CN106589999A - High-breaking-elongation-rate straw 3D printing material - Google Patents
High-breaking-elongation-rate straw 3D printing material Download PDFInfo
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- CN106589999A CN106589999A CN201611156203.5A CN201611156203A CN106589999A CN 106589999 A CN106589999 A CN 106589999A CN 201611156203 A CN201611156203 A CN 201611156203A CN 106589999 A CN106589999 A CN 106589999A
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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
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
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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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Abstract
The invention discloses a high-breaking-elongation-rate straw 3D printing material, and belongs to the technical field of 3D printing material preparing. The high-breaking-elongation-rate straw 3D printing material is prepared from, by weight, 92-124 parts of straw powder, 32-44 parts of polylactic acid, 16-22 parts of potassium tetra-phosphate, 11-16 parts of diethylene glycol butylether acetate, 13-16 parts of tri(2,4-di-tert-butylphenyl) phosphite ester, 6-9 parts of chloroprene rubber, 15-27 parts of a specific synthesis agent and 8-15 parts of a starch synthesis agent. The high-breaking-elongation-rate straw 3D printing material has the quite-good toughness and impact strength, products printed by the 3D printing technology are high in quality, impact resistance and strength, nontoxic, low in carbon, environmentally friendly and low in cost, has the woody color, can be recycled, and has the quite-high economic value and broad market prospects.
Description
【Technical field】
The invention belongs to 3D printing technical field of material, and in particular to a kind of straw 3D of high elongation at tear beats
Printed material 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 adopted
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, the mashed up use of bi-material, colouring
Also have been carried out.But, these material categorys also differ greatly compared with routine use material, moreover, these materials
One kilogram of low-cost hundreds of unit, 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 in order to one is tight
The social problem of weight, much the still direct burning crop straws in the ground of place peasants, cause 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 supporting leading action, playing the decisive role and enterprise's skill of market construction technological innovation resource to socio-economic development
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 straw, 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 pelletize, and its material can be as blowing, pulling-on piece, injection, due to the raw material straw that it is adopted
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 carries out pelletize after blending and modifying by straw and other plastics, and 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 and gradually disintegrate are lost after it.It is poor that its particle adds Pulvis Talci, the toughness of diatomite product, intensity, it is impossible to
Meet 3D printing consumptive material and prepare winding.
Patent CN104312119A discloses a kind of straw 3D printing consumptive material and preparation method thereof, and formula includes following quality
The raw material of ratio：Polylactic acid 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 straw 3D printing consumptive material.
【The content of the invention】
The present invention provides a kind of straw 3D printing material of high elongation at tear, is deposited with solving existing straw 3D printing consumptive material
The problems such as the poor-performings such as toughness, impact strength, anti-impact.Material made by the present invention has good toughness, impact strength,
Product high-quality, high-impact, high intensity, nontoxic, low-carbon environment-friendly, the low cost printed by 3D printing technique, with wood
Matter color and luster, recycling capable of circulation has wide market prospect
To solve above technical problem, the present invention is employed the following technical solutions：
A kind of straw 3D printing material of high elongation at tear, in units of weight portion, including following raw material：Stalk powder
92-124 parts, polylactic acid 32-44 parts, four PA 800K 16-22 parts, butyldiglycol acetass 11-16 parts, three (2,4- bis- uncles
Determine base phenyl) phosphite ester 13-16 parts, neoprene 6-9 parts, specific syntheticses 15-27 parts, Starch synthesis agent 8-15 parts；
