CN107586441B

CN107586441B - Wine lees-based composite material and process for preparing 3D printing wire by using same

Info

Publication number: CN107586441B
Application number: CN201710971325.8A
Authority: CN
Inventors: 邹智挥; 吴进三; 陈建; 李新跃; 胡雪菲; 罗惠波; 赵磊; 万能; 王若尧
Original assignee: Sichuan University of Science and Engineering
Current assignee: Sichuan Bozhiduo Technology Co ltd; Zigong Zhisheng Core Technology Co ltd; Sichuan Zhixiangyi Technology Co Ltd
Priority date: 2017-10-18
Filing date: 2017-10-18
Publication date: 2021-02-26
Anticipated expiration: 2037-10-18
Also published as: CN107586441A

Abstract

The invention relates to a wine residue-based composite material, which comprises the following components: 40%-90% macromolecule and 10%-60% wine residue raw material powder, the total mass percentage is 100%, and the wine residue-based is environmentally friendly The composite material may also include a combination of additives, and the amount of the additive combination is not greater than 50% of the total mass of the polymer and the raw material powder of the lees. It is applied to processed products, such as injection molding products, and filaments for 3D printing, specifically a wine residue-based composite material and environmentally friendly filaments for 3D printing and its manufacturing method. In the present invention, the addition of wine residue raw material powder realizes the concept of resource recovery and reuse, reduces the use cost of polymer raw materials, makes 3D printed products have the effect of imitating wood, and improves material strength, toughness, crystallinity and The crystallization rate also improves its biodegradable performance and biocompatibility, reduces biotoxicity, and increases the application and environmental value of polymer composites and 3D printing filaments.

Description

Wine lees-based composite material and process for preparing 3D printing wire by using same

Technical Field

The invention belongs to the field of preparation of engineering materials, and relates to an environment-friendly wire rod applied to processing products (injection) and 3D printing, in particular to a lees-based composite material and a process for preparing a wire rod for 3D printing by using the composite material.

Background

Due to the development of civilization and the improvement of science and technology, more and more wastes are caused, the global deterioration is accelerated due to environmental pollution, in order to save natural resources of the world, resource recovery systems are established in more advanced countries of the world, and the resource recovery wastes are recycled and rotten, so that the curiosity can be realized.

The Chinese liquor yield exceeds 1 million tons every year, and according to the traditional vinasse output proportion, 1 ton of liquor can generate 3 tons of wine residues, in other words, the yield of the wine residues exceeds 3 million tons every year. The wine dregs can not be effectively used until now except a few applications, and most of the excessive wine dregs can only be buried as waste, which undoubtedly pollutes the environment. The application of the schlempe to polymer research and patents is very few, and if the recycled schlempe can be effectively applied to polymer composite materials, the problem of environmental pollution can be reduced, and great value can be created for the market.

3D printing (3D printing), also known as additive manufacturing, is one of the rapid prototyping technologies, and is a direct manufacturing technology based on a digital model file, which can manufacture almost any shape of three-dimensional entity, and a manufacturing process for building an object by layer-by-layer stacking and accumulating through a technology for building an object by layer-by-layer printing. 3D printing is typically achieved using digital technology material printers. The method is often applied to the fields of mold manufacturing, industrial design and the like. The technique finds application …, among others, in jewelry, wear (e.g., shoes, hats), construction, various engineering, dental and medical industries, and other fields.

At present, the common forming mode of the household 3D printer in the market uses PLA wire rods and ABS wire rods as the most common materials.

Although there are many advantages, the main source of PLA strand is edible corn, and the future of shortage of food source will have disadvantages of food competition with human under the trend of global warming, so the consumption of resources and cost is still not low, and there is room for improvement in the brittleness and crystallization rate of PLA strand. Therefore, the cost of the polylactic acid is reduced, the toughness and the crystallization rate are improved, and the application value of the polylactic acid wire rod can be greatly improved.

ABS is petroleum-based material, except can consume in the limited resource of earth, it can give off the bad smell and slight toxicity when 3D prints, reduce ABS plastic consumption, or add raw materials that can absorb ABS smell or toxicity, it can promote ABS to print the value in the technical field of 3D.

