CN111534066B - Functional master batch for reinforcing and toughening polylactic acid fiber, preparation method thereof and reinforcing and toughening polylactic acid material - Google Patents
Functional master batch for reinforcing and toughening polylactic acid fiber, preparation method thereof and reinforcing and toughening polylactic acid material Download PDFInfo
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- CN111534066B CN111534066B CN202010400382.2A CN202010400382A CN111534066B CN 111534066 B CN111534066 B CN 111534066B CN 202010400382 A CN202010400382 A CN 202010400382A CN 111534066 B CN111534066 B CN 111534066B
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- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
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Abstract
The invention provides a functional master batch for reinforcing and toughening polylactic acid fibers, a preparation method thereof and a reinforcing and toughening polylactic acid material, belonging to the technical field of functional materials. Mixing inorganic mineral powder with a surface modifier, and carrying out surface modification to obtain modified inorganic mineral powder; the surface modifier is at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent; mixing the modified inorganic mineral powder with a dispersant, and performing pre-dispersion treatment to obtain pre-dispersed modified inorganic mineral powder; mixing the pre-dispersed modified inorganic mineral powder with polylactic resin, a modifier, an antioxidant and a stabilizer, and then sequentially plasticizing, mixing, extruding and granulating to obtain functional master batches; the modifier is at least one of ethylene-vinyl acetate copolymer, atactic polypropylene, POE-g-GMA, polyethylene oxide, polybutylene succinate, polysiloxane, N-ethylene bis stearamide and zinc stearate.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a functional master batch for reinforcing and toughening polylactic acid fibers, a preparation method thereof and a reinforcing and toughening polylactic acid material.
Background
Unlike common synthetic polymer materials, polylactic acid (PLA) has two major characteristics of biodegradability and plant-derived property. These two characteristics enable PLA to be used in many very significant applications in terms of reducing environmental pollution, saving petroleum resources, and reducing global warming. Although PLA is a good degradable polymer material, it has a relatively high market price, high crystallinity, high brittleness, hardness, and lack of flexibility and elasticity, which limits its application range.
The inorganic powder modified plastic is taken as a typical representative of environment-friendly plastic materials, and the industrialization process is accelerated continuously. Compared with common plastics, the inorganic powder modified plastics have the basic characteristics of economy, functionality, environmental harmony and the like, and have the main advantages that: firstly, energy is saved, 20-40% or more of inorganic powder is used for replacing synthetic resin in the production process of the inorganic powder modified plastic, and the consumption of resin raw materials is greatly saved; secondly, the waste emission is reduced, the environment-friendly plastic developed by inorganic powder from nature and returning to nature is adopted, and the discharged harmful substances after combustion are much less than those of common plastic; and thirdly, the formula of the inorganic powder modified plastic can be flexibly adjusted according to the application field, so that the functionalization of the inorganic powder modified plastic is realized. Fourthly, the modified material can be recycled, and the use performance is not influenced after the modified material is reprocessed; in addition, the inorganic powder in China has abundant resources, the use of the inorganic powder has economy and safety, and the production cost can be reduced. However, the single fiber diameter of the fiber is generally 10 to 30 μm, the diameter of the spinneret orifice is generally 0.4 to 0.5mm, and the finer the inorganic powder particles are, the larger the specific surface area is, the more easily the "agglomeration" is formed, and when the inorganic powder particles are added and blended in the fiber in a large proportion, the problems of poor spinnability of the fiber and the like exist, and even though the spinnability is solved, the mechanical property problem of each strength of the fiber still exists, so that the polylactic acid fiber can not be used for reinforcing and toughening of the polylactic acid fiber.
Disclosure of Invention
The invention aims to provide a functional master batch for reinforcing and toughening polylactic acid fibers, a preparation method thereof and a reinforcing and toughening polylactic acid material.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a functional master batch for reinforcing and toughening polylactic acid fibers, which comprises the following steps:
mixing inorganic mineral powder with a surface modifier, and carrying out surface modification to obtain modified inorganic mineral powder; the surface modifier is at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent;
mixing the modified inorganic mineral powder with a dispersant, and performing pre-dispersion treatment to obtain pre-dispersed modified inorganic mineral powder;
mixing the pre-dispersed modified inorganic mineral powder with polylactic resin, a modifier, an antioxidant and a stabilizer, and then sequentially plasticizing, mixing, extruding and granulating to obtain a functional master batch for reinforcing and toughening polylactic acid fibers; the modifier is at least one of ethylene-vinyl acetate copolymer, atactic polypropylene, POE-g-GMA, polyethylene oxide, polybutylene succinate, polysiloxane, N-ethylene bis stearamide and zinc stearate.
Preferably, the mass of the surface modifier is 1-5% of the mass of the inorganic mineral powder, and the mass parts of the other raw materials for preparing the functional master batch for reinforcing and toughening the polylactic acid fiber are as follows: 8-55 parts of polylactic resin, 40-80 parts of inorganic mineral powder, 2-10 parts of a dispersing agent, 8-20 parts of a modifying agent, 0.3-2 parts of an antioxidant and 0.5-3 parts of a stabilizing agent.
Preferably, the temperature of the surface modification is 100-120 ℃; the time for the surface modification is based on the activity of the obtained modified inorganic mineral powder reaching 100%.
Preferably, the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane and methacryloxypropyltrimethoxysilane; the titanate coupling agent is at least one of pyrophosphoric acid type monoalkoxy titanate, isopropyldioleate acyloxy (dioctyl phosphate acyloxy) titanate, isopropyl tri (dioctyl phosphate acyloxy) titanate, isopropyl tristearate titanium isopropyl ester, bis (dioctyl pyrophosphate) ethylene titanate and tetraisopropyl di (dioctyl phosphate acyloxy) titanate; the aluminate coupling agent is distearoyl isopropoxy aluminate.