The specific syntheticses are in units of weight portion, including following raw material：Regulator 13-19 parts, propellant 10-16
Part, coupling agent a 9-14 parts, surfactant 2-4 parts, compatilizer 13-15 parts, plasticizer a 8-14 parts, 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, Glutaric Acid Dimethyl ester
10-16 parts, N,N-dimethylacetamide 8-13 part, epoxy chlorobutane 2-5 parts, carbamide 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
Part, plasticizer b 0.4-0.9 parts, toughener 0.3-0.7 parts, viscosifier 0.3-0.6 parts, water-proofing agent 0.2-0.4 parts, antibacterial
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 isopropylformic 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 tetramethylolmethane ether；
The plasticizer b is citrate；
The toughener is poly- propylene diene rubber；
The viscosifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antibacterial is lithium carbonate；
The preparation method of the straw 3D printing material of described high elongation at tear, comprises the following steps：
S1：The crushed stalk that will be selected, crosses 80-100 mesh sieve, and powder is obtained, and the powder is dried 2- at 83-94 DEG C
3h, control moisture is obtained primary raw material stalk powder below 0.05%；
S2：Polylactic acid, four PA 800K, butyldiglycol are added in primary raw material stalk powder obtained in step S1
Acetass, three (2,4- bis- tertiary Ding Ji phenyl) phosphite esters, neoprene, specific syntheticses, are warming up to 180-212 DEG C, are turning
Speed melts 1.7-4.6h for stirring under 100-300r/min, is subsequently cooled to room temperature, and modified two grades of materials of straw 3D printing are obtained
Material；
The preparation method of the specific syntheticses, comprises the following steps：
S21：Propellant, coupling agent a, compatilizer, antioxidant mixing are warming up to into 117-128 DEG C, are 100- in rotating speed
68-82min is reacted under 200r/min, material A is obtained；
S22：Add in material A obtained in step S21 and be warming up to 143-156 DEG C after regulator, flocculation agent mixing, turning
Speed is obtained material B to react 145-232min under 300-400r/min；
S23：Add in material B obtained in step S22 and be cooled to 108-125 DEG C after plasticizer a, terminator mixing,
Rotating speed is to react 62-135min under 200-300r/min, and specific syntheticses are obtained；
S3：The straw 3D printing secondary-material being modified obtained in step S2 is crushed in the case where temperature is for -90--110 DEG C, plus
Enter Starch synthesis agent mix homogeneously, mix homogeneously mixture be put in screw extruding forming machine, be 170-200 DEG C in temperature,
Rotating speed is Jing extruding strands under 102-116r/min, and the straw 3D printing material of high elongation at tear 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：Concentration is added in starch slurry a obtained in step S31 for Glutaric Acid Dimethyl ester, the N of 4%-8%, N- diformazans
Yl acetamide, coupling agent b, catalyst, are then 42-58 DEG C in temperature, and speed of agitator is to carry out crosslinking under 70-100r/min to connect
Branch reaction 2.5-3.5h, is obtained slurry b；
S33：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, carbamide, initiator, plasticizer b, toughener, viscosifier, water-proofing agent, antibacterial, are then 55-61 DEG C in temperature, stirring
Rotating speed is to carry out cross-linking reaction 1.2-1.8h under 80-120r/min, and slurry c is obtained；
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,
Gelatinizing 50-55min, gelatinizing is down to 30-33 DEG C after terminating, add defoamer, and in the case where rotating speed is 90-130r/min 8- is stirred
12min, is obtained Starch synthesis agent.
Preferably, the regulator is regulator ACR.
Preferably, the propellant is aerogel generating agent.
Preferably, the coupling agent a is coupling agent kh570.
Preferably, surfactant is polyoxyethylenated alcohol sodium sulfate.
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 polychlorid.
Preferably, the terminator is p-tert-Butylcatechol.
The invention has the advantages that：
(1) the straw 3D printing material of high elongation at tear made by the present invention has good toughness, impact strength, leads to
Product high-quality, high-impact, high intensity that 3D printing technique is printed are crossed, with wide market prospect；
(2) the straw 3D printing material of high elongation at tear made by the present invention has wooden color and luster, recovery profit capable of circulation
With 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 the present invention's
Protection domain, but do not limit the scope of the invention.