In view of the above, how to provide a different environment-friendly composite material, which can be applied to various processed products such as injection or 3D printing wires, can reduce the usage of polymer plastics to alleviate the worry of food competition with human beings or reduce the consumption of petroleum energy, and make the composite material have the effect of wood-like texture to provide more natural material options for the literary and artistic creators. Most of the current wood-like injection products or 3D printing wires at home and abroad use wood flour as an additive (such as cypress, pine …, etc.) to make the 3D printing products show wood-like effects, but the sources of the wood flour need to fell trees to obtain the source materials, which can make the global warming phenomenon more severe.

Based on the above reasons, it is to recover a great amount of waste wine dregs generated after a great amount of brewing and fermentation of Chinese drinking culture, and to use the waste wine dregs as additives of polymer composite materials after treatment to reduce the cost of the composite materials, reinforce the defects of the polymer and improve various performances, such as: crystallinity, crystallization rate, biodegradable rate and biocompatibility, and reduces the biotoxicity of macromolecules, thereby improving the application value of recycling the waste wine residues.

Disclosure of Invention

Based on the technical problems, the invention provides a lees-based composite material and a process for preparing a 3D printing wire by using the composite material. The process recycles a large amount of waste generated by the people who like drinking wine, treats the waste as the injection composite master batch, and adds the injection composite master batch and the polymer to prepare the composite material, thereby reducing the production cost, reinforcing the defects of the polymer, improving the crystallization property of the polymer and improving the application value of recycling the waste wine residues.

The specific technical scheme of the invention is as follows:

the composite material based on the wine lees comprises the following components in percentage by mass: 40-90% of high molecular compound and 10-60% of lees powder, the total mass percentage content is 100%, the high molecular compound is one or a mixture of more of polylactic acid (PLA), Polyhydroxyalkanoate (PHA), propylene-butadiene-diene copolymer (ABS), polyolefin, polyterephthalate (such as PET, PTT, PBT, PBAT), Polycaprolactone (PCL) and Polyamide (PA) or a copolymer thereof; the lees powder is characterized in that: cleaning fermented wine residue (especially wine residue of miscellaneous cereals such as Daqu, Xiaoqu, Tequ, Touqu, Erqu, and Red Rice), cleaning, sun-drying, drying at high temperature, pulverizing, and grinding to obtain powder with water content of less than 0.1 wt%.

The composite material also comprises an additive combination, and the additive amount of the additive combination is less than or equal to 50% of the total mass of the macromolecular compound and the lees powder.

The additive combination comprises any one or a mixture of more of a compatilizer, a lubricant, a flexibilizer and an antioxidant; the addition amount of the compatilizer is 0-3.5 percent based on the total mass of the macromolecular compound and the lees powder; 0-20% of lubricant; 0-2% of toughening agent; the antioxidant is 0-0.5%.

The compatilizer is any one or a mixture of more of glycidyl ester, oxazoline type, anhydride type, carboxylic acid type, epoxy type, hydroxyl type, epoxy type reaction type, titanate type, silane type, imide type (modified polyacrylate) and isocyanate type.

The toughening agent is divided into a low molecular toughening agent and a high molecular toughening agent, wherein the low molecular toughening agent is selected from DuPont Biomax Strong, BASF ADR4368, BASF ADR4370F or a toughening additive for polymers produced by various manufacturers. The high molecular toughening agent is selected from polybutylene terephthalate adipate

(PBAT), Polyesterlactone (PCL), polybutylene succinate (PBS), polyvinyl alcohol (PVA) or Thermoplastic Polyurethane (TPU).

The lubricant is selected from stearic acid series, paraffin series or plasticizer series.

The antioxidant is any one or a mixture of more of phosphite esters, triaryl phosphite esters, trialkyl aryl phosphate esters, alkyl aryl phosphate esters, trithio alkyl esters, diphosphite esters, polymeric phosphite esters or pentaerythritol esters, dibutyl hydroxy toluene, butyl hydroxy anisole, propyl gallate, di-tert-butyl mixed phenol and tert-butyl hydroquinone.