Preferably, the inorganic mineral powder is at least one of calcite powder, talcum powder and wollastonite powder; the particle size of the inorganic mineral powder is less than submicron; the dispersing agent is at least one of low molecular weight polyethylene wax, low molecular weight polypropylene wax and low molecular weight ethylene-vinyl acetate copolymer wax; the average number average molecular weight of the dispersing agent is 2000-5000.
Preferably, the pre-dispersion treatment is carried out in a high-speed mixer, the temperature of the pre-dispersion treatment is 110-130 ℃, the time is 8-12 min, and the rotating speed of the high-speed mixer is 980 rpm.
Preferably, the plasticizing, mixing, extruding and granulating are carried out in a double-screw extruder, the temperature of the double-screw extruder is 160-220 ℃, and the rotating speed of the double-screw extruder is 200-500 rpm.
Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 1098 and antioxidant 168; the stabilizer is at least one of tricresyl phosphate, triphenyl phosphite, triphenyl phosphate and triethyl phosphate.
The invention provides the functional master batch for reinforcing and toughening the polylactic acid fiber, which is prepared by the preparation method in the technical scheme.
The invention provides a reinforced and toughened polylactic acid material, which comprises reinforced and toughened functional master batches and polylactic acid resin, wherein the reinforced and toughened functional master batches are the functional master batches for reinforcing and toughening polylactic acid fibers in the technical scheme; the mass percentage content of the reinforcing and toughening functional master batch is 10-60%.
The invention provides a preparation method of a functional master batch for reinforcing and toughening polylactic acid fibers, which takes inorganic mineral powder as a reinforcing material, adopts a surface modifier to carry out surface modification on the inorganic mineral powder, and utilizes an interface induction theory and a regulation and control technology to mutually match and cooperate in structure and performance to form an organic modified layer, so that multidentate strong chemical bonding is formed on the surface of a single inorganic mineral powder particle, thereby improving the miscibility between a polylactic acid resin molecular chain and the inorganic mineral powder and enabling the inorganic mineral powder to be uniformly dispersed in the polylactic acid resin; the surface energy of the inorganic particles can be reduced, thereby being beneficial to depolymerization and prevention of agglomeration; the melt viscosity of a filling system can be reduced, and the processing fluidity is improved; the affinity between the inorganic mineral powder and the matrix polymer can be improved, and the dispersibility of the inorganic mineral powder is improved; the surface of the inorganic mineral powder can be organized, so that the fiber forming performance of the fiber is improved, and the functional master batch can effectively strengthen and toughen the polylactic acid fiber.
The outer surface of the modified inorganic mineral powder obtained after surface modification is combined with a modifier containing oleophylic genes, and the inorganic mineral powder containing oleophylic groups can be coupled with polylactic resin, so that the modified polylactic resin composite master batch which can fuse inorganic mineral powder and polylactic resin chain segments together is obtained, and the functional master batch can be used for reinforcing and toughening polylactic fibers.
In addition, the inorganic mineral powder is used as a reinforcing material, so that petroleum resources can be saved, the cost of the functional master batch is reduced, the inorganic mineral powder is easier to degrade than common plastics when used as waste or garbage for landfill treatment, the inorganic mineral powder can return to nature and is harmless to soil, and the inorganic mineral powder is easy to burn fully and has little harm to the environment and is not easy to stick to walls when used as waste or garbage for incineration treatment.
The preparation method of the functional master batch for reinforcing and toughening the polylactic acid fiber provided by the invention is simple, is easy to implement, is suitable for large-scale popularization and application, and has remarkable economic benefit and environmental protection benefit.
Drawings
FIG. 1 shows an areal density of 70g/m obtained from application example 6 using 33% polyaddition polylactic acid resin of the functional master batch of example 1 and 67%2A photograph of the surface of the nonwoven fabric enlarged by 30 times;
FIG. 2 is a graph showing that the areal density of 100g/m prepared by applying example 11 to 50% of the functional masterbatch of example 1 and 50% of the polylactic acid resin2A photograph of the surface of the nonwoven fabric enlarged by 30 times;
FIG. 3 is an areal density of 100g/m prepared from application example 11 with 50% of the masterbatch of example 1 and 50% of a polyaddition polylactic acid resin2A photograph of the surface of the fibers in the nonwoven fabric magnified 1000 times;
FIG. 4 is a graph showing that the areal density of 100g/m in application example 11 prepared from 50% of the functional masterbatch of example 1 and 50% of the polylactic acid resin2A photograph of the surface of the fibers in the nonwoven fabric at a magnification of 5000 times;
FIG. 5 is a graph showing that the areal density of 100g/m in application example 11 prepared from 50% of the functional masterbatch of example 1 and 50% of the polylactic acid resin2A photograph of a cross section of fibers in the nonwoven fabric magnified 1000 times;
FIG. 6 is a graph showing that the areal density of 100g/m in application example 11 prepared from 50% of the functional masterbatch of example 1 and 50% of the polylactic acid resin2A photograph of a cross section of the fibers in the nonwoven fabric magnified 5000 times;
FIG. 7 is a photograph of a cross section of fibers in a nonwoven fabric, which is enlarged by 5000 times in the case where the desired effect cannot be achieved due to abnormality of inorganic powder during the treatment with a coupling agent during the application test.
