CN113321903A

CN113321903A - Preparation process and application of biomass material

Info

Publication number: CN113321903A
Application number: CN202110572390.XA
Authority: CN
Inventors: 安士利; 其他发明人请求不公开姓名
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: 2021-08-31

Abstract

The invention relates to a degradable material, in particular to a preparation process of a biomass material and application thereof. The method comprises the following steps: mixing the preparation raw materials of the biomass material, adding the mixture into an extruder, and performing extrusion molding. The invention limits the length-diameter ratio of the extruder, the diameter of the screw rod and the like, controls the dosage and the adding sequence of raw materials such as polyester, powder and the like in the biomass material, solves the dispersion problem of the powder filler in the extruder in the processing process of using the extruder, promotes the solution of the plasticizing problem and the exhaust problem by controlling the arrangement of the plasticizer adding port and the exhaust port, and ensures the dispersion effect and the plasticizing effect of the filler from the processing technology, so that the completely biodegradable material filled with the biomass powder has complete biodegradation performance under the composting condition, excellent mechanical property and good extrusion molding processability.

Description

Preparation process and application of biomass material

Technical Field

The invention relates to a degradable material, in particular to a preparation process of a biomass material and application thereof.

Background

In recent years, with the gradual replacement of traditional plastics in the fields of packaging materials, disposable tableware, agricultural mulching films, daily products and the like, the dosage and preparation fields are gradually increased. But the existing biodegradable material has single performance and is difficult to prepare, so that the further development of the biodegradable material is limited.

The high polymers used for degrading materials are many, at present, more biomass powder, polylactic acid PLA, polycaprolactone PCL, poly beta-hydroxyalkanoate PHA, dibasic acid diol polyester and other polyester materials are used, but higher requirements are needed in the processing process, for example, the mechanical property of polylactic acid is equivalent to that of PET resin, but the performance is brittle, the thermal deformation temperature is low, special requirements are needed for processing and forming equipment, and the poly beta-hydroxyalkanoate has the defect of brittleness even though the thermal deformation temperature is higher.

By using the filler, such as biomass powder and the like, and utilizing the good biodegradability of the filler, the filler can be used for processing materials such as degradable polyester and the like, and the cost can be reduced. Therefore, a preparation method is needed to solve the problems that the degradation time is long, the degradation is not thorough, the mechanical property is poor, and the comprehensive performance can not meet various practical requirements in practical application in the conventional degradable plastics.

Disclosure of Invention

In order to solve the above problems, a first aspect of the present invention provides a process for producing a biomass material, comprising: mixing the preparation raw materials of the biomass material, adding the mixture into an extruder, and performing extrusion molding;

the length-diameter ratio of the extruder is (30-60): 1, the diameter of a screw of the extruder is 70-100 mm;

the biomass material comprises the following raw materials in parts by weight: 50-70 parts of polyester, 20-30 parts of biomass powder, 1-10 parts of inorganic powder, 5-15 parts of plasticizer and 0.5-3 parts of cross-linking agent.

In a preferred embodiment of the present invention, the polyester is at least one selected from the group consisting of a dibasic acid glycol polyester, a polyhydroxyalkanoate, and polylactic acid.

As a preferable technical scheme of the invention, the biomass powder is selected from one or more of coffee grounds, straw powder and starch.

As a preferable technical scheme of the invention, an exhaust port is arranged on the side surface of the extruder, and the exhaust port is connected with the feeding machine.

As a preferable technical scheme, one end of the feeder is connected with the exhaust port, the other end of the feeder is provided with a feeder feed port, and the feeder feed port is positioned below the feeder.

In a preferred embodiment of the present invention, the number of the exhaust ports is 2 or more.

According to a preferable technical scheme of the invention, the plasticizer comprises a first plasticizer and a second plasticizer, and the weight ratio of the first plasticizer to the second plasticizer is (1-2): (1-2).

As a preferable technical scheme of the present invention, the preparation process comprises:

mixing polyester, biomass powder and inorganic powder, adding a first plasticizer for mixing, adding a cross-linking agent to obtain a mixed raw material, adding the mixed raw material into a main feeding port of an extruder, adding a second plasticizer into a side feeding port of the extruder, and performing extrusion molding.

As a preferable technical scheme of the invention, the main feeding port is positioned above the screw cylinder of the extruder, and the contact surface of the side feeding port and the screw cylinder of the extruder is positioned below the side of the screw cylinder of the extruder.

In a second aspect, the invention provides an application of the preparation process of the biomass material, which is used for preparing the biomass material.

Compared with the prior art, the invention has the following beneficial effects: the invention limits the length-diameter ratio of the extruder, the diameter of the screw rod and the like, controls the dosage and the adding sequence of raw materials such as polyester, powder and the like in the biomass material, solves the dispersion problem of the powder filler in the extruder in the processing process of using the extruder, promotes the solution of the plasticizing problem and the exhaust problem by controlling the arrangement of the plasticizer adding port and the exhaust port, and ensures the dispersion effect and the plasticizing effect of the filler from the processing technology, so that the completely biodegradable material filled with the biomass powder has complete biodegradation performance under the composting condition, excellent mechanical property and good extrusion molding processability.