The process for preparing the wire for 3D printing by using the lees-based composite material comprises the following steps:

1) cleaning the wine residues, solarizing the wine residues in the sun, and drying the wine residues in an oven at the drying temperature of 100-350 ℃ until the water content of the dried wine residues is lower than 0.1 wt%. (ii) a

2) Crushing and grinding the dried lees raw material to ensure that the particle size is less than or equal to 120 microns;

3) a granulation step: mixing a high molecular compound and the powder by using a double-screw granulator to prepare a lees-based composite material;

4) the 3D printing wire material preparation step: and extruding the lees base composite material by a wire extruder for 3D printing, and then drafting and winding the lees base composite material into the environment-friendly wire for 3D printing.

The positive effects of the invention are as follows:

according to the invention, the addition of the lees raw material powder and the application of the concept of resource recycling are adopted, so that the cost of the polymer is reduced, the problem of pollution disposal of the waste lees in a brewing factory can be solved, and more natural recycled material options are provided for art creators or engineering manufacturers.

In the invention, the addition of the lees raw material powder can improve the mechanical strength (such as tensile strength and impact strength) of the polymer.

In the invention, the addition of the lees raw material powder can improve the crystallinity and crystallization rate of the polymer.

According to the invention, the addition of the lees raw material powder can enable the 3D printed finished product to achieve the effect of wood-like texture.

In the invention, the addition of the lees raw material powder in the high polymer plastic can partially replace many wood-like plastics or 3D printing wires added with wood powder on the market, thereby reducing the damage to forests.

According to the invention, the lees raw material powder is added into ABS and PA plastics, and the processed lees powder can absorb the smell emitted by ABS and PA during 3D printing, so that the unpleasant smell is reduced.

And (seventhly), the addition of the lees raw material powder in PLA, PCL, PBAT or PHA plastics can improve the biodegradable efficiency of the lees raw material powder, and when the 3D printing finished product is damaged and discarded, the conversion rate of microbial decomposition of the lees raw material powder after being buried in soil can be promoted, and the lees raw material powder can be used as a nutrient for the growth of crops.

(eighth), in the invention, the addition of the lees raw material powder in the high molecular plastic can reduce the biological toxicity of some plastics (such as ABS), or increase the biocompatibility of the high molecular, so that the composite material has wider application such as food materials and biomedical materials.

Drawings

Fig. 1 is a schematic view of a lees-based 3D printing wire according to the present invention.

Fig. 2 is a schematic flow chart of the preparation of the lees-based composite material and the 3D printing wire material in the invention.

FIG. 3 is a graph comparing the relative crystallinity of neat PLA to a schlempe-based composite.

Wherein, 0-waste schlempe, 1-schlempe-based wire, 2-macromolecule, 3-waste schlempe powder, 4-additive combination, 5-schlempe-based macromolecule composite material, and 6-schlempe-based environment-friendly wire for 3D printing. Cleaning (100), exposing to sunlight and oven drying (200), grinding (300), melt blending (400), solvent wet blending (410), and processing and forming (500).

Detailed Description

The present invention will be described in further detail with reference to specific embodiments for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention as described above, according to the common technical knowledge and conventional means in the field, and the scope of the invention is covered.

In this document,% represents the weight% of the total mass of the polymer compound and the lees raw material powder, unless otherwise specified.

Example 1:

a preparation method of a lees-based composite material comprises the following steps:

(1) preparing the wine dreg recovery raw materials:

collecting waste lees after fermentation of Daqu liquor in a brewing factory, cleaning, solarizing in the sun for 10 hours, drying in an oven at 185 ℃ for 4 hours, pulverizing, grinding, and sieving to 105-75 microns (about 150-200 meshes).

