CN107936186A - 3D printing silk material and preparation method - Google Patents

3D printing silk material and preparation method Download PDF

Info

Publication number
CN107936186A
CN107936186A CN201610892128.2A CN201610892128A CN107936186A CN 107936186 A CN107936186 A CN 107936186A CN 201610892128 A CN201610892128 A CN 201610892128A CN 107936186 A CN107936186 A CN 107936186A
Authority
CN
China
Prior art keywords
cellulose
acid
ester
aliphatic polyester
blend
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610892128.2A
Other languages
Chinese (zh)
Other versions
CN107936186B (en
Inventor
詹姆斯·洪学·王
周炳
贾钦
况军
白瑜
王巍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201610892128.2A priority Critical patent/CN107936186B/en
Publication of CN107936186A publication Critical patent/CN107936186A/en
Application granted granted Critical
Publication of CN107936186B publication Critical patent/CN107936186B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Abstract

The present invention relates to a kind of blend 3D printing silk material, it is high mainly to solve thermoplastic cellulose low temperature process process medium viscosity in the prior art, product poor toughness, and it is set to be difficult to apply the technical problem in 3D printing field, by using the 3D printing silk material of the thermoplastic cellulose containing graft modification and Aliphatic Polyester Blends, in terms of mass fraction, thermoplastic cellulose and the Aliphatic Polyester Blends of the graft modification include following components：(1) 20 to 80 part of thermoplastic cellulose；(2) 80 to 20 parts of aliphatic polyester；(3) 0.1 to 10 parts of reactive monomer；It is characterized in that reactive monomer is at least grafted to thermoplastic cellulose and the technical solution on aliphatic polyester one in the blend, preferably solves the problems, such as this, so as to effectively widen the application range of thermoplastic cellulose blend material, and since blend melt viscosity is low, it can be used for more energy savingly in 3D printing silk material process.

