CN107586441A - A kind of multiple material of schlempe base and the technique for preparing 3D printing wire rod using the multiple material - Google Patents
A kind of multiple material of schlempe base and the technique for preparing 3D printing wire rod using the multiple material Download PDFInfo
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- CN107586441A CN107586441A CN201710971325.8A CN201710971325A CN107586441A CN 107586441 A CN107586441 A CN 107586441A CN 201710971325 A CN201710971325 A CN 201710971325A CN 107586441 A CN107586441 A CN 107586441A
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- schlempe
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Landscapes
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Abstract
The present invention relates to the multiple material of a schlempe base, the multiple material includes following components：40% 90% macromolecules and 10% 60% schlempe material powders, gross mass percentage composition is 100%, and the schlempe basic ring protects multiple material and may also include additive combination, 50% of the addition of additive combination no more than macromolecule and schlempe material powder gross mass.Applied to fabricated product, the wire rod such as on injection-molded product, and 3D printing, specially a kind of schlempe base answers material and 3D printing environmentally friendly wire rod and its preparation method.In the present invention, the addition of schlempe material powder, the theory of resource reclaim recycling is put into practice, reduce the use cost of macromolecule raw material, 3D printing product is had the effect of imitation wood texture, and lift the strength of materials, toughness, crystallinity and crystalline rate, also improve its biodegradable efficiency and biocompatibility in addition, reduce application and the value of environmental protection of bio-toxicity, the multiple material of increase macromolecule and 3D printing wire rod.
Description
Technical field
The invention belongs to the preparation field of engineering material, is related to applied to the environmental protection in fabricated product (injection), 3D printing
Wire rod, the multiple material of specially a kind of schlempe base and the technique for preparing 3D printing wire rod using the multiple material.
Background technology
Due to civilization develop, science and technology progress, cause discarded object more and more more, the pollution of environment also accelerates the whole world
Deterioration, to save the natural resources in the whole world, many more advanced countries in the whole world has established resource reclaim system, and resource is returned
Refuse reclamation is received, it is rotten to turn to mystery.
The annual white wine yield in China is above 1,000 ten thousand tons, and according to traditional poor ratio that goes out, 1 ton of wine can about produce 3 tons
Schlempe amount, in other words, the yield of annual white wine slag is more than 3,000 ten thousand tons.Schlempe is in addition to the application of minority, so far still
It can not effectively be employed, excessive schlempe, landfills can only be treated as mostly, be undoubtedly a kind of pollution to environment.Wine
Research and patent in terms of slag is applied to macromolecule is few, not only can be with if recovery schlempe, which can be efficiently applied to macromolecule, answers material
The problem of reducing environmental pollution, market can also be replaced to create greatly value.
3D printing (3D printing), also referred to as increasing material manufacturing, belong to one kind of RP technique, be one kind with number
Direct manufacturing technology based on word model archives, can almost manufacture arbitrary shape 3D solid, by by successively printing
Mode carry out the technology of constructed object, in a manner of successively stacking accumulation, carry out a kind of manufacturing process of construction object.3D printing
Typically realized using digital technology file printing machine.Often apply in fields such as Making mold, industrial designs.The technology
In Jewelry Accessories, wearing class (such as shoes, cap), building, various engineering constructions, dentistry and medical industries and other field
All applied ... etc..
The molding mode of more typical family expenses 3D printer, used material are most commonly PLA lines on the market at present
Material, ABS wire rods.
Though PLA wire rods have many advantages, such as, its main source is edible corn, under the trend of global warming, food
In the future of thing source shortage, the shortcomings that striving food with the mankind is had, therefore the consumption of resource and cost is not still low, gathers breast in addition
The fragility of sour wire rod is too high, and the excessively slow space that all there is a need to improve of crystalline rate.Therefore seek to reduce poly- sour milk cost,
And its toughness and crystalline rate are lifted, the application value of PLA wire rod can be greatly improved.
ABS is petroleum based material, and except that can consume in addition to the limited resource of the earth, it can give out difficulty in 3D printing
The smell and mild toxicity of news, the dosage of ABS plastic, or the absorbable ABS smells of addition or the raw material of toxicity are reduced, is that it can
To lift values of the ABS in 3D printing technique field.
In view of the above description, how a kind of multiple material of different environmental protection is provided, can be applied to various fabricated products and such as project, or
It is 3D printing wire rod, the dosage of high molecule plastic can be reduced, strives the doubt of food to mitigate with the mankind or reduce petroleum-based energy
Consumption, and multiple material is had the effect of imitation wood texture, to be supplied to the more natural materials options of literary and artistic creation person.It is and domestic
The injection product or 3D printing wire rod of outer current imitation wood, mostly it is used as additive (such as Chinese juniper wood, pine ... by the use of wood powder
Deng), make its 3D printing product that the effect of imitation wood be presented, but the source of these wood powders is expected, it is necessary to fall trees to obtain source,
Such behavior can make global warming phenomenon more violent.