(2) Preparation of a lees-based composite Material

Respectively putting the prepared Daqu liquor residue powder and PHA and PBAT in different proportions of 20%, 40% and 60% into an extruder, adding a compatilizer (a silane coupling agent) accounting for 1wt% of the mass percentage of the substances (the total mass of the PHA or PBAT and the liquor residue powder), a lubricant (paraffin wax) accounting for 1wt% of the mass percentage of the substances and an antioxidant (triaryl phosphite) accounting for 0.4 wt% of the mass percentage of the substances, mixing the mixture and the PHA and PBAT components by using a double-screw extruder, wherein the processing temperature is 145-165 ℃, and after mixing, processing and extrusion, supercooling water tank granulation is carried out to prepare the liquor residue-based composite material; marking the obtained PHA composite material samples as composite material 1, composite material 2 and composite material 3 respectively; the obtained PBAT composite samples were labeled composite 1 ', composite 2 ', and composite 3 ', respectively. The prepared material was subjected to mechanical property tests, and the test results are respectively shown in table one:

watch 1

Sample (I)	Tensile Strength (MPa)	Weight loss after 90 days in soil (%)
			PHA	20.1	2.3
Compound material 1 (20%)	21.7	3.1
			Compound material 2 (40%)	22.5	6.8
Compound material 3 (60%)	20.3	24.3
			PBAT	18.6	2.2
Compound material 1' (20%)	21.5	2.9
			Compound material 2' (40%)	20.8	5.7
Composite material 3' (60%)	18.2	20.6

From the results, it can be seen that the tensile strength of the composite materials prepared from PHA and PBAT and the lees added thereto are higher than those of pure PHA and PBAT, respectively.

For further proving that the addition of the wine residues can improve the biodegradable property of PHA and PBAT, the 8 composite materials are buried in soil for 90 days, then the weight of each sample is weighed to calculate the weight loss rate, the weight loss degree can be observed from the right column at the third column, and the weight loss degree is more obvious along with the increase of the content of the wine residues, so that the addition of the wine residues can improve the biodegradation rate of high molecules.

Example 2:

(1) preparing the wine dreg recovery raw materials:

collecting the waste lees of the fermented Xiaoqu liquor in a brewing factory, cleaning, exposing for 12 hours in the sun, drying for 4 hours in an oven at 185 ℃, crushing, grinding and sieving to 20-25 microns (about 500 meshes and 625 meshes).

(2) Preparation of a lees-based composite Material

And (3) inspecting the strength of the composite material prepared by adding different proportions of the small yeast wine residue powder, drying the ABS in a dehumidifying and drying box for 4 hours at the temperature of 90 ℃ to ensure that the water content is less than 0.1%. And then adding the dried ABS plastic composition into an extruder, mixing the prepared lees powder (20%, 40% and 60%) with the dewatered ABS, adding a compatilizer (cyclic anhydride) accounting for 0.6 wt% of the mass of the substances (the total mass of the ABS and the lees), 10% of a plasticizer (adipate) and 0.7% of an antioxidant (KY-02, 2, 6-di-tert-butyl mixed phenol), blending by using a double-screw extruder together, wherein the processing temperature is 190 ℃ and 220 ℃, and after mixing, processing and extrusion, granulating by using a supercooling water tank to obtain lees-based composite materials, and respectively obtaining the sample labels of composite material 4, composite material 5 and composite material 6. The prepared material is subjected to mechanical property line and MTT cell activity tests, and the test results are respectively shown in Table two

Watch two

Sample (I)	Tensile Strength (MPa)	Relative cell proliferation Rate (%)
			ABS	38.4	78.9
Compound material 4 (20%)	42.2	126.9
			Compound material 5 (40%)	42.6	177.6
Compound material 6 (60%)	38.5	242.8

From the results, it can be seen that the tensile strength of the composite material obtained after different ratios of lees and PLA processing is higher than that of pure ABS. The right column of table two shows the result of day 3 of analyzing the cytotoxicity of ABS and its lees-based composite material in vitro by using the MTT cell activity test method using the cell line of mouse fibroblast (L929), and it can be seen from table two that ABS itself has some microbial toxicity (less than 100%), and the cell activity is greatly improved with the increase of the addition ratio of lees powder, because lees have the nutrients required by cells after microbial fermentation, and the lees may absorb part of the released toxicity, so that the lees-based ABS composite material has no biological toxicity, but also has increased cell activity.

Example 3:

a preparation method of a biodegradable schlempe base composite material with high strength comprises the following steps:

(1) preparing the wine dreg raw material:

collecting the waste lees after the yeast white spirit is made in the brewing factory, cleaning, exposing for 48 hours in the sun, then drying for 10 hours in an oven at 195 ℃, then crushing, grinding and sieving to 15-25 microns (about 500 meshes and 900 meshes).