In embodiment, the straw 3D printing material of the high elongation at tear, in units of weight portion, including following original
Material：Stalk powder 92-124 parts, polylactic acid 32-44 parts, four PA 800K 16-22 parts, butyldiglycol acetass 11-16 parts,
Three (2,4- bis- tertiary Ding Ji phenyl) phosphite ester 13-16 parts, neoprene 6-9 parts, specific syntheticses 15-27 parts, Starch synthesis
Agent 8-15 parts；
The specific syntheticses are in units of weight portion, including following raw material：Regulator 13-19 parts, propellant 10-16
Part, coupling agent a 9-14 parts, surfactant 2-4 parts, compatilizer 13-15 parts, plasticizer a 8-14 parts, antioxidant 8-12 parts,
Flocculation agent 6-8 parts, terminator 4-6 parts；
The regulator is regulator ACR；
The propellant is aerogel generating agent；
The coupling agent a is coupling agent kh570；
Surfactant is polyoxyethylenated alcohol sodium sulfate；
The compatilizer is modified polyacrylate；
The plasticizer a is diisooctyl phthalate；
The antioxidant is anti-oxidant DLTP；
The flocculation agent is aluminium polychlorid；
The terminator is p-tert-Butylcatechol；
The Starch synthesis agent is in units of weight portion, including following raw material：Starch 80-130 parts, Glutaric Acid Dimethyl ester
10-16 parts, N,N-dimethylacetamide 8-13 part, epoxy chlorobutane 2-5 parts, carbamide 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
Part, plasticizer b 0.4-0.9 parts, toughener 0.3-0.7 parts, viscosifier 0.3-0.6 parts, water-proofing agent 0.2-0.4 parts, antibacterial
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 isopropylformic 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 tetramethylolmethane ether；
The plasticizer b is citrate；
The toughener is poly- propylene diene rubber；
The viscosifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antibacterial is lithium carbonate；
The preparation method of the straw 3D printing material of described high elongation at tear, comprises the following steps：
S1：The crushed stalk that will be selected, crosses 80-100 mesh sieve, and powder is obtained, and the powder is dried 2- at 83-94 DEG C
3h, control moisture is obtained primary raw material stalk powder below 0.05%；
S2：Polylactic acid, four PA 800K, butyldiglycol are added in primary raw material stalk powder obtained in step S1
Acetass, three (2,4- bis- tertiary Ding Ji phenyl) phosphite esters, neoprene, specific syntheticses, are warming up to 180-212 DEG C, are turning
Speed melts 1.7-4.6h for stirring under 100-300r/min, is subsequently cooled to room temperature, and modified two grades of materials of straw 3D printing are obtained
Material；
The preparation method of the specific syntheticses, comprises the following steps：
S21：Propellant, coupling agent a, compatilizer, antioxidant mixing are warming up to into 117-128 DEG C, are 100- in rotating speed
68-82min is reacted under 200r/min, material A is obtained；
S22：Add in material A obtained in step S21 and be warming up to 143-156 DEG C after regulator, flocculation agent mixing, turning
Speed is obtained material B to react 145-232min under 300-400r/min；
S23：Add in material B obtained in step S22 and be cooled to 108-125 DEG C after plasticizer a, terminator mixing,
Rotating speed is to react 62-135min under 200-300r/min, and specific syntheticses are obtained；
S3：The straw 3D printing secondary-material being modified obtained in step S2 is crushed in the case where temperature is for -90--110 DEG C, plus
Enter Starch synthesis agent mix homogeneously, mix homogeneously mixture be put in screw extruding forming machine, be 170-200 DEG C in temperature,
Rotating speed is Jing extruding strands under 102-116r/min, and the straw 3D printing material of high elongation at tear 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：Concentration is added in starch slurry a obtained in step S31 for Glutaric Acid Dimethyl ester, the N of 4%-8%, N- diformazans
Yl acetamide, coupling agent b, catalyst, are then 42-58 DEG C in temperature, and speed of agitator is to carry out crosslinking under 70-100r/min to connect
Branch reaction 2.5-3.5h, is obtained slurry b；
S33：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, carbamide, initiator, plasticizer b, toughener, viscosifier, water-proofing agent, antibacterial, are then 55-61 DEG C in temperature, stirring
Rotating speed is to carry out cross-linking reaction 1.2-1.8h under 80-120r/min, and slurry c is obtained；
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,