For the foregoing reasons, carried out if compatriots can drink to culture it is a large amount of brewage it is caused a large amount of useless after fermentation
Schlempe recovery is abandoned, the additive after being processed to as the multiple material of macromolecule reduces the cost of material again and reinforcement macromolecule is in itself
The defects of, improve its multiple performance, such as：Crystallinity, crystalline rate, biodegradable speed and biocompatibility, and reduce height
The bio-toxicity of molecule, and then lift the application value of the recycling of discarded schlempe.
The content of the invention
The present invention be based on above technical problem, there is provided a kind of multiple material of schlempe base and prepares 3D printing use using the multiple material
The technique of wire rod.Compatriots are liked caused a large amount of scrap concretes of drinking by the technique, as the multiple material mother of injection after being processed to
Grain, prepare multiple material with macromolecule addition again, reduce its production cost, and the defects of reinforcement macromolecule itself, improve its crystallinity
The application value of the recycling of discarded schlempe, can be lifted.
The concrete technical scheme of the present invention is as follows：
A kind of multiple material of schlempe base, in terms of weight/mass percentage composition, it includes the component of following content：40%-90% is high
Molecular compound and 10%-60% schlempe powder, gross mass percentage composition are 100%, and described high-molecular compound is poly- breast
It is sour (PLA), polyhydroxyalkanoate (PHA), acrylic-butadiene-benzene diene copolymers (ABS), polyolefin, poly- to benzene two
Formate ester is (such as：PET, PTT, PBT, PBAT), polycaprolactone (PCL), any one or a few mixed in polyamide (PA)
Compound or its copolymer；Described schlempe powder refers to：By after brewing fermentation schlempe (espespecially dairy products schlempe, such as：
Daqu, Chinese yeast, Tequ, cephalic flexure, two bent, red yeast rice) cleaned and cleaned, exposure in sunshine, high temperature drying, make after attrition grinding
Into powder, moisture content is less than 0.1wt%.
Also include additive in the multiple material to combine, the addition≤high-molecular compound and schlempe powder of additive combination
The 50% of last gross mass.
The additive combination includes any one or a few in compatilizer, lubricant, toughener, antioxidant
Mixture；In terms of the gross mass of high-molecular compound and schlempe powder, the addition of compatilizer is 0-3.5%；Lubricant is
0-20%；Toughener is 0-2%；Antioxidant is 0-0.5%.
Described compatilizer selects ethylene oxidic ester, oxazoline type, acid anhydrides type, carboxylic acid type, epoxy type, oh type, epoxy type
Response type, metatitanic acid ester type, silane type, imide-type (for modified polyacrylate) and it is isocyanate-based in any one or
Several mixtures.
Described toughener is divided into low molecule toughener and macromolecular toughening agent, and low molecule toughener is selected from
The polymer toughening that is used for of DuPontBiomaxStrong, BASFADR4368, BASFADR4370F or each manufacturer production adds
Agent.Described macromolecular toughening agent is selected from poly terephthalic acid tetramethylene adipate (PBAT), polyester lactone (PCL), poly- fourth
Succinate adipate (PBS), polyvinyl alcohol (PVA) or heat plasticity polyurethane (TPU).
Described lubricant is selected from stearic acid system, paraffin series or plasticizer system.
Described antioxidant is phosphorous acid esters, triarylphosphite, trialkyl phosphite, tri-alkylated virtue
Base phosphate, alkyl aryl phosphate ester, trithio band Arrcostab, bis-phosphite, aggretion type phosphite ester or pentaerythritol ester,
In dibutyl hydroxy toluene, butylated hydroxy anisole, propylgallate, di-t-butyl mixed phenol and tert-butylhydroquinone
Any one or a few mixture.
The technique that 3D printing wire rod is prepared using the multiple material of schlempe base described above, is comprised the following steps：
1) exposure is carried out after schlempe is cleaned in the sun, then carries out oven drying, drying temperature is 100 DEG C -350
DEG C, schlempe moisture content is less than 0.1wt% after drying.；
2) the schlempe raw material after drying is crushed, ground, make particle diameter≤120 micron；
3) granulation step：High-molecular compound and above-mentioned powder are kneaded with dual-screw pelletizer, schlempe base is made
Multiple material；
4) 3D printing wire rod preparation process：By the multiple material of schlempe base, extruded with 3D printing with wire rod extruder, then
Drawing-off and furl turn into the environmentally friendly wire rod of schlempe base 3D printing.