(2) Biodegradable schlempe-based composite material with high strength

And (3) drying the PLA in a dehumidification drying oven for 4 hours, wherein the temperature of the dehumidification drying oven is 85 ℃, and the dew point temperature is-40 ℃. Mixing the prepared lees raw material and the dewatered PLA according to different lees proportions (10%, 20%, 40% and 60%), adding 1.5 wt% of compatilizer (glycidyl methacrylate), 3% of lubricant (plasticizer-adipate), 0.15% of attapulgite, 1.5% of flexibilizer (DuPont Biomax Strong) and 0.5% of antioxidant (diphosphite) in mass percentage of substances (total mass of the PLA and the lees), mixing by using a double-screw extruder together, processing at the temperature of 180 DEG and 200 ℃, mixing, processing, extruding, granulating by using a supercooling water tank to obtain the lees-based composite material, and respectively marking the obtained samples as composite material 7, composite material 8, composite material 9, composite material 10 and composite material 11. The prepared material is subjected to mechanical property, crystallinity and biological decomposability tests, and the test results are respectively shown in table three:

watch III

From the results, the tensile strength and impact strength of the composite material obtained after different lees proportions and PLA processing are higher than those of pure PLA, and especially the impact strength of all lees composite materials is 6-7 times higher than that of PLA; in addition, the crystallinity of all the composite materials of the lees is 2 to 3 times higher than that of pure PLA. The biodegradation efficiency of PLA is obviously improved along with the increase of the content of the wine dregs.

In order to further prove that the crystallization rate of PLA is relatively slow, the addition of the schlempe can increase the crystallization rate of PLA, and the crystallization rate of PLA, composite material 8 (20%), composite material 9 (40%) and composite material 10 (60%) are analyzed by DSC, as shown in fig. 3, which is a crystallization rate graph at a constant temperature of 112 ℃, the crystallization rate of pure PLA is very slow, and PLA still does not begin to crystallize after 5 minutes, and the crystallization rate is greatly increased after the addition of the waste recycled raw material, wherein the crystallization rate is fastest with the schlempe base (composite material 9), and the crystallization is completed in about 2 minutes.

Example 4:

a preparation method of a high-toughness biodegradable schlempe base composite material comprises the following steps:

(1) preparing the wine dreg raw material:

collecting the waste lees after the yeast white spirit is made in the brewing factory, cleaning, exposing for 48 hours in the sun, then drying for 10 hours in an oven at 185 ℃, then crushing, grinding and sieving to 30-45 microns (about 325-460 mesh).

(2) High-toughness and biodegradable wine residue-based 3D printing wire

And (3) drying the PLA in a dehumidification drying oven for 4 hours, wherein the temperature of the dehumidification drying oven is 85 ℃, and the dew point temperature is-40 ℃. Then mixing and stirring the dried PLA and the PHA in a ratio of 8:2, mixing the prepared lees powder and the PLA/PHA blend in different lees ratios (20%, 40% and 60%), adding a compatilizer (titanate coupling agent) accounting for 0.5 wt% of the mass percentage of the substances (the total mass of the PLA/PHA blend and the lees) and 5% of a plasticizer (acetyl tributyl citrate), blending by using a double-screw extruder together, wherein the processing temperature is 180 DEG and 200 ℃, and after mixing, processing and extrusion, supercooling water tank granulation is carried out to obtain lees-based composite materials, and the obtained samples are respectively marked as composite materials 11, 12 and 13. The prepared material was subjected to mechanical property tests, and the test results are shown in table four, respectively:

watch four

Sample (I)	Tensile Strength (MPa)	Impact strength (J/m)
			PLA/PHA(8:2)	36.2	47.8
Compound material 11 (20%)	47.9	202.5
			Compound material 12 (40%)	48.5	208.1
Compound material 13 (60%)	44.3	212.4

From the results, it can be seen that the tensile strength and impact strength of the composite material obtained after processing with different ratios of the lees and the PLA/PHA blend are significantly higher than those of the single PLA/PHA blend.