Drawings

FIG. 1 is a schematic view of the structure of an extruder.

FIG. 2 is a schematic view of the structure of the vent of the extruder.

Fig. 3 is a schematic view of the extruder head.

FIG. 4 is a schematic front (FIG. 4 left) and side view (FIG. 4 right) of a filter plate of an extruder.

FIG. 5 is a cross-sectional view of the extruder at the side feed port.

FIG. 6 is a schematic view of the screw assembly used in example 1.

FIG. 7 is an enlarged view of part A of the screw assembly used in example 1.

FIG. 8 is an enlarged view of the portion B of the screw assembly used in example 1.

FIG. 9 is a schematic view of the screw assembly used in example 2.

FIG. 10 is an enlarged view of part A of the screw assembly used in example 2.

FIG. 11 is an enlarged view of the portion B of the screw assembly used in example 2.

FIG. 12 is a schematic view of the screw assembly used in example 3.

FIG. 13 is a schematic view of the screw assembly used in example 4.

Fig. 14 is a picture of the biomass material obtained in example 4 (fig. 14 left) and comparative example 1 (fig. 14 right).

Where 1 is lead 96, length 96 transport block; 2 is lead 72, length 72 transport block; lead 56, length 56 transport block 3; 4 is lead 56, length 56 large screw conveying block; 5 is a 45-degree, 56-length shear screw block consisting of 5 kneading sheets; 6 is a 90-degree, 56-length shearing thread block consisting of 5 kneading pieces; 7 is a shear screw block with 45 degrees and the length of 36 formed by 5 kneading sheets; 8 is a 45-degree left-hand shearing thread block with the length of 36 and consists of 5 kneading sheets; lead 76 for 9, length 36 left hand feed block; 10 is a feed opening; 11 is an exhaust port; 12 is lead 44, length 44 transport block; 13 is a 30-degree left-direction shearing thread block consisting of 6 kneading pieces and having the length of 56; 14 left shear screw blocks of 45 degrees, length 56, made up of 5 kneading blocks; lead 44 for lead 15, length 22 left hand feed block; lead 44 at 16, length 22 delivers the block; lead 56, length 28 delivers the block 17.

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.

The term "prepared from …" as used herein 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 …" excludes any unspecified 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 …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the 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 as a range 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 stated, 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 stated number clearly indicates that the singular form is intended.

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

In a first aspect, the present invention provides a process for preparing a biomass material, comprising: mixing the preparation raw materials of the biomass material, adding the mixture into an extruder, and performing extrusion molding.

Biomass material

In one embodiment, the biomass material of the present invention is prepared from raw materials in parts by weight: 50-70 parts of polyester, 20-30 parts of biomass powder, 1-10 parts of inorganic powder, 5-15 parts of plasticizer and 0.5-3 parts of cross-linking agent.

Examples of the polyester include, but are not limited to, dibasic acid glycol polyesters, and there may be mentioned polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), such as PBSA of shandonghui new material science and technology limited, PBSA3a40 of japan showa, poly (butylene terephthalate-co-butylene adipate) ester (PBAT), such as PBAT THJS-5801, PBA THJS-6801, PBAT THJS-6802, PBAT THJS-7801 of southern shantun river limited, PBAT-a 05, PBAT ECO-a20 of taiwan vingo; polyhydroxyalkanoates, enumerated by Kongsu New Fuda composite Co., Ltd

K-8200L、

K-8200D、

K-8200L; polylactic acid, for example, PLA 3001D, PLA 6202D, PLA 3100HP from NatureWorks, PLA L600H, PLA 1002, which are plastically degraded in the guangdong.

Examples of the biomass powder include, but are not limited to, coffee grounds, straw powders, starches, and, for example, tapioca starch, corn starch, and potato starch.

Examples of inorganic powders include, but are not limited to, nano calcium carbonate and talc mixture, nano talc, nano zinc oxide, nano calcium oxide.

Examples of plasticizers include, but are not limited to, vegetable oils such as epoxidized soybean oil, castor oil, linseed oil; glycol esters such as trioctyl trimellitate, dioctyl adipate, tributyl acetyl citrate, dioctyl adipate (DOA); polyhydroxy compounds, such as polyethylene glycol, water, glycerol, polyglycerol. One or more of the plasticizers may be used in the present invention, such as the use of glycol esters and polyols, or the use of one or more of the polyols alone.