Gelatinizing 50-55min, gelatinizing is down to 30-33 DEG C after terminating, add defoamer, and in the case where rotating speed is 90-130r/min 8- is stirred
12min, is obtained Starch synthesis agent.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of straw 3D printing material of high elongation at tear, in units of weight portion, including following raw material：Corn straw
102 parts of powder, 36 parts of polylactic acid, 18 parts of four PA 800K, 14 parts of butyldiglycol acetass, three (2,4- bis- tertiary Ding Ji phenyl)
16 parts of phosphite ester, 8 parts of neoprene, 20 parts of specific syntheticses, 12 parts of Starch synthesis agent；
The specific syntheticses are in units of weight portion, including following raw material：16 parts of regulator, 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 regulator is regulator ACR；
The propellant is aerogel generating agent；
The coupling agent a is coupling agent kh570；
Surfactant is polyoxyethylenated alcohol sodium sulfate；
The compatilizer is modified polyacrylate；
The plasticizer a is diisooctyl phthalate；
The antioxidant is anti-oxidant DLTP；
The flocculation agent is aluminium polychlorid；
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 Glutaric Acid Dimethyl ester,
12 parts of N,N-dimethylacetamide, 4 parts of epoxy chlorobutane, 2.5 parts of carbamide, 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, viscosifier 0.5
Part, 0.3 part of water-proofing agent, 0.1 part of antibacterial；
The coupling agent b is 2,5- dimethyl -2, double (benzoyl the peroxide)-hexanes of 5-；
The initiator is the isopropylformic 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 tetramethylolmethane ether；
The plasticizer b is citrate；
The toughener is poly- propylene diene rubber；
The viscosifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antibacterial is lithium carbonate；
The preparation method of the straw 3D printing material of described high elongation at tear, comprises the following steps：
S1：The crushed stalk that will be selected, crosses 90 mesh sieve, and powder is obtained, and the powder is dried 2.5h at 90 DEG C, controls
Moisture is obtained primary raw material stalk powder below 0.05%；
S2：Polylactic acid, four PA 800K, butyldiglycol are added in primary raw material stalk powder obtained in step S1
Acetass, three (2,4- bis- tertiary Ding Ji phenyl) phosphite esters, neoprene, specific syntheticses, are warming up to 201 DEG C, are in rotating speed
Stirring under 200r/min melts 3.4h, is subsequently cooled to room temperature, and modified straw 3D printing secondary-material is obtained；
The preparation method of the specific syntheticses, comprises the following steps：
S21：Propellant, coupling agent a, compatilizer, antioxidant mixing are warming up to into 122 DEG C, are 150r/min in rotating speed
Lower reaction 75min, is obtained material A；
S22：Add in material A obtained in step S21 and be warming up to 150 DEG C after regulator, flocculation agent mixing, be in rotating speed
190min is reacted under 350r/min, material B is obtained；
S23：Add in material B obtained in step S22 and be cooled to 115 DEG C after plasticizer a, terminator mixing, in rotating speed
To react 100min under 250r/min, specific syntheticses are obtained；
S3：The straw 3D printing secondary-material being modified obtained in step S2 is crushed in the case where temperature is for -100 DEG C, is added and is formed sediment
Powder syntheticses mix homogeneously, mix homogeneously mixture is put in screw extruding forming machine, is 185 DEG C in temperature, and rotating speed is
Under 110r/min, Jing extruding strands are obtained the straw 3D printing material of high elongation at tear；
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：Glutaric Acid Dimethyl ester, N that concentration is 6%, N- dimethyl second are added in starch slurry a obtained in step S31
Amide, coupling agent b, catalyst, are then 50 DEG C in temperature, and speed of agitator is that cross-linked graft reaction 3h, system are carried out under 85r/min
Obtain slurry b；
S33：Paste agent is added in slurry b obtained in step S32, it is 9.6 to adjust pH value, is subsequently added into epoxy neoprene
Alkane, carbamide, initiator, plasticizer b, toughener, viscosifier, water-proofing agent, antibacterial, are then 58 DEG C in temperature, speed of agitator
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, it is 8.4 to adjust pH value, is warming up to 75 DEG C, gelatinizing
52min, gelatinizing is down to 32 DEG C after terminating, add defoamer, and in the case where rotating speed is 110r/min 10min is stirred, and Starch synthesis are obtained
Agent.
