CN113174069B

CN113174069B - Biomass functional master batch and preparation method and application thereof

Info

Publication number: CN113174069B
Application number: CN202110572387.8A
Authority: CN
Inventors: 钟宇科; 安士利
Original assignee: Guangzhou Ruian Material Technology Co ltd
Current assignee: Shandong Ruian New Material Technology Co.,Ltd.
Priority date: 2021-05-25
Filing date: 2021-05-25
Publication date: 2022-11-22
Anticipated expiration: 2041-05-25
Also published as: CN113174069A

Abstract

The invention relates to the technical field of degradable materials, in particular to a biomass functional master batch and a preparation method and application thereof. The preparation raw materials of the degradable material comprise, by weight, 40-70 parts of polyester resin, 10-30 parts of biomass resin and 5-35 parts of bio-based functional polymer. By using the combined action of the bio-based functional polymer, the polyester resin, the biomass resin and the like, the problem of chain scission of a degradable polymer chain after two times of thermal history is solved, the dispersion uniformity of biomass powder in a film is more effectively ensured, the excellent blow molding processing performance and puncture resistance service performance of a finished product are ensured, the aging performance of a consumer in the whole use period is met, and the application cost of the material is reduced. The problem that the existing modified products have single characteristics and cannot realize the production of multifunctional blown film products in the continuous production process is solved, and multifunctional film materials can be prepared according to the requirements of different films.

Description

Biomass functional master batch and preparation method and application thereof

Technical Field

The invention relates to the technical field of degradable materials, in particular to a biomass functional master batch and a preparation method and application thereof.

Background

In recent years, the development of biodegradable plastics is increasing, the application is expanding, and the biodegradable plastics gradually replace the traditional plastics in the fields of packaging materials, disposable tableware, agricultural mulching films, daily products and the like. At present, compared with the traditional plastics, the biodegradable plastics have the characteristics of single performance and high price, which greatly limits the further development of the biodegradable plastics.

In biodegradable high polymer plastics, biomass powder, polylactic acid (PLA), polycaprolactone (PCL), poly beta-hydroxyalkanoate (PHA) and the like are used at present, polylactic acid is obtained through processes of biomass powder fermentation, monomer polymerization and the like, is aliphatic polyester, has mechanical properties equivalent to that of PET resin, is relatively brittle, has low heat deformation temperature, and requires special requirements on processing and forming equipment. Poly beta-hydroxyalkanoates can be synthesized biologically or chemically, and have the same brittleness disadvantage although the heat distortion temperature is higher. The biomass powder is used as a filler, has good biodegradability, has good compatibility with polyester resin after processing, and has cost advantage, but has processing limitation. In summary, the existing biodegradable polymer plastics have the disadvantages of long degradation time, incomplete degradation, poor mechanical properties and incapability of meeting various practical requirements in practical application due to comprehensive properties.

For example, chinese patent 200410081265.5 discloses a completely biodegradable biomass powder/polyester plastic and a preparation method thereof. The plastic material is prepared by performing mechanical force-chemical modification treatment and thermoplastic treatment on biomass powder, then performing melt mixing, grafting reaction and mixing with an aliphatic-aromatic block polyester material, an initiator, a modifier and a stabilizer in a high-speed mixer, cooling, crushing, and performing reaction extrusion granulation by a two-stage double-screw reaction extruder. The plastic material has excellent physical and mechanical properties and can be completely biodegraded. However, in the processing process of the extruder, the dispersing effect and the plasticizing effect of the biomass powder filler are not ideal, the comprehensive performance of the product needs to be further improved, the processing cost is too high, the product cost of a downstream film blowing factory is improved, and the popularization of the completely biodegradable film is further influenced.

Disclosure of Invention

In order to solve the above problems, the first aspect of the present invention provides a biomass functional masterbatch, wherein the biomass functional masterbatch comprises biodegradable polymers and functional components, and the functional components account for 50wt% to 90wt% of the biomass functional masterbatch.