Examples of crosslinking agents include, but are not limited to, bis-2-oxazoline compounds, such as 2, 2' -bis- (2-oxazoline), 1, 4-bis- (2-oxazoline) -benzene, 1, 3-bis- (2-oxazoline) -benzene; isocyanate compounds such as Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Lysine Diisocyanate (LDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI); diglycidyl esters such as diglycidyl tetrahydrophthalate, diglycidyl adipate, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether; siloxane compounds, such as epoxysiloxanes, mercaptosiloxanes. The present invention may use one or more of the crosslinking agents, and is not particularly limited.

In one embodiment, the biomass material further comprises 0-5 parts by weight of an auxiliary agent. The auxiliaries include, but are not limited to, lubricants, antioxidants, compatibilizers, blocking agents, acid-removing agents, water-removing agents.

Examples of lubricants include, but are not limited to, stearamide, oleamide, erucamide, zinc stearate, polymeric complex esters of metal soaps, ethylene bis stearamide, polyethylene wax. In one embodiment, the lubricant is present in the biomass material in an amount of 0 to 1 part by weight.

Examples of the antioxidant include, but are not limited to, bisphenol A, 1, 4-di-tert-butylperoxyisopropyl benzene, 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.,. alpha. -dimethylbenzyl) diphenylamine, dodecylthiopropyl ester, 1, 4-di-tert-butylperoxyisopropyl benzene. In one embodiment, the antioxidant is 0-1 part by weight of the biomass material.

Examples of the compatibilizing agent include, but are not limited to, grafted maleic anhydride copolymers such as ethylene-acrylate-maleic anhydride terpolymer (EMH), PE grafted maleic anhydride, PP grafted maleic anhydride, POE grafted maleic anhydride. In one embodiment, the amount of the compatibilizer is 0 to 2 parts by weight of the biomass material.

Biodegradable high molecules, such as PHA, PBAT and other polyesters, have the problems of brittleness, processability and the like, can promote the improvement of the comprehensive performance of the prepared plastic products by adding biomass powder and inorganic powder as fillers, but have the problem of unmatched degradation time and use time, and in the preparation process, because the properties of the polyesters, the biomass powder and the inorganic powder are different, the biomass powder and the inorganic powder are difficult to be uniformly dispersed in the polyesters and even agglomerated, and the processing flowability is reduced, the inventor finds that the reduction of the intermolecular force of the polyesters can be promoted by adding plasticizers, the movement of polyester molecules can be promoted, but the adsorption and the like of the biomass powder, the inorganic powder and the plasticizers can be caused, so that the local flowability is reduced, and particularly when calcium carbonate and other inorganic powders and unstable inorganic powders and the like are used as the fillers together with the biomass powder, due to local adhesion, the problems of polymer degradation and the like can be caused, and the prepared plastic particles are obviously yellowed, the glossiness disappears, and the mechanical property and the crosslinking degree of the plastic particles are influenced.

In a preferred embodiment, the plasticizer comprises a first plasticizer and a second plasticizer, and the weight ratio of the first plasticizer to the second plasticizer is (1-2): (1 to 2), there may be mentioned, 1: 1. 1: 1.5, 1: 2. 2: 1.5, 2: 1.

in a more preferred embodiment, the preparation process of the present invention comprises:

In a further preferred embodiment, the preparation process according to the invention comprises:

mixing polyester, biomass powder and inorganic powder, adding a first plasticizer for mixing, adding a crosslinking agent and an auxiliary agent to obtain a mixed raw material, adding the mixed raw material into a main feeding port of an extruder, adding a second plasticizer into a side feeding port of the extruder, and performing extrusion molding.

Extruding machine

In one embodiment, as shown in fig. 1, the extruder of the present invention, from left to right, comprises an extruder body and an extruder head; an extruder screw barrel is arranged inside the extruder body, and a screw is arranged inside the extruder screw barrel. The extruder of the present invention may be a single screw extruder or a twin screw extruder, preferably a twin screw extruder, such as a co-rotating parallel twin screw extruder.

Preferably, the length-diameter ratio of the extruder is (30-60): 1, there may be mentioned, 30: 1. 40: 1. 48: 1. 50: 1. 54: 1. 60: 1; the diameter of a screw of the extruder is 70-100 mm, and 70mm, 75mm, 80mm, 85mm, 90mm, 95mm and 100mm can be enumerated; the power of the extruder is more than 100kW, such as 100 to 125kW, and 100kW, 105kW, 110kW, 115kW, 120kW and 125kW can be enumerated. The length-diameter ratio is the ratio of the length of the screw to the diameter of the screw, and the power is the motor power for driving the screw. The extruder of the invention has a screw diameter of 70-100 mm and a power of more than 100kW, and examples of the extruder include a 75A extruder, a 65A extruder, a 75D extruder and a 65D extruder.

