CN106700590A - Crop straw 3D printing material - Google Patents
Crop straw 3D printing material Download PDFInfo
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- CN106700590A CN106700590A CN201611156202.0A CN201611156202A CN106700590A CN 106700590 A CN106700590 A CN 106700590A CN 201611156202 A CN201611156202 A CN 201611156202A CN 106700590 A CN106700590 A CN 106700590A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention discloses a crop straw 3D printing material, and belongs to the technical field of 3D printing material preparation. The crop straw 3D printing material comprises the following raw materials in parts by weight: 82-124 parts of crop straw powder, 32-48 parts of polylactic acid, 18-26 parts of sodium tripolyphosphate, 22-28 parts of n-butyl acetate, 15-22 parts of a specific synthesis agent and 6-12 parts of a starch synthesis agent. The crop straw 3D printing material disclosed by the invention is very good in toughness and impact resistance, and a product printed by using a 3D printing technique is high in quality, good in impact resistance, high in strength, free of toxin, low in carbon content, good in environmental friendliness and low in cost, has the color of wood, can be recycled and has very high economic values and wide market prospects.
Description
【Technical field】
The invention belongs to 3D printing technical field of material, and in particular to a kind of agricultural crop straw 3D printing material.
【Background technology】
One kind of 3D printing, i.e. rapid shaping technique, it is a kind of based on mathematical model file, with powdered gold
Category or agricultural crop straw etc. can jointing material, come the technology of constructed object by way of successively printing.3D printing is typically to adopt
Realized with digital technology file printing machine, be often used for modeling in fields such as Making mold, industrial designs, after gradually
For the direct manufacture of some products, there is a parts printed using this technology, the technology jewelry, footwear,
Industrial design, building, engineering and construction (AEC), automobile, Aero-Space, dentistry and medical industries, education, GIS-Geographic Information System,
Civil engineering, gun and other field have all been applied.Although 3D printing technique has above-mentioned technical advantage, from it
For its aspect, there is certain inferior position again, emphasis is embodied in material aspect, it may be said that be a very big short slab, material
Kind is poor, expensive, directly governs overall development.From for technical standpoint, 3D printing is not that a profundity is difficult
Technology, it is that printed material with the difference of common print.The Object of Israel is the company for grasping most printed materials,
It can using 14 kinds of stocks and on this basis it is mashed up go out 107 kinds of materials, two kinds of mashed up use, colourings of material
Also have been carried out.But, these material categorys also differ greatly compared with routine use material, moreover, these materials
Cheap hundreds of yuan one kilogram, expensive wants 40,000 yuan or so.Chinese recent two decades come due to coal, electricity, natural gas it is general
And, various industrial products it is abundant, rural area is reduced to the demand of agricultural crop straw, and agricultural crop straw is processed into order to one is tight
The social concern of weight, many still direct burning crop straws in the ground of place peasants, triggers air pollution, fire, aircraft
Cannot the consequence such as Normal Take-Off And Landing.Agricultural crop straw 3D printing material not only low production cost, also reduces the discharge capacity of carbon dioxide.
According to the carbon dioxide row that annual 22400t can be reduced about investigation production 14000t agricultural crop straw 3D printing materials
Put.Agricultural crop straw is reclaimed, the waste of crop genetic resource is solved, 3D printing material is translated into.By 3D printing will " in
State manufactures " it is changed into " Chinese intelligence is made ", the friendly economic development policy of China's sustainable developing environment is adapted to, with across epoch weights
Want meaning；To actively practicing innovation, coordination, green, open, shared idea of development, around industrial transformation upgrading, performance science and technology
Innovate the support leading action to socio-economic development, play the decisive role and enterprise's skill of market construction technological innovation resource
The effect of art Innovation Main Body has positive effect.
Existing 3D printing consumptive material is all mostly based on Petroleum refining high molecular polymer, for example：ABS、PP、PE、
Nylon, HIPS, PC belong to non-degradable material, and discarded 3D printing material or product will cause huge bearing to ecological environment
Load, develops a kind of degradable 3D printing material that can make full use of waste agronomic crop, can both make full use of the by-product of crops
Product stalk, can make the material after printing not cause white pollution to ecological environment because of discarding as degradation material again.
Patent CN102153801A discloses a kind of straw plastic and its production method, publication date：August 17 in 2011
Day, disclose appointing in stalk material and polyethylene, polypropylene, polystyrene or acrylonitrile-butadiene-styrene copolymer
Meaning at least one carries out blending extrusion granulation, and its material can be as blowing, pulling-on piece, injection, due to the raw material stalk that it is used
The larger requirement that can not be adapted to 3D printing extruder head of powder.
Patent CN103013150A discloses a kind of straw plastic and its production method for producing building product, open
Date：On April 3rd, 2013, disclose and granulated after stalk and other plastics are carried out into blending and modifying, its product is used primarily in production
The building product such as french drain, draining.But because its product can not use for a long time can not be adapted to the requirement of 3D printing, product is 180
Performance is lost after it and is gradually disintegrated.It is poor that its particle adds talcum powder, the toughness of diatomite product, intensity, it is impossible to
Meet 3D printing consumptive material and prepare winding.