As a preferable technical solution of the present invention, the functional component includes at least one of biomass powder, an inorganic filler, and an auxiliary agent.

As a preferable technical scheme of the invention, the biomass powder comprises coffee grounds, straw powder and at least one of branched or unbranched corn starch, cassava starch and potato starch.

As a preferred technical solution of the present invention, the inorganic filler includes at least one of nano calcium carbonate, nano talc powder, nano calcium oxide, nano magnesium oxide, nano titanium oxide, nano aluminum oxide, and nano zinc oxide.

As a preferred technical solution of the present invention, the biodegradable polymer includes polyester resin, such as at least one of dibasic acid glycol polyester resin, polyhydroxyalkanoate, polycaprolactone, and polylactic acid.

As a preferable technical solution of the present invention, the auxiliary agent includes at least one of a lubricant, an anti-ultraviolet agent, an anti-hydrolysis agent, a nucleating agent, and a crosslinking agent.

In a preferred embodiment of the present invention, the lubricant includes at least one of an epoxy lubricant, an amide lubricant, a fatty acid salt lubricant, and a polymer wax.

In a preferred embodiment of the present invention, the anti-uv agent includes at least one of bisphenol AN, N ' -hexamethylenebis [3, 5-di-tert-butyl-4-hydroxy hydrocinnamamide ], bisphenol a phosphite, octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, 4' bis- (. Alpha. ' -dimethylbenzyl) diphenylamine, dodecathiopropyl ester, 1, 4-di-tert-butylperoxyisopropyl benzene, and 1, 4-di-tert-butylperoxyisopropyl benzene.

The second aspect of the invention provides a preparation method of the biomass functional master batch, which comprises the following steps:

mixing the biodegradable polymer and the functional component at 80-180 deg.c and pelletizing.

The third aspect of the invention provides application of the biomass functional master batch to degradable materials.

Compared with the prior art, the invention has the following beneficial effects:

(1) The invention provides a completely degradable material, which solves the problems that the existing degradable materials such as PHA, PLA, PBAT and other degradable high polymers can not be directly processed by film blowing and need to be modified by designing a bio-based functional polymer, can be directly processed by film blowing, improves the flexibility of film blowing, solves the problems that the characteristics of the existing modified products are single and the multifunctional film blowing product can not be produced in the continuous production process, and can prepare multifunctional film materials according to the requirements of different films.

(2) By using the combined action of the bio-based functional polymer, the polyester resin, the biomass resin and the like, the problem of chain scission of a degradable polymer after two times of thermal history is solved, the dispersion uniformity of biomass powder in a film is more effectively ensured, the excellent blow molding processing performance and puncture-resistant performance of a finished product are ensured, the aging performance of a consumer in the whole use period is met, and the material application cost is reduced.

(3) According to the invention, special raw materials such as bio-based functional polymers, degradable materials and the like are subjected to mixing granulation, such as extrusion, hot pressing and banburying, in the preparation process of the degradable materials, material degradation caused by a strong shearing effect in a double-screw extruder is avoided, and the manufacturing cost is far lower than the double-screw granulation cost.

(4) By utilizing the material and the preparation method provided by the invention, various special raw materials with low purchase cost can be compounded and used in downstream film blowing factories, the performance index of producing products by using the modified material is achieved, the purchase cost of the film blowing factories is reduced on the premise of improving the flexibility of film blowing production, and the market cost of finished bags is further reduced, thereby being beneficial to the national popularization and promotion of completely biodegradable plastic bags.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

As used herein, the term "consisting of 8230; preparation" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of 8230comprises" excludes any non-specified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of 8230is present in a clause of the claim body, rather than immediately after the subject matter, it defines only the elements described in that clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise specified, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.

The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.