Description

3D printing silk material and preparation method
Technical field
The invention belongs to 3D printing silk material field, has body Wataru and a kind of thermoplastic of the graft modification with the special rheological equationm of state Property cellulose and aliphatic polyester blend 3D printing silk material, this invention also Wataru and a kind of prepare with the special rheological equationm of state The thermoplastic cellulose of graft modification and the method for Aliphatic Polyester Blends 3D printing silk material.
Technical background
Cellulose is the organic polymer that reserves are most on the earth, and the most biological material of annual reproducible amounts. Cellulose is the structural material in non-green plant cell wall, and xylophyta contains the cellulose of about 30-40%, cotton fiber then contains There is about 90% cellulose.The major commercial use of cellulose is paper and cardboard, separately has a small amount of cellulose to be used to prepare such as match The regenerated celluloses such as fine jade phenol (Cellophane), viscose glue (Rayon) and some fibre element derivative.
Since cellulose is the natural polymer that plant changes into the carbon dioxide in air and water by photosynthesis, Therefore the carbon in cellulose belong to fixed in the recent period carbon and different from fossil fuel and its petroleum chemicals such as oil or coals In millions of years before fixed carbon, the carbon that different times are fixed can pass through14C isotope standardizations are examined Survey.Due to these difference, had based on bio-based high molecular material prepared by biomass material relative to petroleum base high molecular material There is the advantage of raw material low-carbon, then using low energy consumption and the production technology of low-carbon emission, it is possible to produce the high score of green low-carbon Sub- material.For such consideration, natural polymer, including cellulose, hemicellulose, lignin, starch, chitin etc., and its Derivative and material receive increasingly increased concern and research and development in the whole world, to develop good green low-carbon environment-friendly material. And pass through the extensive use for the green low-carbon material that Life Cycles assessment (Life Cycle Assessment) confirms, it will help In supporting green production and Green Lifestyle, ease up to reduce the content of the greenhouse gases (carbon dioxide etc.) in air The climate change in the solution whole world contributes.
Although cellulose has the advantages that the low-carbon on raw material, the cellulose amount as plastic products application is seldom, this is Since the heat decomposition temperature of cellulose is less than its fusing point without thermoplastic properties.To overcome this defect of cellulose, research Staff development has gone out the regenerated cellulose of solwution method production, i.e., cellulose or cellulose derivative is first dissolved in solvent, passes through Solution machine-shaping is crossed, is changed into cellulose again after being prepared into film or spinning, the viscose rayon in textile industry uses this It is prepared by kind method.
In addition for cellulose derivative when three hydroxyls on each of which repetition dehydrated glucose unit are through enough changes After learning transformation, can also have relatively low fusing or plasticization temperature, limited thermoplastic processing can be carried out, become thermoplastic fibre Element, this kind of material include the cellulose esters and cellulose ether of certain substitution value.Yield and production due to this kind of cellulose derivative Kind class is limited, and the viscosity of industrialized such product is higher, is especially apparent under compared with low processing temperature, is not suitable for needing The processing method of low melt viscosity such as spinning, injection etc.；Cellulose esters and cellulose ether, which have, at present is greatly used as coating Or the additive of adhesive field【High Zhenhua, Di Mingwei,《Biological material and application》, 2008】.
3D printing belongs to the increasing material technology of rapid shaping technique, it is a kind of based on digital model file, by right Material is successively printed to prepare the technology of 3-dimensional block.By the development of nearly 30 years, 3D technology had been considered to change laboratory And one of core technology of industrial mode of production.Currently used 3D printing technique mainly has stereolithography (Stereolithography), ink jet printing (Inkjet Printing), selective laser sintering (Selective Laser Sintering), fused glass pellet (Fused Deposition Modeling) etc..And the material available for 3D printing is then contained Metal dust, ceramic powders, light-cured resin, thermoplastic etc. are covered.[Analytical Chemistry 2014,86 (7),3240-3253.]
Cellulose and its derivates are wide with source, biodegradable, non-toxic, the advantages that chemically and thermally stablizing, and This century receives more and more attention, and is being packed by the cellulose products that conventional method is prepared, medicine, optical thin film Important application [Progress in Polymer Science, 2001,26 (9), 1605-1688.] is shown Deng field.It is near Year, researcher starts 3D printing technique and cellulose being combined to play both advantages.Such as Salmora with Cellulose acetate particulate or starch-cellulose fine particle are raw material, strong by adjusting laser using Selective Laser Sintering The block materials with good mechanical properties and hot property have been prepared in degree, sweep speed and feedstock Particle size etc. [Polymer Testing, 2009,28 (6), 648-652.].Spread out in addition, 3D printing technique is also used to prepare containing cellulose The tablet of biology and medicine.Such as Pietrzak is by twin-screw by the hydroxypropyl cellulose of definite composition and medicine theophylline (Theophylline) mixed and prepare silk material, after pass through the direct 3D printing tablet of fused glass pellet technology.With tradition Prepare tablet method to compare, this method has cost low, and dose controls the advantages that accurate [http://dx.doi.org/ 10.1016/j.jddst.2015.07.016；European Journal of Pharmaceutics and Biopharmaceutics 2015,96,380-387]。
In terms of artificial bone or other prostheses, the material containing celluosic resin that 3D printing technique is prepared displays that Important application [European Journal of Pharmaceutics and Biopharmaceutics 2015,96, 380-387][U.S.Patent 6,932,610B2,U.S.Patent Application,2009/0220917 A1].Pass through Laser sintering technology, will contain the sample preparation of celluosic resin, inorganic particle etc. into the high artificial bone structure of precision, Can be vivid be used for experimental teaching [U.S.Patent 6,932,610B2].In addition, cellulose and its derivates can also be made For processing aid such as bonding agent, thickener etc., play a significant role when preparing other block of material by 3D printing technique [U.S.Patent 7,332,537 B2,104448744 A of CN,U.S.Patent 2012/003002 A1].Preparing gypsum During the block of the 3D structures of particle, cellulose and its derivates can be used as bonding agent, by stone by way of inkjet printing Cream particles stick is into three-dimensional macro material [7,332,537 B2 of U.S.Patent].
Up to now, rarely has the report that thermoplastic cellulose derivative is used for 3D printing material with Biodegradable polyester blend Road.Therefore, from the angle of processed and applied, there is exploitation low viscosity and there is the thermoplastic cellulose derivative of excellent machinability Technical need, to meet the market demand of the cellulosic material in terms of 3D printing.
So far, there has been no reported in literature graft modification thermoplastic cellulose and Aliphatic Polyester Blends it is special Rheological behaviour, and glued in the prior art without the melt for providing effective reduction thermoplastic cellulose and Aliphatic Polyester Blends The method of degree, is restricted the application of this kind of blend.
The continuous of thermoplastic cellulose and Aliphatic Polyester Blends melt viscosity is effectively reduced the invention discloses a kind of Melting extrusion method, it was found that unexpected phenomenon with being formed as a result, disclosing blend with the special rheological equationm of state, and The blend has been applied to 3D printing Material Field by success.
The content of the invention
Present invention solves the technical problem that one of be that thermoplastic cellulose is melted with Aliphatic Polyester Blends in the prior art Body viscosity is excessive and the problem of may not apply to need the field of low melt viscosity, there is provided a kind of connecing with the special rheological equationm of state The modified thermoplastic cellulose of branch and Aliphatic Polyester Blends 3D printing silk material, which can using blend material Effectively the viscosity " unexpected " of blend is fallen below being total to for thermoplastic fibres element and aliphatic polyester starting material Mix into theoretical viscosity；So that the blend has the processing performance realized be prepared into 3D printing silk material at a lower temperature, it is excellent In the similar blend of the prior art, and since blend melt viscosity is low, it can be made more energy saving in process.
The second technical problem to be solved by the present invention, which is to provide, a kind of prepares the graft modification with the special rheological equationm of state Thermoplastic cellulose and Aliphatic Polyester Blends 3D printing silk material method, the melt viscosity for the blend that this method obtains In low shear rate (100s-1) under the conditions of it is at least lower by about 30% than the blending addition theoretical value of two kinds of starting materials；In high shear Speed (1363s-1) under the conditions of it is at least lower by 25% than the blending addition theoretical value of two kinds of starting materials.
One of in order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：A kind of 3D printing silk material, contains The thermoplastic cellulose and Aliphatic Polyester Blends of graft modification, in terms of mass fraction, the thermoplastic fibre of the graft modification Element includes following components with Aliphatic Polyester Blends：
(1) 20 to 80 part of thermoplastic cellulose；
(2) 80 to 20 parts of aliphatic polyester；
(3) 0.1 to 10 parts of reactive monomer；
Wherein, reactive monomer is at least grafted to thermoplastic cellulose and one kind in aliphatic polyester in the blend On.
In above-mentioned technical proposal, the 3D printing silk material is blended by the thermoplastic cellulose of graft modification with aliphatic polyester Thing is made, and thermoplastic cellulose and the Aliphatic Polyester Blends of the graft modification have the special rheological equationm of state, such as described blending The melt viscosity of thing is in low shear rate 100s-1Under the conditions of it is at least lower than the blending addition theoretical value of two kinds of predominant starting materials 30%；In high-rate of shear 1363s-1Under the conditions of it is at least lower than the blending addition theoretical value raw material of two kinds of predominant starting materials 25%.
In above-mentioned technical proposal, " two kinds of predominant starting materials " what is referred to is exactly thermoplastic cellulose and aliphatic poly Ester.
In above-mentioned technical proposal, the substitution value of the thermoplastic cellulose is preferably greater than 1.0；The cellulose being more suitable for spreads out The substitution value of biology is more than 1.5, and the substitution value of particularly suitable cellulose derivative is more than 2.0.
In above-mentioned technical proposal, the thermoplastic cellulose is preferably cellulose acetate-butyrate, acetic acid valeric acid fiber Plain ester, acetic acid cellulose caproate ester, acetic acid enanthic acid cellulose esters, laurate cellulose esters, acetic acid cellulose pelargonate ester, acetic acid Capric acid cellulose esters, acetic acid laurate cellulose esters, acetic acid palmitic acid cellulose esters, acetic acid cellulose stearate ester, propionic acid fourth Acid cellulose ester, propionic acid cellulose valerate ester, propionic acid cellulose caproate ester, propionic acid enanthic acid cellulose esters, propionic acid octanoic acid cellulose Ester, propionic acid cellulose pelargonate ester, propionic acid capric acid cellulose esters, propionic acid laurate cellulose esters, propionic acid palmitic acid cellulose esters, third Sour cellulose stearate ester etc..
In above-mentioned technical proposal, the aliphatic polyester is preferably α, ω-aliphatic diacid or derivatives thereof and fat Race's glycol condensation forms polyester；The α, ω-aliphatic diacid are preferably at least two kinds and contain 2 to 22 backbone c atoms α, ω-aliphatic diacid, including：Oxalic acid, 1,3- malonic acid, butanedioic acid (1, 4- succinic acid), glutaric acid (1,5- glutaric acid), fertilizer Sour (1,6- adipic acid), 1,7- pimelic acid, 1,8- suberic acid, 1,9- azelaic acid, 1,10- decanedioic acid is until carbon number reaches 22 Binary acid；The α, the derivative of ω-aliphatic diacid include the corresponding acid anhydrides of above-mentioned diacid, ester, carboxylic acid halides etc..
In above-mentioned technical proposal, the α, ω-aliphatic diacid is preferably the α containing substituent, ω-aliphatic diacid； Contain 2 α to 22 backbone c atoms, ω-aliphatic diacid more preferably containing substituent；The substituent Preferably straight chained alkyl, the alkyl with side chain, ring-like alkyl, the alkyl with unsaturated structure；With with other substituents Such as the binary acid of cyclohexyl.
In above-mentioned technical proposal, include ethylene glycol suitable for preparing the aliphatic diol of aliphatic polyester of the present invention, 1, 2- propane diols, 1,3-PD, 1,2- butanediol, 1,3-BDO, 1,4-butanediol, 1,2- pentanediol, 1,3- pentanediols, 1, 4- pentanediols, 1,5-PD, 1,2- hexylene glycol, 1,3- hexylene glycols, Isosorbide-5-Nitrae-hexylene glycol, 1,5- hexylene glycols, 1,6- hexylene glycols, 1, 2- heptandiols, 1,3- heptandiols, Isosorbide-5-Nitrae-heptandiol, 1,5- heptandiols, 1,6- heptandiols, 1,7- heptandiols, 1,2- ethohexadiols, 1, 3- ethohexadiols, Isosorbide-5-Nitrae-ethohexadiol, 1,5- ethohexadiols, 1,6- ethohexadiols, 1,7- ethohexadiols, 1,8- ethohexadiols, 1,2- nonanediols, 1, 3- nonanediols, Isosorbide-5-Nitrae-nonanediol, 1,5- nonanediols, 1,6- nonanediols, 1,7- nonanediols, 1,8- nonanediols, 1,9- nonanediols, 1, 2- decanediols, 1,3- decanediols, Isosorbide-5-Nitrae-decanediol, 1,5- decanediols, 1,6- decanediols, 1,7- decanediols, 1,8- decanediols, 1, 9- decanediols, 1,10- decanediols are until carbon number reaches 24 glycol and dihydric alcohol with other substituents such as cyclohexyl.