The positive effect of the present invention is embodied in：
(1), in the present invention, the addition of schlempe material powder, the input application for the theory that resource reclaim is recycled, drop
Low high molecular cost, and the factory that can solve the problems, such as to make wine discards schlempe pollution disposal, there is provided literature and art creator or
Engineering producer more naturally reclaims material option.
(2), in the present invention, the addition of schlempe material powder, high molecular mechanical strength can be lifted (such as：Anti-tensile is strong
Degree, impact strength).
(3), in the present invention, the addition of schlempe material powder, high molecular crystallinity and crystalline rate can be lifted.
(4), in the present invention, the addition of schlempe material powder, 3D printing finished product can be made to reach the effect of imitation wood texture.
(5), in the present invention, addition of the schlempe material powder in high molecule plastic, it can partly substitute and be permitted on the market
The wood-like plasticses or 3D printing wire rod added more with wood powder, reduce the destruction to forest.
(6), in the present invention, addition of the schlempe material powder in ABS, PA plastics, treated schlempe powder can be with
The taste that ABS, PA are given out in 3D printing is absorbed, reduces niff.
(7), in the present invention, addition of the schlempe material powder in PLA, PCL, PBAT or PHA plastics, it can be lifted
Biodegradable efficiency, when 3D printing finished product, which damages, to be abandoned, turn of its microorganism decomposition after soil burial can be promoted
Rate, and can be as the nutrient of the growth of crops.
(8), in the present invention, addition of the schlempe material powder in high molecule plastic, it is possible to reduce the life of some plastics
Thing toxicity is (such as：ABS), or increase high molecular biocompatibility, multiple material is had wider range of application such as food material, life
Cure material.
Brief description of the drawings
Fig. 1 is the schematic diagram of heretofore described schlempe base 3D printing wire rod.
Fig. 2 is that the multiple material of schlempe base, the schematic flow sheet of 3D printing wire rod are prepared in the present invention.
Fig. 3 is pure PLA figures compared with the relative crystallinity of the multiple material of schlempe base.
Wherein, 0 --- discarded schlempe, 1 --- schlempe baseline material, 2 --- macromolecule, 3 --- discarded schlempe powder,
4 --- additive combines, and 5 --- the multiple material of schlempe based high molecular, 6 --- the environmentally friendly wire rod of schlempe base 3D printing.Cleaning (100),
Exposure in sunshine and oven for drying (200), grinding (300), melting blending (400), solvent wet type blending (410), machine-shaping
(500)。
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiment pair
The present invention is described in further detail, but the scope that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following implementations
Example.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make each
Kind is replaced and change, all should be included within the scope of the invention.
In present specification, % unless otherwise specified, represents total matter with high-molecular compound and schlempe material powder
Gauge, the wt% shared by it.
Embodiment 1：
A kind of preparation method of the multiple material of schlempe base, comprises the following steps：
(1) prepared by schlempe recovery raw material：
Cleaned up after discarded schlempe after factory's " Daqu " white spirit fermentation of making wine is collected, after cleaning up, in the sun
Exposure 10 hours, it is then dried into 4 hours with 185 DEG C in baking oven, then will be screened to 105-75 after its attrition grinding
Micron (about 150-200 mesh).
(2) the multiple material of schlempe base is prepared
The Daqu spirit of China ground-slag prepared 20%, 40%, 60% is inserted into extruder with PHA, PBAT respectively in varing proportions
In, the compatilizer that another addition accounts for material (PHA or PBAT and schlempe powder gross mass) weight/mass percentage composition 1wt% is (silane coupled
Agent), 1wt% lubricant (paraffin wax) and 0.4wt% antioxidant (triarylphosphite), formed with PHA, PBAT
Thing is blended with double screw extruder jointly, and processing temperature is 145-165 DEG C, and supercooling tank is made after being kneaded processing extrusion
Grain, the multiple material of schlempe base is made；The multiple material samples of obtained PHA are respectively labeled as multiple material 1, multiple material 2, multiple material 3；By what is obtained
The multiple material samples of PBAT are respectively labeled as multiple material 1 ', multiple material 2 ', multiple material 3 '.The material being prepared is subjected to engineering properties test,
Test result difference is as shown in Table 1：
Table one
| Sample | Tensile strength (MPa) | After soil is covered 90 days weightless (%) |
| PHA | 20.1 | 2.3 |
| Multiple material 1 (20%) | 21.7 | 3.1 |
| Multiple material 2 (40%) | 22.5 | 6.8 |
| Multiple material 3 (60%) | 20.3 | 24.3 |
| PBAT | 18.6 | 2.2 |
| Multiple material 1 ' (20%) | 21.5 | 2.9 |
| Multiple material 2 ' (40%) | 20.8 | 5.7 |
| Multiple material 3 ' (60%) | 18.2 | 20.6 |
By result it is known that PHA, PBAT compare with the tensile strength of multiple material is prepared which are added schlempe respectively
Pure PHA, PBAT's will height.