In order to protect the environment, the use of biodegradable materials is the current development direction, polyesters such as PBSA, PBS, PBAT and the like have good flexibility, impact resistance and processability, PLA, PHA and the like have high strength and modulus but poor toughness and processability, and are difficult to blow into films, the advantages of different macromolecules can be theoretically exerted by blending different biodegradable macromolecules, but in the actual production process, a one-step method is directly used, namely, the direct blending is performed and then the blow molding is performed, the problems of cracking, the existence of unmelted macromolecules and the like are easy to occur, and the film forming is difficult, in order to solve the problems, other functional additives such as a plasticizer and the like are generally added to promote the compatibility of different macromolecules, and the polymers are prepared by a two-step method, namely, firstly, the twin-screw melting mixing is performed, and then, the single screw extrusion and film blowing are performed, on one hand, the macromolecules can be subjected to two thermal processes to cause molecular chain breakage, on the other hand, the process is also complicated, and the cost is increased. The first aspect of the invention provides a biomass functional master batch, which comprises biodegradable high molecules and functional components, wherein the functional components account for 50-90 wt% of the biomass functional master batch, and can be enumerated by 50wt%, 60wt%, 70wt%, 80wt%, 90wt%, such as 70-90 wt%.

The inventor unexpectedly finds that the bio-based functional polymer containing the functional additive prepared by the invention can be directly blended and blown with biodegradable macromolecules, and only one thermal process is needed, so that the breakage of macromolecules is reduced, and the dispersion of the functional additive in the macromolecules is promoted, thereby promoting the increase of the mechanical properties of the macromolecules. In one embodiment, the raw materials for preparing the bio-based functional polymer comprise a biodegradable polymer and a filler. In one embodiment, the functional component includes at least one of biomass powder, inorganic filler, and auxiliary agent.

Biodegradable polymer

Examples of the biodegradable polymer include, but are not limited to, polyester resins such as dibasic acid glycol polyester resins, polyhydroxyalkanoates, polycaprolactone, and polylactic acid.

As examples of the dibasic acid glycol polyester resin, there may be mentioned, but not limited to, aliphatic polyester resins, polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), such as PBSA of shandong shingyi new material science and technology ltd, PBSA3a40 of japan showa; aliphatic-aromatic copolyesters, for example, poly (butylene terephthalate-co-butylene adipate) ester (PBAT), such as PBAT THJS-5801, PBAT THJS-6801, PBAT THJS-6802, PBAT THJS-7801 of Nanshan Tunghe GmbH, PBAT ECO-A05 of Taiwan Changchun, PBAT ECO-A20.

As examples of polyhydroxyalkanoates, there are included, but not limited to, those of Jiangsu New Fuda composite materials, inc

K-8200L、

K-8200D、

K-8200L。

In order to reduce the cost, biomass powder, inorganic filler and the like are generally added as fillers, but the addition of the fillers, particularly the addition of the nano filler, often causes particle agglomeration, but reduces the mechanical properties of the film, even causes large performance difference of the film in different directions, and affects puncture resistance, and organic fillers such as starch, straw and the like are difficult to flow under heat and force in the processing process due to the existence of a large number of hydrogen bonds and crystalline structures, and are also not beneficial to the improvement of the processing properties of biodegradable polymers such as PHA, PLA and the like. The degradable biomass powder is used as the organic filler or the natural mineral powder, so that the whole degradable material can be completely degraded and returns to the nature.

Biomass powder

Examples of biomass powder include, but are not limited to, coffee grounds, straw powders, and branched or unbranched corn starch, tapioca starch, and potato starch.

Inorganic filler

Examples of the inorganic filler include, but are not limited to, nano calcium carbonate, nano talc, nano calcium oxide, nano magnesium oxide, nano titanium oxide, nano aluminum oxide, and nano zinc oxide.

The inventor unexpectedly finds that when the bio-based functional polymer containing the organic filler and the bio-based functional polymer of the inorganic filler are added into the biodegradable polymer together, the bio-based functional polymer and the bio-based functional polymer of the inorganic filler can also play roles in promoting the dispersion of the inorganic filler and avoiding agglomeration, similar to the functional polymer of the amide lubricant, probably because after mixing and granulation, the stretched molecular chains of the starch and the hydroxyl structures of the starch are similar to the amide lubricant, and interact with the filler to reduce agglomeration, and under the action of the filler, the acting force among starch molecules is reduced, the fluidity of the starch is improved, and the retrogradation is avoided, so that a film structure with uniformly intertwined molecules is prepared.