Example 5:

the preparation method of the high-toughness biodegradable schlempe base composite material comprises the following steps:

(1) preparing the wine dreg raw material:

collecting the waste lees after the yeast white spirit is made in the brewing factory, cleaning, exposing for 48 hours in the sun, then drying for 10 hours in an oven at 175 ℃, then crushing, grinding and sieving to 30-45 microns (about 325-460 mesh).

(2) Wire rod for 3D printing with high toughness and biodegradable schlempe base

And (3) drying the PLA in a dehumidification drying oven for 4 hours, wherein the temperature of the dehumidification drying oven is 85 ℃, and the dew point temperature is-40 ℃. And then mixing the dried PLA, the prepared lees powder and the PLA according to different lees proportions (20%, 40% and 60%), adding a compatilizer (titanate coupling agent) accounting for 1wt% of the total mass of the substances (PLA and lees), 12% of a plasticizer (acetyl tributyl citrate), 40% of two polymer toughening agents (total), 12% of a polymer toughening agent (TPU) and 28% of a polymer toughening agent (PBAT), mixing by using a double-screw extruder together at the processing temperature of 175-. The prepared material was subjected to mechanical property tests, and the test results are shown in table five, respectively:

watch five

Sample (I)	Impact strength (J/m)	Elongation at Break (%)
			PLA	20.4	3.9
Compound material 14 (20%)	376.9	280.6
			Compound material 15 (40%)	342.1	225.7
Compound material 16 (60%)	294.8	190.5

From the results, it can be known that the impact strength and the elongation at break of the composite material with ultra-high toughness obtained by processing different proportions of the lees and PLA are much higher than those of pure PLA, and especially, the impact strength is about 15 to 18 times higher than that of pure PLA.

Example 6:

(1) preparing the wine dreg raw material:

collecting waste lees after making Xiaoqu liquor in a brewing factory, cleaning, exposing for 48 hours in the sun, drying for 10 hours in an oven at 175 ℃, crushing, grinding and sieving to 30-45 microns (about 325-460 mesh).

(2) Preparation of the lees-based composite material:

mixing the prepared lees raw materials with high-density polyethylene HDPE according to different proportions (20%, 40% and 60%), adding 10% by mass of maleic anhydride grafted polyethylene (PE-g-MAH), 1% by mass of lubricant (plasticizer-acetyl tri-n-butyl citrate) and 0.4% by mass of antioxidant (antioxidant 1010) into the lees raw materials, mixing the materials by using a double-screw extruder at the processing temperature of 145-165 ℃, performing mixing processing, extruding, and granulating in a supercooling water tank to obtain lees-based composite material, wherein the obtained samples are respectively marked as composite material 17, composite material 18 and composite material 19. The prepared material was subjected to mechanical property tests, and the test results are shown in table six:

watch six

Sample (I)	Tensile Strength (MPa)	Degree of crystallinity (%)	Relative cell proliferation Rate (%)
				HDPE	28.5	76.4	113.4
Compound material 17 (20%)	32.8	79.6	198.3
				Compound material 18 (40%)	29.3	81.2	267.9
Compound material 19 (60%)	26.1	80.5	313.5

From the results, it can be seen that the tensile strength of the composites obtained after processing with different ratios of lees and HDPE is higher than that of HDPE for the composite with lees content except that 60% of the lees content is slightly lower than that of HDPE. The right column of the sixth Table shows the results of the 3 rd day test of the in vitro cytotoxicity of HDPE and its lees composite material by using the MTT cell activity test method of the L929 cell line, from which it can be known that the cell activity of HDPE is greatly improved along with the increase of the content of lees powder

Example 7:

(1) preparing the wine dreg raw material:

collecting waste lees after making Xiaoqu liquor in a brewing factory, cleaning, solarizing for 48 hours in the sun, drying for 10 hours in an oven at 280 ℃, crushing, grinding and sieving to 30-45 microns (about 325-460 mesh).