Proved to be further, the addition of schlempe, PHA and PBAT biodegradable property can be lifted, by above-mentioned 8 kinds
Multiple material, carry out soil and bury 90 days, then the weight of scale each sample calculates its weight-loss ratio, by the most right column of table three it is observed that
With the increase of schlempe content, its weightless degree is more obvious, further demonstrate the addition of schlempe, can lift macromolecule
Biological degradation rate.
Embodiment 2：
A kind of preparation method of the multiple material of schlempe base, comprises the following steps：
(1) prepared by schlempe recovery raw material：
After discarded schlempe after factory's fermentation of making wine after distilled liquor is collected, after cleaning up, exposure 12 in the sun
Hour, it is then dried into 4 hours with 185 DEG C in baking oven, then will be screened to 20-25 microns (about after its attrition grinding
500-625 mesh).
(2) the multiple material of schlempe base is prepared
Investigate and add the multiple material intensity that different Xiaoqu wine ground-slag ratios are prepared, first dry ABS in moisture eliminating drying box
Dry 4h, 90 DEG C of moisture eliminating drying box temperature, makes its moisture content be less than 0.1%.The ABS plastic composition after drying is added afterwards
In extruder, schlempe powder (20%, 40%, 60%) will be prepared and mixed with the ABS after water removal, another add accounts for material (ABS and wine
Slag gross mass) weight/mass percentage composition 0.6wt% compatilizer (cyclic acid anhydride), 10% plasticizer (adipate ester) and 0.7%
Antioxidant (KY-02,2,6- di-t-butyl mixed phenols), blended jointly with double screw extruder, processing temperature is
190-220 DEG C, it is kneaded after processing is extruded after tank granulation is subcooled and becomes the multiple material of schlempe base, respectively obtain sample labeled as again
Material 4, multiple material 5, multiple material 6.The material being prepared is subjected to engineering properties row, the test of MTT cytoactives, test result difference
As shown in Table 2
Table two
| Sample | Tensile strength (MPa) | Cell is with respect to proliferation rate (%) |
| ABS | 38.4 | 78.9 |
| Multiple material 4 (20%) | 42.2 | 126.9 |
| Multiple material 5 (40%) | 42.6 | 177.6 |
| Multiple material 6 (60%) | 38.5 | 242.8 |
By result it is known that through different schlempe ratios and the pure ABS of tensile strength ratio of the multiple material of gained after PLA processing
It is high.The right column of table two is to carry out MTT cytoactives method of testing using the cell line of mouse fibroblast (L929) to analyze ABS
The 3rd day result of material vitro cytotoxicity is answered with its schlempe base, by can be seen that ABS has a little microbial poisons in itself in table two
Property (be less than 100%), and as the adding proportion increase of schlempe powder, cytoactive are also and then substantially improved, this is due to schlempe
By possessing the nutrient needed for cell after microbial fermentation, and schlempe may absorb the release of part toxicity so that wine
Slag base ABS is multiple, and material does not have outside bio-toxicity not only, also add cytoactive.
Embodiment 3：
A kind of preparation method of the multiple material of the biodegradable schlempe base for having high intensity, comprises the following steps：
(1) prepared by schlempe raw material：
After factory of making wine to be made to the discarded schlempe collection after " Daqu " white spirit, after cleaning up, exposure 48 is small in the sun
When, it is then dried into 10 hours with 195 DEG C in baking oven, then will be screened to 15-25 microns (about after its attrition grinding
500-900 mesh).
(2) has the multiple material of the biodegradable schlempe base of high intensity
PLA is carried out to dry 4h, 85 DEG C of moisture eliminating drying box temperature, -40 DEG C of dew-point temperature in moisture eliminating drying box.It will prepare
Good schlempe raw material mixes from the PLA after water removal and then with different schlempe ratios (10%, 20%, 40%, 60%), another to add
Account for material (PLA and schlempe slag gross mass) weight/mass percentage composition 1.5wt% compatilizer (GMA),
3% lubricant (plasticiser-adipate ester), 0.15% attapulgite, 1.5% toughener (DuPontBiomaxStrong)
And 0.5% antioxidant (bis-phosphite), blended jointly with double screw extruder, processing temperature 180-200
DEG C, it is kneaded after processing extrusion to be subcooled after tank is granulated and becomes the multiple material of schlempe base, sample will be obtained and be respectively labeled as multiple material 7, multiple
Material 8, multiple material 9, multiple material 10, multiple material 11.The material being prepared is subjected to engineering properties, crystallinity, surveyed with Biodegradable
Examination, test result difference is as shown in Table 3：
Table three
By result it is known that the tensile strength of material and impact resistance are strong again for gained after different schlempe ratios are processed with PLA
Degree is higher than pure PLA, and the impact strength of the multiple material of especially all schlempes is above as many as PLA6-7 times；It is in addition, all
The crystallinity of the multiple material of schlempe is also higher than pure PLA crystallinity 2-3 times.PLA biodegradable efficiency is also with schlempe content
Increase and be obviously improved.