The inventor unexpectedly finds that when the amount of raw materials for preparing the biomass material is controlled, an extruder with a proper length-diameter ratio, a proper screw diameter and proper power is selected, so that the gloss and mechanical strength of the biomass material are improved, the degradation among macromolecules and the yellowing of color are reduced, the biomass material can be dispersed to a certain degree after being mixed by using a certain amount of biomass material, when the biomass material is added into the extruder, the extruder with a certain length-diameter ratio, power and screw diameter is adopted, the stepwise mixing and dispersive mixing among the substances can be promoted, the problems of local adhesion and temperature rise in the melt extrusion process are reduced, the improvement of the processing performance is promoted, the biomass material with color, gloss and mechanical performance is obtained, and the biomass material can be completely degraded.

And the inventor finds that when the diameter, the length-diameter ratio and the power of the extruder are not properly selected, for example, when the extruder with smaller diameter or power is selected, the fluidity is reduced, the degradation of molecular chains is serious, and the crosslinking agent, the powder and the like cannot be compatible and dispersed with the polyester in the processing process of the biomass material provided by the invention, so that the obtained plastic particles are seriously yellowed, and the mechanical property, the glossiness and the crosslinking degree of the plastic particles are influenced.

As shown in FIG. 2, it is more preferable that the extruder of the present invention is provided with a vent at a side thereof, and the vent is connected to the feeding machine. Further preferably, one end of the feeder is connected with the exhaust port, the other end of the feeder is provided with a feeder feeding port, and the feeder feeding port is positioned below the feeder. More preferably, the number of the exhaust ports of the present invention is 2 or more, and may be, for example, 2, 3, 4, 5 or 6.

The inventor finds that the feeding machine works along with the extruder during the operation of the extruder to promote the gas and the like to be discharged along the screw clearance of the feeding machine on the one hand, and also to obstruct the molten product from being taken out and to promote the molten product to return to the interior of the screw barrel of the extruder on the other hand, and the inventor finds that the gas outlet is arranged at the melt conveying section to facilitate the smooth proceeding of the gas discharge, in addition, the inventor finds that air holes are generated in the melt during the general gas discharge process, and during the extrusion cooling process, the invention can avoid the residue of air holes in the melt and the shrinkage in the cooling process when being used for preparing the biomass material, and obtain the plastic particles with rich luster.

In a preferred embodiment, as shown in fig. 3 and 4, a filter plate is provided at the junction of the extruder head and the extruder according to the present invention. The filter plate of the extruder is provided with a plurality of filter holes, the diameter of each filter hole is 6-12 mm, and 6mm, 7mm, 8mm, 9mm, 10mm, 11mm and 12mm can be listed, as the left middle mark of figure 3

As shown, the thickness of the filter plate of the extruder is 6-12 mm, and 6mm, 7mm, 8mm, 9mm, 10mm, 11mm and 12mm can be listed, as shown by a mark D in the right middle of FIG. 3.

The inventor finds that the proper exhaust device is also favorable for avoiding the influence of unsmooth exhaust on the degradation of high molecules, the proper exhaust device is matched with an extruder with specific parameters, the residence time of the screw cylinder of the extruder is favorably controlled not to exceed 30s, the inventor finds that the residence time is also related to the structure of the extruder head, and when the length of the filter plate added into the filter plate of the extruder and the length of the extruder head along the material conveying direction are controlled to be similar to the length of the extruder head when the filter plate is not added, the length of the extruder head is shortened, the residence time of a melt in the screw cylinder is favorably reduced, and the obtaining of a biomass material with high mechanical strength and appearance performance is promoted.

In a more preferred embodiment, as shown in FIG. 5, the main feed port of the present invention is located above the extruder barrel and the side feed port and extruder barrel interface are located below the side of the extruder barrel.

The inventors found that when a large amount of biomass powder and inorganic powder is added, if a plasticizer is directly added and blended, adsorption or the like may occur and the powders are aggregated, and found that by separately adding the plasticizer, particularly by providing a side feed port for a part of the plasticizer in a direction tangential to a side surface of a screw in a downward direction, smooth addition of the plasticizer is promoted and stability during processing is improved, so that mixing of polyester, powder, crosslinking agent and the like is promoted during heating and melting in a melting section of an extruder, and further found that, on the one hand, in order to avoid excessive degradation and improve processing fluidity, it is necessary to control a residence time of a screw barrel to not more than 30 seconds, but on the other hand, crosslinking of the crosslinking agent and polyester and the like requires a certain time, whereas in the present invention, by providing a plasticizer addition port in a side lower part of the screw barrel, during melting and mixing in the melting section, along with the temperature rise of the screw barrel and the conveying action of the screw rod, the plasticizer gradually promotes the interaction of the cross-linking agent between the high polymer and the powder, thereby promoting the cross-linking with the cross-linking agent while controlling the retention time, improving the mechanical property and controlling the degradation rate.

