parts of epoxidized soybean oil by a turnover internal mixer (the temperature is 220-220 ‒ 230 ℃), and cooling and granulating after the unit mass energy consumption reaches 3.5 kWh/kg to obtain flame-retardant functional master batches;
s53, preparing the degradable high-molecular flame-retardant composite material: and (3) uniformly stirring 30 parts of the functional master batch obtained from S52, 40 parts of PBAT and 30 parts of PLA, and obtaining the degradable high-molecular flame-retardant composite material by a single-screw extruder (interval temperature of 140 ‒ 220 ℃).
Comparative example 1 (No modification of mineral Fine powder, direct addition)
Basically, the method of example 1 is adopted to prepare the master batch and the composite material, except that in the example, no modification is carried out on the mineral micro powder, but 60 parts of montmorillonite micro powder (with the particle size of 1000 meshes), 11.7 parts of PBS, 10 parts of ammonium polyphosphate, 8 parts of melamine, 5 parts of MAH-g-EMA, 0.3 part of hindered amine antioxidant and 5 parts of plasticizer (comprising 3 parts of polysiloxane and 2 parts of erucamide) are stirred and mixed for 10 minutes in a high-speed mixer at 100 ℃, then melt blending is carried out in a turnover internal mixer (at the temperature of 250 ℃), and after the unit mass energy consumption reaches 5 kWh/kg, the mixture is cooled and cut into granules to obtain the master batch with the flame retardant function; and then stirring 10 parts of the obtained functional master batch and 90 parts of PLA uniformly, and obtaining the degradable high-molecular flame-retardant composite material by a double-screw extruder (interval temperature of 140 ‒ 230 ℃).
Comparative example 2 (conventional flame retardant without addition of mineral component)
Basically, the method of example 2 is adopted to prepare the functionalized attapulgite and the microparticles thereof, except that in the present example, no mineral filler is added, and the traditional flame retardant formula is directly adopted, namely, 20 parts of PBS, 20 parts of PBAT, 30 parts of microcapsule coated ammonium polyphosphate with phenolic resin as capsule wall, 25 parts of melamine, 2 parts of MAH-g-EBA, 2 parts of hindered phenol antioxidant and 1 part of zinc stearate are subjected to melt blending by a continuous internal mixer (temperature interval 120 ‒ 220 ℃) and then cooled and cut into particles after the unit mass energy consumption reaches 0.1 kWh/kg, so as to obtain the flame retardant functional master batch; and then uniformly stirring 40 parts of the obtained functional master batch, 30 parts of PHB and 30 parts of PCL, and obtaining the degradable high-molecular flame-retardant composite material by a double-screw extruder (the interval temperature is 120 ‒ 250 ℃).
Comparative example 3 (direct one-step process without masterbatching)
Basically, the method of example 3 is adopted to prepare the master batch and the composite material, except that the master batch technology is not adopted in the embodiment, but the master batch technology is directly adopted for one-step blending molding, namely, 50 parts of talcum powder (with the average grain diameter of 20000 meshes), 50 parts of wollastonite (with the average grain diameter of 10000 meshes) and 1 part of aluminate coupling agent are uniformly mixed at 90 ℃, so that the coupling reaction is carried out for 10 minutes, and the mixture is cooled after the reaction is finished, so that modified mineral micro powder uniformly coated by the coupling agent is obtained; 7.5 parts of the modified mineral micropowder, 5 parts of PLA, 3.25 parts of PVA, 3.75 parts of microcapsule coated ammonium polyphosphate taking melamine formaldehyde resin as a capsule wall, 3.75 parts of melamine, 0.75 part of MAH-g-EEA, 0.25 part of phosphite antioxidant, 0.5 part of polyethylene glycol, 0.25 part of epoxidized soybean oil, 40 parts of PCL and 35 parts of PVA are uniformly stirred, and the degradable high-molecular flame-retardant composite material is obtained by a single-screw extruder (interval temperature of 140 ‒ 220 ℃ C.).
Structural characterization and Performance testing
And (3) testing tensile property: the resulting composite was subjected to injection molding (molding temperatures of 160 ‒ 220 ℃ C. and 220 ℃ C.) to obtain tensile and impact test specimens, and the tensile properties of the composite were measured using a universal tensile machine (model 5900) of Instron, USA, according to the tensile properties test standards for plastics in ASTM D638-2003, American society for testing materials; the impact properties of the composite material were tested according to ASTM D256-1997 Standard test method for Izod impact testing of plastics, of the American society for testing materials. At least 3 parallel test specimens were guaranteed per group and the results were averaged.