PLA crystalline rate is relatively slow, is proved to be further, the addition of schlempe, can lift PLA crystalline rate,
By PLA, multiple material 8 (20%), multiple material 9 (40%) and the above-mentioned 4 kinds of 3D printing wire rods of material 10 (60%) are answered with DSC Instrumental Analysis,
As shown in Figure 3, for thermostat temperature in 112 DEG C of crystalline rate figure, pure PLA crystalline rate is very slow, even across 5
Minute, PLA still not yet starts to crystallize, and after addition discarded recovery raw material, its crystalline rate is substantially improved, wherein with schlempe base
The crystalline rate of (multiple material 9) is most fast, completes crystallization within about 2 minutes.
Embodiment 4：
A kind of preparation method for having the multiple material of high tenacity, biodegradability schlempe base, comprises the following steps：
(1) prepared by schlempe raw material：
After factory of making wine to be made to the discarded schlempe collection after " Daqu " white spirit, after cleaning up, exposure 48 is small in the sun
When, it is then dried into 10 hours with 185 DEG C in baking oven, then will be screened to 30-45 microns (about after its attrition grinding
325-460 mesh).
(2) have high tenacity, biodegradability schlempe base 3D printing wire rod
PLA is carried out to dry 4h, 85 DEG C of moisture eliminating drying box temperature, -40 DEG C of dew-point temperature in moisture eliminating drying box.Afterwards will
PLA and PHA after drying is with 8：2 ratio mixes, by the schlempe powder prepared and PLA/PHA blends, then with not
Mixed with schlempe ratio (20%, 40%, 60%), another add accounts for material (PLA/PHA blends and schlempe gross mass) quality hundred
Point content 0.5wt% compatilizer (titanate coupling agent), 5% plasticiser (tributyl 2-acetylcitrate), jointly with double spiral shells
Bar extruder is blended, and processing temperature is 180-200 DEG C, is kneaded supercooling tank after processing is extruded and is become schlempe after being granulated
The multiple material of base, obtained sample is respectively labeled as multiple material 11, multiple material 12, multiple material 13.The material being prepared is subjected to mechanicalness
Matter is tested, and test result difference is as shown in Table 4：
Table four
| Sample | Tensile strength (MPa) | Impact strength (J/m) |
| PLA/PHA(8：2) | 36.2 | 47.8 |
| Multiple material 11 (20%) | 47.9 | 202.5 |
| Multiple material 12 (40%) | 48.5 | 208.1 |
| Multiple material 13 (60%) | 44.3 | 212.4 |
By result it is known that the tensile strength of multiple material obtained by after different schlempe ratios and the processing of PLA/PHA blends
It is more considerably higher than simple PLA/PHA blends with impact strength.
Embodiment 5：
Have the preparation method of the multiple material of high tenacity, biodegradability schlempe base, comprise the following steps：
(1) prepared by schlempe raw material：
After factory of making wine to be made to the discarded schlempe collection after " Daqu " white spirit, after cleaning up, exposure 48 is small in the sun
When, it is then dried into 10 hours with 175 DEG C in baking oven, then will be screened to 30-45 microns (about after its attrition grinding
325-460 mesh).
