CN106957457A - It is a kind of for natural high molecular composite material of rapid shaping and preparation method thereof - Google Patents
It is a kind of for natural high molecular composite material of rapid shaping and preparation method thereof Download PDFInfo
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- CN106957457A CN106957457A CN201610016076.2A CN201610016076A CN106957457A CN 106957457 A CN106957457 A CN 106957457A CN 201610016076 A CN201610016076 A CN 201610016076A CN 106957457 A CN106957457 A CN 106957457A
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- chitosan
- alkaline solution
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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
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Materials For Medical Uses (AREA)
Abstract
The present invention relates to a kind of for natural high molecular composite material of rapid shaping and preparation method thereof.The present invention is from extensive, biocompatibility and the good material of biological degradability of drawing materials：Chitosan, cellulose, starch are matrix material, and composite is prepared by way of alkalization is handled, and are liquid under the composite normal temperature, possess the characteristic that is heating and curing, available for rapid prototyping manufacturing, can process the arbitrarily complicated model of structure.
Description
Technical field
The present invention relates to a kind of for natural high molecular composite material of rapid shaping and preparation method thereof.
Background technology
Rapid prototyping manufacturing has thoroughly overturned the method that traditional use material removing method reaches part shape and precision, using brand-new " increasing material " mode process component.Rapid prototyping technology provides true visible physical model to designer, producer and user, carries out functional test experiment for the design evaluation cycle of shortening new product, carries out rapid mold manufacture and rapid parts manufacturing, significant.Rapid prototyping manufacturing is widely used in fields such as automobile, aviation, electrical equipment, medical treatment.
Rapid prototyping manufacturing has a variety of classification, is divided into fuse deposition, selective laser sintering, the superposition of constituency lamella and Stereolithography etc. according to process principle, has silk material, dusty material, sheeting and liquid material again according to using the different of material.
Photosensitive resin liquid phase curing molding (SLA), also known as stereolithography apparatus method, it is one kind of rapid prototyping manufacturing, using liquid photosensitive resin raw material, its technical process is to go out threedimensional model by CAD design first, and model is carried out into slicing treatment using discrete program, design scanning pattern, the data of generation are by the motion of precise control laser scanner and lifting platform；The scanner that laser beam is controlled by numerical control device, liquid photosensitive resin surface is irradiated to by the scanning pattern of design, is made after one layer of resin solidification in the specific region of surface, after one layer of completion of processing, just generates a section of part；Then lifting platform to decline and cover another layer of liquid resin on certain distance, cured layer, then carries out second layer scanning, and the second cured layer is bonded on previous cured layer securely, and 3 D workpiece prototype is so formed by stacking from level to level.After prototype is taken out from resin, finally solidified.
The existing liquid material for rapid shaping is photosensitive resin material, be to cause polymerisation under the radiation by laser, complete solidification, material exist in itself materials be difficult, price it is high, the characteristics of difficult, preparation is complicated is preserved, and does not possess biocompatibility and biological degradability.
The content of the invention
An object of the present invention is to provide a kind of liquid material for rapid shaping, and can be heated rapid curing under the irradiation of laser, and the quick preparation of various models is realized on rapid forming equipment.The characteristics of material is that matrix material is easily obtained, and is prepared simply, cheap, and possesses good biocompatibility and biological degradability.
It is a further object to provide the preparation method of above-mentioned composite.
To achieve these goals, present invention employs following technical scheme：
A kind of natural high molecular composite material for rapid shaping, 1~3 is pressed by chitosan alkaline solution, starch and cellulose alkaline solution：(4~5)：1~3 mass ratio is mixed.
A kind of preparation method of natural high molecular composite material for rapid shaping, the preparation method comprises the following steps：
(1) by cellulose (weight average molecular weight 1.0~1.2 × 105), be dispersed in it is pre- be cooled in -10~12 DEG C of alkaline solution, stirring is sufficiently mixed it, obtains the plain alkaline solution of stable fibers.Wherein, the basic solvent component and its weight percentage of dissolving cellulose are：NaOH4~8%, urea 4~12%, remaining is water.
(2) Chitosan powder that deacetylation is 40~80%, molecular weight 20~1,000,000 is dispersed in alkaline solution, stirring makes it fully be swelled, by the chitosan suspension being fully swelled between -20~0 DEG C repeatedly freeze-thaw for several times, the chitosan solution stablized.Wherein, the basic solvent component and its weight percentage of dissolving chitosan are：NaOH4~8%, urea 4~12%, remaining is water.