Patent CN104312119A discloses a kind of stalk 3D printing consumptive material and preparation method thereof, and formula includes following quality
The raw material of ratio：PLA 40%-69%, stalk powder 30%-59%, compatilizer 0%-5% and other auxiliary agents 0.2%-3%,
But there is the shortcoming of the poor-performings such as toughness, impact strength, anti-impact in the stalk 3D printing consumptive material.
【The content of the invention】
The present invention provides a kind of agricultural crop straw 3D printing material, with solve existing stalk 3D printing consumptive material exist toughness,
The problems such as poor-performings such as impact strength, anti-impact.The material that the present invention is made has good toughness, impact strength, by 3D
Product high-quality, high-impact, high intensity, nontoxic, low-carbon environment-friendly, low cost that printing technique is printed, with wooden color and luster,
It is recyclable to recycle, there is economic worth and wide market prospects very high.
To solve above technical problem, the present invention uses following technical scheme：
A kind of agricultural crop straw 3D printing material, in units of weight portion, including following raw material：Stalk powder 82-124
Part, PLA 32-48 parts, sodium tripolyphosphate 18-26 parts, butyl acetate 22-28 parts, specific synthetics 15-22 parts, Starch synthesis
Agent 6-12 parts；
The specific synthetics is in units of weight portion, including following raw material：Conditioning agent 13-19 parts, propellant 10-16
Part, 9-14 parts of coupling agent a, surfactant 2-4 parts, compatilizer 13-15 parts, 8-14 parts of plasticizer a, antioxidant 8-12 parts,
Flocculation agent 6-8 parts, terminator 4-6 parts；
The Starch synthesis agent is in units of weight portion, including following raw material：Starch 80-130 parts, dimethyl glutarate
10-16 parts, DMA 8-13 parts, 2-5 parts of epoxy chlorobutane, urea 1.5-3.5 parts, paste agent 1-2 parts, coupling
0.2-0.6 parts of agent b, initiator 0.1-0.2 parts, catalyst 0.1-0.2 parts, stabilizer 0.1-0.3 parts, defoamer 0.3-0.8
Part, 0.4-0.9 parts of plasticizer b, toughener 0.3-0.7 parts, tackifier 0.3-0.6 parts, water-proofing agent 0.2-0.4 parts, antiseptic
0.1-0.2 parts；
The coupling agent b is 2,5- dimethyl -2, double (benzoyl the peroxide)-hexanes of 5-；
The initiator is the isobutyric acid of azo two (acrylic acid ethylene glycol) ester；
The catalyst is platinum catalyst；
The stabilizer is organic tin stabilizer；
The defoamer is polyoxyethylene polyoxypropylene pentaerythrite ether；
The plasticizer b is citrate；
The toughener is poly- propylene diene rubber；
The tackifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antiseptic is lithium carbonate；
The preparation method of described agricultural crop straw 3D printing material, comprises the following steps：
S1：The crushed stalk that will be selected, crosses 80-100 mesh sieve, and powder is obtained, and the powder dries 2- at 83-94 DEG C
3h, control moisture is obtained primary raw material stalk powder below 0.05%；
S2：To in primary raw material stalk powder obtained in step S1 add PLA, sodium tripolyphosphate, butyl acetate,
Specific synthetics, is warming up to 164-208 DEG C, is stirred in the case where rotating speed is 100-300r/min and melts 2-4h, is subsequently cooled to room temperature,
Modified stalk 3D printing secondary-material is obtained；
The preparation method of the specific synthetics, comprises the following steps：
S21：Propellant, coupling agent a, compatilizer, antioxidant are mixed and is warming up to 117-128 DEG C, be 100- in rotating speed
68-82min is reacted under 200r/min, material A is obtained；
S22：To adding conditioning agent, flocculation agent to be warming up to 143-156 DEG C after mixing in material A obtained in step S21, turning
Speed is obtained material B to react 145-232min under 300-400r/min；
S23：108-125 DEG C is cooled to after mixing to addition plasticizer a, terminator in material B obtained in step S22,
Rotating speed is obtained specific synthetics to react 62-135min under 200-300r/min；
S3：Crushed at being -90--110 DEG C in temperature by the stalk 3D printing secondary-material being modified obtained in step S2, plus
Enter Starch synthesis agent to be well mixed, well mixed mixture be put into screw extruding forming machine, be 170-200 DEG C in temperature,
Under rotating speed is 102-116r/min, through extruding strand, agricultural crop straw 3D printing material is obtained；
The preparation method of the Starch synthesis agent, comprises the following steps：
S31：Compound concentration is 18-25Be ', and pH value is the starch slurry a of 3.1-3.8；
S32：It is dimethyl glutarate, the N of 4%-8%, N- diformazans to concentration is added in starch slurry a obtained in step S31
Yl acetamide, coupling agent b, catalyst, are then 42-58 DEG C in temperature, and speed of agitator connects to carry out crosslinking under 70-100r/min
Branch reaction 2.5-3.5h, is obtained slurry b；
S33：To paste agent is added in slurry b obtained in step S32, regulation pH value is 9.1-9.8, is subsequently added into epoxy chlorine
Butane, urea, initiator, plasticizer b, toughener, tackifier, water-proofing agent, antiseptic, are then 55-61 DEG C in temperature, stirring
Rotating speed is obtained slurry c to carry out cross-linking reaction 1.2-1.8h under 80-120r/min；
S34：Stabilizer will be added in slurry c obtained in step S33, regulation pH value is 8.3-8.5, is warming up to 73-77 DEG C,
Gelatinization 50-55min, gelatinization is down to 30-33 DEG C after terminating, add defoamer, and 8- is stirred in the case where rotating speed is 90-130r/min
12min, is obtained Starch synthesis agent.