Test for flame retardancy: the lowest oxygen concentration (volume percentage content) of the composite material in the nitrogen and oxygen mixed gas for maintaining balanced combustion is tested according to the national standard GB/T2406-93 oxygen index method for testing the plastic combustion performance, so as to evaluate the sensitivity of the composite material to oxygen during combustion. According to the standard GB-T2408-2008 "horizontal method and vertical method for testing plastic combustion performance" evaluates the flame propagation condition, namely the fire resistance rating, of the surface of the composite material. At least 5 replicates of each group were tested and the results averaged.
TABLE 1 mechanical Properties and Combustion Properties test results of the composite materials
The experimental results are as follows: table 1 compares the tensile test results of the high-conductivity nano-mineral modified fully-degradable polymer composite material, and examples 1 ‒ 5 all have higher yield strength (36.8 ‒ 55.7.7 MPa), elongation at break (16 ‒ 375%) and impact strength (9.4 ‒ 25.6.6 kJ/m)2) The composite material embodies excellent comprehensive mechanical properties and meets the basic performance requirements of the packaging material. However, the mechanical properties of comparative example 1 ‒ 3 all showed a significant decrease, e.g., the elongation at break of comparative example 1 was only 9%, the yield strength of comparative example 2 was only 29.5 MPa, and the impact strength of comparative example 3 was only 5.7 kJ/m2Which makes it subject to many limitations when used as a structural material.
Also of significance, examples 1 ‒ 5 all exhibited good flame retardant properties, limiting oxygen index was above 30, and UL94 test results showed a V-0 rating for excellent fire resistance. Especially, the limiting oxygen index of example 2 reaches 35, which is the best level of the degradable high molecular material at present. However, comparative example 1 using only unmodified fine mineral powder and comparative example 2 without adding mineral filler were reduced in fire-resistant grades to V-2 and HB, and were somewhat limited in the field of flame-retardant materials. Compared with the comparative example 3 which does not adopt a masterbatching technical route, the fire resistance level is also reduced to V-2, and meanwhile, the mechanical property is also obviously reduced, so that the reinforcing effect and the flame retardant function of the mineral micro powder can not be fully exerted.
Therefore, the technical scheme provided by the patent enables the affinity of the mineral micro powder to the degradable macromolecules and the mechanical property and flame retardant property of the composite material to be obviously improved, and the affinity of the mineral micro powder to the degradable macromolecules and the mechanical property and flame retardant property of the composite material are possibly benefited by: (1) after the mineral micro powder is coated by the coupling agent, the affinity of the surface of the filler is improved, the interaction between the filler and a matrix is effectively improved, and the dispersibility of the filler in a polymer matrix is effectively improved; (2) the silicate minerals can effectively increase the thickness, the number or the strength of the carbon layer, so that the heat feedback during combustion is limited; (3) the mineral micro powder tightly combined with the matrix serves as an efficient 'group partition wall', so that the passing path and the overflowing difficulty of the combustible gas are increased; (4) the carbon layer reinforced by the mineral micro powder can play a role in effectively reducing the concentration of the smoke; (5) the masterbatching technical route forces the mineral filler, other fillers and the auxiliary agent to be fully stripped and uniformly dispersed in a polymer matrix to form a relatively perfect network structure, and endows the composite material with good reinforcing effect and flame retardant property.
The foregoing is only a preferred embodiment of this invention and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the invention and these modifications should also be considered as the protection scope of the invention.
Claims (18)
1. A preparation method of a natural mineral modified degradable high-molecular flame-retardant composite material is characterized by comprising the following steps:
s1, preparing modified mineral micro powder: placing the natural mineral micro powder and the coupling agent into mixing equipment at the temperature of 60 ‒ 110 ℃ to carry out coupling reaction for 3 minutes ‒ 20 minutes to obtain modified mineral micro powder;
s2, preparing functional master batches: putting the modified mineral micro powder, the degradable polymer, the synergistic flame retardant A, the synergistic flame retardant B, the compatilizer, the antioxidant and the plasticizer into mixing equipment for melt blending to obtain functional master batches;
s3, preparing the degradable high-molecular flame-retardant composite material: and mixing the functional master batches and the degradable polymers, and putting the mixture into melt blending equipment for melt blending to obtain the degradable polymer flame-retardant composite material.