(3) cellulose alkaline solution, chitosan alkaline solution and starch are pressed 1~3：(4~5)：After 1~3 mass ratio mixing, stir, it is static, obtain finished product.
The composite that the present invention is provided is using cellulose, chitosan and starch as main base.Wherein, cellulose is content most abundant natural polymer on the current earth, and annual biomass energy generation just can reach about 1.5 × 1016The cellulose that ton, only photosynthesis are produced just has hundreds billion of tons, is renewable resource.Compared with traditional synthesis macromolecular material, cellulose has the advantages that fully biodegradable, nontoxic, pollution-free, good biocompatibility.
Chitosan is the alkaline carbohydrate natural polymer uniquely found in current nature, and its yield is only second on cellulose, the earth annual nearly hundred billion tons of biosynthesis amount, and resource is extremely enriched.Chitosan has good biocompatibility and biological degradability, catabolite effect harmless to the human body, certain application is obtained in biomedical sector at present, developed includes application on human skin (wound dressing), operation suture thread and bone renovating material, anticoagulant and hemodialysis's film, pharmaceutical preparation and drug release agents etc. with potential application example.In addition, because there is chitosan certain antibacterial to make state, bacterium, toadstool growth can be suppressed, therefore be often added in cure foods or fresh-keeping etc. for marine products, fruit etc..Containing largely free amino, hydroxyl in chitosan molecule, the composite with certain mechanical strength, elasticity and transparent performance can be formed by the interaction of hydrogen bond or electrostatic force and sodium alginate, gelatin, starch, cellulose etc..
Starch is a kind of natural plant polyose, and it is widely present in the fruit of plant in the form of granules！Root！It is the source of the main carbohydrate of the mankind in stem.Starch resource enriches, cheap, has recyclability again and closely bound up with the human survival of the mankind.It all has generation carbon dioxide and water after degradable property, and degraded in various environment, to environment without any pollution.Therefore, starch is constantly subjected to the great attention of people in fields such as agricultural, industry and science and technology, and product is widely used in weaving, papermaking, chemical industry, medicine and other fields.
It is in a liquid state under prepared natural high molecular composite material normal temperature, curable shaping during heating, solidification temperature is according to the difference of component ratio at 60~80 DEG C.On rapid forming equipment, the mode heated using laser realizes the selective layering manufacture of the material, you can realize the quick manufacture of arbitrarily complicated model.The formed precision of molding part is high, mechanical strength is good.Simultaneously as having strong hydrogen bond action between cellulose and chitosan molecule, orderly macromolecular structure is formd, solubility property is very poor, it is impossible to be dissolved among general solvent, therefore the rapid shaping part prepared has preferable chemical stability.
In a word, the present invention prepares a kind of liquid natural polymer composite using chitosan, cellulose, starch as matrix material, possesses Thermocurable energy, available for rapid shaping, is capable of the mold elements of rapid processing any shape.The composite possesses cheap, easily obtains, the biocompatibility and the advantage of biological degradability possessed.
Brief description of the drawings
Fig. 1 is rapid shaping schematic diagram
Embodiment
A kind of natural high molecular composite material for rapid shaping, 1 is pressed by chitosan alkaline solution, starch and cellulose alkaline solution：2：1 mass ratio is mixed.
A kind of preparation method of natural high molecular composite material for rapid shaping, the preparation method comprises the following steps：
(1) by cellulose (weight average molecular weight 1.0 × 105), be dispersed in it is pre- be cooled in -10 DEG C of alkaline solution, stirring is sufficiently mixed it, obtains the plain alkaline solution of stable fibers.Wherein, the basic solvent component and its weight percentage of dissolving cellulose are：NaOH6%, urea 8%, remaining is water.
(2) be that the 60%, Chitosan powder of molecular weight 600,000 is dispersed in alkaline solution by deacetylation, stirring makes it fully be swelled, by the chitosan suspension being fully swelled between -20~0 DEG C repeatedly freeze-thaw for several times, the chitosan solution stablized.Wherein, the basic solvent component and its weight percentage of dissolving chitosan are：NaOH6%, urea 8%, remaining is water.
(3) cellulose alkaline solution, chitosan alkaline solution and starch are pressed 1：2：After 1 mass ratio mixing, stir, it is static, obtain finished product.
It is liquid under prepared natural high molecular composite material normal temperature, possesses good Thermocurable energy, solidification temperature is 70 DEG C, and when using it for rapid prototyping manufacturing, its molding process is：
Three-dimensional modeling is carried out to part model to be prepared by Computerized three-dimensional modeling software (solidworks or UG, CAD etc.), and demixing scan is carried out to threedimensional model using computer software, corresponding machining information is translated into provide rationally effective path for follow-up printing.
Shown in Fig. 1, the natural high molecular composite material 2 for preparing completion is injected into the liquid bath 1 of rapid forming equipment, ensure that workbench 3 is located under the liquid level of composite 2, and 50 DEG C are preheated to composite 2, then rapid forming equipment is started, generating laser 4 launches heating laser beam, starts that the progress heating of composite 2 is allowed to solidify under the irradiation of laser beam.During forming operation, laser beam after focusing presses the instruction of rapid forming equipment by point to line on liquid level, by line to face point by point scanning, the local composite 2 scanned is heat cured for, a part as formation of parts 5, and the place do not scanned is still the composite 2 of liquid condition, after the completion of a plane scan, 6 pairs of this layers of strickle need to be started to carry out finishing and strike off processing, subsequent lifting platform 7 declines the distance of a synusia thickness, so that the top of liquid level workpiece 5 covers one layer of liquid composite material 2 again, second layer scanning is carried out again, one layer newly solidified is strongly adhered in preceding layer, so repeat until whole complicated threedimensional model is completed by printing.
Machined parameters are selected：Using subregion scan mode, laser output power is 400W, and the rate travel of scanning laser light beam is 1800mm/s, and the characteristic radius of laser facula is 0.3mm, and laser beam sweep span is 0.15mm, and lift height is 0.1mm.
Claims (2)
1. a kind of natural high molecular composite material for rapid shaping, molten by chitosan alkaline solution, starch and cellulose alkaline
Liquid presses 1：2：1 mass ratio is mixed.
2. a kind of preparation method of natural high molecular composite material for rapid shaping according to claim 1, the preparation
Method comprises the following steps：
(1) by cellulose (weight average molecular weight 1.0~1.2 × 105), be dispersed in it is pre- be cooled in -10~12 DEG C of alkaline solution, stir
It is sufficiently mixed, the plain alkaline solution of stable fibers is obtained.Wherein, the basic solvent component and its weight percent of cellulose are dissolved
Content is：NaOH4~8%, urea 4~12%, remaining is water.
(2) Chitosan powder that deacetylation is 40~80%, molecular weight 20~1,000,000 is dispersed in alkaline solution, stirred
It is fully swelled, by the chitosan suspension being fully swelled between -20~0 DEG C repeatedly freeze-thaw for several times, the shell stablized
Glycan solution.Wherein, the basic solvent component and its weight percentage of dissolving chitosan are：NaOH4~8%, urea 4~12%,
Remaining is water.
(3) cellulose alkaline solution, chitosan alkaline solution and starch are pressed 1~3：(4~5)：After 1~3 mass ratio mixing,
Stir, it is static, obtain finished product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610016076.2A CN106957457A (en) | 2016-01-12 | 2016-01-12 | It is a kind of for natural high molecular composite material of rapid shaping and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114191601A (en) * | 2021-11-25 | 2022-03-18 | 华南理工大学 | Starch gel hemostatic material based on 3D printing technology and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634040A (en) * | 2012-04-26 | 2012-08-15 | 安徽理工大学 | Basic solvent for dissolving chitosan and method for dissolving chitosan under alkaline condition |
| CN103467760A (en) * | 2013-09-09 | 2013-12-25 | 浙江大学 | Method for preparing high-strength chitosan/cellulose composite hydrogel film |
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- 2016-01-12 CN CN201610016076.2A patent/CN106957457A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634040A (en) * | 2012-04-26 | 2012-08-15 | 安徽理工大学 | Basic solvent for dissolving chitosan and method for dissolving chitosan under alkaline condition |
| CN103467760A (en) * | 2013-09-09 | 2013-12-25 | 浙江大学 | Method for preparing high-strength chitosan/cellulose composite hydrogel film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114191601A (en) * | 2021-11-25 | 2022-03-18 | 华南理工大学 | Starch gel hemostatic material based on 3D printing technology and preparation method and application thereof |
| CN114191601B (en) * | 2021-11-25 | 2022-05-24 | 华南理工大学 | Starch gel hemostatic material based on 3D printing technology and preparation method and application thereof |
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