(2) Composite material with wine lees base

Mixing the prepared lees raw materials with PET in different proportions (15%, 35% and 55%), adding maleic anhydride grafted PET (PET-g-MAH) accounting for 12% of the mass percentage of the substances (total mass of PET and lees), 3% of lubricant (stearic acid) and 0.4% of antioxidant (antioxidant 1010), blending by using a double-screw extruder together at the processing temperature of 260-275 ℃, mixing, processing, extruding, and granulating in a supercooling water tank to obtain lees-based composite material, wherein the obtained samples are respectively marked as composite material 20, composite material 21 and composite material 22. The prepared material was subjected to mechanical property tests, and the test results are shown in table seven:

watch seven

Sample (I)	Tensile Strength (MPa)	Degree of crystallinity (%)
			PET	32.1	12.7
Compound material 20 (15%)	34.3	34.1
			Compound material 21 (35%)	33.5	37.8
Compound material 22 (55%)	32.2	38.4

From the results, it can be seen that the tensile strength and crystallinity of the composite material obtained after processing with different ratios of lees and PET are higher than those of pure PET.

Example 8:

the preparation method of the low-melting-point, high-toughness and biodegradable schlempe base composite material comprises the following steps:

(1) preparing the wine dreg raw material:

collecting waste lees after making Daqu white spirit in a brewing factory, cleaning, exposing for 48 hours in the sun, drying for 10 hours in an oven at 105 ℃, crushing, grinding and sieving to 30-45 microns (325-460 mesh).

(2) Low-melting-point, high-toughness and biodegradable wine residue base composite material and environment-friendly wire for 3D printing

Mixing the prepared lees raw materials with PCL in different proportions (15%, 35% and 55%), adding maleic anhydride grafted PCL (PCL-g-MAH) accounting for 12.5% of the total mass of the materials (PCL and lees), 2% of a lubricant (plasticizer system-stearic acid) and 0.4% of an antioxidant (antioxidant 1010), blending by using a double-screw extruder together, wherein the processing temperature is 75-85 ℃, and after mixing, processing, extrusion and supercooling water tank granulation, the lees-based composite material is obtained, and the obtained samples are respectively marked as composite material 23, composite material 24 and composite material 25. The prepared material was subjected to mechanical property tests, and the test results are shown in table eight:

table eight

The results show that the tensile strength, impact strength and biodegradation rate of the composite material obtained by processing PCL with different proportions of the lees are much higher than those of pure PCL.

Example 9:

the preparation method of the waste composite material and the comparative experiment of the biological toxicity are as follows:

(1) preparing raw materials of wine lees, coffee grounds and rice hulls:

collecting the Daqu liquor dregs, the coffee dregs and the rice hulls, respectively treating, namely cleaning, then solarizing for 48 hours in the sun, then drying the Daqu liquor dregs, the coffee dregs and the rice hulls in an oven at 185 ℃ for 10 hours, then crushing, grinding and sieving to 30-45 microns (325-460 meshes).

(2) Composite material of waste

And (3) drying the PLA in a dehumidification drying oven for 4 hours, wherein the temperature of the dehumidification drying oven is 85 ℃, and the dew point temperature is-40 ℃. Respectively mixing the prepared wine dreg powder, rice hull powder and coffee dreg powder with the dehydrated PLA, mixing the materials according to different waste proportions (20%, 40% and 60%), adding a compatilizer (glycidyl methacrylate) accounting for 1.5 wt% of the total mass of the substances (PLA and waste), a lubricant (plasticizer-acetyl tri-n-butyl citrate) accounting for 3%, a flexibilizer (DuPont Biomax Strong) accounting for 1.2% and an antioxidant (diphosphite) accounting for 0.4%, mixing the materials by using a double-screw extruder together, wherein the processing temperature is 180 DEG and 200 ℃, mixing, processing and extruding the materials, granulating the materials in a supercooling water tank to obtain wine dreg-based composite materials, and respectively marking the obtained wine dreg-based composite material samples as composite materials 26, 27 and 28; marking the obtained rice hull composite material samples as composite material 26 ', composite material 27 ' and composite material 28 ' respectively; the resulting coffee grounds composite samples were also labeled composite 26 ", composite 27", and composite 28 ", respectively. The three prepared composite materials were subjected to MTT cell activity assay, and the assay results are shown in table nine:

watch nine

Table nine shows the results of the 3 rd day that the cell line of L929 was used to perform the MTT cell activity test method to test the cytotoxicity of the three waste composites in vitro, from table nine, it can be seen that PLA itself has excellent biocompatibility, and as the addition proportion of the lees powder increases, the cell activity is greatly improved, because the lees are fermented by microorganisms, it has the nutritional ingredients required for providing L929 cells, so that the lees-based PLA composites have improved the cell activity. In addition, when the content of PLA is increased along with the content of the rice hull powder, the cell activity of the PLA is only slightly improved; however, when PLA is added to coffee grounds, its cellular activity decreases with increasing content of coffee grounds, which should be due to the slight biological toxicity of caffeine contained in the coffee grounds.