Preferably, the conditioning agent is conditioning agent ACR.
Preferably, the propellant is aerogel generating agent.
Preferably, the coupling agent a is coupling agent kh570.
Preferably, surfactant is sodium sulfate of polyethenoxy ether of fatty alcohol.
Preferably, the compatilizer is modified polyacrylate.
Preferably, the plasticizer a is diisooctyl phthalate.
Preferably, the antioxidant is anti-oxidant DLTP.
Preferably, the flocculation agent is aluminium polychloride.
Preferably, the terminator is p-tert-Butylcatechol.
The invention has the advantages that：
(1) the agricultural crop straw 3D printing material that the present invention is made has good toughness, impact strength, by 3D printing
Product high-quality, high-impact, high intensity that technology is printed, with wide market prospects；
(2) the agricultural crop straw 3D printing material that the present invention is made has wooden color and luster, is recycled and recycles, nontoxic,
Low-carbon environment-friendly, low cost, it is easy to industrialized production.
【Specific embodiment】
For ease of more fully understanding the present invention, it is illustrated by following examples, these embodiments belong to of the invention
Protection domain, but do not limit the scope of the invention.
In embodiment, the agricultural crop straw 3D printing material, in units of weight portion, including following raw material：Stalk
Powder 82-124 parts, PLA 32-48 parts, sodium tripolyphosphate 18-26 parts, butyl acetate 22-28 parts, specific synthetics 15-22
Part, 6-12 parts of Starch synthesis agent；
The specific synthetics is in units of weight portion, including following raw material：Conditioning agent 13-19 parts, propellant 10-16
Part, 9-14 parts of coupling agent a, surfactant 2-4 parts, compatilizer 13-15 parts, 8-14 parts of plasticizer a, antioxidant 8-12 parts,
Flocculation agent 6-8 parts, terminator 4-6 parts；
The conditioning agent is conditioning agent ACR；
The propellant is aerogel generating agent；
The coupling agent a is coupling agent kh570；
Surfactant is sodium sulfate of polyethenoxy ether of fatty alcohol；
The compatilizer is modified polyacrylate；
The plasticizer a is diisooctyl phthalate；
The antioxidant is anti-oxidant DLTP；
The flocculation agent is aluminium polychloride；
The terminator is p-tert-Butylcatechol；
The Starch synthesis agent is in units of weight portion, including following raw material：Starch 80-130 parts, dimethyl glutarate
10-16 parts, DMA 8-13 parts, 2-5 parts of epoxy chlorobutane, urea 1.5-3.5 parts, paste agent 1-2 parts, coupling
0.2-0.6 parts of agent b, initiator 0.1-0.2 parts, catalyst 0.1-0.2 parts, stabilizer 0.1-0.3 parts, defoamer 0.3-0.8
Part, 0.4-0.9 parts of plasticizer b, toughener 0.3-0.7 parts, tackifier 0.3-0.6 parts, water-proofing agent 0.2-0.4 parts, antiseptic
0.1-0.2 parts；
The coupling agent b is 2,5- dimethyl -2, double (benzoyl the peroxide)-hexanes of 5-；
The initiator is the isobutyric acid of azo two (acrylic acid ethylene glycol) ester；
The catalyst is platinum catalyst；
The stabilizer is organic tin stabilizer；
The defoamer is polyoxyethylene polyoxypropylene pentaerythrite ether；
The plasticizer b is citrate；
The toughener is poly- propylene diene rubber；
The tackifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antiseptic is lithium carbonate；
The preparation method of described agricultural crop straw 3D printing material, comprises the following steps：
S1：The crushed stalk that will be selected, crosses 80-100 mesh sieve, and powder is obtained, and the powder dries 2- at 83-94 DEG C
3h, control moisture is obtained primary raw material stalk powder below 0.05%；
S2：To in primary raw material stalk powder obtained in step S1 add PLA, sodium tripolyphosphate, butyl acetate,
Specific synthetics, is warming up to 164-208 DEG C, is stirred in the case where rotating speed is 100-300r/min and melts 2-4h, is subsequently cooled to room temperature,
Modified stalk 3D printing secondary-material is obtained；
The preparation method of the specific synthetics, comprises the following steps：
S21：Propellant, coupling agent a, compatilizer, antioxidant are mixed and is warming up to 117-128 DEG C, be 100- in rotating speed
68-82min is reacted under 200r/min, material A is obtained；
S22：To adding conditioning agent, flocculation agent to be warming up to 143-156 DEG C after mixing in material A obtained in step S21, turning
Speed is obtained material B to react 145-232min under 300-400r/min；
S23：108-125 DEG C is cooled to after mixing to addition plasticizer a, terminator in material B obtained in step S22,
Rotating speed is obtained specific synthetics to react 62-135min under 200-300r/min；