In above-mentioned technical proposal, the aliphatic polyester is preferably：Poly- oxalic acid glycol ester, Crude oil ethylene glycol Ester, polyethylene glycol succinate, poly- EGG ethylene glycol glutarate, polyethylene glycol adipate, polyethylene glycol suberate, poly- oxalic acid Propylene glycol ester, Crude oil propylene glycol ester, poly-succinic propylene glycol ester, poly- glutaric acid propylene glycol ester, polypropylene glycol adipate, Poly- suberic acid propylene glycol ester, poly- decanedioic acid propylene glycol ester, poly- oxalic acid butanediol ester, Crude oil butanediol ester, poly-succinic fourth Diol ester, poly- glutaric acid butanediol ester, poly adipate succinic acid ester, poly- suberic acid butanediol ester, poly- oxalic acid hexylene glycol ester, poly- third Diacid hexylene glycol ester, poly-succinic hexylene glycol ester, poly- glutaric acid hexylene glycol ester, polyadipate hexylene glycol ester, poly- suberic acid oneself two At least one of alcohol ester.
In above-mentioned technical proposal, the blending addition theoretical value of the melt index of the blend than two kinds of predominant starting materials It is at least high by about 90%.
In above-mentioned technical proposal, the reactive monomer is with hydroxyl, carboxyl, carbonyl, ester group, amino, sulfydryl, sulphur Acidic group, ehter bond, halogen, peptide bond, anhydride bond isopolarity group, and at least one in the compound also containing unsaturated carbon-carbon double bond Kind.The reactive monomer can react with other components in blend under certain condition, and then be grafted with covalent bond Onto other components, special modified effect is played.
In above-mentioned technical proposal, the reactive monomer is preferably maleic acid anhydride, acrylic compounds, methacrylic acid At least one of compounds such as class, esters of acrylic acid, methyl acrylic ester, acrylic amide, methacryl amine.
In above-mentioned technical proposal, the blend further preferably includes：The initiator of (4) 0.01 to 1 mass parts.
In above-mentioned technical proposal, the initiator is radical initiator, is produced from for decomposable asymmetric choice net under certain condition By the organic compound of base, include but is not limited to：Acyl peroxide, such as benzoyl peroxide (BPO)；Alkyl (dialkyl group) Peroxide, such as dual-tert-butyl peroxide, double cumyl peroxides, cumyl peroxy butyl, 3,3,5- front threes Butylcyclohexane -1,1- diperoxies the tert-butyl group, 2,5- dimethyl -2,5- di-t-butyl peroxyhexanes etc.；Perester, such as crosses trimethyl Tert-butyl acetate, mistake -2 ethyl hexanoic acid tert-butyl ester, t-butyl perbenzoate, peroxidating lauric acid etc.；Alkyl peroxide, Such as tert-butyl hydroperoxide, isopropyl benzene hydroperoxide；Ketone peroxide, such as methyl ethyl ketone peroxide；Azo compound, such as azo Two isobutyl cyanogen (AIBN) etc..
In above-mentioned technical proposal, the initiator is preferably benzoyl peroxide, and azo-bis-isobutyl cyanide, peroxidating two are different Propyl benzene, di-t-butyl peroxide, tert-butyl hydroperoxide, perbenzoic acid, 2,5- dimethyl -2,5- di-t-butyls peroxide oneself At least one of alkane etc..
In above-mentioned technical proposal, the thermoplastic cellulose is preferably cellulose acetate-butyrate, and aliphatic polyester is preferred For poly butylene succinate, polyethylene glycol succinate etc., reactive monomer is preferably hydroxyethyl methacrylate, methyl-prop Olefin(e) acid ethylene oxidic ester etc., initiator are preferably benzoyl peroxide, 2,5- dimethyl -2,5- di-t-butyl hexane peroxides (double two or five) etc., have good compatibility at this time between component of mixture, and mixture shows the special rheological equationm of state, The use scope of starting material can be widened significantly, while relatively low melt viscosity can reduce the energy in material processing Consumption.
In above-mentioned technical proposal, the blend material is most preferably that the blend material contains 20 to 80 mass parts Thermoplastic cellulose, the aliphatic polyester of 80 to 20 mass parts, the reactive monomer of 0.1 to 10 mass parts and 0.01 to 1 quality The initiator of part, the synergistic function between component is most obvious at this time, and obtained blend rheological property and compatibility is most It is good.
In above-mentioned technical proposal, the blend material further preferably contains compatibility agent, inorganic filler, antioxidant, lubrication At least one of agent, colouring agent etc..
In above-mentioned technical proposal, the melt viscosity of the blend 3D printing silk material is preferably in low shear rate (100s-1) under the conditions of 45% (the preferably aliphatic of 65 to 20 mass parts at least lower than the blending addition theoretical value of two kinds of predominant starting materials The thermoplastic cellulose of polyester and 35 to 80 mass parts, reactive monomer are 2 to 8 mass parts, and initiator is 0.05 to 0.2 quality Part), further preferably at least low 55% (the more preferably thermoplasticity of the aliphatic polyester of 50 to 35 mass parts and 50 to 65 mass parts Cellulose, reactive monomer are 2 to 6 mass parts, and initiator is 0.075 to 0.15 mass parts).
In above-mentioned technical proposal, the melt viscosity of the blend 3D printing silk material is preferably in high-rate of shear (1363s-1) under the conditions of it is at least lower by 35% than the blending addition theoretical value of two kinds of predominant starting materials (preferably 65 to 20 mass parts The thermoplastic cellulose of aliphatic polyester and 35 to 80 mass parts, reactive monomer are 2 to 8 mass parts, initiator for 0.05 to 0.2 mass parts), further preferably at least low 45% (the more preferably aliphatic polyester of 50 to 20 mass parts and 50 to 80 mass parts Thermoplastic cellulose, reactive monomer is 2 to 6 mass parts, and initiator is 0.075 to 0.15 mass parts).
In above-mentioned technical proposal, melt index preferably than the two kinds predominant starting materials of the blend 3D printing silk material Blending addition theoretical value it is at least high by about 90%, more preferably at least high about 150% (the preferably fat of 65 to 20 mass parts The thermoplastic cellulose of adoption ester and 35 to 80 mass parts, reactive monomer are 2 to 8 mass parts, and initiator is 0.05 to 0.2 matter Measure part), it is more preferably at least high by about 200% (the more preferably heat of the aliphatic polyester of 50 to 20 mass parts and 50 to 80 mass parts Plasitc fibers element, reactive monomer is 2 to 6 mass parts, and initiator is 0.075 to 0.15 mass parts).
Aliphatic polyester in the present invention can pass through from above-mentioned different aliphatic diacids with aliphatic diol to be polymerize It is prepared by reaction.The catalyst of polymerization includes the compound containing metallic tin, antimony, titanium etc..Aliphatic polyester is included by chain extension Aliphatic polyester, it is a variety of that there is compound or polymer with carboxyl or hydroxyl reaction activity may be used as chain extender, such as include Isocyanates such as hexamethylene diisocyanate (hexamethylene containing two and above functional group diisocyanate,HMDI).Compound of the applicable chain extender including containing multiple epoxy-functionals, such as BASF productionsADR-4368C,ADR-4368CS etc..The chain extender mass content of the present invention is 0.2 to 4%, Chain extender mass content in some concrete embodiments is 0.5 to 3%.
Aliphatic polyester in the present invention includes the linear and polyester with side chain.Polyester of the synthesis with side chain is closing One or more branching agents are added during.Side chain agent be generally with two or more carboxyl polyacid, with two with Polyalcohol or polyhydroxy-acid of upper hydroxyl etc..Applicable side chain agent includes glycerine, trimethylolethane, trimethylolpropane, 1, 2,4- butantriols, pentaerythrite, 1,2,6- hexanetriols, D-sorbite, 1,2,3 benzenetricarboxylic acids (hemimellitic acid), 1, 2,4- benzenetricarboxylic acids (triimellitic acid), 1,3,5- benzenetricarboxylic acids (trimesic acid) and acid anhydrides etc..
In order to solve the above-mentioned technical problem two, the technical solution adopted in the present invention is：One kind prepares above-mentioned 3D printing The method of silk material, using continuous fusion blending extrusion, the desired amount of each component is uniformly mixed in the molten state, and squeezes Go out to be granulated, obtain the thermoplastic cellulose and Aliphatic Polyester Blends particle with the graft modification of the special rheological equationm of state；Will The blends particles melt extrusion in extrusion device, the 3D printing silk material are prepared by mouth mold.
In above-mentioned technical proposal, the desired amount of each component includes the desired amount of thermoplastic cellulose, the desired amount of aliphatic Polyester, the desired amount of reactive monomer, further preferably including the desired amount of initiator.
In above-mentioned technical proposal, thermoplastic cellulose and the Aliphatic Polyester Blends melt blending of the graft modification Method is preferably twin-screw continuous extrusion method.
In above-mentioned technical proposal, thermoplastic cellulose and the Aliphatic Polyester Blends melt blending of the graft modification Method preferably include by thermoplastic cellulose powder by continuous extruding pelletization then again with aliphatic polyester, reactive monomer and Initiator is added on a double screw extruder after being blended according to required ratio and carries out extruding pelletization.
In above-mentioned technical proposal, thermoplastic cellulose and the Aliphatic Polyester Blends melt blending of the graft modification Method preferably include by thermoplastic cellulose powder by continuous extruding pelletization then again with aliphatic polyester, reactive monomer and Initiator is dosed on a double screw extruder and carries out extruding pelletization respectively according to required feeding ratio.
In above-mentioned technical proposal, thermoplastic cellulose and the Aliphatic Polyester Blends melt blending of the graft modification Method is preferably included thermoplastic cellulose powder and aliphatic polyester, reactive monomer and initiator according to certain feeding ratio Example is dosed on a double screw extruder respectively carries out extruding pelletization.
In above-mentioned technical proposal, thermoplastic cellulose and the Aliphatic Polyester Blends melt blending of the graft modification The screw speed of method is preferably 50rpm to 1500rpm.
In above-mentioned technical proposal, thermoplastic cellulose and the Aliphatic Polyester Blends melt blending of the graft modification The temperature of method is preferably 140 DEG C to 240 DEG C.
In above-mentioned technical proposal, the mouth mold is circular mouth mold.
Material therefor of the present invention and preparation method are simply described below below：
1. thermoplastic cellulose
The thermoplastic cellulose of the present invention is the very wide cellulose derivative of a kind of scope, such cellulose derivative Each three hydroxylic moieties repeated on dehydrated glucose unit or all carried out being esterified or be etherified etc. the chemistry of form and changed Property.The extent index for characterizing its modification is substitution value (Degree of Substitution), it is defined as each repetition and is dehydrated The mean number substituted on glucose unit in three hydroxyls, maximum were 3.0 (3 hydroxyls are all substituted), minimum 0 (pure cellulose).
The thermoplastic cellulose ester included in the present invention include cellulose and two kinds and two or more alicyclic organic aliphatic carboxylic acids, The mixed cellulose ester that organic fatty race acid anhydrides and organic fatty race carboxylic acid halides are formed, different alicyclic organic aliphatic carboxylic acids, organic fatty The carbon number difference of race's acid anhydrides and organic fatty race carboxylic acid halides is greater than or equal to 1.
Cellulose esters is usually made by native cellulose and the reactions such as organic acid, acid anhydrides or acyl chlorides, the hydroxyl in cellulose Substitution value is from 0.5 to 2.8.Applicable cellulose ester product includes the Eastman of Eastman Chemical of U.S. productionTMAcetic acid fourth Acid cellulose ester CAB-171-15, CAB-321-0.1, CAB-381-0.1, CAB-381-0.5, CAB-381-20, CAB-485- 10, CAB-500-5, CAB-531-1 etc..Such as：Butyryl component containing 50% mass fraction, 2.8% mass in CAB-531-1 The acetyl component of fraction, the hydroxyl moieties of 1.7% mass fraction, the viscosity measured according to 1343 standards of ASTM are 5.6 pools.It is fine The plain ester of dimension has application in industries such as fiber, weaving, coating, food additives and pharmaceutical industries.In coating industry, with the addition of Coating effect can be improved after cellulose esters, including：Hardness, mobility, planarization, transparency and glossiness etc..Acetate propionate Cellulose esters (CAP) and cellulose acetate-butyrate (CAB) are two kinds of wider mixed fiber element esters of commercial use.
2. aliphatic polyester
The aliphatic polyester of the present invention is a kind of biodegradable plastic, by aliphatic diacid or aliphatic diacid acid anhydride, fat Two carboxylic acid halides of race, two acyl ester of aliphatic are obtained with an aliphatic diol condensation polymerization.
3. reactive monomer
Heretofore described reactive monomer is the vinyl compound with polar group, the polar group bag Include but be not limited to：Hydroxyl, carboxyl, carbonyl, ester group, amino, sulfydryl, sulfonic group, ehter bond, halogen, peptide bond, anhydride bond etc..Institute The reactive monomer stated can react with other components in blend under certain condition, and then be grafted to covalent bond In other components, special modified effect is played.
Preferable reactive monomer is maleic acid anhydride in the present invention, acrylic compounds, methacrylic, acrylate At least one of compounds such as class, methyl acrylic ester, acrylic amide, methacryl amine.Preferred reaction Property monomer is methyl acrylic ester, in such as hydroxyethyl methacrylate (HEMA), glycidyl methacrylate (GMA) At least one.
4. initiator
Heretofore described initiator is radical initiator, its having of generating free radicals of decomposable asymmetric choice net under certain condition Machine compound, including but not limited to：Acyl peroxide, such as benzoyl peroxide (BPO)；Alkyl (dialkyl group) peroxidating Thing, such as dual-tert-butyl peroxide, double cumyl peroxides, cumyl peroxy butyl, 3,3,5- 3-methyl cyclohexanols Alkane -1,1- diperoxies the tert-butyl group, 2,5- dimethyl -2,5- di-t-butyl peroxyhexanes etc.；Perester, such as crosses trimethylace tonitric uncle Butyl ester, mistake -2 ethyl hexanoic acid tert-butyl ester, t-butyl perbenzoate, peroxidating lauric acid etc.；Alkyl peroxide, such as tertiary fourth Base hydrogen peroxide, isopropyl benzene hydroperoxide etc.；Ketone peroxide, such as methyl ethyl ketone peroxide；Azo compound, such as two isobutyl of azo Cyanogen (AIBN) etc..