Embodiment 2
A kind of straw 3D printing material of high elongation at tear, in units of weight portion, including following raw material：Rice straw
92 parts of powder, 32 parts of polylactic acid, 16 parts of four PA 800K, 11 parts of butyldiglycol acetass, three (2,4- bis- tertiary Ding Ji phenyl)
13 parts of phosphite ester, 6 parts of neoprene, 15 parts of specific syntheticses, 8 parts of Starch synthesis agent；
The specific syntheticses are in units of weight portion, including following raw material：13 parts of regulator, 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 regulator is regulator ACR；
The propellant is aerogel generating agent；
The coupling agent a is coupling agent kh570；
Surfactant is polyoxyethylenated alcohol sodium sulfate；
The compatilizer is modified polyacrylate；
The plasticizer a is diisooctyl phthalate；
The antioxidant is anti-oxidant DLTP；
The flocculation agent is aluminium polychlorid；
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 Glutaric Acid Dimethyl ester,
8 parts of N,N-dimethylacetamide, 2 parts of epoxy chlorobutane, 1.5 parts of carbamide, 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 viscosifier,
0.2 part of water-proofing agent, 0.1 part of antibacterial；
The coupling agent b is 2,5- dimethyl -2, double (benzoyl the peroxide)-hexanes of 5-；
The initiator is the isopropylformic 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 tetramethylolmethane ether；
The plasticizer b is citrate；
The toughener is poly- propylene diene rubber；
The viscosifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antibacterial is lithium carbonate；
The preparation method of the straw 3D printing material of described high elongation at tear, comprises the following steps：
S1：The crushed stalk that will be selected, crosses 80 mesh sieve, and powder is obtained, and the powder is dried 3h at 83 DEG C, controls water
Divide content below 0.05%, primary raw material stalk powder is obtained；
S2：Polylactic acid, four PA 800K, butyldiglycol are added in primary raw material stalk powder obtained in step S1
Acetass, three (2,4- bis- tertiary Ding Ji phenyl) phosphite esters, neoprene, specific syntheticses, are warming up to 180 DEG C, are in rotating speed
Stirring under 100r/min melts 4.6h, is subsequently cooled to room temperature, and modified straw 3D printing secondary-material is obtained；
The preparation method of the specific syntheticses, comprises the following steps：
S21：Propellant, coupling agent a, compatilizer, antioxidant mixing are warming up to into 117 DEG C, are 100r/min in rotating speed
Lower reaction 82min, is obtained material A；
S22：Add in material A obtained in step S21 and be warming up to 143 DEG C after regulator, flocculation agent mixing, be in rotating speed
232min is reacted under 300r/min, material B is obtained；
S23：Add in material B obtained in step S22 and be cooled to 108 DEG C after plasticizer a, terminator mixing, in rotating speed
To react 135min under 200r/min, specific syntheticses are obtained；
S3：The straw 3D printing secondary-material being modified obtained in step S2 is crushed in the case where temperature is for -90 DEG C, starch is added
Syntheticses mix homogeneously, mix homogeneously mixture is put in screw extruding forming machine, is 170 DEG C in temperature, and rotating speed is 102r/
Under min, Jing extruding strands are obtained the straw 3D printing material of high elongation at tear；
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：Glutaric Acid Dimethyl ester, N that concentration is 4%, N- dimethyl second are added in starch slurry a obtained in step S31
Amide, coupling agent b, catalyst, are then 42 DEG C in temperature, and speed of agitator is that cross-linked graft reaction 3.5h is carried out under 70r/min,
Prepared slurry b；
S33：Paste agent is added in slurry b obtained in step S32, it is 9.1 to adjust pH value, is subsequently added into epoxy neoprene
Alkane, carbamide, initiator, plasticizer b, toughener, viscosifier, water-proofing agent, antibacterial, are then 55 DEG C in temperature, speed of agitator
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, it is 8.3 to adjust pH value, is warming up to 73 DEG C, gelatinizing
55min, gelatinizing is down to 30 DEG C after terminating, add defoamer, and in the case where rotating speed is 90r/min 12min is stirred, and Starch synthesis are obtained
Agent.