S3：Crushed at being -90--110 DEG C in temperature by the stalk 3D printing secondary-material being modified obtained in step S2, plus
Enter Starch synthesis agent to be well mixed, well mixed mixture be put into screw extruding forming machine, be 170-200 DEG C in temperature,
Under rotating speed is 102-116r/min, through extruding strand, agricultural crop straw 3D printing material is obtained；
The preparation method of the Starch synthesis agent, comprises the following steps：
S31：Compound concentration is 18-25Be ', and pH value is the starch slurry a of 3.1-3.8；
S32：It is dimethyl glutarate, the N of 4%-8%, N- diformazans to concentration is added in starch slurry a obtained in step S31
Yl acetamide, coupling agent b, catalyst, are then 42-58 DEG C in temperature, and speed of agitator connects to carry out crosslinking under 70-100r/min
Branch reaction 2.5-3.5h, is obtained slurry b；
S33：To paste agent is added in slurry b obtained in step S32, regulation pH value is 9.1-9.8, is subsequently added into epoxy chlorine
Butane, urea, initiator, plasticizer b, toughener, tackifier, water-proofing agent, antiseptic, are then 55-61 DEG C in temperature, stirring
Rotating speed is obtained slurry c to carry out cross-linking reaction 1.2-1.8h under 80-120r/min；
S34：Stabilizer will be added in slurry c obtained in step S33, regulation pH value is 8.3-8.5, is warming up to 73-77 DEG C,
Gelatinization 50-55min, gelatinization is down to 30-33 DEG C after terminating, add defoamer, and 8- is stirred in the case where rotating speed is 90-130r/min
12min, is obtained Starch synthesis agent.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of agricultural crop straw 3D printing material, in units of weight portion, including following raw material：Broad bean stalk powder 152
Part, 40 parts of PLA, 22 parts of sodium tripolyphosphate, 25 parts of butyl acetate, 18 parts of specific synthetics, 9 parts of Starch synthesis agent；
The specific synthetics is in units of weight portion, including following raw material：16 parts of conditioning agent, 14 parts of propellant, coupling
12 parts of agent a, 3 parts of surfactant, 14 parts of compatilizer, 12 parts of plasticizer a, 10 parts of antioxidant, 7 parts of flocculation agent, terminator 5
Part；
The conditioning agent is conditioning agent ACR；
The propellant is aerogel generating agent；
The coupling agent a is coupling agent kh570；
Surfactant is sodium sulfate of polyethenoxy ether of fatty alcohol；
The compatilizer is modified polyacrylate；
The plasticizer a is diisooctyl phthalate；
The antioxidant is anti-oxidant DLTP；
The flocculation agent is aluminium polychloride；
The terminator is p-tert-Butylcatechol；
The Starch synthesis agent is in units of weight portion, including following raw material：115 parts of starch, 13 parts of dimethyl glutarate,
12 parts of DMA, 4 parts of epoxy chlorobutane, 2.5 parts of urea, 1.5 parts of paste agent, 0.4 part of coupling agent b, initiator
0.1 part, 0.1 part of catalyst, 0.2 part of stabilizer, 0.5 part of defoamer, 0.6 part of plasticizer b, 0.5 part of toughener, tackifier 0.5
Part, 0.3 part of water-proofing agent, 0.1 part of antiseptic；
The coupling agent b is 2,5- dimethyl -2, double (benzoyl the peroxide)-hexanes of 5-；
The initiator is the isobutyric acid of azo two (acrylic acid ethylene glycol) ester；
The catalyst is platinum catalyst；
The stabilizer is organic tin stabilizer；
The defoamer is polyoxyethylene polyoxypropylene pentaerythrite ether；
The plasticizer b is citrate；
The toughener is poly- propylene diene rubber；
The tackifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antiseptic is lithium carbonate；
The preparation method of described agricultural crop straw 3D printing material, comprises the following steps：
S1：The crushed stalk that will be selected, crosses 90 mesh sieve, and powder is obtained, and the powder dries 2.5h at 90 DEG C, controls
Moisture is obtained primary raw material stalk powder below 0.05%；
S2：To in primary raw material stalk powder obtained in step S1 add PLA, sodium tripolyphosphate, butyl acetate,
Specific synthetics, is warming up to 180 DEG C, is stirred in the case where rotating speed is 200r/min and melts 2.5h, is subsequently cooled to room temperature, is obtained modified
Stalk 3D printing secondary-material；
The preparation method of the specific synthetics, comprises the following steps：
S21：Propellant, coupling agent a, compatilizer, antioxidant are mixed and is warming up to 122 DEG C, be 150r/min in rotating speed
Lower reaction 75min, is obtained material A；
S22：To adding conditioning agent, flocculation agent to be warming up to 150 DEG C after mixing in material A obtained in step S21, it is in rotating speed