(2) have high tenacity, the 3D printing wire rod of biodegradability schlempe base
PLA is carried out to dry 4h, 85 DEG C of moisture eliminating drying box temperature, -40 DEG C of dew-point temperature in moisture eliminating drying box.Afterwards will
PLA after drying, mixed by the schlempe powder and PLA that prepare and then with different schlempe ratios (20%, 40%, 60%), it is another to add
Enter to account for material (PLA and schlempe gross mass) weight/mass percentage composition 1wt% compatilizer (titanate coupling agent), 12% plasticizing
Agent (tributyl 2-acetylcitrate), two kinds of macromolecular toughening agent totally 40%, 12% macromolecular toughening agent (TPU) and 28% high
Molecule toughener (PBAT), is blended with double screw extruder jointly, and processing temperature is 175-205 DEG C, is kneaded processing and is squeezed
It is subcooled after going out after tank is granulated and becomes the multiple material of schlempe base, obtained sample is respectively labeled as multiple material 14, multiple material 15, multiple material
16.The material being prepared is subjected to engineering properties test, test result difference is as shown in Table 5：
Table five
| Sample | Impact strength (J/m) | Fracture elongation (%) |
| PLA | 20.4 | 3.9 |
| Multiple material 14 (20%) | 376.9 | 280.6 |
| Multiple material 15 (40%) | 342.1 | 225.7 |
| Multiple material 16 (60%) | 294.8 | 190.5 |
By result it is known that gained possesses the impact resistance of the multiple material of superhigh tenacity after different schlempe ratios and PLA processing
Intensity and fracture elongation it is more considerably higher than pure PLA go out many, especially impact strength is higher by about 15-18 times than pure PLA.
Embodiment 6：
A kind of preparation method of the multiple material of schlempe base, comprises the following steps：
(1) prepared by schlempe raw material：
After factory of making wine to be made to the discarded schlempe collection after distilled liquor, after cleaning up, exposure 48 is small in the sun
When, it is then dried into 10 hours with 175 DEG C in baking oven, then will be screened to 30-45 microns (about after its attrition grinding
325-460 mesh).
(2) preparation of the multiple material of schlempe base：
The schlempe raw material different proportion (20%, 40%, 60%) prepared is mixed with high density polyethylene, separately
Addition accounts for the maleic anhydride grafted polyethylene (PE-g- of material (HDPE and schlempe gross mass) weight/mass percentage composition 10%
MAH), 1% lubricant (plasticiser-ATBC) and 0.4% antioxidant (antioxidant
1010), blended jointly with double screw extruder, processing temperature is 145-165 DEG C, and tank is subcooled after being kneaded processing extrusion
The multiple material of schlempe base is become after granulation, obtained sample is respectively labeled as multiple material 17, multiple material 18, multiple material 19.It will be prepared
Material carry out engineering properties test, test result respectively as shown in Table 6：
Table six
| Sample | Tensile strength (MPa) | Crystallinity (%) | Cell is with respect to proliferation rate (%) |
| HDPE | 28.5 | 76.4 | 113.4 |
| Multiple material 17 (20%) | 32.8 | 79.6 | 198.3 |
| Multiple material 18 (40%) | 29.3 | 81.2 | 267.9 |
| Multiple material 19 (60%) | 26.1 | 80.5 | 313.5 |
By result it is known that after different schlempe ratios and HDPE processing in the tensile strength of the multiple material of gained, except
Outside 60% schlempe content is more lower slightly than HDPE, the multiple material of other schlempe contents is also higher than HDPE.The right column of table six is to utilize L929's
Cell line carries out MTT cytoactives method of testing to test HDPE and the multiple material vitro cytotoxicity of its schlempe the 3rd day result, by
HDPE can be learnt as the content of schlempe powder increases and its cytoactive is substantially improved in table
Embodiment 7：
A kind of preparation method of the multiple material of schlempe base, comprises the following steps：
(1) prepared by schlempe raw material：
After factory of making wine to be made to the discarded schlempe collection after distilled liquor, after cleaning up, exposure 48 is small under sun
When, it is then dried into 10 hours with 280 DEG C in baking oven, then will be screened to 30-45 microns (about after its attrition grinding
325-460 mesh).
(2) has the multiple material of schlempe base
The schlempe raw material different proportion (15%, 35%, 55%) prepared is mixed with PET, another add accounts for material (PET
With schlempe gross mass) maleic anhydride of weight/mass percentage composition 12% grafting PET (PET-g-MAH), 3% lubricant be (stearic
Acid) and 0.4% antioxidant (antioxidant 1010), blended jointly with double screw extruder, processing temperature is
260-275 DEG C, it is kneaded after processing is extruded after tank granulation is subcooled and becomes the multiple material of schlempe base, sample will be obtained and be respectively labeled as
Multiple material 20, multiple material 21, multiple material 22.The material being prepared is subjected to engineering properties test, test result is respectively such as the institute of table seven
Show：
Table seven
| Sample | Tensile strength (MPa) | Crystallinity (%) |
| PET | 32.1 | 12.7 |
| Multiple material 20 (15%) | 34.3 | 34.1 |
| Multiple material 21 (35%) | 33.5 | 37.8 |
| Multiple material 22 (55%) | 32.2 | 38.4 |
By result it is known that the tensile strength of the multiple material of gained and crystallinity are equal after different schlempe ratios are processed with PET
It is higher than pure PET.