It is preferably benzoyl peroxide to be suitable for the invention initiator, azo-bis-isobutyl cyanide, cumyl peroxide, mistake Aoxidize in di-t-butyl, tert-butyl hydroperoxide, perbenzoic acid, 2,5- dimethyl -2,5- di-t-butyl peroxyhexanes etc. At least one.Preferred initiator is benzoyl peroxide, in 2,5- dimethyl -2,5- di-t-butyl peroxyhexanes extremely Few one kind.
5. the thermoplastic cellulose of graft modification and biodegradable Aliphatic Polyester Blends
The blend that the present invention announces is a kind of by a kind of thermoplastic cellulose, a kind of biodegradable aliphatic polyester Reactive monomer and a kind of initiator composition, wherein the thermoplastic cellulose containing 20 to 80 mass parts, 80 to 20 mass parts The initiator of aliphatic polyester, the reactive monomer of 0.1 to 10 mass parts and 0.01 to 1 mass parts.The blend except comprising Outside above component, following at least one additive is further included：Compatibility agent, inorganic filler, antioxidant, lubricant, colouring agent etc..
Many physico-chemical properties (such as melt viscosity, melt index) of blend polymer are mainly by forming its polymer Species and proportion of composing determine.Type of polymer essentially dictates the " compatibility between blend component (compatibility) ", compatibility is that one to interact between different polymer measures, and is made when between different polymer It is known as (miscible) system of dissolving each other when stable and uniform on molecular scale mixes with it relatively by force, can be made；Other polymer Between interaction it is slightly weak, although cannot dissolve each other in molecular scale, but still can be in nanoscale or micro-meter scale stable and uniform Scattered, this kind of blend is referred to as compatible (compatible) system；Interact between other polymer very weak, even if by Forced Mixing, they also tend to form respective phase region, and this kind of blend is then incompatible (incompatible) system.No Different component has obvious phase separation in compatible system, that is, forms phase-separation system (phase separated system).It is poly- Compound blend glass transition temperature (" Tg") information simple can judge as one of compatibility quality between each component Foundation【《Multicomponent polymeric-principle, structure and performance》, kingdom, which builds, writes, and 2013, p.20-22】If blend is protected respectively Hold the glass transition temperature of raw material components, then compatibility is bad between showing component, and when blend only has a vitrifying During transition temperature, then compatibility is preferable between showing component.In the case where type of polymer determines, some physics and chemistry of blend There are certain functional relation with its proportion of composing for property (such as melt viscosity, melt index)【《The plastic engineering handbook first volume》, Huang Rui is edited, and 2000, p.633-637；Melt Rheology of Polymer Blends from Melt Flow Index, International Journal of Polymeric Materials,1984,10,p.213-235】, people can be accordingly Substantially speculate even blend of the design with special properties.In the bad co-mixing system of some compatibilities, it may occur however that altogether Mixed thing viscosity is less than the situation of raw material components【《JRG-Fourth statistics》, Jin Riguang work, 1998, p.630-633】, there is the phenomenon The reason for there is no final conclusion at present, overall viscosity declines after the interface sliding that one of which is construed between different phases causes mixing. Similar phenomenon has not been reported in the preferable blend system of compatibility, if more than being used in the preferable system of compatibility Phenomenon, must there is great potentiality.
Also containing hydroxyethyl methacrylate, glycidyl methacrylate etc. in the blend composition that the present invention announces With the good reactive monomer and initiator of the blending main component compatibility of thing, the reactive monomer with common plasticizer not Together, it has higher reactivity, in the presence of high-rate of shear, high melt temperature (more than 200 DEG C) and initiator In double screw extruder, radical reaction easily occurs, reactive monomer can be grafted on any C-H in blend component in theory On key (Fig. 1 and the structure diagram that Fig. 2 is two kinds of possible generations in the present invention), its effect differs markedly from plasticizer, and After reactive extrursion, unreacted monomer can be removed in devolatilization processes, therefore reactive monomer simply is considered as plasticizer The decline of explanation mixed system viscosity is simultaneously invalid.Not only addition is seldom for initiator, and it easily decomposes be produced from high temperature It is consumed by base.After reactive grafting, due to grafted monomers, there are between thermoplastic cellulose and Biodegradable polyester The interaction blend non-grafted compared to same composition can be stronger.In conclusion the graft modification that the present invention announces Thermoplastic cellulose and Aliphatic Polyester Blends the special rheological equationm of state, caused by the Specific Interactions between component, And the compatibility between this mixed system component is good, in compatible co-mixing system, the phenomenon that viscosity reduces after mixing is less, Also few documents and materials have related report.
There is the property that a variety of methods can describe blend, addition rule is wherein simplest one kind.Advised using addition It then can substantially speculate the theory property of some polyblends, its addition theory can be expressed (herein only with equation below Consider key component, ignore component of the content below 2%)：
P=c1P1+c2P2
P be blend property, c1And P1For the concentration and property of component 1；c2And P2For the concentration and property of component 2.This The thermoplastic cellulose of invention and the property (P) of Aliphatic Polyester Blends, such as apparent melt viscosity, melt index can profits The numerical value of theoretical prediction is calculated with addition rule, that is, is defined as " addition theoretical value ", which can be with the table of experiment detection The numerical value such as viscosity, melt index are seen to compare.The concentration of component can use mass fraction or volume fraction to express, present invention selection Theoretical numerical value is calculated with mass fraction.
The blend composition of the concrete embodiment of the present invention includes the thermoplasticity acetate butyrate fiber of 20 to 80 mass parts The aliphatic polyester such as plain ester, poly- the ethanedioic acid butanediol ester or poly butylene succinate of 80 to 20 mass parts, 0.1 to 10 quality The hydroxyethyl methacrylate of part or the peroxidating of glycidyl methacrylate isoreactivity monomer and 0.01 to 1 mass parts Benzoyl or double two or five grade initiators, it is characterised in that the melt viscosity of blend is in low shear rate (100s-1) under the conditions of compare The mixing addition theoretical value at least low 30% of two kinds of predominant starting materials.The melt viscosity of some blends more preferably formed exists Low shear rate (100s-1) under the conditions of it is at least lower by 45% than the mixing addition theoretical value of two kinds of predominant starting materials；Some are optimal The melt viscosity of the blend of composition is selected in low shear rate (100s-1) under the conditions of than two kinds of predominant starting materials mixing addition Theoretical value at least low 55%.
The blend composition of the concrete embodiment of the present invention includes the thermoplasticity acetate butyrate fiber of 20 to 80 mass parts The aliphatic polyester such as plain ester, poly- the ethanedioic acid butanediol ester or poly butylene succinate of 80 to 20 mass parts, 0.1 to 10 quality The hydroxyethyl methacrylate of part or the peroxidating of glycidyl methacrylate isoreactivity monomer and 0.01 to 1 mass parts Benzoyl or double two or five grade initiators, it is characterised in that the melt viscosity of blend is in high-rate of shear (1363s-1) under the conditions of compare The mixing addition theoretical value at least low 25% of two kinds of predominant starting materials.The melt viscosity of some blends more preferably formed exists High-rate of shear (1363s-1) under the conditions of it is at least lower by 40% than the mixing addition theoretical value of two kinds of predominant starting materials；Some are optimal The melt viscosity of the blend of composition is selected in high-rate of shear (1363s-1) under the conditions of add than the mixing of two kinds of predominant starting materials Into theoretical value at least low 50%.
The blend composition of the concrete embodiment of the present invention includes the thermoplasticity acetate butyrate fiber of 20 to 80 mass parts The aliphatic polyester such as plain ester, poly- the ethanedioic acid butanediol ester or poly butylene succinate of 80 to 20 mass parts, 0.1 to 10 quality The hydroxyethyl methacrylate of part or the peroxidating of glycidyl methacrylate isoreactivity monomer and 0.01 to 1 mass parts Benzoyl or double two or five grade initiators, it is characterised in that mixing addition of the melt index of blend than two kinds of predominant starting materials Theoretical value is at least high by about 90%.Mixing of the melt index than two kinds of predominant starting materials of some blends more preferably formed adds It is at least high by 200% into theoretical value；Some most preferred groups into blend melt index than two kinds of predominant starting materials mixing Addition theoretical value is at least high by 250%.
The blend " unusually " formed by a certain percentage of the present invention, " unexpectedly " have more former than main starting Material：Pure thermoplastic cellulose and aliphatic polyester starting material mixes the lower apparent shear viscosity of addition theoretical value, that is, exists " concave " curve is presented in " apparent viscosity-composition " graph of a relation, shows as " melt viscosity trap " (Melt Viscosity Well) phenomenon, shows that the blend has " anti-synergistic effect " (Antagonistic Effect or Anti- of apparent viscosity Synergistic Effect)。
The blend " unusually " formed by a certain percentage of the present invention, " unexpectedly " have more former than main starting Material：Melt index (the MFR of the mixing addition theoretical value higher of pure thermoplastic cellulose and aliphatic polyester starting material：Melt Flow Rate), i.e., in " melt index-composition " graph of a relation, " convex " curve is presented, shows as " melt index peak " (MFR Peak) phenomenon, shows that the blend has " cooperative effect " (the Synergistic Effect) of melt index.
6. prepare the method for the thermoplastic cellulose and biodegradable Aliphatic Polyester Blends of graft modification
A kind of method of thermoplastic cellulose and Aliphatic Polyester Blends for preparing graft modification of the present invention.This method The desired amount of thermoplastic cellulose, the desired amount of aliphatic polyester, the desired amount of reactive monomer in a continuous process Uniformly mixed in the molten state with the desired amount of initiator, and extruding pelletization, prepared blend are characterized in that it Melt viscosity is in low shear rate (100s-1) under the conditions of it is at least lower than the blending addition theoretical value of two kinds of predominant starting materials 30%；In high-rate of shear (1363s-1) under the conditions of it is at least lower by 25% than the blending addition theoretical value of two kinds of predominant starting materials, And the melt index of the blend is at least higher by about 90% than the blending addition theoretical value of two kinds of predominant starting materials.
The continuous fusion preparation method of the present invention includes two-step method and one-step method.In two-step method, thermoplastic cellulose powder End first passes around single screw rod or double screw extruder is granulated, then thermoplastic fibre crude granule, aliphatic polyester particle, reaction Property monomer and initiator are added to one according to a certain percentage after mixing, then with a feeding machine according to certain feed rate The spout of a double screw extruder.Feeding machine can be that weight-loss type feeding machine can also be volume type feeding machine.Another tool It is respectively thermoplastic fibre crude granule, aliphatic polyester particle, reactive monomer and initiation using multiple feeding machines that body, which embodies, Agent is dosed to progress reactive extrursion granulation on a double screw extruder respectively according to certain feeding ratio.
The one-step method of the present invention is granulated thermoplastic fibres element powder without hot-working and is directly pressed using a feeding machine Certain feed rate is added into the spout of double screw extruder, while aliphatic polyester particle, reactive monomer and initiation Agent is added into the spout of double screw extruder with other feeding machines by certain feed rate, carries out twin-screw extrusion, extrusion Batten prepares blends particles through water-carrying groove or underwater cutpellet.Extrudate can also pass through air-cooled and then pelletizing with anhydrous process.
The extrusion temperature for being suitable for the present invention is preferably 140 DEG C of thermal decomposition temperature to thermoplastic cellulose and aliphatic polyester Low person is spent, preferred extrusion temperature is 140 DEG C to 240 DEG C.The rotating speed of extruder is preferably 50rpm to 1500rpm, more preferably For 100rpm to 800rpm.
Being suitable for the invention melt blending equipment has many kinds to include kneading machine, Farrel continuous mixers, Banbury Mixer, single screw extrusion machine, double screw extruder, multi-screw extruder (more than two screw rod), reciprocating Single screw extrusion Machine such as Buss co-kneader (Buss Ko-Kneader) etc..Preferable method includes double spiral shells for continuous fusion blending extrusion method Bar extrusion method.Being suitable for the invention continuous twin-screw and squeezing machine includes the double screw extruder of different designs, such as Germany ZSK Mcc18 equidirectional parallel double-screw extruders of Coperion productions etc..