190min is reacted under 350r/min, material B is obtained；
S23：To adding plasticizer a, terminator to be cooled to 115 DEG C after mixing in material B obtained in step S22, in rotating speed
To react 100min under 250r/min, specific synthetics is obtained；
S3：Crushed at being -100 DEG C in temperature by the stalk 3D printing secondary-material being modified obtained in step S2, add and form sediment
Powder synthetics is well mixed, and well mixed mixture is put into screw extruding forming machine, is 185 DEG C in temperature, and rotating speed is
Under 110r/min, through extruding strand, agricultural crop straw 3D printing material is obtained；
The preparation method of the Starch synthesis agent, comprises the following steps：
S31：Compound concentration is 22Be ', and pH value is 3.5 starch slurry a；
S32：To dimethyl glutarate, N that addition concentration in starch slurry a obtained in step S31 is 6%, N- dimethyl second
Acid amides, coupling agent b, catalyst, are then 50 DEG C in temperature, and speed of agitator is made to carry out cross-linked graft reaction 3h under 85r/min
Obtain slurry b；
S33：To paste agent is added in slurry b obtained in step S32, regulation pH value is 9.6, is subsequently added into epoxy neoprene
Alkane, urea, initiator, plasticizer b, toughener, tackifier, water-proofing agent, antiseptic, are then 58 DEG C, speed of agitator in temperature
To carry out cross-linking reaction 1.5h under 100r/min, slurry c is obtained；
S34：Stabilizer will be added in slurry c obtained in step S33, regulation pH value is 8.4, be warming up to 75 DEG C, gelatinization
52min, gelatinization is down to 32 DEG C after terminating, add defoamer, and 10min is stirred in the case where rotating speed is 110r/min, and Starch synthesis are obtained
Agent.
Embodiment 2
A kind of agricultural crop straw 3D printing material, in units of weight portion, including following raw material：Soybean stalk powder 82
Part, 32 parts of PLA, 18 parts of sodium tripolyphosphate, 22 parts of butyl acetate, 15 parts of specific synthetics, 6 parts of Starch synthesis agent；
The specific synthetics is in units of weight portion, including following raw material：13 parts of conditioning agent, 10 parts of propellant, coupling
9 parts of agent a, 2 parts of surfactant, 13 parts of compatilizer, 8 parts of plasticizer a, 8 parts of antioxidant, 6 parts of flocculation agent, 4 parts of terminator；
The conditioning agent is conditioning agent ACR；
The propellant is aerogel generating agent；
The coupling agent a is coupling agent kh570；
Surfactant is sodium sulfate of polyethenoxy ether of fatty alcohol；
The compatilizer is modified polyacrylate；
The plasticizer a is diisooctyl phthalate；
The antioxidant is anti-oxidant DLTP；
The flocculation agent is aluminium polychloride；
The terminator is p-tert-Butylcatechol；
The Starch synthesis agent is in units of weight portion, including following raw material：80 parts of starch, 10 parts of dimethyl glutarate,
8 parts of DMA, 2 parts of epoxy chlorobutane, 1.5 parts of urea, 1 part of paste agent, 0.2 part of coupling agent b, initiator 0.1
Part, 0.1 part of catalyst, 0.1 part of stabilizer, 0.3 part of defoamer, 0.4 part of plasticizer b, 0.3 part of toughener, 0.3 part of tackifier,
0.2 part of water-proofing agent, 0.1 part of antiseptic；
The coupling agent b is 2,5- dimethyl -2, double (benzoyl the peroxide)-hexanes of 5-；
The initiator is the isobutyric acid of azo two (acrylic acid ethylene glycol) ester；
The catalyst is platinum catalyst；
The stabilizer is organic tin stabilizer；
The defoamer is polyoxyethylene polyoxypropylene pentaerythrite ether；
The plasticizer b is citrate；
The toughener is poly- propylene diene rubber；
The tackifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antiseptic is lithium carbonate；
The preparation method of described agricultural crop straw 3D printing material, comprises the following steps：
S1：The crushed stalk that will be selected, crosses 80 mesh sieve, and powder is obtained, and the powder dries 3h at 83 DEG C, controls water
Divide content below 0.05%, primary raw material stalk powder is obtained；
S2：To in primary raw material stalk powder obtained in step S1 add PLA, sodium tripolyphosphate, butyl acetate,
Specific synthetics, is warming up to 164 DEG C, is stirred in the case where rotating speed is 100r/min and melts 4h, is subsequently cooled to room temperature, is obtained what is be modified
Stalk 3D printing secondary-material；
The preparation method of the specific synthetics, comprises the following steps：
S21：Propellant, coupling agent a, compatilizer, antioxidant are mixed and is warming up to 117 DEG C, be 100r/min in rotating speed
Lower reaction 82min, is obtained material A；
