CN107880325A - A kind of 3D printing material based on modification of chitosan - Google Patents
A kind of 3D printing material based on modification of chitosan Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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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
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- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
The present invention relates to a kind of 3D printing material based on modification of chitosan, its raw material includes by weight：80 100 parts of modification of chitosan, 20 40 parts of butadiene-styrene rubber, 20 35 parts of kaolin, 10 15 parts of organo silane coupling agent, 10 15 parts of hydroxypropyl methyl cellulose, 14 parts of polycaprolactone, 14 parts of atoleine, 15 parts of polyethylene glycol, nanometer porous 25 parts of activated carbon, 26 parts of sodium polyphosphate, 39 parts of nano silicon, 39 parts of talcum powder, 26 parts of zeolite powder, 14 parts of surfactant, 35 parts of antioxidant.Pass through the addition of modification of chitosan, add the biological degradation rate of material, add the pliability of material and the amalgamation with the high-molecular organic material component such as rubber, compounded by raw material and play synergy, with the advantages of toughness is strong, tensile strength is high, shaping is easy, and moulding process is simple.
Description
Technical field
The present invention relates to the technical field of 3D printing material, more particularly to one kind is using Biodegradable material as main component
Environment-friendly type 3D printing material.
Background technology
3D printing technique is also known as increases material manufacturing technology, is one kind of the rapid shaping field currently gradually to grow up
Emerging manufacturing technology, it be one kind based on mathematical model file, with powdery metal or plastics etc. can jointing material, lead to
Carry out the technology of constructed object after the mode successively printed.This is a kind of environmental protection and highlights the RP technique of personalization, has
Personalization level is high, shaping small volume, the advantages that cost is low, pollution is low, easy to use.Its general principle is mainly with macromolecule
Material is base material, and using fused glass pellet technology, the construction to object and formation are completed by successively printing accumulation mode.With
The development and application of 3D printing technique, material turns into one of key of limitation 3D printing technique future trend, to a certain degree
On, the development of material decides that 3D printing can have wider application.At present, 3D printing material mainly include engineering plastics,
Photosensitive resin, rubber type of material, metal material and ceramic material etc., in addition, coloured plaster material, artificial bone meal, cell
The food materials such as biological raw material, wood materials and granulated sugar are also applied in 3D printing field.
Most materials for being most widely some and being capable of natural degradation of 3D printing material, these materials have ring now
Protect, be easy to the features such as post-processing, but the problem of mechanical property is not strong, production cost is higher again be present in many degradable materials,
Therefore seeking one kind can meet that 3D printing technique requirement is readily available again, lower-cost degradation material turns into performance
It is currently needed for solving the problems, such as.
Chitin also known as chitin, scientific name chitin (chitin), it is a kind of straight chain native amino polysaccharide, and hair at present
Existing unique edibility animal origin for carrying positive charge.The yield of annual natural chitin is up to as many as hundred billion tons, ocean life
Chitin yield is next in number only to the second largest natural biomass materials of cellulose in nature up to more than 10,000,000,000 tons in thing.
As structural material, chitin is distributed mainly on fungi, protist and invertebrate, is then distributed mainly in higher mammal
The joint of joint, hoof, foot etc. and muscle and bone.For a long time, due to chitin is not soluble in water, diluted acid, diluted alkaline and mostly
The inertia feature of number organic solvents, never by should have attention.But in recent decades, with life science and biotechnology
Huge advance, physicochemical property, bioactivity and the functional characteristics of chitin gradually recognize by people, particularly chitin and
Its derivative is as a kind of novel material and material in pharmacy, organizational project, fine chemistry industry, material and textile industry, food work
Industry, agricultural and all many application values of environmental protection, are rapidly shown, by the extensive pass of people
Note, the depth and range of its industrialization vigorously promote, and its " green material " characteristic harmless to human body and environmental beneficial,
Even more meet the tendency of the day, obtained the favor of people, illustrate very fine market prospects.
Chitosan (chitosan), also known as chitosan, it is the chitin (chitin) being widely present by nature
Obtained by deacetylation, chemical name is Chitosan (1-4) -2- amino-B-D glucose.Chitosan exists
The numerous areas such as medicine, food, chemical industry, cosmetics, water process, METAL EXTRACTION and recovery, biochemistry and biomedical engineering should
Major progress is achieved with research.At present, the raw materials for production main source of chitosan is shrimp and crab shells, first therefrom chitin extraction,
It is deacetylated again to obtain chitosan..
Procambius clarkii is widely present in the sufficient ground of moisture all the year round such as the rivers lakes and marshes, pool wetland and irrigation canals and ditches in China
Side, based on popular one of the food feature, the food materials that Procambius clarkii is generally liked as the domestic masses of our people, often produce per year
The quantity of raw discarded shrimp shell is very huge, and discarded shrimp shell collection collection is convenient easily, cost is low, chitin content for these
It is high, if it is possible to rational be used makes it produce higher-value, can reduce environmental pollution, make full use of discarded object,
It is a very worthy wealth in society.
