CN114539728B

CN114539728B - Black talc modified biodegradable film blowing grade composite material and preparation method thereof

Info

Publication number: CN114539728B
Application number: CN202210086441.2A
Authority: CN
Inventors: 应忠
Original assignee: Shangrao Black Talc Industry Research Institute; Shangrao Juweixing Technology Co ltd
Current assignee: Shangrao Black Talc Industry Research Institute; Shangrao Juweixing Technology Co ltd
Priority date: 2022-01-25
Filing date: 2022-01-25
Publication date: 2022-12-20
Anticipated expiration: 2042-01-25
Also published as: CN114539728A

Abstract

The invention discloses a black talc modified biodegradable blown film grade composite material and a preparation method thereof. The black talc modified biodegradable film blowing grade composite material comprises the following components in parts by mass: 55-95 parts of biodegradable main material, 1-20 parts of biodegradable auxiliary material, 3-40 parts of black talcum powder, 0.05-2.5 parts of coupling agent, 0.05-2.5 parts of surface modifier and 0.02-10 parts of biodegradable compatilizer; the black talcum powder is subjected to surface modification treatment by a coupling agent and a surface modifier. The black talc modified biodegradable blown film grade composite material provided by the invention utilizes the characteristic of organic conjugated molecules coexisting in the black talc to reduce the surface polarity of the talc and improve the compatibility, and meanwhile, the black talc powder has a lamellar oolitic structure, can orient and enhance a biodegradable film material, improves the tensile strength and puncture resistance of the biodegradable film material, and also has the advantages of high light shielding property and low cost.

Description

Black talc modified biodegradable film blowing grade composite material and preparation method thereof

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a black talc modified biodegradable film blowing grade composite material and a preparation method thereof.

Background

China is the most important world producing and consuming country of plastic products for packaging, and most of the plastic products for packaging are in the forms of films, plastic shopping bags, garbage bags and the like, and are abandoned in natural environment after being used. These waste plastic packages are scattered in urban areas, tourist scenic areas, water areas, etc., causing pollution to the surrounding environment and causing long-term damage to the ecological environment because they are difficult to degrade.

At present, the global treatment method for waste plastics comprises methods of landfill, incineration, regeneration granulation and the like, and the landfill can increase the use pressure of land resources and cause secondary pollution to the land; burning plastics can generate toxic and harmful gases, and if the efficiency of the incinerator is not high, the waste gases can enter the environment; the recycling granulation process also has limitations and is not suitable for use with plastic films, pouches and other laminated plastics, which are typically sent to landfills or incinerated. The development of full-biodegradable materials as environment-friendly products for replacing traditional plastics has wide development prospect and practicability.

The fully biodegradable plastic can be biodegraded under certain conditions, so that the environmental load is not increased, and the fully biodegradable plastic is an effective way for solving white pollution. Among them, poly (terephthalic acid) -butylene adipate (PBAT), poly (lactic acid) (PLA) and poly (butylene succinate) (PBS) are three biodegradable plastics which are the most widely used in the industry at the present stage, but because the raw materials of these fully biodegradable plastics are expensive, the manufacturing cost is high, and the compatibility of the materials is not good, so that the wide application of the fully biodegradable plastics in the market is limited.

The addition of mineral powder to reduce material cost is an effective technical route, and the commonly used powder is wollastonite, calcium carbonate and the like. For example, calcium carbonate powder modified PBAT adopts Mohs hardness 3 calcite, the jaw crushing is carried out, then the procedures of Raymond mill, jet mill and the like are carried out, the superfine calcium carbonate can be obtained, and the superfine calcium carbonate is subjected to surface modification and then is blended with PBAT to obtain the composite material particles. But the grinding energy consumption is higher due to the large hardness of the calcite. In order to realize a green process, further reduce energy consumption and promote low carbon emission reduction, minerals with low hardness are adopted to reduce power consumption of a main machine in the grinding process, the Mohs hardness of the white talc minerals is 1, the power of the main machine in the grinding process is low, and the grinding energy consumption can be reduced; however, the overall cost of the white talc powder is high, for example, 2 times as much as the calcium carbonate powder and three times as much as the black talc powder for 2000 mesh.

In addition, the degradable composite material modified by the white talc powder, especially the degradable blown film grade composite material has the problems of low strength, poor puncture resistance and poor light shielding property.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a black talc modified biodegradable blown film grade composite material and a preparation method thereof.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

in a first aspect, the invention provides a black talc modified biodegradable blown film grade composite material, which comprises the following components in parts by mass:

55-95 parts of biodegradable main material, 1-20 parts of biodegradable auxiliary material, 3-40 parts of black talcum powder, 0.05-2.5 parts of coupling agent, 0.05-2.5 parts of surface modifier and 0.02-10 parts of biodegradable compatilizer;

wherein the black talcum powder is subjected to surface modification treatment by a coupling agent and a surface modifier.

In a second aspect, the invention also provides a preparation method of the black talc modified biodegradable blown film grade composite material, which comprises the following steps:

fully mixing 3-40 parts by mass of black talcum powder, 0.05-2.5 parts by mass of coupling agent and 0.05-2.5 parts by mass of surface modifier, and reacting at the temperature of 70-130 ℃ to prepare modified black talcum powder;

fully mixing 55-95 parts of biodegradable main material, 1-20 parts of biodegradable auxiliary material and 0.02-10 parts of biodegradable compatilizer to obtain biodegradable material mixed particles;

and fully mixing the modified black talcum powder and the mixed granules of the biodegradable material, melting and extruding, and cooling to obtain the black talcum modified biodegradable film blowing grade composite material.

Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that at least:

according to the black talc modified biodegradable blown film composite material and the preparation method thereof, the surface polarity of the black talc is reduced by utilizing the characteristic of organic conjugated molecules coexisting in the black talc, the compatibility between the black talc and a biodegradable material is improved, and meanwhile, the black talc powder has a lamellar oolitic structure, so that the biodegradable film material can be oriented and enhanced, and the tensile strength and the puncture resistance of the biodegradable film material are improved; in addition, the black talc has a dark color, so that the film has good black brown and good light shading property on the premise of not adding an additional coloring agent and an additional light shading agent; in addition, the black talc has wide sources and low price, and the cost of the biodegradable film blowing composite material is obviously reduced.