S22：To adding conditioning agent, flocculation agent to be warming up to 143 DEG C after mixing in material A obtained in step S21, it is in rotating speed
232min is reacted under 300r/min, material B is obtained；
S23：To adding plasticizer a, terminator to be cooled to 108 DEG C after mixing in material B obtained in step S22, in rotating speed
To react 135min under 200r/min, specific synthetics is obtained；
S3：Crushed at being -90 DEG C in temperature by the stalk 3D printing secondary-material being modified obtained in step S2, add starch
Synthetics is well mixed, and well mixed mixture is put into screw extruding forming machine, is 170 DEG C in temperature, and rotating speed is 102r/
Under min, through extruding strand, agricultural crop straw 3D printing material is obtained；
The preparation method of the Starch synthesis agent, comprises the following steps：
S31：Compound concentration is 18Be ', and pH value is 3.1 starch slurry a；
S32：To dimethyl glutarate, N that addition concentration in starch slurry a obtained in step S31 is 4%, N- dimethyl second
Acid amides, coupling agent b, catalyst, are then 42 DEG C in temperature, and speed of agitator reacts 3.5h to carry out cross-linked graft under 70r/min,
Slurry b is obtained；
S33：To paste agent is added in slurry b obtained in step S32, regulation pH value is 9.1, is subsequently added into epoxy neoprene
Alkane, urea, initiator, plasticizer b, toughener, tackifier, water-proofing agent, antiseptic, are then 55 DEG C, speed of agitator in temperature
To carry out cross-linking reaction 1.8h under 80r/min, slurry c is obtained；
S34：Stabilizer will be added in slurry c obtained in step S33, regulation pH value is 8.3, be warming up to 73 DEG C, gelatinization
55min, gelatinization is down to 30 DEG C after terminating, add defoamer, and 12min is stirred in the case where rotating speed is 90r/min, and Starch synthesis are obtained
Agent.
Embodiment 3
A kind of agricultural crop straw 3D printing material, in units of weight portion, including following raw material：Maize straw powder 124
Part, 48 parts of PLA, 26 parts of sodium tripolyphosphate, 28 parts of butyl acetate, 22 parts of specific synthetics, 12 parts of Starch synthesis agent；
The specific synthetics is in units of weight portion, including following raw material：19 parts of conditioning agent, 16 parts of propellant, coupling
14 parts of agent a, 4 parts of surfactant, 15 parts of compatilizer, 14 parts of plasticizer a, 12 parts of antioxidant, 8 parts of flocculation agent, terminator 6
Part；
The conditioning agent is conditioning agent ACR；
The propellant is aerogel generating agent；
The coupling agent a is coupling agent kh570；
Surfactant is sodium sulfate of polyethenoxy ether of fatty alcohol；
The compatilizer is modified polyacrylate；
The plasticizer a is diisooctyl phthalate；
The antioxidant is anti-oxidant DLTP；
The flocculation agent is aluminium polychloride；
The terminator is p-tert-Butylcatechol；
The Starch synthesis agent is in units of weight portion, including following raw material：130 parts of starch, 16 parts of dimethyl glutarate,
13 parts of DMA, 5 parts of epoxy chlorobutane, 3.5 parts of urea, 2 parts of paste agent, 0.6 part of coupling agent b, initiator
0.2 part, 0.2 part of catalyst, 0.3 part of stabilizer, 0.8 part of defoamer, 0.9 part of plasticizer b, 0.7 part of toughener, tackifier 0.6
Part, 0.4 part of water-proofing agent, 0.2 part of antiseptic；
The coupling agent b is 2,5- dimethyl -2, double (benzoyl the peroxide)-hexanes of 5-；
The initiator is the isobutyric acid of azo two (acrylic acid ethylene glycol) ester；
The catalyst is platinum catalyst；
The stabilizer is organic tin stabilizer；
The defoamer is polyoxyethylene polyoxypropylene pentaerythrite ether；
The plasticizer b is citrate；
The toughener is poly- propylene diene rubber；
The tackifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antiseptic is lithium carbonate；
The preparation method of described agricultural crop straw 3D printing material, comprises the following steps：
S1：The crushed stalk that will be selected, crosses 100 mesh sieve, and powder is obtained, and the powder dries 2h at 94 DEG C, controls
Moisture is obtained primary raw material stalk powder below 0.05%；
S2：To in primary raw material stalk powder obtained in step S1 add PLA, sodium tripolyphosphate, butyl acetate,
Specific synthetics, is warming up to 208 DEG C, is stirred in the case where rotating speed is 300r/min and melts 2h, is subsequently cooled to room temperature, is obtained what is be modified
Stalk 3D printing secondary-material；
The preparation method of the specific synthetics, comprises the following steps：