In a further preferred embodiment, the extruder body of the present invention comprises, from left to right, a melting section, a melt conveying section and an extrusion section. In a further preferred embodiment, the gas outlet according to the invention is located in the melt conveying section. In a further preferred embodiment, the main and side feed openings are located in the melting section. The main feeding port is generally arranged on the first screw barrel from left to right of the melting section, and the side feeding port can be arranged on the same screw barrel as the main feeding port or on the adjacent screw barrel of the screw barrel on which the main feeding port is arranged. In a further preferred embodiment, the number of the screw barrels of the extruder of the present invention is 10 to 20, preferably 10 to 17, and more preferably 12 to 16.

In a further preferred embodiment, the number of extruder barrels in the melt zone of the present invention is 2 to 6, and may be, for example, 2, 3, 4, 5 or 6. The temperature range of the melting section is 50-170 ℃, preferably 60-160 ℃, and the temperature of the screw cylinder of the melting section gradually rises from left to right.

In a further preferred embodiment, the number of extruder barrels of the melt conveying section according to the invention is 7 to 15, and may be, for example, 7, 8, 9, 10, 11, 12, 13, 14 or 15. The temperature range of the melt conveying section is 150-200 ℃, and preferably 160-180 ℃. The melt conveying section comprises a first melt conveying section and a second melt conveying section from left to right, the temperature range of the first melt conveying section is 170-200 ℃, and the temperature range of the second melt conveying section is 150-170 ℃. The number of the extruder screw cylinders of the second melt conveying section is 1-3.

In a further preferred embodiment, the number of the extruder screw barrels of the extrusion section is 1 to 3, and the temperature range of the extrusion section is 170 to 180 ℃.

In a further preferred embodiment, the screw is provided with a conveying screw thread element and a shearing screw thread element; the screw of the melt conveying section comprises a conveying thread element and a shearing thread element. The conveying screw element comprises at least one of a right-hand conveying screw element and a left-hand conveying screw element. The shear threaded elements include one or more of right-hand shear threaded elements, neutral shear threaded elements, and left-hand shear threaded elements.

The conveying direction of the right-hand conveying threaded element is the same as the extruding direction and is also called forward conveying threaded element, and the conveying direction of the left-hand conveying threaded element is opposite to the extruding direction and is also called reverse conveying threaded element. The right-hand shearing screw elements form a staggered angle which is consistent with that of the right-hand conveying screw elements and is also called a forward kneading block, the left-hand shearing screw elements form a staggered angle which is consistent with that of the left-hand conveying screw elements and is also called a reverse kneading block, and the staggered angle of the neutral shearing screw elements is 90 degrees.

The invention ensures the consistent compatibility of the biomass powder and the biodegradable plastic through extruders with different length-diameter ratios, meanwhile, the high-efficiency plasticizer and the like are used as auxiliary materials, the agglomeration of the powder is effectively prevented, the dispersibility of the powder in the extrusion process is ensured, the processing performance is improved, and by using the biomass powder and the inorganic powder from natural sources, while the complete degradation can be realized, the inorganic powder is also beneficial to improving the crystallinity of the macromolecule, and by selecting proper raw materials, the extruder head, the plasticizer inlet, the exhaust port and the like are designed, so that the dispersion, plasticization, exhaust and the like of the raw materials in the screw are promoted, the obtained plastic particles have complete biodegradation performance under the composting condition, and the high-temperature-resistant polypropylene composite material has excellent mechanical properties and good extrusion molding processability, can improve subsequent blow molding processability, obtains high puncture resistance, and meets the aging performance of the full service cycle of consumers.

The extrusion molding is followed by granulation, and the granulation method can be exemplified by that the bracing strip passes through a water tank and enters a white steel knife granulator for granulation, underwater granulation or water ring granulation.

In a second aspect the present invention provides the use of a process for the preparation of a biomass material as described above for the preparation of a biomass material.

Examples

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. PBSA from Shandong Hui New Material science and technology Limited, coffee grounds from coffee shop, PBAT from PBAT THJS-5801 of Nanshan Tun river Ltd, corn starch from big group, PHA from big group

K-8200L, and other preparation raw materials are all sold in the market.

Example 1

The present example provides a process for preparing a biomass material, comprising:

mixing glycerol and DOA to serve as a plasticizer, mixing PBSA, coffee grounds and nano calcium carbonate, adding half of the plasticizer, mixing for 135s, adding other preparation raw materials, mixing for 40s to obtain a mixed raw material, adding the mixed raw material into a main feeding port of an extruder, adding the rest of the plasticizer into a side feeding port of the extruder, and carrying out extrusion molding and underwater pelletizing to obtain the biomass material.