2. The method according to claim 1, wherein the natural mineral fine powder in step S1 is silicate-based material with a particle size of 1000 ‒ 20000 mesh.
3. The method according to claim 2, wherein the silicate-based substance is at least one of montmorillonite, attapulgite, kaolin, sepiolite, talc, wollastonite, mica powder, diatom powder, vermiculite, bentonite, and tourmaline.
4. The method according to claim 1, wherein the coupling agent in step S1 is a silane coupling agent, and the mass ratio of the silane coupling agent to the natural mineral micro powder is 1:50 ‒ 1: 5.
5. The method according to claim 1, wherein the coupling agent in step S1 is at least one of an octadecyl amine coupling agent, an isocyanate coupling agent, an aluminate coupling agent, and a titanate coupling agent, and the mass ratio of the coupling agent to the natural mineral micropowder is 1:100 ‒ 1: 10.
6. The method of claim 1, wherein the mixing device in step S1 is at least one of a high-speed mixer, an open mill, an internal mixer, a Z-type kneader, a screw kneader, a vacuum kneader, and a horizontal twin-screw mixer.
7. The method according to claim 1, wherein the degradable polymer is at least one of polylactic acid, polycaprolactone, polyvinyl alcohol, polybutylene succinate, polyhydroxyalkanoate, and polybutylene adipate terephthalate.
8. The preparation method according to claim 1, wherein the modified mineral micro powder in the functional masterbatch in the step S2 has a mass fraction of 10% ‒ 60%.
9. The preparation method of claim 1, wherein the synergistic flame retardant A in the step S2 is ammonium polyphosphate or a derivative thereof, and the mass fraction of the synergistic flame retardant A in the functional master batch is 10% to ‒ 30%.
10. The preparation method of claim 1, wherein the synergistic flame retardant B in the step S2 is melamine, and the mass fraction of the synergistic flame retardant B in the functional master batch is 8% to ‒ 25%.
11. The method according to claim 1, wherein the compatibilizer in step S2 is at least one selected from the group consisting of maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted ethylene-methyl acrylate copolymer, maleic anhydride grafted ethylene-ethyl acrylate copolymer, maleic anhydride grafted ethylene-butyl acrylate copolymer, and glycidyl methacrylate, and the weight percentage of the compatibilizer in the functional masterbatch is 2% ‒ 5%.
12. The method according to claim 1, wherein in step S2, the compatibilizer is at least one of tetrabutyl titanate, a reactive polyepoxy compatibilizer, and tri-n-butyl acetylcitrate, and the mass fraction of the compatibilizer in the functional masterbatch is 0.2% ‒ 1.5.5%.
13. The preparation method of claim 1, wherein the antioxidant in step S2 is at least one of hindered amine antioxidant, hindered phenol antioxidant and phosphite antioxidant, and the mass fraction of the antioxidant in the functional masterbatch is 0.3% ‒ 2%.
14. The method according to claim 1, wherein the plasticizer in step S2 is at least one selected from the group consisting of polysiloxane, erucamide, pentaerythritol, dipentaerythritol, tripentaerythritol, polyethylene glycol, epoxidized soybean oil, stearic acid, stearate, and polyethylene wax, and the mass fraction of the functional masterbatch is 1% ‒ 5%.
15. The method according to claim 1, wherein the mixing device in step S2 is at least one of a high-speed mixer, an open mill, a roll-over mixer, a continuous internal mixer, a reciprocating screw extruder, a twin-screw extruder, a single-screw extruder, a Z-type kneader, a screw kneader, a vacuum kneader and a horizontal twin-screw mixer, the mixing temperature is 100 ‒ 250 ℃, and the energy consumption per unit mass of the mixing process is 0.1 ‒ 5 kWh/kg.
16. The preparation method according to claim 1, wherein the mass ratio of the functional masterbatch to the degradable polymer in the step S3 is 1:9 ‒ 2: 3.
17. The method according to claim 1, wherein the melt blending device in the step S3 is at least one of a roll-over type internal mixer, a continuous type internal mixer, a reciprocating screw extruder, a twin screw extruder, and a single screw extruder, and the melt blending temperature is 120 ‒ 250 ℃.
18. The natural mineral modified degradable high molecular flame retardant composite material obtained by the preparation method of any one of claims 1 to 17, wherein the limit oxygen index of the degradable high molecular composite material is more than 28%, and the UL-94 flame retardant grade is V-0 grade.
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