The above description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical means of the present invention and to implement the technical means according to the content of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.

Drawings

FIG. 1 is a physical representation of a black talc modified biodegradable blown film grade composite particle provided in accordance with an exemplary embodiment of the present invention;

FIG. 2 is a diagram of a product after a black talc modified biodegradable film blowing grade composite material is formed by film blowing according to an exemplary embodiment of the present invention;

FIG. 3 is a diagram of a film blowing process of a talc white modified biodegradable film blowing grade composite according to the prior art;

fig. 4 is a diagram of a film blowing process of a black talc modified biodegradable film blowing grade composite material according to an exemplary embodiment of the present invention.

Detailed Description

In view of the defects in the prior art, the inventor of the present invention has made extensive research and practice to propose the technical solution of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein and, therefore, the scope of the present invention is not limited by the specific embodiments disclosed below.

The white talc is widely applied to modification of macromolecules, the black talc is directly used for replacing the white talc to modify the macromolecules, a lot of difficulties are faced, although the surface of the black talc is covered with an organic matter molecular layer, the main component of the black talc is still a talc component, the polarity of the whole structure is larger, the chemical structure of the black talc is greatly different from that of a biodegradable material, and although compared with the white talc with the same mesh number, trace organic matters coexisted on the surface of the black talc cannot improve the compatibility of black talc powder and the biodegradable material. However, when the amount of the black talc powder is relatively high (more than 5% by weight), agglomeration and uneven dispersion of the black talc powder in the composite material are likely to occur, which may cause film rupture during film processing or rough feel of the film, resulting in fish eyes, nodules, and significant granular feel of the appearance of the blown product. Meanwhile, the phenomena including the reduction of elongation at break, ductility and tensile strength are caused, so that the direct application of the high-addition-amount black talc powder to the biodegradable material film blowing-grade composite material faces many problems and cannot be implemented.

In order to solve the above problems, the inventors of the present invention have conducted intensive studies on black talc, and found that, by means of characterization means such as two-dimensional nuclear magnetic spectrum and raman spectrum, the surface of black talc has no carbon of the "graphite-like structure", but has a surface having an organic conjugated molecule which contains phenolic hydroxyl groups and derivatives thereof, has a centrosymmetric structure, and has an organic conjugated chromophore satisfying the huckel law, and the organic structure as a whole can reduce the polarity of the talc surface. In order to further improve the compatibility with the black talc powder, the inventor proposes that a PBST material containing a semi-aromatic structure is used as a compatilizer, the compatibility of the black talc powder and an organic polymer material can be further improved due to the fact that a terephthalic acid conjugated structure in the PBST structure and organic conjugated small molecules on the surface of the black talc form a pi-pi interaction, and the black talc powder can be fully combined with a biodegradable material by matching with a surface modifier and a synergistic effect, so that the black talc powder can greatly save the cost, and has the characteristics of high strength and high light shielding.

Based on the principle, the embodiment of the invention provides a black talc modified biodegradable film blowing grade composite material which comprises the following components in parts by mass: 55-95 parts of biodegradable main material, 1-20 parts of biodegradable auxiliary material, 3-40 parts of black talcum powder, 0.05-2.5 parts of coupling agent, 0.05-2.5 parts of surface modifier and 0.02-10 parts of biodegradable compatilizer; wherein the black talcum powder is subjected to surface modification treatment by a coupling agent and a surface modifier.

The invention is calledThe biodegradable material (including the biodegradable main material, the biodegradable auxiliary material, the biodegradable compatilizer and the like) is degraded under the action of microorganisms existing in nature under the conditions of nature such as soil and/or sandy soil and the like and/or under specific conditions such as composting conditions or anaerobic digestion conditions or in aqueous culture solution, and finally completely degraded into carbon dioxide (CO) ₂ ) Or/and methane (CH) ₄ ) Water (H) ₂ O) and mineralized inorganic salts of the elements contained therein, and new plastics or other polymeric materials of biomass.

In some embodiments, the biodegradable main material may include one or a combination of two or more of polybutylene terephthalate-adipate (PBAT), resin and carbon dioxide/propylene oxide copolymer (PPC), and polybutylene succinate-adipate (PBSA).

In some embodiments, the mass part of the biodegradable main material may be preferably 58 to 88 parts, and further may be preferably 60 to 85 parts.

In some embodiments, the biodegradable excipients may include one or a combination of two or more of polybutylene succinate (PBS), polycaprolactone (PCL), polyglycolide (PGA), polyhydroxyalkanoate (PHA), poly-3-hydroxybutyrate (PHB), polyhydroxybutyrate valerate (PHBV), polylactic acid (PLA), and poly-3-hydroxybutyrate/4-hydroxybutyrate (P (3hb, 4hb)).

In some embodiments, the biodegradable auxiliary material is 1 to 15 parts by mass, more preferably 2 to 10 parts by mass, and still more preferably 3 to 5 parts by mass.

The biodegradable main material and the biodegradable auxiliary material can be in a granular form or a powder form, and a specific preferred scheme of the invention is preferably in a powder form, and the powder form is easy to be uniformly mixed with other materials. The main biodegradable material and the auxiliary biodegradable material may be new material or recovered material. However, the melt index is required to be less than 10g/10min under the test condition of 2.16kg at 190 ℃.

In some embodiments, the black talc has a particle size of 1000 to 5000 mesh.

In some embodiments, the particle size of the black talc powder may preferably be 1500 to 3500 mesh, and further may preferably be 2000 to 2500 mesh.

The black talcum powder is mainly produced from a huge storage amount of black talcum resources in the central south and the southwest regions of China, and is subjected to micronization processing by using a jet mill, a Raymond mill, a dry method, a wet method and other methods as a typical example of Guangfeng black talcum ore deposit in Jiangxi. In the Guangfeng black talc mine, in the Shanghai Ganfeng region of Shanghai province of Jiangxi province, a few ore veins are located in the Yushan county of Shanghai, and are mainly exposed in the middle section of a seismic denier system upper system lamp shadow group (551 Ma to-542 Ma, the Addis Carla and the Cambri boundary), and the ore mainly has a oolitic structure. The black talc and white talc [ Mg ₃ Si ₄ O ₁₀ (OH) ₂ ]Quite similar, wherein the contents of impurity elements such as Fe, al and the like are extremely low. The infrared absorption spectrum of the black talc is very similar to that of the white talc, so that the black talc is not significantly different from the white talc in terms of the micro morphology, chemical composition and crystal structure of minerals. The difference is mainly that a single layer or a plurality of layers of organic conjugated small molecular layers exist among layers of the black talc crystal.