Embodiment 8：
Have the preparation method of the multiple material of low melting point, high tenacity, biodegradability schlempe base, comprise the following steps：
(1) prepared by schlempe raw material：
After factory of making wine to be made to the discarded schlempe collection after " Daqu " white spirit, after cleaning up, exposure 48 is small under sun
When, it is then dried into 10 hours with 105 DEG C in baking oven, then will be screened to 30-45 microns after its attrition grinding
(325-460 mesh).
(2) have the multiple material of low melting point, high tenacity, biodegradability schlempe base and the environmentally friendly wire rod of 3D printing
The schlempe raw material different proportion (15%, 35%, 55%) prepared is mixed with PCL, another add accounts for material (PCL
With schlempe gross mass) maleic anhydride of weight/mass percentage composition 12.5% grafting PCL (PCL-g-MAH), 2% lubricant (increase
Mould agent system-stearic acid) and 0.4% antioxidant (antioxidant 1010), blended jointly with double screw extruder,
Processing temperature is 75-85 DEG C, is kneaded supercooling tank after processing is extruded and the multiple material of schlempe base is become after being granulated, will obtain sample point
Biao Ji not be material 23, multiple material 24, multiple material 25.The material being prepared is subjected to engineering properties test, test result is respectively such as
Shown in table eight：
Table eight
By result it is known that the tensile strength of material, impact resistance are strong again for gained after different schlempe ratios are processed with PCL
Degree is more high than pure PCL with biodegradation rate.
Embodiment 9：
The preparation method of the multiple material of discarded object and bio-toxicity comparative experiments：
(1) prepared by schlempe, coffee grounds, rice husk raw material：
After Daqu schlempe, coffee grounds, rice husk are collected, be respectively processed, that is, after cleaning up, exposure in the sun
48 hours, it is then dried into 10 hours with 185 DEG C in baking oven, then will be screened to 30-45 microns after its attrition grinding
(325-460 mesh).
(2) the multiple material of discarded object
PLA is carried out to dry 4h, 85 DEG C of moisture eliminating drying box temperature, -40 DEG C of dew-point temperature in moisture eliminating drying box.It will prepare
Good schlempe powder, powdered rice hulls, coffee grounds powder raw material, are mixed with the PLA after water removal respectively, with different discarded object ratios (20%,
40%th, 60%) mix, it is another to add the compatilizer (first for accounting for material (PLA and discarded object gross mass) weight/mass percentage composition 1.5wt%
Base glycidyl acrylate), 3% lubricant (plasticiser-ATBC), 1.2% toughener
(DuPontBiomaxStrong) and 0.4% antioxidant (bis-phosphite), mixed jointly with double screw extruder
Mixed, processing temperature is 180-200 DEG C, is subcooled after kneading processing extrusion after tank is granulated and becomes schlempe base material again, will obtained
The multiple material sample of schlempe base is respectively labeled as multiple material 26, multiple material 27, multiple material 28；The multiple material sample of rice husk will be obtained to be respectively labeled as again
Material 26 ', multiple material 27 ', multiple material 28 '；The multiple material sample of coffee grounds will be obtained in addition is respectively labeled as multiple material 26 ", multiple material 27 ", multiple
Material 28 ".Above-mentioned preparation-obtained three kinds multiple materials are subjected to MTT cytoactive methods of testing respectively, test result is respectively such as table nine
It is shown：
Table nine
Table nine is that to test three kinds of discarded objects, material is external again using L929 cell line progress MTT cytoactives method of testing
3rd day result of cytotoxicity, by can be seen that PLA has splendid biocompatibility in itself in table nine, and with schlempe powder
Adding proportion increase, cytoactive is and then substantially improved, and this is due to that schlempe is fermentation by microorganism, therefore is possessed
The nutrition needed for L929 cells can be provided so that schlempe base PLA is multiple, and material improves cytoactive.In addition, when PLA with
The content increase of powdered rice hulls, its cytoactive only has lifting slightly；However, after PLA adds coffee grounds, its cell is lived
Property reduced with the lifting of coffee grounds content, this should be due to that caffeine contained in coffee grounds has biology slightly
Caused by toxicity.
All multiple materials being prepared in above example, can be extruded, so with 3D printing with wire rod extruder again
First break draft and furl applied as the 3D printing of schlempe base with environmentally friendly wire rod, it is possessed more extensive purposes.
Example described above is only the preferred embodiment of this patent, but the protection domain of this patent is not limited thereto.
It should be pointed out that for those skilled in the art, on the premise of this patent principle is not departed from, according to this
The technical scheme and its inventional idea of patent, can also make some improvements and modifications, and these improvements and modifications also should be regarded as this
The protection domain of patent.