Generally, when the particles are not uniformly dispersed, the friction can be increased, and the inventor unexpectedly finds that when the bio-based functional polymer containing the organic filler and the inorganic filler is added, the prepared film is beneficial to improving the friction performance while improving the mechanical performance.

Auxiliary agent

In one embodiment, the adjuvant of the present invention comprises at least one of a lubricant, an anti-uv agent, an anti-hydrolysis agent, a nucleating agent, and a cross-linking agent.

As examples of lubricants, including, but not limited to, epoxy-based lubricants; amide lubricants such as stearamide, oleamide, erucamide, ethylene bis stearamide; fatty acid salt lubricants, such as zinc stearate, aluminum stearate, polymeric complex esters of metal soaps; high molecular waxes such as polyethylene wax, etc.

The inventor finds that when a certain amount of inorganic filler and macromolecules are blended at a certain temperature, a small amount of macromolecules and the inorganic filler are adsorbed and wound, so that the dispersion of the electrodeless filler in the subsequent preparation process is facilitated, and the agglomeration is avoided.

The inventor finds that the preparation temperature and the use amount of each raw material of the bio-based functional polymer and the functional polymer need to be controlled, and when the preparation temperature of the bio-based functional polymer is low or the preparation temperature of the functional polymer is high, the processing performance of the obtained film material is limited, shrinkage, fish eyes and the like can be caused, and the mechanical property and the friction property of the material can be affected.

Examples of the anti-ultraviolet agent include, but are not limited to, bisphenol AN, N ' -hexamethylenebis [3, 5-di-tert-butyl ] -4-hydroxy-phenylacrylamide ], bisphenol a phosphite, octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, 4' -bis- (. Alpha. ' -dimethylbenzyl) diphenylamine, dodecathiopropyl ester, 1, 4-di-tert-butylperoxyisopropylbenzene.

As examples of the hydrolysis resistance agent, there may be mentioned, but not limited to, carbodiimide hydrolysis resistance agents such as polyaromatic carbodiimide, poly [ nitrilomethane tetraazayl [2,4, 6-tris (1-methylethyl) -1, 3-phenylene ], or poly-1, 3, 5-triisopropyl-phenylene-2, 4-carbodiimide.

Examples of the nucleating agent include, but are not limited to, phosphate-based nucleating agents, sorbitol ester-based nucleating agents, benzoate-based nucleating agents such as sodium dodecylbenzoate, sodium 2,2 '-methylene-bis (4, 6-di-t-butylphenyl) phosphate, aluminum bis [2,2' -methylene-bis (4, 6-di-t-butylphenyl) ] phosphate and the like.

As examples of the crosslinking agent, there are, but not limited to, isocyanate crosslinking agents such as Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), lysine Diisocyanate (LDI); epoxy crosslinking agents such as epoxy silane, triphenylglycidyl ether methane, bis (2, 3-epoxycyclopentyl) ether, and the like.

In order to improve the performances of the film such as wear resistance, ultraviolet resistance, hydrolysis resistance and the like, functional polymers comprising other additives can be added, and the method provided by the invention is firstly used for forming the degradable polymers at a certain temperature, so that the one-step forming in the film blow molding is facilitated, the preparation method is simplified, and the application field of the functional material prepared by the invention is improved. The invention establishes a basic formula with different functional collocation on the basis of the preparation raw materials of the degradable material, and can guide a downstream film blowing processing plant. The adjustment range of the film blowing ratio and the corresponding film material performance data are provided, and the flexibility of preparing the completely biodegradable plastic film in a film blowing factory and the diversity of functional films are improved. The dispersion effect and the plasticizing effect of various functional additives are ensured in the aspect of a film blowing process, so that the obtained biomass powder filled completely biodegradable material not only has complete biodegradability under a composting condition, but also has excellent mechanical properties and good extrusion molding processability.