Embodiment 3
A kind of straw 3D printing material of high elongation at tear, in units of weight portion, including following raw material：Stalk powder
124 parts, 44 parts of polylactic acid, 22 parts of four PA 800K, 16 parts of butyldiglycol acetass, three (2,4- bis- tertiary Ding Ji phenyl) phosphorous
16 parts of acid esters, 9 parts of neoprene, 27 parts of specific syntheticses, 15 parts of Starch synthesis agent；
The specific syntheticses are in units of weight portion, including following raw material：19 parts of regulator, 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 regulator is regulator ACR；
The propellant is aerogel generating agent；
The coupling agent a is coupling agent kh570；
Surfactant is polyoxyethylenated alcohol sodium sulfate；
The compatilizer is modified polyacrylate；
The plasticizer a is diisooctyl phthalate；
The antioxidant is anti-oxidant DLTP；
The flocculation agent is aluminium polychlorid；
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 Glutaric Acid Dimethyl ester,
13 parts of N,N-dimethylacetamide, 5 parts of epoxy chlorobutane, 3.5 parts of carbamide, 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, viscosifier 0.6
Part, 0.4 part of water-proofing agent, 0.2 part of antibacterial；
The coupling agent b is 2,5- dimethyl -2, double (benzoyl the peroxide)-hexanes of 5-；
The initiator is the isopropylformic 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 tetramethylolmethane ether；
The plasticizer b is citrate；
The toughener is poly- propylene diene rubber；
The viscosifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antibacterial is lithium carbonate；
The preparation method of the straw 3D printing material of described high elongation at tear, comprises the following steps：
S1：The crushed stalk that will be selected, crosses 100 mesh sieve, and powder is obtained, and the powder is dried 2h at 94 DEG C, controls
Moisture is obtained primary raw material stalk powder below 0.05%；
S2：Polylactic acid, four PA 800K, butyldiglycol are added in primary raw material stalk powder obtained in step S1
Acetass, three (2,4- bis- tertiary Ding Ji phenyl) phosphite esters, neoprene, specific syntheticses, are warming up to 212 DEG C, are in rotating speed
Stirring under 300r/min melts 1.7h, is subsequently cooled to room temperature, and modified straw 3D printing secondary-material is obtained；
The preparation method of the specific syntheticses, comprises the following steps：
S21：Propellant, coupling agent a, compatilizer, antioxidant mixing are warming up to into 128 DEG C, are 200r/min in rotating speed
Lower reaction 68min, is obtained material A；
S22：Add in material A obtained in step S21 and be warming up to 156 DEG C after regulator, flocculation agent mixing, be in rotating speed
145min is reacted under 400r/min, material B is obtained；
S23：Add in material B obtained in step S22 and be cooled to 125 DEG C after plasticizer a, terminator mixing, in rotating speed
To react 62min under 300r/min, specific syntheticses are obtained；
S3：The straw 3D printing secondary-material being modified obtained in step S2 is crushed in the case where temperature is for -110 DEG C, is added and is formed sediment
Powder syntheticses mix homogeneously, mix homogeneously mixture is put in screw extruding forming machine, is 200 DEG C in temperature, and rotating speed is
Under 116r/min, Jing extruding strands are obtained the straw 3D printing material of high elongation at tear；
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：Glutaric Acid Dimethyl ester, N that concentration is 8%, N- dimethyl second are added in starch slurry a obtained in step S31
Amide, coupling agent b, catalyst, are then 58 DEG C in temperature, and speed of agitator is to carry out cross-linked graft reaction under 100r/min
2.5h, is obtained slurry b；
S33：Paste agent is added in slurry b obtained in step S32, it is 9.8 to adjust pH value, is subsequently added into epoxy neoprene
Alkane, carbamide, initiator, plasticizer b, toughener, viscosifier, water-proofing agent, antibacterial, are then 61 DEG C in temperature, speed of agitator
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, it is 8.5 to adjust pH value, is warming up to 77 DEG C, gelatinizing
50min, gelatinizing is down to 33 DEG C after terminating, add defoamer, and in the case where rotating speed is 130r/min 8min is stirred, and Starch synthesis are obtained
Agent.
The straw 3D printing material property of the high elongation at tear in embodiment 1-3 is detected, as a result such as following table institute
Show.
Above content it cannot be assumed that the present invention is embodied as being confined to these explanations, for the technical field of the invention
Those of ordinary skill for, under the premise of without departing from present inventive concept, some simple deduction or replace can also be made, all should
When being considered as belonging to the scope of patent protection that determined by the claims submitted to of the present invention.
Claims (10)
1. the straw 3D printing material of a kind of high elongation at tear, it is characterised in that in units of weight portion, including following original
Material：Stalk powder 92-124 parts, polylactic acid 32-44 parts, four PA 800K 16-22 parts, butyldiglycol acetass 11-16 parts,
Three (2,4- bis- tertiary Ding Ji phenyl) phosphite ester 13-16 parts, neoprene 6-9 parts, specific syntheticses 15-27 parts, Starch synthesis
Agent 8-15 parts；
The specific syntheticses are in units of weight portion, including following raw material：Regulator 13-19 parts, propellant 10-16 parts, idol
Connection agent a 9-14 parts, surfactant 2-4 parts, compatilizer 13-15 parts, plasticizer a 8-14 parts, 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, Glutaric Acid Dimethyl ester 10-16
Part, N,N-dimethylacetamide 8-13 part, epoxy chlorobutane 2-5 parts, carbamide 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
Modeling agent b 0.4-0.9 parts, toughener 0.3-0.7 parts, viscosifier 0.3-0.6 parts, water-proofing agent 0.2-0.4 parts, antibacterial 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 isopropylformic 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 tetramethylolmethane ether；
The plasticizer b is citrate；
The toughener is poly- propylene diene rubber；
The viscosifier are propyl trimethoxy silicane；
The water-proofing agent is boric acid；
The antibacterial is lithium carbonate；
The preparation method of the straw 3D printing material of described high elongation at tear, comprises the following steps：
S1：The crushed stalk that will be selected, crosses 80-100 mesh sieve, and powder is obtained, and the powder is dried 2-3h at 83-94 DEG C,
Control moisture is obtained primary raw material stalk powder below 0.05%；
S2：Polylactic acid, four PA 800K, butyldiglycol acetic acid are added in primary raw material stalk powder obtained in step S1
Ester, three (2,4- bis- tertiary Ding Ji phenyl) phosphite esters, neoprene, specific syntheticses, are warming up to 180-212 DEG C, are in rotating speed
Stirring under 100-300r/min melts 1.7-4.6h, is subsequently cooled to room temperature, and modified straw 3D printing secondary-material is obtained；
The preparation method of the specific syntheticses, comprises the following steps：
S21：Propellant, coupling agent a, compatilizer, antioxidant mixing are warming up to into 117-128 DEG C, are 100-200r/ in rotating speed
68-82min is reacted under min, material A is obtained；
S22：Add in material A obtained in step S21 and be warming up to 143-156 DEG C after regulator, flocculation agent mixing, be in rotating speed
145-232min is reacted under 300-400r/min, material B is obtained；
S23：Add in material B obtained in step S22 and be cooled to 108-125 DEG C after plasticizer a, terminator mixing, in rotating speed
To react 62-135min under 200-300r/min, specific syntheticses are obtained；
S3：The straw 3D printing secondary-material being modified obtained in step S2 is crushed in the case where temperature is for -90--110 DEG C, is added and is formed sediment
Powder syntheticses mix homogeneously, mix homogeneously mixture is put in screw extruding forming machine, is 170-200 DEG C in temperature, rotating speed
For under 102-116r/min, Jing extruding strands are obtained the straw 3D printing material of high elongation at tear；
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：Concentration is added in starch slurry a obtained in step S31 for Glutaric Acid Dimethyl ester, the N of 4%-8%, N- dimethyl second
Amide, 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：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, carbamide, initiator, plasticizer b, toughener, viscosifier, water-proofing agent, antibacterial, 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, is warming up to 73-77 DEG C, gelatinizing
50-55min, gelatinizing is down to 30-33 DEG C after terminating, add defoamer, and in the case where rotating speed is 90-130r/min 8-12min is stirred, and makes
Obtain Starch synthesis agent.
2. the straw 3D printing material of high elongation at tear according to claim 1, it is characterised in that the regulator
For regulator ACR.
3. the straw 3D printing material of high elongation at tear according to claim 1, it is characterised in that the propellant is gas
Colloidal sol propellant.
4. the straw 3D printing material of high elongation at tear according to claim 1, it is characterised in that the coupling agent a is
Coupling agent kh570.
5. the straw 3D printing material of high elongation at tear according to claim 1, it is characterised in that surfactant is fat
Fat polyoxyethylenated alcohol sodium sulfate.
6. the straw 3D printing material of high elongation at tear according to claim 1, it is characterised in that the compatilizer is to change
Property polyacrylate.
7. the straw 3D printing material of high elongation at tear according to claim 1, it is characterised in that the plasticizer a is
Diisooctyl phthalate.
8. the straw 3D printing material of high elongation at tear according to claim 1, it is characterised in that the antioxidant is anti-
Oxygen agent DLTP.
9. the straw 3D printing material of high elongation at tear according to claim 1, it is characterised in that the flocculation agent is poly-
Close aluminum chloride.
10. the straw 3D printing material of high elongation at tear according to claim 1, it is characterised in that the terminator is
P-tert-Butylcatechol.
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| CN201611156203.5A CN106589999A (en) | 2016-12-15 | 2016-12-15 | High-breaking-elongation-rate straw 3D printing material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110157209A (en) * | 2018-03-16 | 2019-08-23 | 淄博名堂教育科技有限公司 | A kind of plastics and preparation method thereof for 3D printing |
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