The biomass material is prepared from the following raw materials in percentage by weight:

as shown in FIGS. 1 to 5, the length-diameter ratio of the extruder is 56: 1, a 75A machine type co-rotating parallel double-screw extruder; the extruder comprises an extruder body and an extruder head from left to right; an extruder screw barrel is arranged inside the extruder body, and a screw is arranged inside the extruder screw barrel. The side of the extruder is provided with an exhaust port, the exhaust port 11 is connected with a feeder, one end of the feeder is connected with the exhaust port 11, the other end of the feeder is provided with a feed inlet of the feeder, the feed inlet of the feeder is positioned below the feeder, and the number of the exhaust ports 11 is 4 and is positioned in the melt conveying section. And the joint of the extruder head and the extruder is provided with an extruder filter plate. The filter plate of the extruder is provided with a plurality of filter holes, the diameter of each filter hole is 10mm, and the thickness of the filter plate of the extruder is 10 mm; the main feeding port 10 is positioned above the screw barrel of the extruder, the contact surface of the side feeding port and the screw barrel of the extruder is positioned below the side of the screw barrel of the extruder, the main feeding port 10 is positioned at the first section, and the side feeding port is positioned at the second section.

The extruder main body is from left to right, and the mixing temperature is as follows: a melting section: one section is 60-70 ℃, two sections are 90-100 ℃, three sections are 120-130 ℃ and four sections are 150-160 ℃; a melt conveying section: five sections of 170-180 ℃, six sections of 170-180 ℃, seven sections of 170-180 ℃, eight sections of 170-180 ℃, nine sections of 170-180 ℃, ten sections of 170-180 ℃, eleven sections of 160-170 ℃, twelve sections of 160-170 ℃ and thirteen sections of 160-170 ℃; an extrusion section: 170 ℃ and 180 ℃.

As shown in fig. 6 to 8, the screw combination method is: 4/1/1/2/3/3/3/3/3/5/5/3/5/6/2/3/7/2/5/5/6/8/1/4/5/5/6/8/1/4/5/5/9/2/2/1/2/2/2/7/5/7/2/1/2/3/4/3/2/2/2/2/5/5/7/7/2/2/2/2/9/2/1/2/3/3/3/3/3/3. Where 1 is lead 96, length 96 transport block; 2 is lead 72, length 72 transport block; lead 56, length 56 transport block 3; 4 is lead 56, length 56 large screw conveying block; 5 is a 45-degree, 56-length shear screw block consisting of 5 kneading sheets; 6 is a 90-degree, 56-length shearing thread block consisting of 5 kneading pieces; 7 is a shear screw block with 45 degrees and the length of 36 formed by 5 kneading sheets; 8 is a 45-degree left-hand shearing thread block with the length of 36 and consists of 5 kneading sheets; lead 76 for 9, length 36 left hand feed block; 10 is a feed opening; 11 is an exhaust port; 12 is lead 44, length 44 transport block; 13 is a 30-degree left-direction shearing thread block consisting of 6 kneading pieces and having the length of 56; 14 left shear screw blocks of 45 degrees, length 56, made up of 5 kneading blocks; lead 44 for lead 15, length 22 left hand feed block; lead 44 at 16, length 22 delivers the block; lead 56, length 28 delivers the block 17.

This example also provides biomass material prepared by the above-described preparation process.

Example 2

mixing decaglycerol and water to serve as a plasticizer, mixing PBAT, corn starch and nano talcum powder, adding half of the plasticizer, mixing for 135 seconds, adding other preparation raw materials, mixing for 40 seconds to obtain a mixed raw material, adding the mixed raw material into a main feeding port of an extruder, adding the rest plasticizer into a side feeding port of the extruder, and carrying out extrusion molding and underwater pelletizing to obtain the biomass material.

as shown in FIGS. 1 to 5, the length-diameter ratio of the extruder is 56: 1, a 75A machine type co-rotating parallel double-screw extruder; the extruder comprises an extruder body and an extruder head from left to right; an extruder screw barrel is arranged inside the extruder body, and a screw is arranged inside the extruder screw barrel. The side of the extruder is provided with an exhaust port, the exhaust port 11 is connected with a feeder, one end of the feeder is connected with the exhaust port 11, the other end of the feeder is provided with a feed inlet of the feeder, the feed inlet of the feeder is positioned below the feeder, and the number of the exhaust ports 11 is 3 and is positioned in the melt conveying section. And the joint of the extruder head and the extruder is provided with an extruder filter plate. The filter plate of the extruder is provided with a plurality of filter holes, the diameter of each filter hole is 10mm, and the thickness of the filter plate of the extruder is 10 mm; the main feeding port 10 is positioned above the screw barrel of the extruder, the contact surface of the side feeding port and the screw barrel of the extruder is positioned below the side of the screw barrel of the extruder, the main feeding port 10 is positioned at the first section, and the side feeding port is positioned at the second section.

As shown in fig. 9 to 11, the screw combination method is: 4/1/1/2/3/3/3/3/3/3/5/5/3/5/6/3/5/6/2/3/7/2/5/5/6/8/14/5/5/1/2/2/7/8/7/2/7/5/7/2/1/2/3/2/2/2/2/3/5/2/2/2/2/2/9/2/1/2/3/3/3/3/3/3. Where 1 is lead 96, length 96 transport block; 2 is lead 72, length 72 transport block; lead 56, length 56 transport block 3; 4 is lead 56, length 56 large screw conveying block; 5 is a 45-degree, 56-length shear screw block consisting of 5 kneading sheets; 6 is a 90-degree, 56-length shearing thread block consisting of 5 kneading pieces; 7 is a shear screw block with 45 degrees and the length of 36 formed by 5 kneading sheets; 8 is a 45-degree left-hand shearing thread block with the length of 36 and consists of 5 kneading sheets; lead 76 for 9, length 36 left hand feed block; 10 is a feed opening; 11 is an exhaust port; 12 is lead 44, length 44 transport block; 13 is a 30-degree left-direction shearing thread block consisting of 6 kneading pieces and having the length of 56; 14 left shear screw blocks of 45 degrees, length 56, made up of 5 kneading blocks; lead 44 for lead 15, length 22 left hand feed block; lead 44 at 16, length 22 delivers the block; lead 56, length 28 delivers the block 17.

Example 3

mixing glycerol and DOA to serve as a plasticizer, mixing PHA, corn starch and nano talcum powder, adding half of the plasticizer, mixing for 135 seconds, adding other preparation raw materials, mixing for 40 seconds to obtain a mixed raw material, adding the mixed raw material into a main feeding port of an extruder, adding the rest plasticizer into a side feeding port of the extruder, and carrying out extrusion molding and underwater pelletizing to obtain the biomass material.

as shown in FIGS. 1 to 5, the length-diameter ratio of the extruder is 56: 1, a 75D type co-rotating parallel double-screw extruder; the extruder comprises an extruder body and an extruder head from left to right; an extruder screw barrel is arranged inside the extruder body, and a screw is arranged inside the extruder screw barrel. The side of the extruder is provided with an exhaust port, the exhaust port 11 is connected with a feeder, one end of the feeder is connected with the exhaust port 11, the other end of the feeder is provided with a feed inlet of the feeder, the feed inlet of the feeder is positioned below the feeder, and the number of the exhaust ports 11 is 3 and is positioned in the melt conveying section. And the joint of the extruder head and the extruder is provided with an extruder filter plate. The filter plate of the extruder is provided with a plurality of filter holes, the diameter of each filter hole is 10mm, and the thickness of the filter plate of the extruder is 10 mm; the main feeding port 10 is positioned above the screw barrel of the extruder, the contact surface of the side feeding port and the screw barrel of the extruder is positioned below the side of the screw barrel of the extruder, the main feeding port 10 is positioned at the first section, and the side feeding port is positioned at the second section.

As shown in fig. 12, the screw combination is 4/2/2/2/2/2/3/3/3/3/7/12/12/12/5/5/14/12/12/13/2/13/7/2/2/15/12/12/2/2/3/12/16/6/13/15/12/3/3/3/12/16/6/6/13/12/3/12/12/15/12/3/3/2/2/2/3/3/3/17. Where 1 is lead 96, length 96 transport block; 2 is lead 72, length 72 transport block; lead 56, length 56 transport block 3; 4 is lead 56, length 56 large screw conveying block; 5 is a 45-degree, 56-length shear screw block consisting of 5 kneading sheets; 6 is a 90-degree, 56-length shearing thread block consisting of 5 kneading pieces; 7 is a shear screw block with 45 degrees and the length of 36 formed by 5 kneading sheets; 8 is a 45-degree left-hand shearing thread block with the length of 36 and consists of 5 kneading sheets; lead 76 for 9, length 36 left hand feed block; 10 is a feed opening; 11 is an exhaust port; 12 is lead 44, length 44 transport block; 13 is a 30-degree left-direction shearing thread block consisting of 6 kneading pieces and having the length of 56; 14 left shear screw blocks of 45 degrees, length 56, made up of 5 kneading blocks; lead 44 for lead 15, length 22 left hand feed block; lead 44 at 16, length 22 delivers the block; lead 56, length 28 delivers the block 17.

Example 4

mixing glycerol and water to serve as a plasticizer, mixing PBAT, corn starch and nano talcum powder, adding half of the plasticizer, mixing for 135 seconds, adding other preparation raw materials, mixing for 40 seconds to obtain a mixed raw material, adding the mixed raw material into a main feeding port of an extruder, adding the rest plasticizer into a side feeding port of the extruder, and carrying out extrusion molding and underwater pelletizing to obtain the biomass material.

as shown in FIGS. 1 to 5, the length-diameter ratio of the extruder is 56: 1, a 75D type co-rotating parallel double-screw extruder; the extruder comprises an extruder body and an extruder head from left to right; an extruder screw barrel is arranged inside the extruder body, and a screw is arranged inside the extruder screw barrel. The side of the extruder is provided with an exhaust port, the exhaust port 11 is connected with a feeder, one end of the feeder is connected with the exhaust port 11, the other end of the feeder is provided with a feed inlet of the feeder, the feed inlet of the feeder is positioned below the feeder, and the number of the exhaust ports 11 is 2 and is positioned at a melt conveying section. And the joint of the extruder head and the extruder is provided with an extruder filter plate. The filter plate of the extruder is provided with a plurality of filter holes, the diameter of each filter hole is 10mm, and the thickness of the filter plate of the extruder is 10 mm; the main feeding port 10 is positioned above the screw barrel of the extruder, the contact surface of the side feeding port and the screw barrel of the extruder is positioned below the side of the screw barrel of the extruder, the main feeding port 10 is positioned at the first section, and the side feeding port is positioned at the second section.