The second aspect of the present invention provides a method for preparing the above biomass functional masterbatch, which comprises:

mixing the biodegradable polymer and the functional component at 80-180 deg.c and pelletizing. When the functional components are biomass powder or inorganic filler, mixing and granulating at 120-180 ℃; when the functional component is an auxiliary agent, mixing and granulating at 80-120 ℃. The mixing granulation can be performed by extrusion, hot pressing or internal mixing, and the like, for example, by mixing the components in a ratio of length to diameter of 40:1, a 65D type or 75A type extruder or hot-pressing type granulation equipment, an internal mixer and the like, and extruding or pressing at a certain processing temperature to prepare the biomass resin. Such as various film materials, such as winding functional films, agricultural mulching films, plastic bag films, disposable glove films and the like, and meets various application requirements.

The third aspect of the invention provides application of the biomass functional master batch to degradable materials. The preparation raw materials of the degradable material comprise, by weight, 40-70 parts of polyester resin, 10-30 parts of biomass resin and 5-35 parts of biomass functional master batch containing functional components of biomass powder and/or inorganic filler.

The biomass resin comprises at least one of polylactic acid, thermoplastic starch and cellulose. Examples of polylactic acids include, but are not limited to, PLA 3001D, PLA 6202D, PLA 3100HP from NatureWorks, PLA L600H, PLA1002, which is a plastic degradation in the guangdong. Examples of thermoplastic starches include, but are not limited to, corn starch, wheat starch, pea starch, tapioca starch, potato starch. Examples of cellulose include, but are not limited to, cellulose fiber, chitin fiber.

The preparation raw materials of the degradable material also comprise biomass functional master batches with functional components of auxiliaries. In one embodiment, the weight parts of the biomass functional master batch with the auxiliary agent as the lubricant in the preparation raw material of the degradable material are 2 to 8 parts, and can be exemplified by 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts and 8 parts. In one embodiment, the weight parts of the biomass functional masterbatch, in which the auxiliary agent is an anti-ultraviolet agent, in the preparation raw material of the degradable material are 2 to 8 parts, which may be, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, and 8 parts. In one embodiment, the weight parts of the biomass functional masterbatch of which the assistant is an anti-hydrolysis agent in the raw materials for preparing the degradable material are 2 to 8, such as 2,3, 4, 5, 6, 7 and 8. In one embodiment, the biomass functional masterbatch with the nucleating agent as the auxiliary agent is 2 to 8 parts by weight of the raw material for preparing the degradable material, such as 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts and 8 parts. In one embodiment, the weight parts of the biomass functional masterbatch with the cross-linking agent as the auxiliary agent in the raw materials for preparing the degradable material are 2-8 parts, such as 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts and 8 parts.

In one embodiment, the method for preparing a degradable material of the invention comprises:

drying the preparation raw materials of the degradable material, and mixing and blowing the film. The drying temperature is 70-100 ℃, and the drying time is 1-10 h. The film blowing of the invention can be processed in a film blowing machine without specific limitation, and the temperature of the film blowing is 120-140 ℃.

Examples

The present invention will be specifically described below by way of examples. It is to be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention described above will now occur to those skilled in the art. In the raw materials for preparing the invention, PBSA is purchased from Shandong Huigungnew material science and technology limited, PLA is purchased from NatureWorks PLA 3001D, and PHA is purchased from Jiangsu Xinfuda composite material limited

K-8200L, PBAT was purchased from PBATTHJS-5801, a product of Yangttun, hedges, inc.Examples 1 to 5 provide formulations and preparations of bio-based functional polymers and functional macromolecules Method

Example 1

The embodiment provides a mixture of PBSA-based nano calcium carbonate and nano talcum powder, wherein the nano calcium carbonate and the nano talcum powder account for 90wt% of the mixture of the PBSA-based nano calcium carbonate and the nano talcum powder, and the weight ratio of the nano calcium carbonate to the nano talcum powder is 1:1.

the embodiment also provides a preparation method of the mixture of PBSA-based nano calcium carbonate and nano talcum powder, which comprises the following steps: mixing PBSA, nano calcium carbonate and nano talcum powder at 160 deg.c and pelletizing.