The content of the invention
Reducing production cost for current 3D printing material and improving the insufficient and a large amount of now of mechanics aspect of performance
The discarded shrimp shell of Procambius clarkii does not obtain the effective and reasonable deficiency utilized, is gathered the invention provides one kind based on modified shell
Sugar 3D printing material, it is intended to make the material on the basis of the original performance of high polymer material polymer is kept, increase product into
The pliability and mechanical strength of type, the biodegradability of material is improved, while effectively make use of house refuse discarded object,
Reach green purpose.
To achieve the above object, the present invention adopts the following technical scheme that：
The 3D printing material based on modification of chitosan of the present invention, its raw material include by weight：Modification of chitosan 80-
100 parts, butadiene-styrene rubber 20-40 parts, kaolin 20-35 parts, organo silane coupling agent 10-15 parts, hydroxypropyl methyl cellulose 10-
15 parts, polycaprolactone 1-4 parts, atoleine 1-4 parts, polyethylene glycol 1-5 parts, nanometer porous activated carbon 2-5 parts, polyphosphoric acids
Sodium 2-6 parts, nano silicon 3-9 parts, talcum powder 3-9 parts, zeolite powder 2-6 parts, surfactant 1-4 parts, antioxidant 3-5
Part.
Wherein, modification of chitosan is prepared by following technique：
(1) excessive 2mol/L hydrochloric acid solutions immersion reaction is added after taking the former superfluous shrimp shell cleaning of kirschner, drying, crushing
24h, be filtrated to get solid, be washed to neutrality, by gained solid add excessive 50g/L sodium hydroxide solutions about 90 DEG C-
Handled 5 hours at 95 DEG C, appropriate absolute ethyl alcohol washing is added after filtering, natural chitin is dried to obtain, it is natural to weigh gained
Chitin and water are put into reaction vessel, and stirring makes natural chitin be distributed in water, forms uniform suspension solution, natural first
The weight ratio of shell element and water is 1：(7-8)；
(2) suspension solution is increased the temperature to 50 DEG C, hydrogen peroxide and acetic acid mixed solution is added dropwise, is dripped in 40min；
3-4h is stirred at a temperature of 60-70 DEG C, obtains plain half settled solution of low-molecular weight crust；It is double in hydrogen peroxide and acetic acid mixed solution
Oxygen water concentration is 50%, the concentration of acetic acid is 60%；Hydrogen peroxide and acetic acid mixed solution gross weight are suspension solution weight
3.0-4.5%；
(3) sodium hydroxide solution is added in plain half settled solution of low-molecular weight crust, keeps system temperature in 65-70
DEG C, 20h is stirred, forms the oligopolymerization chitosan sugar juice of homogeneous clarification；The concentration of sodium hydroxide solution is 50%；Low molecule amount first
The weight ratio of shell half settled solution of element and sodium hydroxide solution is (1.9-2.1)：1；
(4) gained oligopolymerization chitosan sugar juice is heated to temperature as 65-70 DEG C, oxirane is added dropwise, in 40-60min drops
Add complete；Oxirane dosage is the 5% of chitosan oligomer solution quality；
(5) after adding oxirane, rise solution temperature to 80-85 DEG C reaction 4-5h after, addition molecular weight regulator after
Continuous reaction 3-4h, naturally cools to environment temperature, 2-3 hours is cured in reaction vessel；Hydroxyethylation is obtained after freeze-drying
Chitosan derivatives；
(6) according to 1：(0.3-0.5): the mass ratio of (0.1-0.2) weighs above-mentioned hydroxyethylated chitosan derivative respectively
Thing, bentonite and polyvinyl alcohol, above-mentioned three kinds of components are mixed and obtain modification of chitosan after grinding.
Described antioxidant is butylated hydroxy anisole or butylated hydroxytoluene.
Described surfactant be neopelex, cetyl benzenesulfonic acid sodium, octadecyl benzenesulfonic acid sodium,
One or more in lauryl sodium sulfate, NPE, OPEO.
A kind of preparation method of the 3D printing material based on modification of chitosan, it is concretely comprised the following steps：
(1) each raw material is weighed by following weight proportion：Modification of chitosan 80-100 parts, butadiene-styrene rubber 20-40 parts, kaolin
20-35 parts, organo silane coupling agent 10-15 parts, hydroxypropyl methyl cellulose 10-15 parts, polycaprolactone 1-4 parts, atoleine
1-4 parts, polyethylene glycol 1-5 parts, nanometer porous activated carbon 2-5 parts, sodium polyphosphate 2-6 parts, nano silicon 3-9 parts,
Talcum powder 3-9 parts, zeolite powder 2-6 parts, surfactant 1-4 parts, antioxidant 3-5 parts；
(2) kaolin, nanometer porous activated carbon, sodium polyphosphate, nano silicon, talcum powder, zeolite powder are put
Enter and mixing be ground in ball mill,
(3) mixed material obtained in step (2) is poured into the container for filling surfactant and antioxidant, stirred
Mix；
(4) polyethylene glycol, atoleine, polycaprolactone, hydroxypropyl methyl are sequentially added in the material obtained to step (3)
It is uniformly mixed after cellulose, organo silane coupling agent, adds modification of chitosan and butadiene-styrene rubber, is stirred at 70-85 DEG C
Mixing 3-4h is mixed, gains are cooled to 50-65 DEG C, are put into extruder, extruded material, is dried in vacuo and produces.