All the composite materials prepared in the above embodiments can be extruded by a wire extruder for 3D printing, and then are drawn and reeled into environment-friendly wires for 3D printing of the lees base for application, so that the environment-friendly wires have wider application.

The above examples are only preferred embodiments of the patent, but the scope of protection of the patent is not limited thereto. It should be noted that, for those skilled in the art, without departing from the principle of this patent, several improvements and modifications can be made according to the patent solution and its patent idea, and these improvements and modifications should also be regarded as the protection scope of this patent.

Claims

1. a technique for preparing a 3D printing wire by a wine residue-based composite material, characterized in that the wine residue-based composite material comprises the following components by mass percentage: 40%-90% macromolecular compound and 10%-60% wine Slag, the total mass percentage is 100%, and the wine dregs are: the waste wine dregs after brewing and fermentation are cleaned, exposed to sunlight, dried at high temperature, pulverized and ground into powder; the polymer compound is Any one of polylactic acid, polyhydroxyalkanoate, polyolefin, PET, and PBAT; the wine residue-based composite material is used to prepare 3D printing wires;

The specific preparation process includes the following steps:

1) After cleaning the wine residue, expose it to the sun, and then dry it in an oven. After drying, the water content of the wine residue is lower than 0.1wt%;

2) Pulverize and grind the dried lees raw material to make the particle size 1-120 microns;

3) Granulation step: the polymer compound and the above powder are mixed with a twin-screw granulator to obtain a wine residue-based composite material;

4) 3D printing wire preparation steps: extrude the wine residue-based composite material with a wire extruder for 3D printing, and then draw and roll it into an environmentally friendly wire for wine residue-based 3D printing;

When the polymer compound is any one of polyhydroxyalkanoate, polyolefin or PBAT, the drying temperature in step 1) is 175-350°C, and the mixing temperature in step 3) is 145-165°C; when When the polymer compound is PET, the drying temperature in step 1) is 280°C, and the mixing temperature in step 3) is 260-275°C; when the polymer compound is polylactic acid, the drying temperature in step 1) is 195°C °C, the mixing temperature in step 3) is 180-200 °C;

The wine residue-based composite component also includes an additive combination, and the addition amount of the additive combination is less than or equal to 50% of the total mass of the polymer and the wine residue powder; the additive combination includes a compatibilizer, a lubricant, a toughening agent, and an antioxidant. A mixture of any three or more of them; based on the total mass of the polymer compound and the lees powder, the compatibilizer is added in an amount of 0-3.5%; the lubricant is 0-15%; if the toughening agent is used If it is a low molecular toughening agent, its addition amount is 0-2%, if it is a polymer toughening agent, it is 2-40%; the antioxidant is 0-0.5%; the compatibilizer is selected from oxazoline type , acid anhydride type, carboxylic acid type, epoxy type, hydroxyl type, titanate type, silane type, imide type and isocyanate type, any one or a mixture of several, the toughening agent includes low molecular weight and polymer toughening agent, wherein, the low molecular weight toughening agent is selected from DuPont Biomax Strong, BASF ADR4368, BASF ADR4370F; Lactone, polybutylene succinate, thermoplastic polyurethane; the lubricant is selected from paraffin or stearic acid series; the antioxidant is phosphite, alkyl aryl phosphate, tris Any one or a mixture of thioalkyl ester, pentaerythritol ester, dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate and tert-butyl hydroquinone.

2. technique according to claim 1 is characterized in that: described wine dregs is selected from five grains class wine dregs or other wine dregs, and the five grains class is Daqu, Xiaoqu, Tequ, Touqu, Erqu, bran Koji or red yeast, the particle size of which is ≤120 microns.