Claims (10)
1. the multiple material of a kind of schlempe base, it is characterised in that include the component of following weight/mass percentage composition：40%-90% high-molecular compounds
With 10%-60% schlempes, gross mass percentage composition is 100%, and described schlempe is：By the discarded schlempe after brewing fermentation it is cleaned,
Manufactured powder after exposure in sunshine, high temperature drying, attrition grinding.
2. the multiple material of schlempe base according to claim 1, it is characterised in that：Described high-molecular compound is PLA, gathered
It is any in hydroxy fatty acid, acrylic-butadiene-benzene diene copolymers, polyolefin, polyester terephthalate class, polyamide
The copolymer of one or more of mixtures.
3. the multiple material of schlempe base according to claim 1, it is characterised in that the multiple material component of the schlempe base also includes additive and combined,
Addition≤macromolecule of additive combination and the 50% of schlempe powder gross mass.
4. the multiple material of schlempe base according to claim 3, it is characterised in that：The additive combination includes compatilizer, lubrication
Any one or a few mixture in agent, toughener, antioxidant；With the gross mass of high-molecular compound and schlempe powder
Meter, the addition of compatilizer is 0-3.5%；Lubricant is 0-15%；Toughener is according to low molecule toughener, its addition
It is then 2-40% if macromolecular toughening agent for 0-2%；Antioxidant is 0-0.5%.
5. the multiple material of schlempe base according to claim 1, it is characterised in that：Described schlempe be selected from dairy products schlempe or
Other schlempes, dairy products are Daqu, Chinese yeast, Tequ, cephalic flexure, two bent, wheat brans or red yeast rice, its particle diameter≤120 micron.
6. the multiple material of schlempe base according to claim 4, it is characterised in that：Described compatilizer is selected from oxazoline type, acid anhydrides
Type, carboxylic acid type, epoxy type, oh type, epoxy type response type, metatitanic acid ester type, silane type, imide-type and it is isocyanate-based in
Any one or a few mixture, wherein, imide-type is modified polyacrylate.
7. the multiple material of schlempe base according to claim 4, it is characterised in that：Described toughener includes low molecule and macromolecule
Toughener, wherein, low molecule toughener is selected from DuPont Biomax Strong, BASF ADR4368, BASF
ADR4370F；Described macromolecular toughening agent is poly terephthalic acid tetramethylene adipate, polycaprolactone, poly-succinic fourth two
Alcohol ester, heat plasticity polyurethane.
8. the multiple material of schlempe base according to claim 4, it is characterised in that：Described lubricant is selected from paraffin series, stearic acid
System or plasticizer system.
9. the multiple material of schlempe base according to claim 4, it is characterised in that：Described antioxidant is phosphorous acid esters, three virtues
Base phosphite ester, trialkyl phosphite, tri-alkylated aryl phosphate ester, alkyl aryl phosphate ester, trithio band Arrcostab, double Asias
Phosphate, aggretion type phosphite ester or pentaerythritol ester, dibutyl hydroxy toluene, butylated hydroxy anisole, propylgallate
With any one or a few the mixture in tert-butylhydroquinone.
10. the multiple material of the schlempe base as described in any one claim in claim 1 to claim 9 prepares 3D and beaten using one kind
The technique of print wire rod, it is characterised in that comprise the following steps：1）Exposure is carried out after schlempe is cleaned in the sun, then is dried
Case is dried, and drying temperature is 100 DEG C -350 DEG C, and schlempe moisture content is less than 0.1wt% after drying；2）By the schlempe raw material after drying
Crushed, ground, make particle diameter≤120 micron >=1 micron；3）Granulation step：High-molecular compound and above-mentioned powder are used double
Screw pelletizer is kneaded, and the multiple material of schlempe base is made；4）3D printing wire rod preparation process：Schlempe base is answered into material, with 3D printing
Extruded with wire rod extruder, then drawing-off and furl turn into the environmentally friendly wire rod of schlempe base 3D printing.
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| IT201900022884A1 (en) * | 2019-12-03 | 2020-03-03 | Univ Degli Studi Di Modena E Reggio Emilia | Composite material consisting of a biofiller and a thermoplastic matrix and process for making an article with such a composite material |
| CN113831704A (en) * | 2021-08-10 | 2021-12-24 | 珠海市三绿实业有限公司 | Biodegradable PHA composite material for 3D printer consumable and preparation method thereof |
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| CN113831704A (en) * | 2021-08-10 | 2021-12-24 | 珠海市三绿实业有限公司 | Biodegradable PHA composite material for 3D printer consumable and preparation method thereof |
| CN113861710A (en) * | 2021-09-01 | 2021-12-31 | 四川轻化工大学 | Antibacterial raw material powder, antibacterial wood-plastic composite material and preparation method thereof |
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