S21：Propellant, coupling agent a, compatilizer, antioxidant are mixed and is warming up to 128 DEG C, be 200r/min in rotating speed
Lower reaction 68min, is obtained material A；
S22：To adding conditioning agent, flocculation agent to be warming up to 156 DEG C after mixing in material A obtained in step S21, it is in rotating speed
145min is reacted under 400r/min, material B is obtained；
S23：To adding plasticizer a, terminator to be cooled to 125 DEG C after mixing in material B obtained in step S22, in rotating speed
To react 62min under 300r/min, specific synthetics is obtained；
S3：Crushed at being -110 DEG C in temperature by the stalk 3D printing secondary-material being modified obtained in step S2, add and form sediment
Powder synthetics is well mixed, and well mixed mixture is put into screw extruding forming machine, is 200 DEG C in temperature, and rotating speed is
Under 116r/min, through extruding strand, agricultural crop straw 3D printing material is obtained；
The preparation method of the Starch synthesis agent, comprises the following steps：
S31：Compound concentration is 25Be ', and pH value is 3.8 starch slurry a；
S32：To dimethyl glutarate, N that addition concentration in starch slurry a obtained in step S31 is 8%, N- dimethyl second
Acid amides, coupling agent b, catalyst, then temperature be 58 DEG C, speed of agitator be 100r/min under carry out cross-linked graft reaction
2.5h, is obtained slurry b；
S33：To paste agent is added in slurry b obtained in step S32, regulation pH value is 9.8, is subsequently added into epoxy neoprene
Alkane, urea, initiator, plasticizer b, toughener, tackifier, water-proofing agent, antiseptic, are then 61 DEG C, speed of agitator in temperature
To carry out cross-linking reaction 1.2h under 120r/min, slurry c is obtained；
S34：Stabilizer will be added in slurry c obtained in step S33, regulation pH value is 8.5, be warming up to 77 DEG C, gelatinization
50min, gelatinization is down to 33 DEG C after terminating, add defoamer, and 8min is stirred in the case where rotating speed is 130r/min, and Starch synthesis are obtained
Agent.
Agricultural crop straw 3D printing material property in embodiment 1-3 is detected, it is as a result as shown in the table.
Above content is confined to these explanations it cannot be assumed that the present invention is embodied, for the technical field of the invention
Those of ordinary skill for, under the premise of present inventive concept is not departed from, some simple deduction or replace can also be made, all should
When being considered as belonging to the scope of patent protection that claims by being submitted to of the present invention determine.
Claims (10)
1. a kind of agricultural crop straw 3D printing material, it is characterised in that in units of weight portion, including following raw material：Powder of straw
It is last 82-124 parts, PLA 32-48 parts, sodium tripolyphosphate 18-26 parts, butyl acetate 22-28 parts, specific synthetics 15-22 parts,
6-12 parts of Starch synthesis agent；
The specific synthetics is in units of weight portion, including following raw material：Conditioning agent 13-19 parts, propellant 10-16 parts, idol
Connection 9-14 parts of agent a, surfactant 2-4 parts, compatilizer 13-15 parts, 8-14 parts of plasticizer a, antioxidant 8-12 parts, flocculation agent
6-8 parts, terminator 4-6 parts；
The Starch synthesis agent is in units of weight portion, including following raw material：Starch 80-130 parts, dimethyl glutarate 10-16
Part, DMA 8-13 parts, 2-5 parts of epoxy chlorobutane, urea 1.5-3.5 parts, paste agent 1-2 parts, coupling agent b
0.2-0.6 parts, initiator 0.1-0.2 parts, catalyst 0.1-0.2 parts, stabilizer 0.1-0.3 parts, defoamer 0.3-0.8 parts, increasing
0.4-0.9 parts of agent b of modeling, toughener 0.3-0.7 parts, tackifier 0.3-0.6 parts, water-proofing agent 0.2-0.4 parts, antiseptic 0.1-0.2
Part；
The coupling agent b is 2,5- dimethyl -2, double (benzoyl the peroxide)-hexanes of 5-；
The initiator is the isobutyric acid of azo two (acrylic acid ethylene glycol) ester；
The catalyst is platinum catalyst；
The stabilizer is organic tin stabilizer；
The defoamer is polyoxyethylene polyoxypropylene pentaerythrite ether；
The plasticizer b is citrate；
The toughener is poly- propylene diene rubber；
The tackifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antiseptic is lithium carbonate；
The preparation method of described agricultural crop straw 3D printing material, comprises the following steps：
S1：The crushed stalk that will be selected, crosses 80-100 mesh sieve, and powder is obtained, and the powder dries 2-3h at 83-94 DEG C,
Control moisture is obtained primary raw material stalk powder below 0.05%；
S2：To adding PLA, sodium tripolyphosphate, butyl acetate, specific in primary raw material stalk powder obtained in step S1