In some embodiments, the coupling agent may include one or a combination of two or more of a titanate coupling agent, an aluminate coupling agent, a zirconate coupling agent, and calcium stearate. Among these, the preferred titanate coupling agent in the embodiment of the present invention may be one or a combination of two or more of isopropyl tris (isostearyl) titanate, isopropyl tris (dioctylphosphoryl) titanate, bis (dioctylphosphoryl) oxoacetate titanium, bis (dioctylphosphoryl) ethylene titanate, isopropyl bis (methacryloyl) isostearoyl titanate, isopropyl tris (dioctylphosphoryl) titanate, isopropyl tris (dodecylbenzenesulfonyl) titanate, and isopropyl tris (n-ethylamino) titanate. When one embodiment of the present invention selects an aluminate coupling agent, the optional ranges are; triisopropyl aluminate [ Al (OC 3H 7-i) 3] n, tribenzyl aluminate [ Al (OC 6H5CH 2) 3] n. The selectable varieties of aluminate coupling agents are: SG-Al821 (distearoyl isopropyl aluminate), DL-411AF, DL-411D, DL-411DF, and anti-settling aluminate ASA.

In some embodiments, the coupling agent is present in an amount of 0.2 to 1.25 parts by mass.

In some embodiments, the surface modifier may include one or a combination of two or more of gum arabic, sodium fatty alcohol-polyoxyethylene ether sulfate, triethanolamine dodecylbenzene sulfonate, α -olefin sulfonate, sodium abietate, triethanolamine dodecylbenzene sulfonate, disodium fatty alcohol-polyoxyethylene ether sulfosuccinate monoester, sodium dodecylbenzene sulfonate, sodium tetradecyl benzene sulfonate, sodium diisooctyl succinate sulfonate, sodium hexadecylbenzene sulfonate, and sodium octadecyl benzene sulfonate.

In some embodiments, the surface modifier may preferably be 0.2 to 1.5 parts by mass.

The surface modifier mainly refers to a surfactant and a small part of other auxiliary agents, wherein the surfactant refers to a substance which has strong surface activity and can obviously reduce the surface tension of liquid. The classification methods of the surfactants are various, and the surfactants are classified according to the structures of hydrophobic groups, such as straight chains, branched chains, aromatic chains, long fluorine-containing chains and the like; classified according to hydrophilic group into carboxylate, sulfate, quaternary ammonium salt, PEO derivative, lactone, etc.; some researchers have classified into ionic type, nonionic type, etc. according to the ionic nature of their molecular constitution, and also classified into various methods according to their water solubility, chemical structural characteristics, raw material source, etc.

In some embodiments, the biodegradable compatibilizer comprises one or a combination of polybutylene succinate and polybutylene terephthalate (PBST). Further preferably, the biodegradable compatilizer is selected from one or two of linear polybutylene terephthalate and branched polybutylene terephthalate; the PBST is aliphatic-aromatic copolyester which is prepared by polycondensation of components such as succinic acid, terephthalic acid or terephthalic acid esters, butanediol and the like, and the polymer can be prepared by polymerization of the conventional PBT industrial polyester device.

In some embodiments, the biodegradable compatibilizer is 0.1 to 2 parts by mass.

In some embodiments, the black talc modified biodegradable blown film grade composite may further comprise the following components in parts by mass: 0.01-5 parts of wetting assistant, 0.01-5 parts of lubricant and 0.01-1 part of antioxidant; wherein, the wetting auxiliary agent can comprise one or the combination of more than two of oleic acid, epoxidized soybean oil and natural animal and vegetable oil; further, the natural animal and vegetable oil comprises soybean oil, olive oil and palm oil; still further, the wetting assistant is 0.05-3 parts by mass.

In the above embodiment, the lubricant may include one or a combination of two or more of calcium stearate, stearic acid, glyceryl oleate, span 20, span 40, span 60, span 80, span 65, span 85, tween 20, tween 40, tween 60, tween 80, glyceryl monostearate, glyceryl tristearate, erucamide, oleamide, higher fatty alcohol lubricants and soap lubricants; further, the lubricant may preferably be 0.05 to 3 parts by mass; the antioxidant can comprise one or the combination of more than two of antioxidant 1010, antioxidant 626, antioxidant 1178 and antioxidant 168; preferably one or a combination of both of antioxidant 1010 and antioxidant 168. The antioxidant is a preferred embodiment of the present invention, and the antioxidant may further include antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP, antioxidant TNP, antioxidant TPP, antioxidant MB, antioxidant 264, vitamin C, and the like. The addition amount of the antioxidant is preferably: 0.1 to 1 portion.

The wetting auxiliary is mainly used for wetting the particles by the wetting auxiliary when the main material of the biodegradable material is in a particle form, adding the powder into the particles to obtain a mixture of the powder-coated particles, and easily adding the mixture into a hopper of a screw through a spiral feeder. Oleic acid, also known as cis-octadec-9-enoic acid, is a typical unsaturated fatty acid. Epoxidized soybean oil is composed of various fatty acid esters: epoxy linoleate (51-57%), epoxy oleate (32-36%), epoxy palmitate (2.4-6.8%), etc. Soybean oil, olive oil, and palm oil, as well as other natural animal and vegetable oil esters. The natural animal and vegetable oil is required to be liquid with good fluidity at 35-60 ℃. When the main material of the biodegradable material is in a powder state, the wetting assistant can not be added.

The embodiment of the invention also provides a preparation method of the black talc modified biodegradable blown film grade composite material, which comprises the following steps:

the black talcum powder, the coupling agent and the surface modifier are fully mixed and react at the temperature of 70-130 ℃ to prepare the modified black talcum powder.