Detailed Description
The invention provides a preparation method of a functional master batch for reinforcing and toughening polylactic acid fibers, which comprises the following steps:
mixing inorganic mineral powder with a surface modifier, and carrying out surface modification to obtain modified inorganic mineral powder; the surface modifier is at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent;
mixing the modified inorganic mineral powder with a dispersant, and performing pre-dispersion treatment to obtain pre-dispersed modified inorganic mineral powder;
mixing the pre-dispersed modified inorganic mineral powder with polylactic resin, a modifier, an antioxidant and a stabilizer, and then sequentially plasticizing, mixing, extruding and granulating to obtain functional master batches for reinforcing and toughening polylactic acid fibers; the modifier is at least one of ethylene-vinyl acetate copolymer, atactic polypropylene, POE-g-GMA, polyethylene oxide, polybutylene succinate, polysiloxane, N-ethylene bis stearamide and zinc stearate.
The invention mixes the inorganic mineral powder with the surface modifier to carry out surface modification, thus obtaining the modified inorganic mineral powder.
In the present invention, the inorganic mineral powder is preferably at least one of calcite powder, talc powder and wollastonite powder, more preferably calcite powder, talc powder or wollastonite powder, and most preferably calcite powder or wollastonite powder; the particle size of the inorganic mineral powder is preferably submicron or less, and more preferably 3500 to 5000 mesh.
In the present invention, the inorganic mineral powder is preferably dried inorganic mineral powder, and when the inorganic mineral powder contains water, the inorganic mineral powder is preferably subjected to a drying treatment; in the embodiment of the present invention, the temperature of the drying treatment is preferably 100 to 120 ℃, more preferably 110 ℃, the time of the drying treatment is preferably 8 to 12min, more preferably 10min, the drying treatment process is preferably maintained in a stirring state, and the rotation speed of the stirring is not particularly limited in the present invention, so that the material can be dried. In the present invention, the drying apparatus is not particularly limited, and drying may be achieved, and in the embodiment of the present invention, the drying process is preferably performed in a high-speed mixer.
In the invention, the surface modifier is at least one of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent, and is more preferably the silane coupling agent, the titanate coupling agent or the aluminate coupling agent; the silane coupling agent is preferably at least one of gamma-aminopropyltriethoxysilane (KH550), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH560) and methacryloxypropyltrimethoxysilane (KH570), and more preferably KH 560; the titanate coupling agent is preferably at least one of isopropyldioleacyloxy (dioctylphosphatoxy) titanate, isopropyltris (dioctylphosphatoxy) titanate, isopropyl triisostearate, bis (dioctyloxypyrophosphate) ethylene titanate and tetraisopropylbis (dioctylphosphatoxy) titanate; the aluminate coupling agent is preferably distearoyl isopropoxy aluminate.
In the present invention, the mass of the surface modifier is preferably 1 to 5% of the mass of the inorganic mineral powder, and more preferably 2.1 to 3.6%. In the present invention, the surface modifier is preferably used in the form of a diluent, the diluent used in the diluent is preferably isopropyl alcohol, the mass ratio of the surface modifier to the diluent is preferably 1:1, and the process of mixing the inorganic mineral powder and the surface modifier is preferably performed by spraying the diluent of the surface modifier on the surface of the inorganic mineral powder under stirring (980 rpm).
In the invention, the temperature of the surface modification is preferably 100-120 ℃, and more preferably 110 ℃; the time for the surface modification is preferably based on the activity of the obtained modified inorganic mineral powder reaching 100%; the activity is not specifically defined in the invention, and the activity is understood according to the definition well known in the field; the process of testing the activity of the inorganic mineral powder according to the present invention is not particularly limited, and may be performed according to a method well known in the art. In the present invention, the surface modification is preferably performed under stirring, and the process of surface modification specifically comprises: placing the inorganic mineral powder in a high-speed mixer, heating to 110 ℃, starting stirring, stirring at 490rpm for 1 minute, stirring at 980rpm for 3 minutes, discharging the water in the material, and spraying the diluent of the surface modifier on the surface of the inorganic mineral powder under stirring (980rpm) until the activity of the modified inorganic mineral powder reaches 100%.
The polylactic acid resin is a high-molecular linear polymer, and the inorganic mineral powder has hydrophilicity, has obvious difference with the polylactic acid resin in chemical structure and physical form, and lacks affinity; in addition, the invention can reduce the surface energy of the inorganic mineral powder through surface modification, reduce the van der Waals force among the particles, and generate new repulsion of steric hindrance, thereby preventing the particles from agglomerating and improving the dispersibility of the inorganic mineral powder. In addition, the surface modification of the inorganic mineral powder can reduce the melt viscosity of the filling system and improve the processing fluidity; the inorganic mineral powder surface is organized, and the fiber forming performance of the fiber can be improved.
The invention uses surface modifier to process inorganic particles, uses interface induction theory and regulation technology, and combines and cooperates with each other in structure and performance to form an organic modified layer, thus forming multidentate strong chemical combination on the surface of single inorganic particle, reducing the surface energy of inorganic particle, and being helpful to depolymerization and prevention of agglomeration.
After the modified inorganic mineral powder is obtained, the modified inorganic mineral powder is mixed with a dispersant and subjected to pre-dispersion treatment to obtain the pre-dispersed modified inorganic mineral powder.
In the present invention, the dispersant is preferably at least one of a low molecular weight polyethylene wax, a low molecular weight polypropylene wax, and a low molecular weight ethylene-vinyl acetate copolymer wax; the average molecular weight of the dispersant is preferably 2000-5000, and more preferably 2500-4000. In the invention, the dispersant has low molecular weight, good fluidity and good compatibility with polylactic resin. After the surface of the inorganic mineral powder is modified, the dispersant is added, so that the modified inorganic mineral powder can have wetting, dispersing and stabilizing effects and is less prone to agglomeration. Meanwhile, under the full kneading action of a subsequent double-screw extruder, the dispersing agent can enable inorganic mineral powder, polylactic acid resin chain segments, other modifiers and additives to be mutually fused, so that the overall dispersibility is improved.