The thermoplastic cellulose of graft modification prepared by the method for twin-screw continuous fusion that the present invention is shown coextrusion with Low melt viscosity of the aliphatic polyester blending with " unexpected ".The present invention it is a kind of embody be under the same conditions, Mixing addition theoretical value of the melt viscosity of blend less than thermoplastic cellulose and aliphatic polyester starting material.The viscosity drops It is low that there is generality, it is included in compared with low shear rate such as 100s-1With in higher shear rate such as 1363s-1.In 100s-1Shearing Under speed, the melt viscosity of its blend is at least lower by 30% than the mixing addition theoretical value of two kinds of predominant starting materials.Some are more Preferably constitute (aliphatic polyester of 65 to 20 mass parts and the thermoplastic cellulose of 35 to 80 mass parts, reactive monomer for 2 to 8 mass parts, initiator are 0.05 to 0.2 mass parts) mixing of the melt viscosity than two kinds of predominant starting materials of blend add Into theoretical value at least low 45%, some most preferred groups are into (aliphatic polyester of 50 to 35 mass parts and the heat of 50 to 65 mass parts Plasitc fibers element, reactive monomer is 2 to 6 mass parts, and initiator is 0.075 to 0.15 mass parts) the melt of blend glue Degree is at least lower by 55% than the mixing addition theoretical value of two kinds of predominant starting materials.In 1363s-1Under shear rate, blend melts The mixing addition theoretical value at least low 25% of two kinds of predominant starting materials of body ratio of viscosities, some more preferably form (preferably 65 to 20 The thermoplastic cellulose of the aliphatic polyester of mass parts and 35 to 80 mass parts, reactive monomer are 2 to 8 mass parts, initiator For 0.05 to 0.2 mass parts) blend melt viscosity it is at least lower than the mixing addition theoretical value of two kinds of predominant starting materials 35%, some most preferred groups are into (aliphatic polyester of 50 to 20 mass parts and the thermoplastic cellulose of 50 to 80 mass parts, react Property monomer be 2 to 6 mass parts, initiator is 0.075 to 0.15 mass parts) blend melt viscosity starting main than two kinds The mixing addition theoretical value at least low 45% of raw material.
The thermoplastic fibres element of graft modification prepared by the present invention and a kind of concrete embodiment of Aliphatic Polyester Blends material It is mixing addition theoretical value of the melt index higher than two kinds of predominant starting materials of blend.The melting of the blend preferably constituted Index more preferably forms (65 to 20 mass parts higher than the mixing addition theoretical value at least about 90% of two kinds of predominant starting materials The thermoplastic cellulose of aliphatic polyester and 35 to 80 mass parts, reactive monomer are 2 to 8 mass parts, initiator for 0.05 to 0.2 mass parts) blend melt index higher than two kinds of predominant starting materials mixing addition theoretical value at least 200%, most Preferably constitute (aliphatic polyester of 50 to 35 mass parts and the thermoplastic cellulose of 50 to 65 mass parts, reactive monomer for 2 to 6 mass parts, initiator are 0.075 to 0.15 mass parts) the melt index body of blend can be higher than two kinds of main startings former The mixing addition theoretical value at least 250% of material.
7. prepare the method for the thermoplastic cellulose and Aliphatic Polyester Blends 3D printing silk material of graft modification
The present invention announces a kind of thermoplastic cellulose and aliphatic poly for preparing the graft modification with the special rheological equationm of state The method of ester blend 3D printing silk material, it is characterised in that the blend by 20 to 80 mass parts thermoplastic cellulose, 80 to The initiator composition of the aliphatic polyester of 20 mass parts, the reactive monomer of 0.1 to 10 mass parts and 0.01 to 1 mass parts.Should The continuous fusion extrusion blending method of blend by mentioned earlier is prepared.The melt viscosity of blend is in low shear rate (100s-1) under the conditions of it is at least lower by 30% than the addition theoretical value of two kinds of primary raw materials；In high-rate of shear (1363s-1) under the conditions of Addition theoretical value than two kinds of primary raw materials is at least low by 25%.
The present invention announces a kind of thermoplastic cellulose and aliphatic poly for preparing the graft modification with the special rheological equationm of state The method of ester blend 3D printing silk material is preferably Single screw extrusion into silk method.In the method, blending well prepared in advance Thing particle and some auxiliary agents are added to a single screw extrusion machine, and single screw extrusion machine is generally divided into three ranks in effective length Section, first stage is transportation section, in this stage blend by preheating and extruding；Second segment is compression section, thread groove Depth from large to small, melt temperature reach make blend be plasticized and fusing degree, the section can also include increase mixed effect Thread segment；3rd section is metering section, and blend melt is conveyed to 3D printing silk under screw rod rotation by certain melt flow Material mould.There are one or more circular apertures on mould, circular hole can need to select different diameters according to printer, generally A diameter of 1.75 millimeters (mm) or 3.00 millimeters (mm).The printing silk material of extrusion is wound through supercooling after detection.The method of cooling There are a variety of, including water cooling or air cooling.
The present invention announces a kind of thermoplastic cellulose and aliphatic poly for preparing the graft modification with the special rheological equationm of state The method of ester blend 3D printing silk material, it is also an option that twin-screw extrusion is into silk method.In the method, it is well prepared in advance Blends particles and some auxiliary agents pass through plasticizing in twin-screw in machine extruder, melting, after mixing, is extruded, mould from mould On have one or more circular apertures, circular hole can need to select different diameters according to printer, general a diameter of 1.75 Millimeter (mm) or 3.00 millimeters (mm), water cooled or air cooling, on-line monitoring silk material diameter, by adjusting rolling speed control Silk material diameter is within the scope of required.Preferably 140 DEG C to 240 DEG C of the extrusion temperature of double screw extruder, extruder rotating speed is excellent Select 50rpm to 1500rpm, more preferably 100rpm to 800rpm.
The present invention announces a kind of thermoplastic cellulose and aliphatic poly for preparing the graft modification with the special rheological equationm of state The method of ester blend 3D printing silk material, it is also an option that melting extruding process.In the method, blend grain well prepared in advance Son extrudes after simple melting from mouth mold, by control pressure, realizes a diameter of 1.75 millimeters (mm) for extruding silk material Or 3.00 millimeters (mm) left and right.
The 3D printing silk material being prepared according to the method described above, 3D printing is prepared available for fused glass pellet method (FDM) Product.
The graft modification with the special rheological equationm of state that the continuous extrusion blend method announced using the present invention is prepared Thermoplastic cellulose and Aliphatic Polyester Blends 3D printing silk material, there are than two kinds predominant starting material mixing additions theories The lower melt viscosity of value, the melt index of higher, has taken into account toughness and intensity, has 3D printing more more preferable than raw material performance, There is wide application potential, achieve preferable technique effect.
Brief description of the drawings
A kind of structure diagrams of possible HEMA graft modifications PBS (PBS-g-HEMA) of Fig. 1
A kind of structure diagrams of possible HEMA graft modifications CAB (CAB-g-HEMA) of Fig. 2
At 180 DEG C of Fig. 3, the relation of each mixture particle apparent shear viscosity and shear rate.
At 180 DEG C of Fig. 4, each mixture particle is in 100s-1Shear rate under, the pass between apparent shear viscosity and composition It is that dotted line is the addition theoretical calculation numerical value line of PBS and CAB in figure.
At 180 DEG C of Fig. 5, each mixture particle is in 1363s-1Shear rate under, the pass between apparent shear viscosity and composition It is that dotted line is the addition theoretical calculation numerical value line of PBS and CAB in figure.
The DSC temperature lowering curves of each mixture particles of Fig. 6.
Second of heating curve of DSC of each mixture particles of Fig. 7.
Each mixture particle glass transition temperatures of Fig. 8 and the relation of composition.
The TGA curves of each mixture particles of Fig. 9 in air atmosphere.
Relation between the melt index (190 DEG C, 2.16kg) of each mixture particles of Figure 10 and composition, dotted line is PBS in figure With the addition theoretical calculation numerical value line of CAB.
The present invention carries out performance measurement by the following method：
Melt index (MFR) assay method：By 1133 standards of ISO, melted using Lloyd Davenport MFI-10/230 Melt Index Instrument measure, 190 DEG C, weight loading 2.16kg, port mould diameter 2.095mm of barrel temperature, length 8mm, preheating time For 4min, sample is cut automatically every setting time, take 5 times and average, represent to measure with the grams of every 10 minutes (g/10min) As a result.
Rheological behaviour assay method：Using Malvern Instruments Rosand RH7 thermal high capillary rheometers Measure, processing software is Launch8.60 version.The sensor and 16/ that pressure is 10000Psi is selected in test 1.0/180 circular hole capillary die.It is compacted when filling sample for filling in batches, the precompressed by 0.5MPa twice is needed before test With the warm of 2 minutes, with ensure particle at a temperature selected (180 DEG C) completely melting and compacting.Measure is selected during test Apparent shear viscosity under following shear rate：100,192,369,709,1363,2615,and 5019s-1。
Thermogravimetric analysis (TGA)：Test is enterprising in the Discovery series thermogravimetric analyzers of TA Instruments companies OK, it is TA Instruments Trios 3.1.4 editions to handle software.The temperature stabilization for needing to wait balance cavity before test is 40 ℃.During test, weigh 5~10mg samples and be placed in ceramic crucible, tested in the air atmosphere that flow velocity is 20mL/min, Temperature elevating range is 30~600 DEG C, and heating rate is 10 DEG C/min.
Thermal performance analysis (DSC)：Test the Discovery series of differential scanning amounts in the production of TA Instruments companies Carried out on hot instrument (DSC), processing software is TA Instruments Trios 3.1.5 editions, which is furnished with TA 90 mechanical refrigeration annexes of Refrigerated Cooling System.Measurement atmosphere is the nitrogen of 50mL/min, needed for test Sample size is 5~10mg.Test program is as follows：First by temperature stabilization at 40 DEG C, then 250 DEG C and constant temperature are warming up to 10 DEG C/min 2min removes thermal history, cools to -70 DEG C with 10 DEG C/min afterwards, is then warming up to 250 DEG C with 10 DEG C.Record temperature-fall period with And second of temperature-rise period, with the hot property of study sample.Tested by DSC, there can be the crystallization that software immediately arrives at sample Temperature (" Tc"), melting temperature (" Tm"), glass transition (" Tg"), the information such as heat content change (" △ H ").
Embodiment
The present invention is specifically described by the following examples.Herein it is important to point out that once embodiment is only right It is further described in the present invention, it is impossible to be interpreted as limiting the scope of the invention, the those of skill in the art in the field Some nonessential modifications and adaptations can be made according to foregoing invention content.
【Comparative example 1】
Used poly butylene succinate (PBS) is produced by Japanese Showa electrician in the present invention, and the trade mark isMD 1001.Raw materialMD 1001PBS particles, with Thermo Fisher scientific ＆ technical corporation of the U.S. PolyLab HAAKE Rheomex OS PTW16 parallel dual-screw extruding machines (screw diameter 16mm, L/D=40) extruding pelletization, As a comparison case.For the extruder totally 11 sections from spout to mouth mold, numbering 1-11, wherein paragraph 1 only serve the effect of charging, It can not heat.The subsidiary volume type particle feeder of extruder, being used for after calibration willMD 1001 PBSA Raw material is fed in twin-screw, blanking velocity 2000g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170℃,180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, after stablizing, melts Temperature is at 204 DEG C or so, and moment of torsion is in 50-56%.The extruder is furnished with the circular mouth mold of a diameter of 3mm, and batten is squeezed from mouth mold Go out after water-bath cooling, the cylindrical particle of 3mm or so is cut into pelleter.Particle is collected, in 60 DEG C of vacuum drying chambers After taking out 4hr, encapsulation is spare.Melt index of the particle under 190 DEG C, 2.16kg is 4.5g/10min.
【Comparative example 2】
Used cellulose acetate-butyrate (CAB) is by U.S. Eastman in the present inventionTMCompany produces, and the trade mark is EastmanTMCAB-531-1.Raw material EastmanTMCAB-531-1 powder, with Thermo Fisher scientific ＆ technical corporation of the U.S. PolyLab HAAKE Rheomex OS PTW16 parallel dual-screw extruding machines (screw diameter 16mm, L/D=40) extruding pelletization, As a comparison case.For the extruder totally 11 sections from spout to mouth mold, numbering 1-11, wherein paragraph 1 only serve the effect of charging, It can not heat.The subsidiary volume type powder feeder of extruder, is used for Eastman after calibrationTMCAB-531-1 is former Material is fed in twin-screw, blanking velocity 1500g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170℃,180℃, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, after stablizing, melt temperature Degree is at 205 DEG C or so, and moment of torsion is in 58-61.5%.The extruder is furnished with the circular mouth mold of a diameter of 3mm, and batten is from die extrusion After water-bath cooling, the cylindrical particle of 3mm or so is cut into pelleter.Particle is collected, is taken out in 60 DEG C of vacuum drying chambers After 4hr, encapsulation is spare.Melt index of the particle under 190 DEG C, 2.16kg is 6.1g/10min.
【Embodiment 1】
The grafted monomers hydroxyethyl methacrylate (HEMA) that the present invention uses is Tokyo HuaCheng Industry Co., Ltd (TCI) Analysis net product, dosage is the 2% of PBS and CAB gross masses.Two uncles of initiator 2,5- dimethyl -2,5- that the present invention uses (double two or five) are the analysis net product of lark prestige Science and Technology Ltd. to butyl peroxy hexane, and dosage is the 5% of HEMA dosages, i.e., PBS and the 1 ‰ of CAB gross masses.WillMD 1001PBS and EastmanTMCAB-531-1 is according to 4:1 mass ratio, And the desired amount of HEMA and double 25 are added, stir, in PolyLab HAAKE Rheomex OS mentioned above Melt blending extruding pelletization in PTW16 parallel dual-screw extruding machines.In the paragraph 1 of extruder, calibrated volume type particle adds Glassware is used for the feeding of stuff and other stuff, and speed is：2000g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, stablizes Afterwards, melt temperature is at 208 DEG C or so, and moment of torsion is in 35.5-40%.The extruder be furnished with a diameter of 3mm circular mouth mold, batten from Die extrusion is cut into the cylindrical particle of 3mm or so with pelleter after water-bath cooling.Particle is collected, is done in 60 DEG C of vacuum After taking out 4hr in dry case, encapsulation is spare.Melt index of the particle under 190 DEG C, 2.16kg is 9.4g/10min.According to the above Feed intake and processing conditions, in addition to some side reactions, the PBS of HEMA graft modifications can be generated in system, and (Fig. 1 can for one kind Can PBS-g-HEMA structure diagrams) and/or the CAB structures of HEMA graft modifications (Fig. 2 is a kind of possible CAB-g-HEMA Structure diagram), while increasing component molecular amount to a certain extent, moreover it is possible to strengthen the compatibility and phase interaction between component With.