Example 2

The embodiment provides a mixture of PBSA-based cassava starch and straw powder, wherein the cassava starch and the straw powder account for 85wt% of the mixture of PBSA-based cassava starch and straw powder, and the weight ratio of the cassava starch to the straw powder is 2:1.

the embodiment also provides a preparation method of the mixture of PBSA-based cassava starch and straw powder, which comprises the following steps: mixing and granulating the PBSA, the cassava starch and the straw powder at 140 ℃.

Example 3

This example provides a PBSA-based oil acid amide and ethylene bis stearamide complex, oleic acid amide and ethylene bis stearamide accounting for 75wt% of the PBSA-based tapioca starch and straw powder mixture, the weight ratio of oleic acid amide and ethylene bis stearamide being 1:3.

this example also provides a process for preparing a mixture of PBSA based oil acid amide and ethylene bis stearamide comprising: PBSA, oleamide and ethylene bis stearamide are mixed and granulated at 110 ℃.

Example 4

This example provides a mixture of PBSA-based benzotriazole and benzophenone in an amount of 80wt% of the mixture of PBSA-based benzotriazole and benzophenone in a weight ratio of 1:1.

this example also provides a method for preparing a mixture of PBSA-based benzotriazole and benzophenone comprising: PBSA, benzotriazole and benzophenone are mixed and granulated at 90 ℃.

Example 5

This example provides a PLA-based toluene diisocyanate which accounted for 65wt% of the PBSA-based benzotriazole and benzophenone mixture.

The present example also provides a method for preparing PLA-based toluene diisocyanate, comprising: PLA and toluene diisocyanate were mixed and granulated at 100 ℃.

Examples 6 to 9 provide degradable polymers comprising the bio-based functional polymers and functional polymers provided in examples 1 to 5 Formula and preparation method of decomposing material

Example 6

The example provides a degradable material for preparing a winding functional film, and the degradable material is prepared by weighing the following raw materials in percentage by weight:

this example also provides a method of making the degradable material described above, comprising:

PBSA, PLA, PBSA base nano calcium carbonate and nano talcum powder mixture, PBSA base oil acid amide and ethylene bis stearamide compound are respectively placed in a feeder of a film blowing machine with a drying tank, after drying for 2H at 90 ℃, the film blowing machine is used for mixing and blowing the film at the heating temperature of 120-140 ℃ to prepare the winding functional film with the thickness of 12 mu m.

Example 7

The embodiment provides a degradable material for preparing an agricultural mulching film, and the degradable material is prepared by weighing the following raw materials in percentage by weight:

PBSA, PLA, a mixture of PBSA-based benzotriazole and benzophenone, a mixture of PBSA-based nano calcium carbonate and nano talcum powder, and PLA-based toluene diisocyanate are respectively placed in a feeder of a film blowing machine with a drying tank, dried for 2H at 90 ℃, and mixed and blown by the film blowing machine at the heating temperature of 120-140 ℃ to prepare the agricultural mulching film with the thickness of 12 mu m.

Example 8

The example provides a degradable material for preparing a conventional plastic bag film, and the degradable material is prepared by weighing the following raw materials in percentage by weight:

PHA, PLA, PBSA-based nano calcium carbonate and nano talcum powder mixture, PBSA-based cassava starch and straw powder mixture and PLA-based toluene diisocyanate are respectively placed in a film blowing machine feeder with a drying tank and dried for 2H at 90 ℃. The film blowing machine is used for mixing and blowing films at the heating temperature of 120-140 ℃ to prepare the conventional plastic bag films such as 12 mu m shopping bags, garbage bags and the like.