Synthetics, is warming up to 164-208 DEG C, is stirred in the case where rotating speed is 100-300r/min and melts 2-4h, is subsequently cooled to room temperature, is obtained
Modified stalk 3D printing secondary-material；
The preparation method of the specific synthetics, comprises the following steps：
S21：Propellant, coupling agent a, compatilizer, antioxidant are mixed and is warming up to 117-128 DEG C, be 100-200r/ in rotating speed
68-82min is reacted under min, material A is obtained；
S22：To adding conditioning agent, flocculation agent to be warming up to 143-156 DEG C after mixing in material A obtained in step S21, it is in rotating speed
145-232min is reacted under 300-400r/min, material B is obtained；
S23：To adding plasticizer a, terminator to be cooled to 108-125 DEG C after mixing in material B obtained in step S22, in rotating speed
To react 62-135min under 200-300r/min, specific synthetics is obtained；
S3：Crushed at being -90--110 DEG C in temperature by the stalk 3D printing secondary-material being modified obtained in step S2, add and form sediment
Powder synthetics is well mixed, and well mixed mixture is put into screw extruding forming machine, is 170-200 DEG C, rotating speed in temperature
Under for 102-116r/min, through extruding strand, agricultural crop straw 3D printing material is obtained；
The preparation method of the Starch synthesis agent, comprises the following steps：
S31：Compound concentration is 18-25Be ', and pH value is the starch slurry a of 3.1-3.8；
S32：It is dimethyl glutarate, the N of 4%-8%, N- dimethyl second to concentration is added in starch slurry a obtained in step S31
Acid amides, coupling agent b, catalyst, are then 42-58 DEG C in temperature, and speed of agitator is anti-to carry out cross-linked graft under 70-100r/min
2.5-3.5h is answered, slurry b is obtained；
S33：To paste agent is added in slurry b obtained in step S32, regulation pH value is 9.1-9.8, is subsequently added into epoxy neoprene
Alkane, urea, initiator, plasticizer b, toughener, tackifier, water-proofing agent, antiseptic, are then 55-61 DEG C in temperature, and stirring turns
Speed is obtained slurry c to carry out cross-linking reaction 1.2-1.8h under 80-120r/min；
S34：Stabilizer will be added in slurry c obtained in step S33, regulation pH value is 8.3-8.5, be warming up to 73-77 DEG C, gelatinization
50-55min, gelatinization is down to 30-33 DEG C after terminating, add defoamer, and 8-12min is stirred in the case where rotating speed is 90-130r/min, makes
Obtain Starch synthesis agent.
2. agricultural crop straw 3D printing material according to claim 1, it is characterised in that the conditioning agent is conditioning agent
ACR。
3. agricultural crop straw 3D printing material according to claim 1, it is characterised in that the propellant is that aerosol occurs
Agent.
4. agricultural crop straw 3D printing material according to claim 1, it is characterised in that the coupling agent a is coupling agent
kh570。
5. agricultural crop straw 3D printing material according to claim 1, it is characterised in that surfactant is fatty alcohol polyoxy
Ethene ether sodium sulfate.
6. agricultural crop straw 3D printing material according to claim 1, it is characterised in that the compatilizer is modified polypropene
Acid esters.
7. agricultural crop straw 3D printing material according to claim 1, it is characterised in that the plasticizer a is O-phthalic
Sour two isodecyl esters.
8. agricultural crop straw 3D printing material according to claim 1, it is characterised in that the antioxidant is antioxidant
DLTP。
9. agricultural crop straw 3D printing material according to claim 1, it is characterised in that the flocculation agent is polyaluminium
Aluminium.
10. agricultural crop straw 3D printing material according to claim 1, it is characterised in that the terminator is to the tert-butyl group
Catechol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611156202.0A CN106700590A (en) | 2016-12-15 | 2016-12-15 | Crop straw 3D printing material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109679189A (en) * | 2018-12-28 | 2019-04-26 | 苏州丽雅特新材料科技有限公司 | A kind of preparation method of preserving jar |
| CN110172257A (en) * | 2019-03-28 | 2019-08-27 | 贵州森塑宇木塑有限公司 | A kind of corrosion resistant fiber plate |
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| CN105907121A (en) * | 2016-07-12 | 2016-08-31 | 广西南宁桂尔创环保科技有限公司 | Wood-plastic material |
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| CN104312119A (en) * | 2014-11-06 | 2015-01-28 | 芜湖瀚博电子科技有限公司 | Straw 3D printing consumable and preparation method thereof |
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