Preferably, raw material includes by weight：80 parts of modification of chitosan, 20 parts of butadiene-styrene rubber, 20 parts of kaolin, organosilicon
10 parts of alkane coupling agent, 10 parts of hydroxypropyl methyl cellulose, 1 part of polycaprolactone, 1 part of atoleine, 1 part of polyethylene glycol, nanoscale
2 parts of porous activated carbon, 2 parts of sodium polyphosphate, 3 parts of nano silicon, 3 parts of talcum powder, 2 parts of zeolite powder, surfactant 1
Part, 3 parts of antioxidant.
Preferably, raw material includes by weight：90 parts of modification of chitosan, 20 parts of butadiene-styrene rubber, 20 parts of kaolin, organosilicon
10 parts of alkane coupling agent, 12 parts of hydroxypropyl methyl cellulose, 4 parts of polycaprolactone, 4 parts of atoleine, 2 parts of polyethylene glycol, nanoscale
3 parts of porous activated carbon, 2 parts of sodium polyphosphate, 3 parts of nano silicon, 4 parts of talcum powder, 2 parts of zeolite powder, surfactant 2
Part, 4 parts of antioxidant.
Preferably, raw material includes 95 parts of modification of chitosan, 24 parts of butadiene-styrene rubber, 22 parts of kaolin, organosilicon by weight
12 parts of alkane coupling agent, 11 parts of hydroxypropyl methyl cellulose, 2 parts of polycaprolactone, 3 parts of atoleine, 4 parts of polyethylene glycol, nanoscale
4 parts of porous activated carbon, 4 parts of sodium polyphosphate, 6 parts of nano silicon, 7 parts of talcum powder, 3 parts of zeolite powder, surfactant 3
Part, 4 parts of antioxidant.
Preferably, raw material includes by weight：95 parts of modification of chitosan, 30 parts of butadiene-styrene rubber, 28 parts of kaolin, organosilicon
12 parts of alkane coupling agent, 13 parts of hydroxypropyl methyl cellulose, 4 parts of polycaprolactone, 4 parts of atoleine, 4 parts of polyethylene glycol, nanoscale
4 parts of porous activated carbon, 6 parts of sodium polyphosphate, 6 parts of nano silicon, 6 parts of talcum powder, 4 parts of zeolite powder, surfactant 3
Part, 4 parts of antioxidant.
Preferably, raw material includes by weight：100 parts of modification of chitosan, 40 parts of butadiene-styrene rubber, 35 parts of kaolin are organic
15 parts of silane coupler, 10 parts of hydroxypropyl methyl cellulose, 4 parts of polycaprolactone, 4 parts of atoleine, 5 parts of polyethylene glycol, nanometer
4 parts of porous activated carbon of level, 3 parts of sodium polyphosphate, 8 parts of nano silicon, 7 parts of talcum powder, 6 parts of zeolite powder, surfactant 3
Part, 4 parts of antioxidant.
Compared with the prior art, the beneficial effects of the invention are as follows：
The 3D printing material based on modification of chitosan adds the biodegradation of material by the addition of modification of chitosan
Rate, by carrying out graft modification to chitosan, add material pliability and with the high-molecular organic material component such as rubber
Amalgamation, compounded by raw material and play synergy, there is the advantages of toughness is strong, tensile strength is high, shaping is easy,
Moulding process is simple, meets the various requirement of 3D printing material, can preferably be applied to 3D printing technique field, natural chitin
Raw material sources are extensive, commercially available cheap, and are easy to transport, and production cost is relatively low, and market popularization value is good.
Embodiment
Technical scheme is described in further detail with reference to embodiment.
Embodiment 1
A kind of 3D printing material based on modification of chitosan, its raw material include by weight：80 parts of modification of chitosan, butylbenzene
20 parts of rubber, 20 parts of kaolin, 10 parts of organo silane coupling agent, 10 parts of hydroxypropyl methyl cellulose, 1 part of polycaprolactone, liquid
1 part of paraffin, 1 part of polyethylene glycol, nanometer porous 2 parts of activated carbon, 2 parts of sodium polyphosphate, 3 parts of nano silicon, talcum powder 3
Part, 2 parts of zeolite powder, 1 part of surfactant, 3 parts of antioxidant.