In the invention, the pre-dispersion treatment is preferably carried out in a high-speed mixer, the temperature of the pre-dispersion treatment is preferably 110-130 ℃, more preferably 115-120 ℃, the time is preferably 8-12 min, more preferably 9-10 min, and the rotating speed of the high-speed mixer is preferably 980 rpm. In the present invention, the pre-dispersion treatment serves to increase the dispersibility and compatibility of the modified inorganic mineral powder in the polylactic acid resin.
After the pre-dispersion treatment is completed, the invention preferably cools the obtained material to room temperature to obtain the pre-dispersed modified inorganic mineral powder. The cooling process is not particularly limited in the present invention, and may be performed according to a process known in the art.
After the pre-dispersed modified inorganic mineral powder is obtained, the pre-dispersed modified inorganic mineral powder is mixed with the polylactic resin, the modifier, the antioxidant and the stabilizer, and then plasticizing, mixing, extruding and granulating are carried out in sequence to obtain the functional master batch for reinforcing and toughening the polylactic fiber.
In the present invention, the polylactic acid resin is preferably a fiber-grade polylactic acid resin, i.e., a polylactic acid resin that can be used for preparing fibers; the specific specification of the polylactic acid resin is not particularly limited, and the polylactic acid resin can be any commercially available polylactic acid resin. In the embodiment of the invention, the particle size of the polylactic acid resin is preferably 2-4 mm, and the melt index (190 ℃, 2.16kg) of the polylactic acid resin is preferably (1-30) g/10 min; the density of the polylactic acid resin is preferably 1.25 +/-0.05 g/cm3. In the invention, the polylactic acid resin is preferably dried in a vacuum dryer before use, the drying temperature is preferably 85-100 ℃, more preferably 90-95 ℃, and the drying time is preferably 24-35 h, more preferably 28-32 h.
In the invention, the modifier is at least one of ethylene-vinyl acetate copolymer, atactic polypropylene, POE-g-GMA (polyolefin elastomer POE grafted glycidyl methacrylate GMA synthetic compound), polyethylene oxide, polybutylene succinate, polysiloxane, N-ethylene bis stearamide and zinc stearate; more preferably ethylene-vinyl acetate copolymer, atactic polypropylene, POE-g-GMA, polysiloxane, N-ethylene bis-stearamide and zinc stearate in a mass ratio of 5:2:0.5: 0.6: 04, or more preferably a mixture obtained by compounding ethylene-vinyl acetate copolymer, atactic polypropylene, POE-g-GMA, polyethylene oxide, polybutylene succinate and N, N-ethylene bis-stearamide in a mass ratio of 8.7-10: 3:1.5: 1.5-2: 0.5-1.2, and most preferably a mixture obtained by compounding in a weight ratio of 10:3:1.5:2:0.5 or 8.7:3:1.5:1.5: 1.2. The specific type of the modifier is not particularly limited in the invention, and a commercially available product well known in the art can be selected. In the invention, the modifier can reduce the crystallinity of the polylactic acid, reduce the glass transition temperature of the polylactic acid resin, improve the processability and improve the toughness of the polylactic acid.
In the present invention, the antioxidant is preferably at least one of an antioxidant 1010 (i.e., pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), an antioxidant 1076 (N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), an antioxidant 1098(N, N' -1, 6-hexylene-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ]) and an antioxidant 168 (tris (2, 4-di-tert-butylphenyl) phosphite), more preferably the antioxidant 1010, the antioxidant 1076, the antioxidant 1098 or the antioxidant 168, or more preferably the antioxidant 1010 and the antioxidant 168 are included, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is preferably 1: 1.
In the present invention, the stabilizer is preferably at least one of tricresyl phosphate, triphenyl phosphite, triphenyl phosphate, and triethyl phosphate, more preferably tricresyl phosphate, triphenyl phosphite, triphenyl phosphate, or triethyl phosphate, and most preferably triphenyl phosphite or triphenyl phosphate. In the invention, the polylactic acid is easy to degrade under the action of heat or oxygen in the processing process, and the stabilizer can act with water molecules decomposed in a high-temperature reaction, thereby reducing the degradation of low-molecular substances and ensuring the structural stability of the polylactic acid.
In the invention, the raw materials for preparing the functional master batch for reinforcing and toughening the polylactic acid fiber preferably comprise the following components in parts by weight: 8-55 parts of polylactic resin, 40-80 parts of inorganic mineral powder, 2-10 parts of a dispersing agent, 8-20 parts of a modifying agent, 0.3-2 parts of an antioxidant and 0.5-3 parts of a stabilizing agent.
In the invention, the inorganic mineral powder is more preferably 60 to 70 parts by mass, and the polylactic acid resin is more preferably 8.4 to 27 parts by mass; the mass part of the dispersing agent is more preferably 3-10 parts; the mass part of the modifier is more preferably 8.5-17 parts; the antioxidant is more preferably 0.3-0.6 part by mass; the mass part of the stabilizer is more preferably 1.5-2 parts.
In the invention, the pre-dispersed modified inorganic mineral powder, the polylactic acid resin, the modifier, the antioxidant and the stabilizer are preferably mixed by high-speed stirring, the rotation speed of the high-speed stirring is preferably 980rpm, and the time is preferably 8-12 min, and more preferably 10 min; the high speed stirring is preferably carried out in a high speed mixer.