Example 9

The example provides a degradable material for preparing a disposable glove film, wherein the degradable material is prepared by weighing the following raw materials in percentage by weight:

respectively placing the mixture of PBAT, PLA, PBSA-based nano calcium carbonate and nano talcum powder, the PBSA-based oil acid amide and the ethylene bis stearamide compound in a feeder of a film blowing machine with a drying tank, and drying for 2H at 90 ℃. The film blowing machine carries out mixed film blowing according to the heating temperature of 120-140 ℃ to prepare the disposable receiving special film with the thickness of 12 mu m.

Comparative example 1: providing a completely biodegradable film modified material according to Jinhui million high-tech science and technology GmbH Preparing conventional plastic bagThe preparation method comprises the following steps: and (3) placing the completely biodegradable film modified material in a film blowing machine feeder with a drying tank, and drying for 2H at 90 ℃. The film blowing machine is used for mixing and blowing films at the heating temperature of 120-140 ℃ to prepare the conventional plastic bag films such as 12 mu m shopping bags, garbage bags and the like.

Evaluation of Performance

The films provided in examples 6 to 9 and comparative example 1 were tested according to GB T9639.1-2008 free fall dart, GB T1040.3-2006 plastic tensile properties, GB T10006-1988 method for determining the coefficient of friction of plastic films and sheets, GB 16578.2-2009-T plastic films and sheets, respectively, part 2 of the determination of tear resistance, the results of which are given in Table 1.

Table 1 performance characterization test

According to the test results, the biomass functional master batch provided by the invention can be used for degradable materials, various film materials can be prepared by a direct mixing and blowing method, the processing performance of various substances in the blowing process is improved, the biodegradability is ensured, and the mechanical property, puncture resistance and friction performance of the film are improved.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as can be conceived and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Where the claims recite a range of values, such ranges are intended to include all sub-ranges subsumed therein, and variations within the ranges are intended to be encompassed by the claims as appended hereto where possible.

Claims

1. The application of a degradable material in preparing a plastic bag film is characterized in that,

the degradable material is prepared by weighing the following raw materials in percentage by weight: 50% of PHA, 10% of PLA, 20% of a mixture of PBSA-based cassava starch and straw powder, 15% of a mixture of PBSA-based nano calcium carbonate and nano talcum powder and 5% of PLA-based toluene diisocyanate;

the PBSA-based cassava starch and straw powder mixture comprises 85wt% of cassava starch and straw powder mixture, and the weight ratio of the cassava starch to the straw powder is 2:1;

the preparation method of the mixture of the PBSA-based cassava starch and the straw powder comprises the following steps: mixing and granulating the PBSA, the cassava starch and the straw powder at 140 ℃;

the PBSA-based nano calcium carbonate and nano talcum powder mixture comprises nano calcium carbonate and nano talcum powder which account for 90wt% of the PBSA-based nano calcium carbonate and nano talcum powder mixture, and the weight ratio of the nano calcium carbonate to the nano talcum powder is 1:1;

the preparation method of the mixture of the PBSA-based nano calcium carbonate and the nano talcum powder comprises the following steps: mixing and granulating PBSA, nano calcium carbonate and nano talcum powder at 160 ℃;

the PLA-based toluene diisocyanate, the toluene diisocyanate accounted for 65wt% of the PLA-based toluene diisocyanate;

the preparation method of the PLA-based toluene diisocyanate comprises the following steps: mixing PLA and toluene diisocyanate at 100 ℃ for granulation;

the method for preparing the plastic bag film by the degradable material comprises the following steps:

placing PHA, PLA, PBSA-based nano calcium carbonate and nano talcum powder mixture, PBSA-based cassava starch and straw powder mixture and PLA-based toluene diisocyanate in a film blowing machine feeder with a drying tank respectively, and drying for 2H at 90 ℃; the film blowing machine is used for mixing and blowing the film at the heating temperature of 120-140 ℃ to prepare a shopping bag with the size of 12 mu m and a conventional plastic bag film of a garbage bag.