A kind of preparation method of the 3D printing material based on modification of chitosan, it is concretely comprised the following steps：
(1) each raw material is weighed by above-mentioned weight proportion；
(2) kaolin, nanometer porous activated carbon, sodium polyphosphate, nano silicon, talcum powder, zeolite powder are put
Enter and mixing be ground in ball mill,
(3) mixed material obtained in step (2) is poured into the container for filling surfactant and antioxidant, stirred
Mix；
(4) polyethylene glycol, atoleine, polycaprolactone, hydroxypropyl methyl are sequentially added in the material obtained to step (3)
It is uniformly mixed after cellulose, organo silane coupling agent, adds modification of chitosan and butadiene-styrene rubber, is stirred at 75 DEG C mixed
3h is closed, gains are cooled to 50 DEG C, is put into extruder, extruded material, is dried in vacuo and produces.
Wherein, modification of chitosan is prepared by following technique：
(1) excessive 2mol/L hydrochloric acid solutions immersion reaction is added after taking the cleaning of Procambius clarkii shell, drying, crushing
24h, solid is filtrated to get, is washed to neutrality, gained solid is added into excessive 50g/L sodium hydroxide solutions is handled at 90 DEG C
5 hours, appropriate absolute ethyl alcohol washing is added after filtering, natural chitin is dried to obtain, weighs gained natural chitin and water
It is put into reaction vessel, stirring makes natural chitin be distributed in water, forms uniform suspension solution, natural chitin and water
Weight ratio is 1: 7；
(2) suspension solution is increased the temperature to 50 DEG C, hydrogen peroxide and acetic acid mixed solution is added dropwise, is dripped in 40min；
3h is stirred at a temperature of 65 DEG C, obtains plain half settled solution of low-molecular weight crust；In hydrogen peroxide and acetic acid mixed solution, hydrogen peroxide is dense
The concentration spent for 50%, acetic acid is 60%；Hydrogen peroxide and acetic acid mixed solution gross weight are the 3.0% of suspension solution weight；
(3) sodium hydroxide solution is added in plain half settled solution of low-molecular weight crust, keeps system temperature to be stirred at 65 DEG C
20h is mixed, forms the oligopolymerization chitosan sugar juice of homogeneous clarification；The concentration of sodium hydroxide solution is 50%；Low-molecular weight crust element half
The weight of settled solution and sodium hydroxide solution ratio is 1.9: 1；
(4) gained oligopolymerization chitosan sugar juice is heated to temperature as 65 DEG C, oxirane is added dropwise, is dripped in 40-60min
Finish；Oxirane dosage is the 5% of chitosan oligomer solution quality；
(5) after adding oxirane, after rise solution temperature to 80 DEG C of reaction 4h, add molecular weight regulator and continue to react
3h, environment temperature is naturally cooled to, cured 2 hours in reaction vessel；Hydroxyethylated chitosan is obtained after freeze-drying to spread out
Biology；
(6) above-mentioned hydroxyethylated chitosan derivatives, bentonite are weighed respectively according to 1: 0.3: 0.1 mass ratio and gather
Vinyl alcohol, above-mentioned three kinds of components are mixed and obtain modification of chitosan after grinding.
Described antioxidant is butylated hydroxy anisole.
Described surfactant is neopelex.
After tested, the tensile strength of gained 3D printing material is 56MPa, elongation at break 140%.
Embodiment 2
A kind of 3D printing material based on modification of chitosan, its raw material include by weight：90 parts of modification of chitosan, butylbenzene
20 parts of rubber, 20 parts of kaolin, 10 parts of organo silane coupling agent, 12 parts of hydroxypropyl methyl cellulose, 4 parts of polycaprolactone, liquid
4 parts of paraffin, 2 parts of polyethylene glycol, nanometer porous 3 parts of activated carbon, 2 parts of sodium polyphosphate, 3 parts of nano silicon, talcum powder 4
Part, 2 parts of zeolite powder, 2 parts of surfactant, 4 parts of antioxidant.
A kind of preparation method of the 3D printing material based on modification of chitosan, it is concretely comprised the following steps：
(1) each raw material is weighed by above-mentioned weight proportion；
(2) kaolin, nanometer porous activated carbon, sodium polyphosphate, nano silicon, talcum powder, zeolite powder are put
Enter and mixing be ground in ball mill,
(3) mixed material obtained in step (2) is poured into the container for filling surfactant and antioxidant, stirred
Mix；
(4) polyethylene glycol, atoleine, polycaprolactone, hydroxypropyl methyl are sequentially added in the material obtained to step (3)
It is uniformly mixed after cellulose, organo silane coupling agent, adds modification of chitosan and butadiene-styrene rubber, is stirred at 75 DEG C mixed
4h is closed, gains are cooled to 55 DEG C, is put into extruder, extruded material, is dried in vacuo and produces.
Wherein, modification of chitosan is prepared by following technique：
(1) excessive 2mol/L hydrochloric acid solutions immersion reaction is added after taking the cleaning of Procambius clarkii shell, drying, crushing
24h, solid is filtrated to get, is washed to neutrality, gained solid is added into excessive 50g/L sodium hydroxide solutions at about 95 DEG C
Processing 5 hours, appropriate absolute ethyl alcohol washing is added after filtering, is dried to obtain natural chitin, weighs gained natural chitin
Be put into water in reaction vessel, stirring makes natural chitin be distributed in water, forms uniform suspension solution, natural chitin and
The weight ratio of water is 1: 8；
(2) suspension solution is increased the temperature to 50 DEG C, hydrogen peroxide and acetic acid mixed solution is added dropwise, is dripped in 40min；
4h is stirred at a temperature of 70 DEG C, obtains plain half settled solution of low-molecular weight crust；In hydrogen peroxide and acetic acid mixed solution, hydrogen peroxide is dense
The concentration spent for 50%, acetic acid is 60%；Hydrogen peroxide and acetic acid mixed solution gross weight are the 4.5% of suspension solution weight；
(3) sodium hydroxide solution is added in plain half settled solution of low-molecular weight crust, keeps system temperature to be stirred at 70 DEG C
20h is mixed, forms the oligopolymerization chitosan sugar juice of homogeneous clarification；The concentration of sodium hydroxide solution is 50%；Low-molecular weight crust element half
The weight of settled solution and sodium hydroxide solution ratio is 2.1: 1；
(4) gained oligopolymerization chitosan sugar juice is heated to temperature as 70 DEG C, oxirane is added dropwise, is dripped in 40-60min
Finish；Oxirane dosage is the 5% of chitosan oligomer solution quality；
(5) after adding oxirane, after rise solution temperature to 85 DEG C of reaction 5h, add molecular weight regulator and continue to react
4h, environment temperature is naturally cooled to, cured 3 hours in reaction vessel；Hydroxyethylated chitosan is obtained after freeze-drying to spread out
Biology；
(6) above-mentioned hydroxyethylated chitosan derivatives, bentonite are weighed respectively according to 1: 0.5: 0.2 mass ratio and gather
Vinyl alcohol, above-mentioned three kinds of components are mixed and obtain modification of chitosan after grinding.
Described antioxidant is butylated hydroxytoluene.
Described surfactant is the mixture of NPE and OPEO.
After tested, the tensile strength of gained 3D printing material is 60MPa, elongation at break 150%.
Embodiment 3
A kind of 3D printing material based on modification of chitosan, its raw material include by weight：95 parts of modification of chitosan, butylbenzene
24 parts of rubber, 22 parts of kaolin, 12 parts of organo silane coupling agent, 11 parts of hydroxypropyl methyl cellulose, 2 parts of polycaprolactone, liquid
3 parts of paraffin, 4 parts of polyethylene glycol, nanometer porous 4 parts of activated carbon, 4 parts of sodium polyphosphate, 6 parts of nano silicon, talcum powder 7
Part, 3 parts of zeolite powder, 3 parts of surfactant, 4 parts of antioxidant.
A kind of preparation method of the 3D printing material based on modification of chitosan, it is concretely comprised the following steps：
(1) each raw material is weighed by above-mentioned weight proportion；
(2) kaolin, nanometer porous activated carbon, sodium polyphosphate, nano silicon, talcum powder, zeolite powder are put
Enter and mixing be ground in ball mill,
(3) mixed material obtained in step (2) is poured into the container for filling surfactant and antioxidant, stirred
Mix；
(4) polyethylene glycol, atoleine, polycaprolactone, hydroxypropyl methyl are sequentially added in the material obtained to step (3)
It is uniformly mixed after cellulose, organo silane coupling agent, adds modification of chitosan and butadiene-styrene rubber, is stirred at 75 DEG C mixed
3h is closed, gains are cooled to 55 DEG C, is put into extruder, extruded material, is dried in vacuo and produces.
Wherein, modification of chitosan is prepared by following technique：
(1) excessive 2mol/L hydrochloric acid solutions immersion reaction is added after taking the cleaning of Procambius clarkii shell, drying, crushing
24h, solid is filtrated to get, is washed to neutrality, gained solid is added into excessive 50g/L sodium hydroxide solutions at about 95 DEG C
Processing 5 hours, appropriate absolute ethyl alcohol washing is added after filtering, is dried to obtain natural chitin, weighs gained natural chitin
Be put into water in reaction vessel, stirring makes natural chitin be distributed in water, forms uniform suspension solution, natural chitin and
The weight ratio of water is 1: 7.5；
(2) suspension solution is increased the temperature to 50 DEG C, hydrogen peroxide and acetic acid mixed solution is added dropwise, is dripped in 40min；
4h is stirred at a temperature of 65 DEG C, obtains plain half settled solution of low-molecular weight crust；In hydrogen peroxide and acetic acid mixed solution, hydrogen peroxide is dense
The concentration spent for 50%, acetic acid is 60%；Hydrogen peroxide and acetic acid mixed solution gross weight are the 3.5% of suspension solution weight；
(3) sodium hydroxide solution is added in plain half settled solution of low-molecular weight crust, keeps system temperature to be stirred at 70 DEG C
20h is mixed, forms the oligopolymerization chitosan sugar juice of homogeneous clarification；The concentration of sodium hydroxide solution is 50%；Low-molecular weight crust element half
The weight of settled solution and sodium hydroxide solution ratio is 2.0: 1；
(4) gained oligopolymerization chitosan sugar juice is heated to temperature as 70 DEG C, oxirane is added dropwise, is added dropwise in 50min；
Oxirane dosage is the 5% of chitosan oligomer solution quality；
(5) after adding oxirane, after rise solution temperature to 85 DEG C of reaction 5h, add molecular weight regulator and continue to react
4h, environment temperature is naturally cooled to, cured 3 hours in reaction vessel；Hydroxyethylated chitosan is obtained after freeze-drying to spread out
Biology；
(6) above-mentioned hydroxyethylated chitosan derivatives, bentonite are weighed respectively according to 1: 0.4: 0.1 mass ratio and gather
Vinyl alcohol, above-mentioned three kinds of components are mixed and obtain modification of chitosan after grinding.
Described antioxidant is butylated hydroxy anisole.
Described surfactant is lauryl sodium sulfate.
After tested, the tensile strength of gained 3D printing material is 60MPa, elongation at break 130%.
Embodiment 4
A kind of 3D printing material based on modification of chitosan, its raw material include by weight：95 parts of modification of chitosan, butylbenzene
30 parts of rubber, 28 parts of kaolin, 12 parts of organo silane coupling agent, 13 parts of hydroxypropyl methyl cellulose, 4 parts of polycaprolactone, liquid
4 parts of paraffin, 4 parts of polyethylene glycol, nanometer porous 4 parts of activated carbon, 6 parts of sodium polyphosphate, 6 parts of nano silicon, talcum powder 6
Part, 4 parts of zeolite powder, 3 parts of surfactant, 4 parts of antioxidant.
A kind of preparation method of the 3D printing material based on modification of chitosan, it is concretely comprised the following steps：
(1) each raw material is weighed by above-mentioned weight proportion；
(2) kaolin, nanometer porous activated carbon, sodium polyphosphate, nano silicon, talcum powder, zeolite powder are put
Enter and mixing be ground in ball mill,
(3) mixed material obtained in step (2) is poured into the container for filling surfactant and antioxidant, stirred
Mix；
(4) polyethylene glycol, atoleine, polycaprolactone, hydroxypropyl methyl are sequentially added in the material obtained to step (3)
It is uniformly mixed after cellulose, organo silane coupling agent, adds modification of chitosan and butadiene-styrene rubber, is stirred at 75 DEG C mixed
4h is closed, gains are cooled to 65 DEG C, is put into extruder, extruded material, is dried in vacuo and produces.
Wherein, modification of chitosan is prepared by following technique：
(1) excessive 2mol/L hydrochloric acid solutions immersion reaction is added after taking the cleaning of Procambius clarkii shell, drying, crushing
24h, solid is filtrated to get, is washed to neutrality, gained solid is added into excessive 50g/L sodium hydroxide solutions at about 90 DEG C
Processing 5 hours, appropriate absolute ethyl alcohol washing is added after filtering, is dried to obtain natural chitin, weighs gained natural chitin
Be put into water in reaction vessel, stirring makes natural chitin be distributed in water, forms uniform suspension solution, natural chitin and
The weight ratio of water is 1: 8；
(2) suspension solution is increased the temperature to 50 DEG C, hydrogen peroxide and acetic acid mixed solution is added dropwise, is dripped in 40min；
4h is stirred at a temperature of 70 DEG C, obtains plain half settled solution of low-molecular weight crust；In hydrogen peroxide and acetic acid mixed solution, hydrogen peroxide is dense
The concentration spent for 50%, acetic acid is 60%；Hydrogen peroxide and acetic acid mixed solution gross weight are the 4.5% of suspension solution weight；
(3) sodium hydroxide solution is added in plain half settled solution of low-molecular weight crust, keeps system temperature to be stirred at 70 DEG C
20h is mixed, forms the oligopolymerization chitosan sugar juice of homogeneous clarification；The concentration of sodium hydroxide solution is 50%；Low-molecular weight crust element half
The weight of settled solution and sodium hydroxide solution ratio is 2.1: 1；
(4) gained oligopolymerization chitosan sugar juice is heated to temperature as 70 DEG C, oxirane is added dropwise, is dripped in 60min
Finish；Oxirane dosage is the 5% of chitosan oligomer solution quality；
(5) after adding oxirane, after rise solution temperature to 85 DEG C of reaction 5h, add molecular weight regulator and continue to react
4h, environment temperature is naturally cooled to, cured 3 hours in reaction vessel；Hydroxyethylated chitosan is obtained after freeze-drying to spread out
Biology；
(6) above-mentioned hydroxyethylated chitosan derivatives, bentonite are weighed respectively according to 1: 0.5: 0.2 mass ratio and gather
Vinyl alcohol, above-mentioned three kinds of components are mixed and obtain modification of chitosan after grinding.
Described antioxidant is butylated hydroxytoluene.
Described surfactant is neopelex, cetyl benzenesulfonic acid sodium and octadecyl benzenesulfonic acid sodium
Mixture.
After tested, the tensile strength of gained 3D printing material is 65MPa, elongation at break 150%.
Embodiment 5
A kind of 3D printing material based on modification of chitosan, its raw material include by weight：100 parts of modification of chitosan, fourth
40 parts of benzene rubber, 35 parts of kaolin, 15 parts of organo silane coupling agent, 10 parts of hydroxypropyl methyl cellulose, 4 parts of polycaprolactone, liquid
4 parts of body paraffin, 5 parts of polyethylene glycol, nanometer porous 4 parts of activated carbon, 3 parts of sodium polyphosphate, 8 parts of nano silicon, talcum
7 parts of powder, 6 parts of zeolite powder, 3 parts of surfactant, 4 parts of antioxidant.
A kind of preparation method of the 3D printing material based on modification of chitosan, it is concretely comprised the following steps：
(1) each raw material is weighed by above-mentioned weight proportion；
(2) kaolin, nanometer porous activated carbon, sodium polyphosphate, nano silicon, talcum powder, zeolite powder are put
Enter and mixing be ground in ball mill,
(3) mixed material obtained in step (2) is poured into the container for filling surfactant and antioxidant, stirred
Mix；
(4) polyethylene glycol, atoleine, polycaprolactone, hydroxypropyl methyl are sequentially added in the material obtained to step (3)
It is uniformly mixed after cellulose, organo silane coupling agent, adds modification of chitosan and butadiene-styrene rubber, is stirred at 85 DEG C mixed
3-4h is closed, gains are cooled to 55 DEG C, is put into extruder, extruded material, is dried in vacuo and produces.
Wherein, modification of chitosan is prepared by following technique：
(1) excessive 2mol/L hydrochloric acid solutions immersion reaction is added after taking the cleaning of Procambius clarkii shell, drying, crushing
24h, solid is filtrated to get, is washed to neutrality, gained solid is added into excessive 50g/L sodium hydroxide solutions at about 95 DEG C
Processing 5 hours, appropriate absolute ethyl alcohol washing is added after filtering, is dried to obtain natural chitin, weighs gained natural chitin
Be put into water in reaction vessel, stirring makes natural chitin be distributed in water, forms uniform suspension solution, natural chitin and
The weight ratio of water is 1: 7；
(2) suspension solution is increased the temperature to 50 DEG C, hydrogen peroxide and acetic acid mixed solution is added dropwise, is dripped in 40min；
4h is stirred at a temperature of 65 DEG C, obtains plain half settled solution of low-molecular weight crust；In hydrogen peroxide and acetic acid mixed solution, hydrogen peroxide is dense
The concentration spent for 50%, acetic acid is 60%；Hydrogen peroxide and acetic acid mixed solution gross weight are the 4.0% of suspension solution weight；
(3) sodium hydroxide solution is added in plain half settled solution of low-molecular weight crust, keeps system temperature to be stirred at 70 DEG C
20h is mixed, forms the oligopolymerization chitosan sugar juice of homogeneous clarification；The concentration of sodium hydroxide solution is 50%；Low-molecular weight crust element half
The weight of settled solution and sodium hydroxide solution ratio is 2.0；1；
(4) gained oligopolymerization chitosan sugar juice is heated to temperature as 70 DEG C, oxirane is added dropwise, is dripped in 60min
Finish；Oxirane dosage is the 5% of chitosan oligomer solution quality；
(5) after adding oxirane, after rise solution temperature to 85 DEG C of reaction 5h, add molecular weight regulator and continue to react
4h, environment temperature is naturally cooled to, cured 3 hours in reaction vessel；Hydroxyethylated chitosan is obtained after freeze-drying to spread out
Biology；
(6) according to 1；0.4；0.2 mass ratio weighs above-mentioned hydroxyethylated chitosan derivatives, bentonite and gathered respectively
Vinyl alcohol, above-mentioned three kinds of components are mixed and obtain modification of chitosan after grinding.
Described antioxidant is butylated hydroxytoluene.
Described surfactant is neopelex, cetyl benzenesulfonic acid sodium, octadecyl benzenesulfonic acid sodium
With the mixture of lauryl sodium sulfate.
After tested, the tensile strength of gained 3D printing material is 64MPa, elongation at break 135%.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (5)
1. a kind of 3D printing material based on modification of chitosan, it is characterised in that its raw material includes by weight：Modification of chitosan
80-100 parts, butadiene-styrene rubber 20-40 parts, kaolin 20-35 parts, organo silane coupling agent 10-15 parts, hydroxypropyl methyl cellulose
10-15 parts, polycaprolactone 1-4 parts, atoleine 1-4 parts, polyethylene glycol 1-5 parts, nanometer porous activated carbon 2-5 parts, poly
Sodium phosphate 2-6 parts, nano silicon 3-9 parts, talcum powder 3-9 parts, zeolite powder 2-6 parts, surfactant 1-4 parts are anti-oxidant
Agent 3-5 parts.
A kind of 2. 3D printing material based on modification of chitosan according to claim 1, it is characterised in that described modification
Chitosan is prepared by following technique：(1) excessive 2mol/L is added after taking the cleaning of Procambius clarkii shell, drying, crushing
Hydrochloric acid solution immersion reaction 24h, is filtrated to get solid, is washed to neutrality, gained solid is added to excessive 50g/L sodium hydroxides
Solution is handled 5 hours at about 90 DEG C -95 DEG C, and appropriate absolute ethyl alcohol washing is added after filtering, is dried to obtain natural crust
Element, weighs gained natural chitin and water is put into reaction vessel, and stirring makes natural chitin be distributed in water, is formed uniform
The weight ratio of suspension solution, natural chitin and water is 1: (7-8)；(2) suspension solution is increased the temperature to 50 DEG C, dioxygen is added dropwise
Water and acetic acid mixed solution, are dripped in 40min；3-4h is stirred at a temperature of 60-70 DEG C, it is clear to obtain low-molecular weight crust element half
Clear solution；In hydrogen peroxide and acetic acid mixed solution, the mass percent concentration of hydrogen peroxide is that the 50%, mass percent of acetic acid is dense
Spend for 60%；Hydrogen peroxide and the 3.0-4.5% that acetic acid mixed solution gross weight is suspension solution weight；(3) in low molecule amount first
Sodium hydroxide solution is added in shell half settled solution of element, keeps system temperature to stir 20h at 65-70 DEG C, forms homogeneous, clarification
Oligopolymerization chitosan sugar juice；The mass percent concentration of sodium hydroxide solution is 50%；Low-molecular weight crust half settled solution of element
Weight ratio with sodium hydroxide solution is (1.9-2.1): 1；(4) it is 65-70 gained oligopolymerization chitosan sugar juice to be heated into temperature
DEG C, oxirane is added dropwise, is added dropwise in 40-60min；Oxirane dosage is the 5% of chitosan oligomer solution quality；
(5) after adding oxirane, after rise solution temperature to 80-85 DEG C of reaction 4-5h, add molecular weight regulator and continue to react 3-
4h, environment temperature is naturally cooled to, 2-3 hours are cured in reaction vessel；Hydroxyethylated chitosan is obtained after freeze-drying
Derivative；(6) according to 1: (0.3-0.5): the mass ratio of (0.1-0.2) weighs above-mentioned hydroxyethylated chitosan derivative respectively
Thing, bentonite and polyvinyl alcohol, above-mentioned three kinds of components are mixed and obtain modification of chitosan after grinding.
A kind of 3. 3D printing material based on modification of chitosan according to claim 1, it is characterised in that described antioxygen
Agent is butylated hydroxy anisole or butylated hydroxytoluene.
A kind of 4. 3D printing material based on modification of chitosan according to claim 1, it is characterised in that described surface
Activating agent is neopelex, cetyl benzenesulfonic acid sodium, octadecyl benzenesulfonic acid sodium, lauryl sodium sulfate, nonyl
One or more in base phenol polyethenoxy ether, OPEO.
A kind of 5. preparation method of 3D printing material based on modification of chitosan as described in claim 1-4, it is characterised in that
Concretely comprise the following steps：(1) each raw material is weighed by following weight proportion：Modification of chitosan 80-100 parts, butadiene-styrene rubber 20-40 parts are high
Ridge soil 20-35 parts, organo silane coupling agent 10-15 parts, hydroxypropyl methyl cellulose 10-15 parts, polycaprolactone 1-4 parts, liquid
Paraffin 1-4 parts, polyethylene glycol 1-5 parts, nanometer porous activated carbon 2-5 parts, sodium polyphosphate 2-6 parts, nano silicon 3-9
Part, talcum powder 3-9 parts, zeolite powder 2-6 parts, surfactant 1-4 parts, antioxidant 3-5 parts；(2) it is kaolin, nanoscale is more
Mesoporous activated carbon, sodium polyphosphate, nano silicon, talcum powder, zeolite powder, which are put into ball mill, is ground mixing, and (3) will
The mixed material obtained in step (2) is poured into the container for filling surfactant and antioxidant, is stirred and evenly mixed；(4) to step
Suddenly polyethylene glycol, atoleine, polycaprolactone, hydroxypropyl methyl cellulose, organosilan are sequentially added in the material that (3) obtain
It is uniformly mixed after coupling agent, adds modification of chitosan and butadiene-styrene rubber, 3-4h is stirred at 70-85 DEG C, by institute
Obtain thing and be cooled to 50-65 DEG C, be put into extruder, extruded material, be dried in vacuo and produce.
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