In the invention, the plasticizing, mixing, extruding and granulating are preferably carried out in a double-screw extruder, the temperature of the double-screw extruder is preferably 160-220 ℃, and the rotating speed of the double-screw extruder is preferably 200-500 rpm; the temperature in the zones of the twin-screw extruder is preferably: the temperature of the first zone is 100-130 ℃, the temperature of the second zone is 170-195 ℃, the temperature of the third zone is 185-220 ℃, the temperature of the fourth zone is 185-220 ℃, the temperature of the fifth zone is 195-220 ℃, the temperature of the sixth zone is 195-220 ℃, the temperature of the seventh zone is 195-220 ℃, the temperature of the eighth zone is 195-220 ℃, the temperature of the ninth zone is 195-220 ℃, and the temperature of the machine head is 200-225 ℃; the feeding speed is preferably 25-28 rpm.
The invention also provides the functional master batch for reinforcing and toughening the polylactic acid fiber, which is obtained by the preparation method in the technical scheme; the granularity of the functional master batch for reinforcing and toughening the polylactic acid fiber is preferably the granularity
The water content is preferably less than or equal to 0.2 percent, and the whiteness value is preferably more than or equal to 94 percent; the reinforcing and toughening latexThe content of the inorganic mineral powder in the functional master batch of the acid fiber is preferably 60-65%.
The invention also provides a reinforced and toughened polylactic acid material, which comprises reinforced and toughened functional master batches and polylactic acid resin, wherein the reinforced and toughened functional master batches are the functional master batches for reinforcing and toughening polylactic acid fibers in the technical scheme; the mass percentage content of the reinforcing and toughening functional master batch is 10-60%. In the present invention, the polylactic acid resin is the same as the polylactic acid resin used for preparing the functional master batch, and is not described herein again.
In the invention, the form of the reinforced and toughened polylactic acid material is preferably short fiber, non-woven fabric or filament.
The preparation method of the reinforced and toughened polylactic acid material is not particularly limited, and a conventional preparation process is selected according to the form of the reinforced and toughened polylactic acid material to be prepared, in the application example of the invention, preferably, the polylactic acid non-woven fabric is prepared by a spun-bonded method by taking the application in the polylactic acid non-woven fabric as an example, and the specific process is as follows: placing the functional master batches and the fiber-grade polylactic resin in a plastic mixer, stirring for 30 minutes at normal temperature, and uniformly mixing to obtain a mixture; drying the mixture in a vacuum dryer at 90 ℃ and a vacuum degree of 760mmHg for about 30 hours to obtain a dried material; the dry materials are pumped to a feeding system of a large screw extruder through a vacuum device, the mixture enters the large screw extruder under the action of gravity, the temperature of each area of the large screw extruder is controlled within the range of 180-220 ℃, and the temperature of an oil tank is controlled within the range of 215-225 ℃; melting, mixing and propelling the mixture, gradually conveying the mixture to a filtering device of the melt, filtering impurities influencing spinning in the mixture by the filtering device, conveying the melt to a spinning die head through a metering pump, spinning the melt into birth fibers (the spinning temperature is 200 ℃) through spinneret holes under the action of pressure, cooling and blowing the sprayed fibers on two sides, then randomly laying the continuous fibers on a mesh belt which runs forwards under the action of airflow dispersion of a fiber divider through negative pressure airflow drafting to form a fiber mesh, carrying out local melting and hot rolling on the fiber mesh after the fiber mesh passes through a hot rolling mill, and obtaining the reinforced and toughened polylactic acid non-woven fabrics with different areal densities after reeling. Wherein the temperatures of an upper roller, a lower roller and a press roller of the hot rolling are respectively in the range of 130-147 ℃, and are adjusted according to the required surface density. The web forming line speed, the rolling mill line speed and the winding line speed are adjusted according to the required surface density by a conventional method.
The functional master batch for reinforcing and toughening polylactic acid fiber, the preparation method thereof and the reinforcing and toughening polylactic acid material provided by the present invention are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
In the embodiment of the invention, the components are weighed according to the parts by mass; in the following examples, reagents of which the types are not specified are commercially available products known in the art, and are not limited to specific types.
Example 1
Putting 60 parts of 4500-mesh calcite powder into a high-speed mixer, heating to 110 ℃, starting stirring, stirring at 490rpm for about 1 minute, stirring at 980rpm for 3 minutes, discharging water, adding 1.5 parts of pyrophosphoric acid type monoalkoxy titanate (TM-38 s brand of Nay Tianyang chemical Co., Ltd.) diluted by taking isopropanol as a diluent according to the mass ratio of 1:1 in a spraying method under the high-speed stirring state, and continuously stirring and heating at 110 ℃ at 980rpm for 10 minutes to obtain modified calcite powder with the activation degree of 100%;
placing the modified calcite powder into a high-speed mixer, adding 5 parts of low-molecular-weight ethylene-vinyl acetate copolymer wax (EVA wax) (product of Tsingtao high-tech materials Co., Ltd., molecular weight of 2300, and brand number of EVAWax 400), heating to 110 ℃, performing pre-dispersion treatment for 10min at the rotating speed of 980rpm, and then cooling to room temperature to obtain pre-dispersed modified calcite powder;
the pre-dispersed modified calcite powder and 23 parts of fiber grade polylactic acid resin (REVODE 190, trade name: Zhejiang Hainan biomaterial Co., Ltd.), 5 parts of ethylene-vinyl acetate copolymer (VA 28%), 2.4 parts of random polypropylene (molecular weight 25000), 0.6 part of N, N-ethylene bis-stearoylAmine, 2 parts of triphenyl phosphate, 0.3 part of antioxidant 1010 and 0.3 part of antioxidant 168 are placed in a high-speed mixer, stirred for 10min at the rotating speed of 980rpm, and then fed into a double-screw extruder for plasticizing, mixing, extruding and granulating to obtain the product with the particle size of
The functional master batch for reinforcing and toughening the polylactic acid fiber contains 60 percent of inorganic powder, wherein the temperature intervals of the double-screw extruder are respectively as follows: first zone 115 ℃, second zone 193 ℃, third zone 195 ℃, fourth zone 210 ℃, fifth zone 212 ℃, sixth zone 215 ℃, seventh zone 215 ℃, eighth zone 220 ℃, ninth zone 220 ℃, head 220 ℃, feeding speed: 26rpm, extruder speed: 320 rpm.
Example 2
Placing 65 parts of 4000-mesh calcite powder into a high-speed mixer, heating to 110 ℃, stirring at the rotating speed of 490rpm for 1 minute, then stirring at the rotating speed of 980rpm for 3 minutes, discharging water, then adding 2 parts of isopropyl tristearate (trade name of Nanjing Authentic chemical Co., Ltd is AC-100) diluted by taking isopropanol as a diluent according to the mass ratio of 1:1 under the high-speed stirring state by a spraying method, and continuously stirring and heating at the rotating speed of 980rpm at 110 ℃ for 10 minutes to obtain modified calcite powder with the activation degree of 100%;
placing the modified calcite powder into a kneader, adding 5 parts of low-molecular-weight polypropylene wax (product of plastic high-new material Co., Ltd. in Qingdao, the trade name is H-525), heating to 110 ℃, performing pre-dispersion treatment for 10min at the rotating speed of 980rpm, and then cooling to room temperature to obtain pre-dispersed modified calcite powder;
pre-dispersed modified calcite powder and 9 parts of fiber-grade polylactic acid (product of Zhejiang Hainan biomaterial GmbH, Inc., brand: REVODE190), 10 parts of ethylene-vinyl acetate copolymer (VA is 28%), 3 parts of random polypropylene (molecular weight is about 25000), 1.5 parts of polyethylene oxide (molecular weight is 4000), 2 parts of polybutylene succinate (PBS) with melt index of more than or equal to 15g/10min, product of Wuhan Haishan science Inc.), 0.4 part of N, N-ethylene bis stearamide, 9 parts of calcium carbonate, sodium bicarbonate and sodium bicarbonate, which are dried in a vacuum dryer (85 ℃, 35 hours), wherein,0.3 part of antioxidant 1010, 0.3 part of antioxidant 168 and 1.5 parts of triphenyl phosphite are placed in a high-speed mixer, stirred for 10min at the rotating speed of 980rpm, and then fed into a double-screw extruder for plasticizing, mixing, extruding and granulating to obtain the product with the particle size of
The functional master batch for reinforcing and toughening the polylactic acid fiber, wherein the content of the inorganic powder is 65%, and the temperature of the double-screw extruder is as follows: first zone 105 ℃, second zone 192 ℃, third zone 194 ℃, fourth zone 198 ℃, fifth zone 198 ℃, sixth zone 198 ℃, seventh zone 205 ℃, eighth zone 205 ℃, ninth zone 205 ℃, head 205 ℃, feed rate: extruder rotation speed of 26 rpm: 330 rpm.
Example 3
Putting 65 parts of 4000-mesh wollastonite powder into a high-speed mixer, heating to 110 ℃, starting stirring, stirring at 490rpm for about 1 minute, stirring at 980rpm for about 3 minutes, discharging water, adding 2 parts of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (silane coupling agent KH560) (product of Yingtian Yangyang chemical Co., Ltd.) diluted by taking isopropanol as a diluent according to the mass ratio of 1:1 under the high-speed stirring state by a spraying method, stirring and heating at 110 ℃ at 980rpm for 10 minutes to obtain modified wollastonite powder with the activation degree of 100%;
putting the modified wollastonite powder into a kneader, adding 3 parts of low molecular weight ethylene-vinyl acetate copolymer Wax (the molecular weight is 2300, and the product is EVA Wax 400, and the trade name is Qingdao plastic high and new materials Co., Ltd.), heating to 110 ℃, performing pre-dispersion treatment for 10min at the rotating speed of 980rpm, and then cooling to room temperature to obtain pre-dispersed wollastonite powder;
the pre-dispersed modified wollastonite powder, 12.5 parts of fiber-grade polylactic acid (product of Zhejiang Haizheng biomaterial GmbH, trademark: REVODE190) dried in a vacuum drier (100 ℃, 24h), 8.7 parts of ethylene-vinyl acetate copolymer (VA is 28%), 3 parts of random polypropylene (molecular weight is about 25000), 2.5 parts of POE-g-GMA, 1.2 parts of polysiloxane, 0.3 part of antioxidant 1010, 0.3 part of antioxidant 168 and 1.5 parts of triphenyl phosphate are placed in a high-speed mixer, and the mixture is subjected to vacuum drying in a vacuum drier (100 ℃, 24h)Stirring for 10min at the rotating speed of 980rpm, then feeding into a double-screw extruder, plasticizing, mixing, extruding and granulating to obtain the product with the particle size of
The functional master batch for reinforcing and toughening the polylactic acid fiber, wherein the content of the inorganic powder is 65%, and the temperature of the double-screw extruder is as follows: first zone 102 ℃, second zone 172 ℃, third zone 195 ℃, fourth zone 198 ℃, fifth zone 198 ℃, sixth zone 199 ℃, seventh zone 202 ℃, eighth zone 205 ℃, ninth zone 206 ℃, head 210 ℃, feed rate: 28rpm, extruder speed: 350 rpm.
Example 4
Putting 65 parts of 4000-mesh calcite powder into a high-speed mixer, heating to 110 ℃, starting stirring, stirring at 490rpm for about 1 minute, stirring at 980rpm for about 3 minutes, discharging water, and adding 2 parts of aluminate coupling agent (product molecular formula (C) of Nanjing Aucheng chemical company Limited) diluted by taking isopropanol as a diluent according to the mass ratio of 1:1 under the high-speed stirring state by a spraying method3H7O)xAL(OCOR1)(OCOR2)n) Continuously stirring and heating at 110 ℃ at the rotating speed of 980rpm for 10min to obtain modified calcite powder with the activation degree of 100%;
placing the modified calcite powder into a kneader, adding 5 parts of low molecular weight polyethylene wax (product of plastic high and new materials Co., Ltd., in Qingdao, brand number is YL-300, molecular weight is 4000), heating to 110 ℃, performing pre-dispersion treatment for 10min at the rotating speed of 980rpm, and then cooling to room temperature to obtain pre-dispersed modified calcite powder;
placing the pre-dispersed modified calcite powder and 14 parts of fiber-grade polylactic acid (product of Zhejiang Hainan biomaterial GmbH, product of REVODE190, trademark) dried in a vacuum drier (95 ℃, 24h), 5 parts of ethylene-vinyl acetate copolymer (VA is 28%), 3 parts of random polypropylene (molecular weight is about 25000), 3.5 parts of POE-g-GMA, 0.4 part of polysiloxane, 0.3 part of antioxidant 1010, 0.3 part of antioxidant 168 and 1.5 parts of triphenyl phosphite in a high-speed mixer, stirring for 10min at the rotating speed of 980rpm, then feeding a double-screw rod and a double-screw rod into the mixer, and stirring for 10minAn extruder for plasticizing, mixing, extruding and granulating to obtain the product with a particle size of
The functional master batch for reinforcing and toughening the polylactic acid fiber, wherein the content of the inorganic powder is 65%, and the temperature of the double-screw extruder is as follows: first zone 115 ℃, second zone 185 ℃, third zone 196 ℃, fourth zone 195 ℃, fifth zone 203 ℃, sixth zone 202 ℃, seventh zone 202 ℃, eighth zone 202 ℃, ninth zone 206 ℃, head 206 ℃, feed rate: 25rpm, extruder speed: 320 rpm.
Application example
Placing the functional master batch obtained in the embodiment 1-4 and fiber-grade polylactic resin in a plastic mixer, and stirring for 30 minutes at normal temperature to uniformly mix to obtain a mixture; drying the mixture in a vacuum dryer at 90 ℃ and a vacuum degree of 760mmHg for about 30 hours to obtain a dried material; pumping the dry material to a feeding system of a large screw extruder through a vacuum device, feeding the mixture into the large screw extruder under the action of gravity, controlling the temperature of each area of the large screw extruder to be 180-220 ℃, and controlling the temperature of an oil tank to be 215-225 ℃; melting, mixing and propelling the mixture, gradually conveying the mixture to a filtering device of the melt, filtering impurities influencing spinning in the mixture by the filtering device, conveying the melt to a spinning die head through a metering pump, spinning the melt into birth fibers (the spinning temperature is 200 ℃) through spinneret holes under the action of pressure, cooling and blowing the sprayed fibers on two sides, then randomly laying the continuous fibers on a mesh belt which runs forwards under the action of airflow dispersion of a fiber divider through negative pressure airflow drafting to form a fiber mesh, carrying out local melting and hot rolling on the fiber mesh after the fiber mesh passes through a hot rolling mill, and obtaining the reinforced and toughened polylactic acid non-woven fabrics with different areal densities after reeling. Wherein the temperatures of the upper roller, the lower roller and the press roll for hot rolling are respectively in the range of 130-147 ℃, and are adjusted according to the required surface density. The web forming line speed, the rolling mill line speed and the winding line speed are adjusted according to the required surface density by a conventional method.
Comparative example
Polylactic acid nonwoven fabrics with different areal densities were prepared from only fiber-grade polylactic acid resin as a raw material by the method of application example 1.
The polylactic acid non-woven fabrics are prepared by the following raw materials of examples 1 to 4 and comparative examples according to the following raw material ratio shown in the following table 1, the specific data are shown in the table 1, and the application examples are respectively marked as application examples 1 to 15 in sequence according to the serial numbers shown in the table 1 and are numbered as 1 to 15 in sequence.
TABLE 1 polylactic acid nonwoven application test protocol
TABLE 2 application test Process conditions of polylactic acid nonwoven fabrics
And (3) performance testing:
1) SEM tests were performed on the nonwoven fabrics prepared in application examples 6 and 11, and the results are shown in FIGS. 1 to 6:
FIG. 1 is a graph showing that the areal density of the resin prepared in application example 6 from 33% of the functional masterbatch of example 1 and 67% of the polylactic acid resin was 70g/m2A photograph of the surface of the nonwoven fabric enlarged by 30 times;
FIG. 2 is a graph showing that the areal density of 100g/m prepared by applying example 11 to 50% of the functional masterbatch of example 1 and 50% of the polylactic acid resin2A photograph of the surface of the nonwoven fabric enlarged by 30 times;
FIG. 3 is an areal density of 100g/m prepared from application example 11 with 50% of the masterbatch of example 1 and 50% of a polyaddition polylactic acid resin2A photograph of the surface of the fibers in the nonwoven fabric magnified 1000 times;
FIG. 4 is a graph showing that the functional masterbatch of example 1 prepared from 50% of the polylactic acid resin of application example 11 and having an areal density of 100g/m2A photograph of the surface of the fibers in the nonwoven fabric at a magnification of 5000 times;
FIG. 5 is a graph showing that the areal density of 100g/m in application example 11 prepared from 50% of the functional masterbatch of example 1 and 50% of the polylactic acid resin21000 times enlarged nonwovenA photograph of the cross section of the fibers in the cloth;
FIG. 6 is a graph showing that the areal density of 100g/m in application example 11 prepared from 50% of the functional masterbatch of example 1 and 50% of the polylactic acid resin2A photograph of a cross section of the fibers in the nonwoven fabric magnified 5000 times;
FIG. 7 is a photograph of a cross section of fibers in a nonwoven fabric, which is enlarged by 5000 times in the case where the desired effect cannot be achieved due to abnormality of inorganic powder during the treatment with a coupling agent during the application test.
As can be seen from fig. 1 to 6, the inorganic mineral powder particles are uniformly dispersed in the matrix of the polylactic acid resin, and there are no large aggregates, and the interface between the inorganic powder particles dispersed in the fiber and the polylactic acid resin is relatively fuzzy, and there are no gaps and holes (as shown in fig. 7), which indicates that the inorganic powder and the polylactic acid have been chemically "coupled" together, and thus have excellent mechanical properties.
2) The polylactic acid nonwoven prepared by the application example is subjected to performance test:
breaking strength and elongation at break: the sample size was 25cm × 5cm, 5 pieces were taken for each sample in the longitudinal and transverse directions, the gauge was 200mm, the stretching speed was 100mm/min, the pre-tension was 2cN, and the measurement was performed by using HD026N + fabric strength tester, with reference to FZ/T60005-1991 "determination of breaking strength and breaking elongation of nonwoven fabric", and the specific results are shown in table 3.
Tearing strength: the size of the test specimen is 20cm multiplied by 5cm, 10 pieces of each test specimen are taken in the longitudinal direction and the transverse direction, and the test is carried out by adopting an HD026N + fabric strength tester and referring to FZ/T60006-1991 determination of tearing strength of non-woven fabric, and the specific results are shown in a table 3.
Table 3 application test results of polylactic acid nonwoven fabric in application examples
As shown in Table 3, the functional masterbatch obtained by modifying the polylactic acid fiber with the inorganic mineral powder has excellent mechanical properties, and can realize the reinforcement and toughening of the polylactic acid fiber while greatly reducing the market cost of the polylactic acid fiber.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a functional master batch for reinforcing and toughening polylactic acid fiber is characterized by comprising the following steps:
mixing inorganic mineral powder with a surface modifier, and carrying out surface modification to obtain modified inorganic mineral powder; the surface modifier is at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent;
mixing the modified inorganic mineral powder with a dispersant, and performing pre-dispersion treatment to obtain pre-dispersed modified inorganic mineral powder;
mixing the pre-dispersed modified inorganic mineral powder with polylactic resin, a modifier, an antioxidant and a stabilizer, and then sequentially plasticizing, mixing, extruding and granulating to obtain a functional master batch for reinforcing and toughening polylactic acid fibers; the modifier is at least one of ethylene-vinyl acetate copolymer, atactic polypropylene, POE-g-GMA, polyethylene oxide, polybutylene succinate, polysiloxane, N-ethylene bis stearamide and zinc stearate.
2. The preparation method of the polylactic acid fiber reinforced plastic composite material, according to the claim 1, wherein the surface modifier accounts for 1-5% of the inorganic mineral powder, and the other raw materials for preparing the functional master batch for reinforcing and toughening the polylactic acid fiber comprise the following components in parts by weight: 8-55 parts of polylactic resin, 40-80 parts of inorganic mineral powder, 2-10 parts of a dispersing agent, 8-20 parts of a modifying agent, 0.3-2 parts of an antioxidant and 0.5-3 parts of a stabilizing agent.
3. The preparation method according to claim 1, wherein the temperature of the surface modification is 100 to 120 ℃; the time for the surface modification is based on the activity of the obtained modified inorganic mineral powder reaching 100%.
4. The method according to any one of claims 1 to 3, wherein the silane coupling agent is at least one of γ -aminopropyltriethoxysilane, γ - (2, 3-glycidoxy) propyltrimethoxysilane and methacryloxypropyltrimethoxysilane; the titanate coupling agent is at least one of pyrophosphoric acid type monoalkoxy titanate, isopropyldioleate acyloxy (dioctyl phosphate acyloxy) titanate, isopropyl tri (dioctyl phosphate acyloxy) titanate, isopropyl tristearate titanium isopropyl ester, bis (dioctyl pyrophosphate) ethylene titanate and tetraisopropyl di (dioctyl phosphate acyloxy) titanate; the aluminate coupling agent is distearoyl isopropoxy aluminate.
5. The production method according to any one of claims 1 to 3, wherein the inorganic mineral powder is at least one of calcite powder, talc powder and wollastonite powder; the particle size of the inorganic mineral powder is less than submicron; the dispersing agent is at least one of low molecular weight polyethylene wax, low molecular weight polypropylene wax and low molecular weight ethylene-vinyl acetate copolymer wax; the average number average molecular weight of the dispersing agent is 2000-5000.
6. The preparation method according to claim 1, wherein the pre-dispersion treatment is carried out in a high-speed mixer, the temperature of the pre-dispersion treatment is 110-130 ℃, the time is 8-12 min, and the rotating speed of the high-speed mixer is 980 rpm.
7. The method of claim 1, wherein the plasticizing, mixing, extruding and granulating are performed in a twin-screw extruder having a temperature of 160 to 220 ℃ and a rotation speed of 200 to 500 rpm.
8. The method according to claim 1 or 2, wherein the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 1098, and antioxidant 168; the stabilizer is at least one of tricresyl phosphate, triphenyl phosphite, triphenyl phosphate and triethyl phosphate.
9. The functional master batch for reinforcing and toughening the polylactic acid fiber, which is prepared by the preparation method of any one of claims 1 to 8.
10. A reinforced and toughened polylactic acid material comprises reinforced and toughened functional master batches and polylactic acid resin, wherein the reinforced and toughened functional master batches are the functional master batches for reinforcing and toughening polylactic acid fibers, which are disclosed by claim 9; the mass percentage content of the reinforcing and toughening functional master batch is 10-60%.
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