【Embodiment 2】
WillMD 1001PBS and EastmanTMCAB-531-1 is according to 13:7 mass ratio, and needed for addition The HEMA of amount and double 25, stirs, in the same direction in PolyLab HAAKE Rheomex OS PTW16 mentioned above Melt blending extruding pelletization in double screw extruder.In the paragraph 1 of extruder, calibrated volume type particle feeder is used for The feeding of stuff and other stuff, speed are：1500g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170℃,180℃,180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, after stablizing, melt temperature At 201 DEG C or so, moment of torsion is in 33-38.5%.The extruder is furnished with the circular mouth mold of a diameter of 3mm, and batten is passed through from die extrusion After crossing water-bath cooling, the cylindrical particle of 3mm or so is cut into pelleter.Particle is collected, 4hr is taken out in 60 DEG C of vacuum drying chambers Afterwards, encapsulate spare.Melt index of the particle under 190 DEG C, 2.16kg is 13.9g/10min.
【Embodiment 3】
WillMD 1001PBS and EastmanTMCAB-531-1 is according to 1:1 mass ratio, and add aequum HEMA and double 25, stir, it is double in the same direction in PolyLab HAAKE Rheomex OS PTW16 mentioned above Melt blending extruding pelletization in screw extruder.In the paragraph 1 of extruder, calibrated volume type particle feeder be used to mix The feeding of particle is closed, speed is：1500g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170℃,180℃,180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, after stablizing, melt temperature At 204 DEG C or so, moment of torsion is in 31-37%.The extruder is furnished with the circular mouth mold of a diameter of 3mm, and batten passes through from die extrusion After water-bath cooling, the cylindrical particle of 3mm or so is cut into pelleter.Particle is collected, 4hr is taken out in 60 DEG C of vacuum drying chambers Afterwards, encapsulate spare.Melt index of the particle under 190 DEG C, 2.16kg is 18.8g/10min.
【Embodiment 4】
WillMD 1001PBS and EastmanTMCAB-531-1 is according to 7:13 mass ratio, and needed for addition The HEMA of amount and double 25, stirs, in the same direction in PolyLab HAAKE Rheomex OS PTW16 mentioned above Melt blending extruding pelletization in double screw extruder.In the paragraph 1 of extruder, calibrated volume type particle feeder is used for The feeding of stuff and other stuff, speed are：1500g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170℃,180℃,180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, after stablizing, melt temperature At 202 DEG C or so, moment of torsion is in 31-36%.The extruder is furnished with the circular mouth mold of a diameter of 3mm, and batten passes through from die extrusion After water-bath cooling, the cylindrical particle of 3mm or so is cut into pelleter.Particle is collected, 4hr is taken out in 60 DEG C of vacuum drying chambers Afterwards, encapsulate spare.Melt index of the particle under 190 DEG C, 2.16kg is 20.8g/10min.
【Embodiment 5】
WillMD 1001PBS and EastmanTMCAB-531-1 is according to 1:4 mass ratio, and add aequum HEMA and double 25, stir, it is double in the same direction in PolyLab HAAKE Rheomex OS PTW16 mentioned above Melt blending extruding pelletization in screw extruder.In the paragraph 1 of extruder, calibrated volume type particle feeder be used to mix The feeding of particle is closed, speed is：1500g/hr.The temperature that 2-11 sections of extruder is respectively：160℃,170℃,180℃,180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C, 180 DEG C and 180 DEG C, screw speed is set in 200rpm, after stablizing, melt temperature At 201.5 DEG C or so, moment of torsion is in 32-38.5%.The extruder is furnished with the circular mouth mold of a diameter of 3mm, and batten is from die extrusion After water-bath cooling, the cylindrical particle of 3mm or so is cut into pelleter.Particle is collected, is taken out in 60 DEG C of vacuum drying chambers After 4hr, encapsulation is spare.Melt index of the particle under 190 DEG C, 2.16kg is 18.1g/10min.
【Embodiment 6】
7 kinds of particles of all of the above, including comparative example 1-2 and embodiment 1-5, in Malvern Instruments Rheological behaviour measure is carried out on Rosand RH7 thermal high capillary rheometers, test method is as described above.At 180 DEG C The apparent shear viscosity of each particle and the relation of shear rate are shown in Fig. 3.Its medium shear rate is in 100s-1And 1363s-1Under table See shear viscosity and the relation of composition is shown in Fig. 4 and Fig. 5 respectively, concrete numerical value is listed in Tables 1 and 2.
Obvious shear shinning phenomenon as can see from Figure 3, i.e. the bigger shear viscosity of shear rate is smaller, this phenomenon It is very common in polymeric system, show that the fundamental property of system after being blended does not have significant change.The apparent shearing of mixture Viscosity is under the same conditionsMD 1001PBS and EastmanTMBelow CAB-531-1, that is, system viscosity after mixing It is decreased obviously.Specifically see Fig. 4 and Fig. 5, can find the apparent shear viscosity starting material all purer than any one of particle after blending All small, viscograph into " concave " i.e. unexpected " viscosity trap " phenomenon, no matter go back in high speed by the particle after this explanation blending It is that viscosity diminishes under low velocity shear.
Hydroxyethyl methacrylate (HEMA) is added in entirety as small molecule can be considered a kind of plasticizer, may play The effect of overall viscosity being reduced, but HEMA is different with common plasticizer, it has higher reactivity, in high-rate of shear, In double screw extruder in the presence of high melt temperature (more than 200 DEG C) and initiator double 25, free radical easily occurs Reaction, in theory reactive monomer can be grafted in blend component on any c h bond that (Fig. 1 and Fig. 2 can for two kinds in of the invention Can generation structure diagram), it is clear that HEMA is simply considered as plasticizer explain mixed system viscosity decline and it is invalid.It is double Two or five not only addition it is seldom, and its at high temperature easily decompose generate free radicals and be consumed, and play prevent it is processed The effect that raw material molecular weight reduces in journey, therefore double 25 addition is not the reason for mixed system viscosity reduces yet.To sum up Described, mixed system viscosity, which reduces, to be caused by the Specific Interactions between component, and the phase between this mixed system component Capacitive is good, and in compatible co-mixing system, the phenomenon that viscosity reduces after mixing is less, and also few documents and materials have related report Lead.
Some performance parameters after polymer blending can be speculated with addition theoretical value, specifically true according to the following formula It is fixed (only consider key component herein, ignore content 2% and following component)：
P=c1P1+c2P2
P is addition theoretical values in formula, P1For the corresponding parametric values of component in mixture 1, c1For its mass fraction, P2For The corresponding parametric values of component 2, c in mixture2For its mass fraction.If the measured value of mixture parameter and the addition theoretical value phase Difference is bigger, and collaboration (or anti-collaboration) effect is more notable between showing component.
As can be found from Table 1, when shear rate is 100s-1When, actual blend apparent shear viscosity is than addition theoretical value Low about 33.8% (embodiment 1) is to 55.6% (embodiment 4).
As can be found from Table 2, when shear rate is 1363s-1When, actual blend apparent shear viscosity is than addition theoretical value Low about 26.9% (embodiment 1) is to 48.8% (embodiment 5).
【Embodiment 7】
7 kinds of particles of all of the above, including comparative example 1-2 and embodiment 1-5, as described above the step of carried out difference Show scanning calorimetric (DSC) test, temperature lowering curve and second of heating curve are shown in Fig. 6 and Fig. 7.Directly can therefrom it be obtained with software Each particle glass transition temperature (" Tg") with composition relation see Fig. 8.
As can be seen from Figure 6 the former crystallinity is decreased obviously after CAB is added in PBS, the cooling of 1 particle of embodiment Crystallization peak temperature is less than comparative example 1, and crystallization peak area is relatively low, and embodiment 2-5 is then substantially not visible decrease temperature crystalline peak.Heating curve On, the melting temperature of embodiment 1 is also lower than comparative example 1, and melting peak area is also smaller (see Fig. 7), and embodiment 2 is in temperature-rise period There are crystallization and melting peak, but peak area is smaller, and embodiment 3-5 particles both no peak crystallization had not had then in temperature-rise period yet Melting peak.Understand that stuff and other stuff only has a glass transition temperature (" T from Fig. 6-8g"), show respectively to form in blending particle Compatibility it is fine, and TgNumerical value raised with the increase of CAB contents.
【Embodiment 8】
7 kinds of particles of all of the above, including comparative example 1-2 and embodiment 1-5, as described above the step of carried out heat Weight analysis (TGA) are tested, and test result is shown in Fig. 9.From the figure, it can be seen that the heat decomposition curve of particle is substantially all right after blending Between ratio 1-2 curves, show that the heat endurance that front and rear CAB and PBS is blended does not have too big change, this is consistent with expection Close.
【Embodiment 9】
7 kinds of particles of all of the above, including comparative example 1-2 and embodiment 1-5, as described above the step of melted Melt index (MFR) test (190 DEG C, 2.16kg), the relation between the MFR numerical value and composition that measure is shown in Figure 10.Obtained from Figure 10 Concrete numerical value be listed in table 3, including " addition theoretical value " mentioned above.
As can be found from Table 3, after each group lease making melt blending, the actual melt index of embodiment 1 is higher than addition theoretical value 4.5g/10min, percentage are about 93.5%, are that percent value is minimum in embodiment 1-5；The actual melt index of embodiment 4 Higher 15.2g/10min than addition theoretical value, percentage is about 274%, is that percent value is maximum in embodiment 1-5.Remaining reality It is higher than addition theoretical value between 93.5%-274% to apply example.The extremely high melt index of the above be all it is unexpected, It is rare in the good polymer blends of compatibility, and the still undiscovered phenomenon in CAB and PBS blends.
【Embodiment 10】
3D printing wire rod is in a Malvern Instruments for being furnished with Haul-Off/Melt Strength devices Prepared on Rosand RH7 capillary rheometers, be configured with the circular mouth mold of a diameter about 2mm, grain prepared by embodiment 3 and 5 Item material chamber loads about 50 grams of sample altogether to son several times, is compacted every time with compression bar, after sample installs, carries out a precompressed and pre- Thermal process, precompressed set pressure as 0.5MPa, and preheating time is 2 minutes.Squeezed after sample melting under the pressure of compression bar through mouth mold Go out, compression bar speed is 30mm/min, and the silk material of extrusion reaches winding roller after more series cylinders, by adjust hauling speed come Control the diameter of silk material.Design parameter is as shown in table 4.
As shown in table 4, different samples is formed for content, by controlling heating-up temperature, compression bar speed and roller speed It is prepared for 3D printing silk material.Formed for different mixture thing, the setting rate of wire rod and soft or hard degree are different, in CAB contents When higher (embodiment 5), the glass transition temperature of material is higher, and the wire rod pulled out from mouth mold can be after hardening and obtain silk faster Material is also harder, and at CAB contents relatively low (embodiment 3), glass transition temperature is relatively low, and wire rod needs longer time hardening simultaneously And obtained sample is also relatively soft.
【Embodiment 11】
The 3D printing silk material prepared in embodiment 10, carries out on MakerBot Replicator 2X 3D printers 3D printing.Batten is sized to the length of 130.97 × 12.70 × 3.20mm by MakerBot Desktop.Lnk softwares Cube, and print parameters are specific as follows:Resolution ratio (resolution) is standard, and nozzle extruded velocity is 90mm/s, mobile speed It is 100% to spend for 150mm/s, batten filling rate, and each layer of height is 200 μm, and nozzle temperature is 190 DEG C, and baseplate temp is 60℃.File is preserved into STL forms and is transmitted on printer (MakerBot Replicator 2X).
Too soft after silk material melting prepared by embodiment 3, sample introduction is difficult.And silk material spinning prepared by embodiment 5 is more smooth, Cuboid batten can preferably be printed.Silk material prepared by pure CAB (comparative example 2), also there is good 3D printing performance, but compares For have it is following some deficiency：Print temperature and baseplate temp are respectively necessary for 230 DEG C and 110 DEG C, are above embodiment 5, energy consumption It is higher；Batten hardening is very fast, causes easy warpage；Product is more crisp, poor toughness.Therefore the blend that the present invention announces can smoothly be made Standby 3D printing silk material, and compared to also there is excellent 3D printing performance for raw material, achieve good technique effect.
In shear rate it is 100s at 1 180 DEG C of table-1When actual measurement apparent shear viscosity, theoretical apparent shear viscosity and Both differences and difference percentage
Actual measurement apparent shear viscosity at 2 180 DEG C of table when shear rate is 1363s-1, theoretical apparent shear viscosity with And both differences and difference percentage
Table 3 surveys melt index (190 DEG C, 2.16kg) and addition theory melt index and both difference and difference hundred Fraction
Table 4 prepares the fabrication process condition of 3D printing silk material