Fully mixing the biodegradable main material, the biodegradable auxiliary material and the biodegradable compatilizer to obtain the biodegradable material mixed particles.

In some embodiments, the method of making may further comprise the step of blow molding the black talc modified biodegradable blown film grade composite.

In some embodiments, the preparation method specifically comprises the following steps:

and (3) fully mixing the black talcum powder and the coupling agent for 1-30min at the temperature of 70-130 ℃ and the stirring speed of 100-600r/min to prepare a modified precursor mixture.

Adding a surface modifier into the modified precursor mixture, and reacting for 1-45min at a stirring speed of 100-700r/min to obtain the modified black talcum powder.

As some typical specific application cases, the preparation method provided by the invention can be implemented by adopting the following preparation method:

3 to 40 parts of dry black talcum powder dried for 1 to 5 hours at the temperature of between 80 and 130 ℃ is added into a high-speed mixer at the temperature of between 70 and 130 ℃; adding 0.05-2.5 parts of coupling agent, and treating for 1-45min at a rotating speed of 100-600 r/min; adding 0.05-2.5 parts of surface modifier, and treating at a rotating speed of 100-700r/min for 1-45min to obtain surface modified black talcum powder, which is referred to as modified black talcum powder;

adding 55-95 parts of main biodegradable material, 1-20 parts of auxiliary biodegradable material and 0.02-10 parts of biodegradable compatilizer into another high-speed mixer at 35-60 ℃, and processing at the room temperature at the rotating speed of 100-600r/min for 1-30min to obtain biodegradable material mixed particles; continuously adding 0.01-5 parts of wetting auxiliary agent, and treating at the rotating speed of 100-600r/min for 1-45min to obtain biodegradable material mixed particles with wetted surfaces; sequentially adding 3-40 parts of modified black talcum powder, 0.01-5 parts of lubricant and 0.01-1 part of antioxidant, processing at the rotating speed of 100-600r/min for 1-45min, and uniformly mixing the modified black talcum powder, the main biodegradable material, the auxiliary agent and the auxiliary biodegradable material to obtain a mixture; and extruding and molding the mixture at 140-230 ℃ through a double-screw extruder, and performing air cooling to obtain the black talc modified biodegradable material film blowing grade composite material particles.

The composite material particles are added into film blowing equipment suitable for biodegradable materials, and blow molding is carried out at the temperature of 150-230 ℃, so that a uniform film material with the thickness of 10-60 micrometers can be obtained, the surface is smooth, no fish eyes or burrs exist, the mechanical property is good, and the composite material particles are suitable for the fields of degradable sanitation bags, garbage bags, express bags and the like.

The foregoing is a summary of embodiments of the present invention, and in order to provide a thorough understanding of the technical concepts of the present invention, the following detailed description of the embodiments of the present invention is provided by way of several specific examples and with reference to the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.

Further, unless otherwise specified, the materials, fillers, modifiers and various auxiliaries used in the examples of the present invention are commercially available.

Example 1

The embodiment provides a preparation method of a black talc modified biodegradable film blowing grade composite material, which comprises the following steps:

300g of dried 1000-mesh black talcum powder dried for 5 hours at 80 ℃ is added into a high-speed mixer at 70 ℃; adding 5g of isopropyl tri (isostearyl) titanate coupling agent, and treating at the rotating speed of 100r/min for 45 min; continuously adding 5g of Arabic gum powder surface modifier, and processing at a rotation speed of 100r/min for 45min to obtain surface-modified black talc powder, namely modified black talc powder;

in another high-speed mixer with the temperature of 35 ℃, 5500g of PBAT as a main material, 100g of PBS as an auxiliary material and 2g of PBST as a biodegradable compatilizer are added, and the mixture is processed for 30min at the rotating speed of 100r/min at room temperature to obtain biodegradable material mixed particles; continuously adding 10g of oleic acid serving as a wetting auxiliary agent, and treating at the rotating speed of 100r/min for 5min to obtain biodegradable material mixed particles with wetted surfaces; sequentially adding 300g of modified black talcum powder, 1g of span 40 lubricant and 1g of antioxidant, processing at the rotating speed of 100r/min for 45min, and uniformly mixing the modified black talcum powder, the biodegradable material main material, the auxiliary agent and the biodegradable material auxiliary material to obtain a mixture; extruding and molding the mixture by a double-screw extruder at the double-screw temperature of 140-155-160-165-165-170-160-165-150 (unit ℃) in sequence, and air cooling to obtain the black talc modified biodegradable material film blowing grade composite material particles;

in the above steps, the names and the amounts of the raw materials, the auxiliary agents, the modifiers and the like are shown in the following table:

adding the composite material particles into a degradable material film blowing machine, sequentially carrying out blow molding at the temperature of 155-160-165-165-170-160 ℃ to obtain a uniform film material with the thickness of 60 micrometers, wherein the film material has a smooth surface, is free of fish eyes and burrs, has good mechanical properties, and is suitable for the fields of sanitation bags, garbage bags, express bags and the like;

the mechanical property tests of the film material prepared in the embodiment are shown in the following table, and if no special indication is made, the mechanical property test methods of the film material adopted in the embodiment of the invention are all the test methods recorded in the national standard GB/T1040.3-2006:

test items	Modulus of elasticity (MPa)	Tensile Strength (MPa)	Elongation at Break (%)
				Example 1	45	18	678

Example 2

The embodiment provides a preparation method of a black talc modified biodegradable blown film grade composite material, which comprises the following steps:

600g of dried 1250-mesh black talcum powder which is dried for 4.5 hours at 90 ℃ is added into a high-speed mixer at 75 ℃; adding 15g of isopropyl tri (dioctyl pyrophosphoryl) titanate coupling agent, and treating for 10min at the rotating speed of 120 r/min; continuously adding 15g of sodium octadecyl benzene sulfonate surface modifier, and processing at a rotation speed of 120r/min for 10min to obtain surface-modified black talcum powder, which is referred to as modified black talcum powder;

5500g of PPC as a main material, 200g of PBS as an auxiliary material and 2g of PBST as a biodegradable compatilizer are added into another high-speed mixer at 45 ℃, and the mixture is treated at the rotating speed of 100r/min at room temperature for 4min to obtain biodegradable material mixed particles; continuously adding 2g of epoxy soybean oil as a wetting assistant, and treating at the rotating speed of 100r/min for 5min to obtain biodegradable material mixed particles with wetted surfaces; sequentially adding 300g of modified black talcum powder, 2g of oleamide lubricant and 2g of antioxidant 626, processing at the rotating speed of 120r/min for 10min, and uniformly mixing the modified black talcum powder, the biodegradable material main material, the auxiliary agent and the biodegradable material auxiliary material to obtain a mixture; extruding and molding the mixture by a double-screw extruder at the temperature of 142-154-161-164-166-172-161-160-145 (unit ℃) in sequence, and air-cooling to obtain the black talc modified biodegradable material film blowing grade composite material particles;

in the above steps, the names and amounts of the raw materials, the additives, the modifiers and the like are shown in the following table:

adding the composite material particles into a degradable material film blowing machine, sequentially carrying out blow molding at the temperature of 142-156-158-165-150-140 ℃ to obtain a uniform film material with the thickness of 28 microns, wherein the film material has a smooth surface, is free of fish eyes and burrs, has good mechanical properties, and is suitable for the fields of sanitation bags, garbage bags, express bags and the like;

the mechanical properties of the film material prepared in this example are shown in the following table:

test items	Modulus of elasticity (MPa)	Tensile Strength (MPa)	Elongation at Break (%)
				Example 2	25	13	718

Example 3

adding 800g of dried 1500 mesh black talcum powder dried for 4 hours at 95 ℃ into a high-speed mixer at 80 ℃; adding 16g of bis (dioctyl pyrophosphoryl) oxyacetate titanium coupling agent, and treating at the rotating speed of 180r/min for 12 min; continuously adding 16g of fatty alcohol-polyoxyethylene ether sulfosuccinic acid monoester disodium surface modifier, and treating at the rotating speed of 180r/min for 12min to obtain surface-modified black talcum powder, which is called modified black talcum powder for short;

in another high-speed mixer at 45 ℃, 5500g of PBSA as a main material, 400g of polyglycolide PGA as an auxiliary material and 3g of PBST as a biodegradable compatilizer are added, and the mixture is processed at the room temperature at a rotating speed of 180r/min for 5min to obtain biodegradable material mixed particles; continuously adding 3g of soybean oil as a wetting aid, and treating at a rotating speed of 180r/min for 3min to obtain biodegradable material mixed particles with wetted surfaces; sequentially adding 800g of modified black talcum powder, 3g of stearic acid triglyceride lubricant and 3g of antioxidant 1178, processing for 5min at a rotating speed of 180r/min, and uniformly mixing the modified black talcum powder, the biodegradable material main material, the auxiliary agent and the biodegradable material auxiliary material to obtain a mixture; extruding and molding the mixture at a twin-screw temperature of 212-224-230-230-216-212-211-200-195 (unit ℃) in sequence by a twin-screw extruder, and air cooling to obtain black talc modified biodegradable material film blowing grade composite material particles;

adding the composite material particles into a degradable material film blowing machine, sequentially carrying out blow molding at the temperature of 202-220-228-225-210-195 ℃ to obtain a uniform film material with the thickness of 35 microns, wherein the film material has a smooth surface, is free of fish eyes and burrs, has good mechanical properties, and is suitable for the fields of sanitation bags, garbage bags, express bags and the like;

test item	Modulus of elasticity (MPa)	Tensile Strength (MPa)	Elongation at Break (%)
				Example 3	369	23	461

Example 4

1000g of dried 1500-mesh black talcum powder dried for 4 hours at 100 ℃ is added into a high-speed mixer at 85 ℃; adding 18g of di (dioctyl pyrophosphoryl) ethylene titanate coupling agent, and treating for 14min at the rotating speed of 200 r/min; continuously adding 18g of diisooctyl succinate sodium sulfonate surface modifier, and treating at the rotating speed of 200r/min for 14min to prepare surface-modified black talcum powder, namely modified black talcum powder;

in another high-speed mixer at 47 ℃, 5500g of PBAT as a main material, 500g of polyhydroxyalkanoate PHA material as an auxiliary material and 5g of PBST as a biodegradable compatilizer are added, and the mixture is processed at the rotating speed of 200r/min at room temperature for 5min to obtain biodegradable material mixed particles; continuously adding 5g of olive oil as a wetting aid, and treating at a rotating speed of 200r/min for 5min to obtain biodegradable material mixed particles with wetted surfaces; adding 1000g of modified black talcum powder, 5g of glycerol monostearate and 5g of Tween 80 serving as a composite lubricant and 5g of antioxidant 168 in sequence, processing at the rotating speed of 200r/min for 5min, and uniformly mixing the modified black talcum powder, the biodegradable material main material, the auxiliary agent and the biodegradable material auxiliary material to obtain a mixture; extruding and molding the mixture at the twin-screw temperature of 179-184-191-194-196-192-181-170-165 (unit ℃) by a twin-screw extruder, and air cooling to obtain the black talc modified biodegradable material film blowing grade composite material particles;

the composite material particles are added into a degradable material film blowing machine, and are subjected to blow molding at 162-176-188-175-170-160 ℃ in sequence to obtain a uniform film material with the thickness of 36 micrometers, wherein the film material has a smooth surface, is free of fish eyes and burrs, has good mechanical properties, and is suitable for the fields of sanitation bags, garbage bags, express bags and the like;

the mechanical properties of the film materials prepared in this example are shown in the following table:

test items	Modulus of elasticity (MPa)	Tensile Strength (MPa)	Elongation at Break (%)
				Example 4	169	16.4	353

Example 5

1200g of dried 2000-mesh black talcum powder dried for 3 hours at 105 ℃ is added into a high-speed mixer at 90 ℃; adding 20g of di (dioctyl pyrophosphoryl) ethylene titanate coupling agent, and treating for 15min at the rotating speed of 220 r/min; continuously adding 20g of alpha-olefin sulfonate and 20g of Arabic gum powder as a compound surface modifier, and treating at the rotating speed of 220r/min for 15min to obtain surface-modified black talcum powder, namely modified black talcum powder;

5500g of PBAT serving as a main material, 700g of polylactic acid (PLA) material serving as an auxiliary material and 7g of PBST serving as a biodegradable compatilizer are added into another high-speed mixer at 48 ℃, and the mixture is treated at the rotating speed of 220r/min at room temperature for 7min to obtain biodegradable material mixed particles; continuously adding 6g of palm oil as a wetting auxiliary agent, and treating at the rotating speed of 220r/min for 6min to obtain biodegradable material mixed particles with wetted surfaces; sequentially adding 1200g of modified black talcum powder, 6g of Tween 20 and 6g of span 20 as a composite lubricant and 5g of antioxidant 168, processing at a rotating speed of 220r/min for 6min, and uniformly mixing the modified black talcum powder, the biodegradable material main material, the auxiliary agent and the biodegradable material auxiliary material to obtain a mixture; extruding and molding the mixture by a double-screw extruder at the temperature of 165-174-181-196-196-192-180-170-166 (unit ℃) in sequence, and air cooling to obtain the black talc modified biodegradable material film blowing grade composite material particles;

adding the composite material particles into a degradable material film blowing machine, performing blow molding at the temperature of 176-186-198-185-180-170 ℃ to obtain a uniform film material with the thickness of 18 microns, wherein the surface of the uniform film material is smooth, has no fisheyes or burrs, has good mechanical properties, and can be suitable for the fields of sanitation bags, garbage bags, express bags and the like;

test items	Modulus of elasticity (MPa)	Tensile Strength (MPa)	Elongation at Break (%)
				Example 5	154	19.9	708

Example 6

1800g of dried 2000-mesh black talcum powder dried for 2.5 hours at 115 ℃ is added into a high-speed mixer at 110 ℃; adding 27g of isopropyl tri (dioctyl phosphoryl) titanate coupling agent, and treating at the rotating speed of 300r/min for 18 min; continuously adding 36g of sodium abietate and 9g of sodium hexadecylbenzene sulfonate as compound surface modifiers, and treating at the rotating speed of 350r/min for 25min to obtain surface-modified black talcum powder, namely modified black talcum powder;

in another high-speed mixer at 53 ℃, 5500g of PBAT as a main material, 800g of polylactic acid PLA as an auxiliary material and 240g of PBST as a biodegradable compatilizer are added, and the mixture is processed at the rotating speed of 300r/min at room temperature for 10min to obtain biodegradable material mixed particles; continuously adding 50g of sunflower seed oil as a wetting auxiliary agent, and treating at the rotating speed of 320r/min for 16min to obtain biodegradable material mixed particles with wetted surfaces; adding 1800g of modified black talcum powder, 36g of erucamide and 36g of span 40 as a composite lubricant and 36g of antioxidant 626 in sequence, processing at the rotating speed of 320r/min for 16min, and uniformly mixing the modified black talcum powder, the biodegradable material main material, the auxiliary agent and the biodegradable material auxiliary material to obtain a mixture; extruding and molding the mixture by a double-screw extruder at the twin-screw temperature of 166-176-186-196-196-192-186-176-166 (unit ℃) in sequence, and air cooling to obtain black talc modified biodegradable material film blowing grade composite particles;

adding the composite material particles into a degradable material film blowing machine, performing blow molding at the temperature of 176-186-196-186-186-170 ℃ to obtain a uniform film material with the thickness of 29 microns, wherein the surface of the uniform film material is smooth, has no fisheyes and burrs, has good mechanical properties, and can be suitable for the fields of sanitation bags, garbage bags, express bags and the like;

test item	Modulus of elasticity (MPa)	Tensile Strength (MPa)	Elongation at Break (%)
				Example 6	118	23	638

Example 7

adding 32kg of dried 3000-mesh black talcum powder dried for 1.5h at 125 ℃ into a high-speed mixer at 120 ℃; adding 450g of isopropyl tri (dodecyl benzene sulfonyl) titanate coupling agent, and treating for 28min at the rotating speed of 450 r/min; continuously adding 420g of Arabic gum powder and 380g of sodium dodecyl benzene sulfonate as a compound surface modifier, and treating for 28min at the rotating speed of 450r/min to obtain surface-modified black talcum powder, namely modified black talcum powder;

adding 55kg of PBAT serving as a main material, 10kg of polylactic acid PLA serving as an auxiliary material and 8kg of PBST serving as a biodegradable compatilizer into another high-speed mixer at 57 ℃, and processing at the rotating speed of 400r/min for 3min at room temperature to obtain biodegradable material mixed particles; continuously adding 520g of oleic acid serving as a wetting aid, and treating at the rotating speed of 520r/min for 36min to obtain biodegradable material mixed particles with wetted surfaces; sequentially adding 32kg of modified black talcum powder, 480g of oleamide serving as a lubricant and 660g of antioxidant 1178, treating at the rotating speed of 420r/min for 6min, and uniformly mixing the modified black talcum powder, the biodegradable material main material, the auxiliary agent and the biodegradable material auxiliary material to obtain a mixture; extruding and molding the mixture by a double-screw extruder at the temperature of 167-177-187-197-197-197-187-177-167 (unit ℃) in sequence, and performing air cooling to obtain the black talc modified biodegradable material film-blowing grade composite material particles;

adding the composite material particles into a degradable material film blowing machine, sequentially carrying out blow molding at the temperature of 175-185-195-185-185-170 ℃ to obtain a uniform film material with the thickness of 38 micrometers, wherein the surface of the uniform film material is smooth, free of fish eyes and burrs, good in mechanical property and suitable for the fields of sanitation bags, garbage bags, express bags and the like;

test items	Modulus of elasticity (MPa)	Tensile Strength (MPa)	Elongation at Break (%)
				Example 7	178	21	438

Example 8

40kg of dried 5000-mesh black talcum powder dried for 1h at 130 ℃ is added into a high-speed mixer at 130 ℃; adding 1kg of isopropyl tri (n-ethylamino) titanate coupling agent, and treating at a rotation speed of 600r/min for 10 min; continuously adding 1kg of fatty alcohol-polyoxyethylene ether sodium sulfate surface modifier, and treating at the rotating speed of 700r/min for 10min to prepare surface-modified black talc powder, namely modified black talc powder;

adding 55kg of PBAT serving as a main material, 20kg of PLA serving as an auxiliary material and 10kg of PBST serving as a biodegradable compatilizer into another high-speed mixer at 60 ℃, and processing at the rotating speed of 600r/min for 1min at room temperature to obtain biodegradable material mixed particles; continuously adding 3kg of oleic acid serving as a wetting assistant, and treating at the rotating speed of 600r/min for 1min to obtain biodegradable material mixed particles with wetted surfaces; adding 40kg of modified black talcum powder, 3kg of stearic acid triglyceride and 0.5kg of antioxidant 168 in sequence, processing at the rotating speed of 600r/min for 1min, and uniformly mixing the modified black talcum powder, the biodegradable material main material, the auxiliary agent and the biodegradable material auxiliary material to obtain a mixture; extruding and molding the mixture by a double-screw extruder at the temperature of 170-185-190-195-205-190-180-175-160 (unit ℃) in sequence, and air cooling to obtain the black talc modified biodegradable material film blowing grade composite material particles;

the composite material particles are added into a degradable material film blowing machine, and are subjected to blow molding at the temperature of 165-180-185-195-180-170 ℃ in sequence to obtain a uniform film material with the diameter of 20 microns, the surface is smooth, no fish eyes or burrs exist, the mechanical property is good, and the composite material particles are suitable for the fields of sanitation bags, garbage bags, express bags and the like;

test items	Modulus of elasticity (MPa)	Tensile Strength (MPa)	Elongation at Break (%)
				Example 8	125	18	432

Example 9

330g of dried 2000-mesh black talcum powder dried for 4 hours at 100 ℃ is added into a high-speed mixer at 90 ℃; adding 3.3g of OL-AT1618 aluminum-titanium composite coupling agent, and processing AT a rotation speed of 300r/min for 15 min; continuously adding 7g of sodium hexadecylbenzene sulfonate and 7g of Arabic gum powder as composite surface modifiers, and treating at the rotating speed of 600r/min for 10min to obtain surface-modified black talcum powder, which is called modified black talcum powder for short;

in another high-speed mixer at 40 ℃, 625g of PBAT serving as a main material, 30g of PLA serving as an auxiliary material and 1g of PBST serving as a biodegradable compatilizer are added, and the mixture is processed at the rotating speed of 450r/min at room temperature for 3min to obtain biodegradable material mixed particles; continuously adding 1g of oleic acid as a wetting aid, and treating at the rotating speed of 600r/min for 3min to obtain biodegradable material mixed particles with wetted surfaces; sequentially adding 330g of modified black talcum powder, 0.3g of glycerol monostearate, 0.4g of span 20 and 0.2g of antioxidant 1010, mixing at the rotating speed of 600r/min for 10min, and uniformly mixing the modified black talcum powder, the biodegradable material main material, the auxiliary agent and the biodegradable material auxiliary material to obtain a mixture; extruding and molding the mixture at the twin-screw temperature of 145-155-160-165-165-160-160-155-145 (unit ℃) by a twin-screw extruder, and air cooling to obtain the black talc modified biodegradable material film blowing grade composite material particles;

the composite material particles are added into a small degradable material film blowing machine, and subjected to blow molding at the temperature of 145-160-175-175-160-150 ℃ to obtain a 25-micron uniform film material which is smooth in surface, free of fish eyes and burrs, good in mechanical property and applicable to the fields of sanitation bags, garbage bags, express bags and the like.

Example 10

This example provides a method for preparing a black talc modified biodegradable blown film grade composite, which is substantially the same as example 9 except that: when the modified black talcum powder is prepared, 3.3g of tribenzyl aluminate is added as a coupling agent;

the prepared composite material particles can be subjected to film blowing to obtain a film material with mechanical properties similar to those of example 9.

Example 11

This example provides a method for preparing a black talc modified biodegradable blown film grade composite, which is substantially the same as example 9 except that: when the modified black talcum powder is prepared, 3.3g of calcium stearate is added as a coupling agent;

example 12

This example provides a method for preparing a black talc modified biodegradable blown film grade composite, which is substantially the same as example 9 except that: when the modified black talcum powder is prepared, 3.3g of tetra-n-propyl zirconate is added as a coupling agent;

the prepared composite material particles can obtain a film material with mechanical properties similar to those of the film material in the example 9 through film blowing.

Comparative example 1

adding 330g of dried 2000-mesh talcum powder dried for 4 hours at 100 ℃ into a high-speed mixer at 90 ℃; adding 7g of isopropyl tri (isostearyl) titanate coupling agent, and treating for 15min at the rotating speed of 300 r/min; continuously adding 7g of sodium hexadecylbenzene sulfonate and 7g of Arabic gum powder as surface modifiers, and treating at the rotating speed of 600r/min for 10min to obtain surface-modified black talcum powder, namely modified black talcum powder;

in another high-speed mixer at 40 ℃, 625g of PBAT serving as a main material, 30g of PLA serving as an auxiliary material and 1g of PBST serving as a biodegradable compatilizer are added, and the mixture is processed at the rotating speed of 450r/min at room temperature for 3min to obtain biodegradable material mixed particles; continuously adding 1g of oleic acid serving as a wetting assistant, and treating at the rotating speed of 600r/min for 3min to obtain biodegradable material mixed particles with wetted surfaces; sequentially adding 330g of modified white talcum powder, 0.3g of glyceryl monostearate, 0.4g of span 20 and 0.2g of antioxidant 1010, mixing at the rotating speed of 600r/min for 10min, and uniformly mixing the modified white talcum powder, the biodegradable material main material, the auxiliary agent and the biodegradable material auxiliary material to obtain a mixture; extruding and molding the mixture at the twin-screw temperature of 145-155-160-165-165-160-160-155-145 (unit ℃) by a twin-screw extruder, and performing air cooling to obtain the film blowing grade composite material particles of the talc modified biodegradable material, wherein the particles are relatively poor in cooling and non-uniform in grain cutting;

the composite material particles are added into a small degradable material film blowing machine, and subjected to blow molding at the temperature of 145-160-175-175-160-150 ℃ in sequence to obtain a 25-micron uniform film material, wherein the surface of the uniform film material has nodes, obvious fish eyes and burrs, poor mechanical property and rough hand touch feeling.

The mechanical properties of the film materials prepared in example 9 and comparative example 1 are measured as follows:

it can be seen from the comparison of example 9 with comparative example 1 that the black talc powder can be dispersed more uniformly and has better mechanical properties under the same treatment method, and the density of the white talc particles is slightly lower, which may not achieve a close connection relationship with the poor compatibility of the white talc powder and PBAT; and the film morphology of the degradable film blowing material modified by the black talc is also obviously better than that of the film formed by the white talc.

It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims

1. The black talc modified biodegradable film blowing grade composite material is characterized by comprising the following components in parts by mass:

55-95 parts of biodegradable main material, 1-20 parts of biodegradable auxiliary material, 3-40 parts of black talcum powder, 0.05-2.5 parts of coupling agent, 0.05-2.5 parts of surface modifier, 0.02-10 parts of biodegradable compatilizer, 0.01-5 parts of wetting auxiliary agent, 0.01-5 parts of lubricant and 0.01-1 part of antioxidant; the biodegradable compatilizer is selected from polybutylene terephthalate; organic conjugated molecules are remained on the surface of the black talcum powder, contain phenolic hydroxyl and derivatives thereof, are in central symmetry structures, and have organic conjugated chromogenic groups meeting the Huckel law;

the black talcum powder is subjected to surface modification treatment by a coupling agent and a surface modifier, and the biodegradable main material comprises one or a combination of more than two of polybutylene terephthalate-adipate, a carbon dioxide/propylene oxide copolymer and polybutylene succinate-adipate; the biodegradable auxiliary materials comprise one or the combination of more than two of polybutylene succinate, polycaprolactone, polyglycolide, polyhydroxyalkanoate, poly-3-hydroxybutyric acid, polyhydroxybutyrate valerate, polylactic acid and poly-3-hydroxybutyric acid/4-hydroxybutyrate;

the particle size of the black talcum powder is 1000-5000 meshes.

2. The black talc modified biodegradable blown film grade composite material according to claim 1, wherein the mass portion of the biodegradable main material is 58-88.

3. The black talc modified biodegradable blown film grade composite material according to claim 2, wherein the biodegradable main material is 60 to 85 parts by mass.

4. The black talc modified biodegradable blown film grade composite material according to claim 1, wherein the biodegradable auxiliary material is 1 to 15 parts by mass.

5. The black talc modified biodegradable blown film grade composite material according to claim 4, wherein the biodegradable auxiliary material is 2 to 10 parts by mass.

6. The black talc modified biodegradable blown film grade composite material according to claim 5, wherein the biodegradable auxiliary material is 3 to 5 parts by mass.

7. The black talc modified biodegradable blown film grade composite of claim 1, wherein said coupling agent comprises one or a combination of two or more of titanate coupling agent, aluminate coupling agent, zirconate coupling agent and calcium stearate.

8. The black talc modified biodegradable blown film grade composite of claim 7, wherein said titanate coupling agent comprises one or a combination of two or more of isopropyl tris (isostearoyl) titanate, isopropyl tris (dioctylphosphoryl) titanate, titanium bis (dioctylphosphoryl) oxoacetate, bis (dioctylphosphoryl) ethylene titanate, isopropyl bis (methacryloyl) isostearoyl titanate, isopropyl tris (dioctylphosphoryl) titanate, isopropyl tris (dodecylbenzenesulfonyl) titanate, and isopropyl tris (n-ethylamino) -ethylamino titanate;

the coupling agent is 0.2-1.25 parts by mass.

9. The talc-modified biodegradable blown film grade composite of claim 1, wherein said surface modifier comprises one or a combination of two or more of gum arabic, sodium fatty alcohol-polyoxyethylene ether sulfate, triethanolamine dodecylbenzene sulfonate, alpha-olefin sulfonate, sodium abietate, triethanolamine dodecylbenzene sulfonate, disodium fatty alcohol-polyoxyethylene ether sulfosuccinate, sodium dodecylbenzene sulfonate, sodium tetradecyl benzene sulfonate, sodium diisooctyl succinate sulfonate, sodium hexadecylbenzene sulfonate, and sodium octadecyl benzene sulfonate;

the mass portion of the surface modifier is 0.2-1.5.

10. The black talc modified biodegradable blown film grade composite of claim 1, wherein said biodegradable compatibilizer is selected from one or a combination of two of linear polybutylene terephthalate and branched polybutylene terephthalate.

11. The black talc modified biodegradable blown film grade composite of claim 1, wherein:

the wetting auxiliary agent comprises one or the combination of more than two of oleic acid, epoxidized soybean oil and natural animal and vegetable oil; the natural animal and vegetable oil comprises soybean oil, olive oil and palm oil; the wetting assistant is 0.05-3 parts by mass;

and/or the lubricant comprises one or the combination of more than two of calcium stearate, stearic acid, glycerol oleate, span 20, span 40, span 60, span 80, span 65, span 85, tween 20, tween 40, tween 60, tween 80, glycerol monostearate, glycerol tristearate, erucamide, oleamide, higher fatty alcohol lubricants and soap lubricants; the mass part of the lubricant is 0.05-3 parts;

and/or the antioxidant comprises one or the combination of more than two of antioxidant 1010, antioxidant 626, antioxidant 1178 and antioxidant 168.

12. A method for preparing a black talc modified biodegradable blown film grade composite of any one of claims 1 to 11 comprising:

fully mixing the black talcum powder, the coupling agent and the surface modifier, and reacting at the temperature of 70-130 ℃ to prepare modified black talcum powder;

fully mixing the biodegradable main material, the biodegradable auxiliary material and the biodegradable compatilizer to obtain biodegradable material mixed particles;

and fully mixing the modified black talcum powder and the mixed granules of the biodegradable material, melting, extruding, and cooling to obtain the black talcum powder modified biodegradable film blowing grade composite material.

13. The method of claim 12, further comprising the step of blow molding the black talc modified biodegradable blown film grade composite;

the preparation method specifically comprises the following steps: fully mixing the black talcum powder and the coupling agent for 1-30min at the temperature of 70-130 ℃ and the stirring speed of 100-600r/min to prepare a modified precursor mixture;