As shown in FIG. 13, the screw is combined in 4/2/2/2/2/2/3/3/3/3/7/12/12/12/5/5/5/5/14/12/12/13/2/13/7/7/7/2/2/3/12/16/7/7/7/2/2/3/12/16/7/7/13/3/12/16/6/13/15/12/3/3/3/12/16/6/13/13/12/3/12/12/12/15/3/3/2/2/2 ^ based on the basis of 3/3/3/17. Where 1 is lead 96, length 96 transport block; 2 is lead 72, length 72 transport block; lead 56, length 56 transport block 3; 4 is lead 56, length 56 large screw conveying block; 5 is a 45-degree, 56-length shear screw block consisting of 5 kneading sheets; 6 is a 90-degree, 56-length shearing thread block consisting of 5 kneading pieces; 7 is a shear screw block with 45 degrees and the length of 36 formed by 5 kneading sheets; 8 is a 45-degree left-hand shearing thread block with the length of 36 and consists of 5 kneading sheets; lead 76 for 9, length 36 left hand feed block; 10 is a feed opening; 11 is an exhaust port; 12 is lead 44, length 44 transport block; 13 is a 30-degree left-direction shearing thread block consisting of 6 kneading pieces and having the length of 56; 14 left shear screw blocks of 45 degrees, length 56, made up of 5 kneading blocks; lead 44 for lead 15, length 22 left hand feed block; lead 44 at 16, length 22 delivers the block; lead 56, length 28 delivers the block 17.

Comparative example 1

The present example provides a biomass material preparation process, the specific implementation manner is the same as example 1, except that the length-diameter ratio of the extruder is 60: 1, a 75D type co-rotating parallel twin-screw extruder (screw diameter 65mm, power 75 kW).

Evaluation of Performance

The biomass materials provided in examples and comparative examples were tested for tensile strength, elongation at break, flexural strength, flexural modulus according to GBT _1040.3-2006, and for melt index at 190 ℃ of 2.16KG, and density using the mass-to-volume test, the results of which are shown in table 1.

Table 1 performance characterization test

According to the test results, the biomass material obtained by the preparation process provided by the invention has high mechanical properties, and as can be seen from fig. 14, the biomass material provided by the embodiment 4 has flat and light surface and luster, the biomass material obtained by the embodiments 1-3 has similar appearance to that of the biomass material obtained by the embodiment 4, while the biomass material obtained by the comparative example 1 has yellow and dull luster, low flatness and obvious performance attenuation; in addition, the biomass materials obtained in the embodiments 1 to 4 are degraded under the composting condition, and the degradation rate of 90 days is found to reach 90%, which shows that the biomass material obtained by the preparation process provided by the invention has complete biodegradability under the composting condition, and also has excellent mechanical properties and good extrusion molding processability.

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 is contemplated, 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. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims

1. A process for the preparation of a biomass material, comprising: mixing the preparation raw materials of the biomass material, adding the mixture into an extruder, and performing extrusion molding;

2. The process for preparing biomass material according to claim 1, wherein the polyester is at least one selected from dibasic acid glycol polyester, polyhydroxyalkanoate, and polylactic acid.

3. The process for preparing the biomass material according to claim 1, wherein the biomass powder is selected from one or more of coffee grounds, straw powder and starch.

4. The process for preparing biomass material according to claim 1, wherein the side of the extruder is provided with a vent, and the vent is connected with the feeder.

5. The process of preparing a biomass material according to claim 4, wherein one end of the feeder is connected to an exhaust port, and the other end is provided with a feeder feed inlet, and the feeder feed inlet is positioned below the feeder.

6. The process of preparing a biomass material according to claim 4, wherein the number of said exhaust ports is 2 or more.

7. The process for preparing the biomass material according to any one of claims 1 to 6, wherein the plasticizer comprises a first plasticizer and a second plasticizer, and the weight ratio of the first plasticizer to the second plasticizer is (1-2): (1-2).

8. The process for the preparation of biomass material according to claim 7, characterized in that it comprises:

9. The process of making biomass material according to claim 8, wherein the main feed port is located above the extruder barrel and the side feed port and extruder barrel interface is located below the extruder barrel side.

10. Use of the process according to any one of claims 1 to 9 for the preparation of a biomass material.