Claims (10)

1. a kind of 3D printing silk material, thermoplastic cellulose and Aliphatic Polyester Blends containing graft modification, with mass fraction Meter, thermoplastic cellulose and the Aliphatic Polyester Blends of the graft modification include following components：
(1) 20 to 80 part of thermoplastic cellulose；
(2) 80 to 20 parts of aliphatic polyester；
(3) 0.1 to 10 parts of reactive monomer；
It is characterized in that in the blend reactive monomer be at least grafted to thermoplastic cellulose and aliphatic polyester one it On.
2. 3D printing silk material according to claim 1, it is characterised in that the melt viscosity of the blend is in low sheraing Speed 100s-1Under the conditions of it is at least lower by about 30% than the blending addition theoretical value of two kinds of predominant starting materials, in high-rate of shear 1363s-1Under the conditions of it is at least lower by 25% than the blending addition theoretical value raw material of two kinds of predominant starting materials.
3. 3D printing silk material according to claim 1, it is characterised in that the substitution value of the thermoplastic cellulose is more than 1.0。
4. 3D printing silk material according to claim 1, it is characterised in that the thermoplastic cellulose is acetate butyrate fiber Plain ester, acetic acid cellulose valerate ester, acetic acid cellulose caproate ester, acetic acid enanthic acid cellulose esters, laurate cellulose esters, acetic acid Cellulose pelargonate ester, acetic acid capric acid cellulose esters, acetic acid laurate cellulose esters, acetic acid palmitic acid cellulose esters, acetic acid are stearic Acid cellulose ester, cellulose propionate butyrate ester, propionic acid cellulose valerate ester, propionic acid cellulose caproate ester, propionic acid enanthic acid cellulose Ester, propionic acid octanoic acid cellulose esters, propionic acid cellulose pelargonate ester, propionic acid capric acid cellulose esters, propionic acid laurate cellulose esters, propionic acid At least one of palmitic acid cellulose esters, propionic acid cellulose stearate ester.
5. 3D printing silk material according to claim 1, it is characterised in that the aliphatic polyester contains 2 to 22 for main chain The polyester that the α of a carbon atom, ω-aliphatic diacid or derivatives thereof is formed with aliphatic diol condensation.
6. 3D printing silk material according to claim 1, it is characterised in that the aliphatic polyester is included by chain extension Aliphatic polyester.
7. 3D printing silk material according to claim 1, it is characterised in that the reactive monomer preferably with hydroxyl, Carboxyl, carbonyl, ester group, amino, sulfydryl, sulfonic group, ehter bond, halogen, peptide bond, anhydride bond polar group and also contain unsaturated carbon At least one of compound of carbon double bond；More preferably maleic acid anhydride, acrylic compounds, methacrylic, propylene At least one of esters of gallic acid, methyl acrylic ester, acrylic amide, methacryl amine compound；More preferably third At least one of olefin(e) acid esters and methyl acrylic ester compound, are most preferably acrylic acid hydroxy alkyl ester class and metering system At least one of sour hydroxyalkyl esters.
8. according to any 3D printing silk material of claim 1~7, it is characterised in that the blend further includes：(4)0.01 To 1 part of initiator.
9. 3D printing silk material according to claim 8, it is characterised in that the initiator is radical initiator；Preferably At least one of peroxide initiator, azo-initiator；More preferably：Acyl peroxide, alkyl peroxide, mistake At least one of acid esters, alkyl peroxide, ketone peroxide, azo compound；More preferably：Benzoyl peroxide first Acyl, azo-bis-isobutyl cyanide, cumyl peroxide, di-t-butyl peroxide, tert-butyl hydroperoxide, perbenzoic acid, 2, At least one of 5- dimethyl -2,5- di-t-butyl peroxyhexanes；Most preferably：Benzoyl peroxide, 2,5- dimethyl- At least one of 2,5- di-t-butyl hexane peroxides.
10. a kind of method for preparing any 3D printing silk material of claim 1~9, will using continuous fusion blending extrusion The desired amount of each component is uniformly mixed in the molten state, and extruding pelletization, obtains blends particles；By blends particles Fusing extrudes, the 3D printing silk material is prepared by mouth mold in extrusion device.
CN201610892128.2A 2016-10-13 2016-10-13 3D printing wire and preparation method thereof Active CN107936186B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610892128.2A CN107936186B (en) 2016-10-13 2016-10-13 3D printing wire and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610892128.2A CN107936186B (en) 2016-10-13 2016-10-13 3D printing wire and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107936186A true CN107936186A (en) 2018-04-20
CN107936186B CN107936186B (en) 2020-06-09

Family

ID=61928838

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610892128.2A Active CN107936186B (en) 2016-10-13 2016-10-13 3D printing wire and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107936186B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111918914A (en) * 2018-04-23 2020-11-10 伍德利有限公司 Homogeneous polymer mixtures, methods relating thereto and uses thereof
CN113501916A (en) * 2021-07-27 2021-10-15 中国科学院兰州化学物理研究所 Degradable shape memory polymer, preparation method and application thereof, and 4D printing degradable inferior vena cava filter

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5734113A (en) * 1980-08-01 1982-02-24 Koppers Co Inc Polyester resin for high speed pull-formation and method thereof
CN1062740A (en) * 1990-11-30 1992-07-15 伊斯曼柯达公司 The blend composition of aliphatic-Aromatic copolyesters and cellulose ester/polymkeric substance
CN1628151A (en) * 2002-02-05 2005-06-15 三井化学株式会社 Biodegradable resin composition and molded object thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5734113A (en) * 1980-08-01 1982-02-24 Koppers Co Inc Polyester resin for high speed pull-formation and method thereof
CN1062740A (en) * 1990-11-30 1992-07-15 伊斯曼柯达公司 The blend composition of aliphatic-Aromatic copolyesters and cellulose ester/polymkeric substance
CN1628151A (en) * 2002-02-05 2005-06-15 三井化学株式会社 Biodegradable resin composition and molded object thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111918914A (en) * 2018-04-23 2020-11-10 伍德利有限公司 Homogeneous polymer mixtures, methods relating thereto and uses thereof
CN111918914B (en) * 2018-04-23 2022-09-23 伍德利有限公司 Homogeneous polymer mixtures, methods relating thereto and uses thereof
CN113501916A (en) * 2021-07-27 2021-10-15 中国科学院兰州化学物理研究所 Degradable shape memory polymer, preparation method and application thereof, and 4D printing degradable inferior vena cava filter
CN113501916B (en) * 2021-07-27 2022-04-22 中国科学院兰州化学物理研究所 Degradable shape memory polymer, preparation method and application thereof, and 4D printing degradable inferior vena cava filter

Also Published As

Publication number Publication date
CN107936186B (en) 2020-06-09

Similar Documents

Publication Publication Date Title
Xie et al. Rheology to understand and optimize processibility, structures and properties of starch polymeric materials
CN103146164B (en) For the nanometer plasticizing polylactic acid material and preparation method thereof of rapid shaping
Govender et al. Polymers in pharmaceutical additive manufacturing: A balancing act between printability and product performance
CN103547628A (en) Molded articles of starch-polymer-wax-oil compositions
CN107793710A (en) Thermoplastic cellulose and aliphatic copolyester blend 3D printing silk material and preparation method
Korol et al. Manufacture and research of TPS/PE biocomposites properties
CN107955212A (en) Full-biodegradable plastic film and preparation method
CN105980123B (en) Prepare soft pvc process of semi-finished
CN109666272A (en) 3D printing modified polylactic acid material, printing silk thread and preparation method thereof
CN107936186A (en) 3D printing silk material and preparation method
EP3917749B1 (en) Method for the preparation of starch blends
CN105566825B (en) A kind of fused glass pellet polyvinyl alcohol silk material and preparation method thereof
CN107936444A (en) The thermoplastic cellulose of graft modification and Aliphatic Polyester Blends and preparation method
CN106189011A (en) A kind of normal-temperature water dissolubility 3D printing consumables
CN104053718A (en) Plant-derived plastic blend and production method therefor
CN107936443A (en) thermoplastic film and preparation method
CN102143991B (en) Soft, pelletized poly(vinyl chloride) plastisol
CN107793711A (en) Thermoplastic cellulose and aliphatic aromatic copolyester blends injection-molded item and preparation method
CN107793714A (en) Thermoplastic film and preparation method
CN107793712A (en) Thermoplastic cellulose and aliphatic aromatic copolyester blends 3D printing silk material and preparation method
CN107938022A (en) Fiber and preparation method thereof
CN107936196A (en) Injection-molded item and preparation method
CN107936442A (en) 3D printing silk material and preparation method thereof
CN107793589A (en) thermoplastic cellulose and aliphatic copolyester blend and preparation method
CN107793592A (en) Poly- polysaccharide blend thing of biodegradable fatty race aromatic copolyester toughened thermoplastic and preparation method thereof and film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant