CN105418874A - 3D-printing thermoplastic polyurethane material and preparation method of same - Google Patents
3D-printing thermoplastic polyurethane material and preparation method of same Download PDFInfo
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- CN105418874A CN105418874A CN201510979494.7A CN201510979494A CN105418874A CN 105418874 A CN105418874 A CN 105418874A CN 201510979494 A CN201510979494 A CN 201510979494A CN 105418874 A CN105418874 A CN 105418874A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
- C08G18/3812—Polyhydroxy compounds having fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
- C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
Abstract
The invention discloses a 3D-printing thermoplastic polyurethane material and a preparation method of same. The 3D-printing thermoplastic polyurethane material includes, by weight, 35-75 parts of a macro-molecular polyol, 0-10 parts of a fluorine-containing polyol, 2-25 parts of a small-molecular chain extender, 0-7 parts of a fluorine-containing chain extender, 5-60 parts of isocyanate, 0-8 parts of a hydrolysis stabilizing agent, and 0-10 parts of other additives. Compared with a method in the prior art, an in-situ polymerization one-step method is employed in the preparation method. By means of one or more of the fluorine-containing polyol and the fluorine-containing chain extender, fluorine is introduced into the thermoplastic polyurethane material to prepare the 3D-printing thermoplastic polyurethane material which has the advantages of both the fluorine-containing compound and the TPU. The material is excellent in thermal-stability, is low in shrinking rate, is high in mechanical performance and is low in water absorption. A 3D-printing product prepared from the material is excellent in performance.
Description
Technical field
The present invention relates to 3D and print polymkeric substance technology of preparing, relate to a kind of 3D more specifically and print thermoplastic polyurethane material and preparation method thereof, belong to macromolecular material research field.
Background technology
3D prints the one belonging to rapid prototyping technique, it is a kind of quick increasing material manufacturing technology generating 3D solid by successively increasing accumulation material, not only overcome tradition and subtract the loss that material manufacture produces, and make that product manufacturing is more intelligent, precision and high efficiency.3D printing technique comprises fusion stacking shaping (FDM) technology, Stereolithography (SLA) technology, selective laser sintering (SLS) technology and 3 D stereo printing (3DP) etc.Wherein, FDM, because of its advantage in formed material and cost value etc., has become a kind of technique having market outlook in 3D printing technique most.3D printed material is the basic substance that 3D prints, and is also that restriction 3D prints the technical bottleneck further developed.The raw material that FDM uses is generally thermal plastic high polymer, comprise acrylonitrile-butadiene-styrene copolymer (ABS), poly(lactic acid) (PLA), polycarbonate (PC), Polyphenylene Sulfone (PPSF) etc., but it more or less all also exists the problems such as shrinking percentage is larger, harmful.
The linear block copolymers of Polyurethane Thermoplastic Elastomer (TPU) to be a kind of by soft section of oligomer polyol and isocyanic ester-small molecule chain extender be hard section, containing the carbamate groups (-NH-CO-O-) repeated in main chain, it has excellent tensile strength, elongation at break, good wear resistance, be easy to the feature such as shaping, and is widely used in the multiple fields such as automobile, weaving, footwear material.Due to over-all properties and its lower melt temperature of TPU excellence, be a kind of potential 3D printed material, but the feature that its price is higher, dimensional contraction rate is larger limit it prints for 3D.
Summary of the invention
The present invention is based on above-mentioned prior art Problems existing, the present invention proposes a kind of 3D and print thermoplastic polyurethane material and preparation method thereof, it is by in-situ polymerization single stage method, fluorine element is introduced in thermoplastic polyurethane material by one or more adopting in fluorine-containing polyvalent alcohol or fluorine-containing chainextender, and the fluorine-containing 3D of the one prepared prints thermoplastic polyurethane material.This matrix material has the advantage of fluorochemicals and TPU concurrently, and not only thermostability, low-shrinkage, strong mechanical performance, low water absorption increase.Allow and surface property, resistant to chemical media, use temperature etc. all make moderate progress, its 3D product properties is excellent.
The present invention solves above-mentioned technical problem by following technical proposals: a kind of 3D prints thermoplastic polyurethane material, and it is characterized in that, it is composed as follows, by weight:
Preferably, the PTMG of described macromolecular polyol to be molecular weight be 500 ~ 5000g/mol, polyoxypropyleneglycol, tetrahydrofuran (THF)-propylene oxide copolyether glycol, polyoxytetramethylene ether glycol, polycarbonate diol, polycaprolactone glycol, polyethylene glycol adipate glycol, polybutylene glyool adipate, poly-adipate glycol propylene glycol ester glycol, poly-adipate glycol butanediol ester glycol one or more combination wherein;
Described fluorine-containing polyvalent alcohol is one or more combinations wherein of tetrafluoro Resorcinol, phenyl-hexafluoride hexafluoro pentanediol, hexafluoro pentamethylene adipic acid ester, hexafluoro pentamethylene malonic ester;
Described small molecule chain extender is ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 2, one or more the combination wherein of 2-dimethyl-penten glycol, 1,6-hexylene glycol, cyclohexanedimethanol, glycol ether, glycerol, quadrol, trolamine, tri-isopropanolamine, diethyl toluene diamine, N methyldiethanol amine;
Described fluorine-containing chainextender is one or more combination of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexylene glycol, light cured fluorine carbon resin;
Described isocyanic ester is one or more combination of diphenylmethanediisocyanate, tolylene diisocyanate, isofoer diisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, PPDI, dimethyl diphenyl vulcabond, hexamethylene diisocyanate;
Described hydrolysis stabilizer is one or more the combination in carbodiimide, 2-oxazoline compound, phenyl glycidyl ether, dihydroxyphenyl propane bisglycidyl ether, tetraphenyl glycidyl ether ethane, γ-glycidyl ether oxygen propyl trimethoxy silicane;
Other auxiliary agents described are one or more combinations of look mother, static inhibitor, enhancing inorganic particulate.
Preferably, described look mother is one or more combination of cadmium red, cadmium yellow, titanium dioxide, carbon black, red iron oxide, iron oxide yellow; Described static inhibitor is one or more combination of oxygen base aliphatic alkylamine, alkylsulphonic acid an alkali metal salt, phosphoric acid alkali metal salt, dithiocarbamic acid an alkali metal salt; One or more combination of described enhancing inorganic particulate nano silver, nano silicon, polynite, calcium carbonate, carbon nanotube.
The present invention also provides a kind of 3D to print the preparation method of thermoplastic polyurethane material, and it is characterized in that, it comprises the following steps:
Step one, takes macromolecular polyol 35-75 part, fluorine-containing polyvalent alcohol 0-10 part, small molecule chain extender 2-25 part, fluorine-containing chainextender 0-7 part, hydrolysis stabilizer 0-8 part, other auxiliary agents 0-10 part, is positioned over melting dehydration 2 ~ 4h under 30 ~ 150 DEG C of conditions respectively;
Step 2, added in double screw rod extruder by 5-60 part isocyanic ester of melting at macromolecular polyol, fluorine-containing polyvalent alcohol, small molecule chain extender, hydrolysis stabilizer and other auxiliary agents after melting dehydration and 50 ~ 120 DEG C simultaneously and react, extrusion temperature is 130 ~ 250 DEG C and obtains Thermoplastic polyurethane composite material particle through underwater cutpellet;
Step 3, is placed in 60 ~ 200 DEG C of baking ovens oven dry, slaking 4 ~ 72h, obtains required 3D and print thermoplastic polyurethane material by gained Thermoplastic polyurethane composite material particle.
Useful achievement of the present invention is: (1) the present invention adopt in fluorine-containing polyvalent alcohol or fluorine-containing chainextender one or more fluorine element is introduced in thermoplastic polyurethane material, synthesized a kind of 3D and printed thermoplastic polyurethane material.This matrix material has the mechanical property of the excellence of the characteristics such as the superior thermostability of fluoropolymer, low surface energy, weathering resistance and urethane itself concurrently, meets the requirement of FDM3D printing to macromolecular material high mechanical strength, high temperature tolerance etc.It is smooth that 3D prepared by the present invention prints thermoplastic polyurethane material's print procedure, and free from extraneous odour, product surface is bright and clean, dimensional stabilizing, not easily shrinks.(2) stable preparation process of the present invention, not high to equipment requirements, easy to process, there is good industrial applications prospect.The price of product material is slightly low compared with the price of market common 3D printed material, penetration and promotion preferably.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
3D of the present invention prints the composed as follows of thermoplastic polyurethane material, by weight:
Wherein, the PTMG of described macromolecular polyol to be molecular weight be 500 ~ 5000g/mol, polyoxypropyleneglycol, tetrahydrofuran (THF)-propylene oxide copolyether glycol, polyoxytetramethylene ether glycol, polycarbonate diol, polycaprolactone glycol, polyethylene glycol adipate glycol, polybutylene glyool adipate, poly-adipate glycol propylene glycol ester glycol, poly-adipate glycol butanediol ester glycol one or more combination wherein; Described fluorine-containing polyvalent alcohol is one or more combinations wherein of tetrafluoro Resorcinol, phenyl-hexafluoride hexafluoro pentanediol, hexafluoro pentamethylene adipic acid ester, hexafluoro pentamethylene malonic ester; Described small molecule chain extender is ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 2, one or more the combination wherein of 2-dimethyl-penten glycol, 1,6-hexylene glycol, cyclohexanedimethanol, glycol ether, glycerol, quadrol, trolamine, tri-isopropanolamine, diethyl toluene diamine, N methyldiethanol amine; Described fluorine-containing chainextender is one or more combination of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexylene glycol, light cured fluorine carbon resin; Described isocyanic ester is one or more combination of diphenylmethanediisocyanate, tolylene diisocyanate, isofoer diisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, PPDI, dimethyl diphenyl vulcabond, hexamethylene diisocyanate; Described hydrolysis stabilizer is one or more the combination in carbodiimide, 2-oxazoline compound, phenyl glycidyl ether, dihydroxyphenyl propane bisglycidyl ether, tetraphenyl glycidyl ether ethane, γ-glycidyl ether oxygen propyl trimethoxy silicane; Other auxiliary agents described are one or more combinations of look mother, static inhibitor, enhancing inorganic particulate.Described look mother can be one or more combination of cadmium red, cadmium yellow, titanium dioxide, carbon black, red iron oxide, iron oxide yellow; Described static inhibitor is one or more combination of oxygen base aliphatic alkylamine, alkylsulphonic acid an alkali metal salt, phosphoric acid alkali metal salt, dithiocarbamic acid an alkali metal salt; One or more combination of described enhancing inorganic particulate nano silver, nano silicon, polynite, calcium carbonate, carbon nanotube.
The preparation method that the present invention also provides a kind of 3D to print thermoplastic polyurethane material comprises the following steps:
Step one, takes macromolecular polyol 35-75 part, fluorine-containing polyvalent alcohol 0-10 part, small molecule chain extender 2-25 part, fluorine-containing chainextender 0-7 part, hydrolysis stabilizer 0-8 part, other auxiliary agents 0-10 part, is positioned over melting dehydration 2 ~ 4h under 30 ~ 150 DEG C of conditions respectively;
Step 2, added in double screw rod extruder by 5-60 part isocyanic ester of melting at macromolecular polyol, fluorine-containing polyvalent alcohol, small molecule chain extender, hydrolysis stabilizer and other auxiliary agents after melting dehydration and 50 ~ 120 DEG C simultaneously and react, extrusion temperature is 130 ~ 250 DEG C and obtains Thermoplastic polyurethane composite material particle through underwater cutpellet;
Step 3, is placed in 60 ~ 200 DEG C of baking ovens oven dry, slaking 4 ~ 72h, obtains required 3D and print thermoplastic polyurethane material by gained Thermoplastic polyurethane composite material particle.
Embodiment one
Take PTMG 35 parts, BDO 2 parts, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexylene glycol 7 parts, be positioned over melting dehydration 3h (hour) under 70 DEG C of conditions respectively.PTMG, 2 after melting is dewatered, 2,3,3,4,4,5,5-octafluoro-1, at 6-hexylene glycol, BDO and 80 DEG C, 5 parts of diphenylmethanediisocyanates of melting add in double screw rod extruder simultaneously and react, and extrusion temperature is 130 DEG C.Thermoplastic polyurethane composite material particle is obtained through underwater cutpellet.Vacuum drying oven gained Thermoplastic polyurethane composite material particle being placed in 150 DEG C is dried, slaking 9h, obtains required 3D and prints thermoplastic polyurethane material.
It is 33MPa that gained 3D prints thermoplastic polyurethane material's tensile strength, elongation at break 649%, and its product wire-drawing performance is excellent, and the good 3D that can make prints goods.
Embodiment two
Take polyoxypropyleneglycol 51 parts, phenyl-hexafluoride hexafluoro pentanediol 6 parts, 1,3-PD 15 parts, melting dehydration 4h at being positioned over 30 DEG C respectively.Polyoxypropyleneglycol, phenyl-hexafluoride hexafluoro pentanediol, 1 after melting is dewatered, at ammediol, 2 parts of carbodiimide and 5 parts of polynites and 50 DEG C, 30 parts of tolylene diisocyanates of melting add in double screw rod extruder simultaneously and react, and extrusion temperature is 200 DEG C.Thermoplastic polyurethane composite material particle is obtained through underwater cutpellet.Vacuum drying oven gained Thermoplastic polyurethane composite material particle being placed in 100 DEG C is dried, slaking 50h, obtains required 3D and prints thermoplastic polyurethane material.
It is 27MPa that gained 3D prints thermoplastic polyurethane material's tensile strength, elongation at break 549%, and its product wire-drawing performance is excellent, and the good 3D that can make prints goods.
Embodiment three
Take polyethylene glycol adipate glycol 48 parts, hexafluoro pentamethylene malonic ester 10 parts, BDO 13 parts, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexylene glycol 2 parts, melting dehydration 3h at being positioned over 90 DEG C respectively.Polyethylene glycol adipate glycol, hexafluoro pentamethylene malonic ester, 1 after melting is dewatered, 4-butyleneglycol, 2,2,3,3,4,4,5,5-octafluoro-1, at 6-hexylene glycol, phenyl glycidyl ether 8 parts and oxygen base aliphatic alkylamine 6 parts and 100 DEG C, 42 parts of diphenylmethanediisocyanates of melting add in double screw rod extruder simultaneously and react, and extrusion temperature is 150 DEG C.Thermoplastic polyurethane composite material particle is obtained through underwater cutpellet.Vacuum drying oven gained Thermoplastic polyurethane composite material particle being placed in 200 DEG C is dried, slaking 4h, obtains required 3D and prints thermoplastic polyurethane material.
It is 30MPa that gained 3D prints thermoplastic polyurethane material's tensile strength, elongation at break 589%, and its product wire-drawing performance is excellent, and the good 3D that can make prints goods.
Embodiment four
Take polyoxytetramethylene ether glycol 75 parts, light cured fluorine carbon resin 8 parts, trolamine 25 parts, melting dehydration 2h at being positioned over 110 DEG C respectively.Added in double screw rod extruder by 60 parts of hexamethylene diisocyanates of melting at polyoxytetramethylene ether glycol, light cured fluorine carbon resin, trolamine, γ-glycidyl ether oxygen propyl trimethoxy silicane 1 part and titanium dioxide 10 parts and 105 DEG C after melting dehydration simultaneously and react, extrusion temperature is 250 DEG C.Thermoplastic polyurethane composite material particle is obtained through underwater cutpellet.Vacuum drying oven gained Thermoplastic polyurethane composite material particle being placed in 60 DEG C is dried, slaking 72h, obtains required 3D and prints thermoplastic polyurethane material.
It is 28MPa that gained 3D prints thermoplastic polyurethane material's tensile strength, elongation at break 603%, and its product wire-drawing performance is excellent, and the good 3D that can make prints goods.
Embodiment five
Take poly-adipate glycol butanediol ester glycol 63 parts, hexafluoro pentamethylene malonic ester 3 parts, BDO 20 parts, light cured fluorine carbon resin 4 parts, melting dehydration 2h at being positioned over 150 DEG C respectively.Poly-adipate glycol butanediol ester glycol, hexafluoro pentamethylene malonic ester, 1 after melting is dewatered, at 4-butyleneglycol, light cured fluorine carbon resin, dihydroxyphenyl propane bisglycidyl ether 6 parts and carbon nanotube 8 parts and 120 DEG C, 51 parts of dimethyl diphenyl vulcabond of melting add in double screw rod extruder simultaneously and react, and extrusion temperature is 176 DEG C.Thermoplastic polyurethane composite material particle is obtained through underwater cutpellet.Vacuum drying oven gained Thermoplastic polyurethane composite material particle being placed in 80 DEG C is dried, slaking 32h, obtains required 3D and prints thermoplastic polyurethane material.
It is 32MPa that gained 3D prints thermoplastic polyurethane material's tensile strength, elongation at break 623%, and its product wire-drawing performance is excellent, and the good 3D that can make prints goods.
Above-described specific embodiment, the technical problem of solution of the present invention, technical scheme and beneficial effect are further described, be understood that, the foregoing is only specific embodiments of the invention, be not limited to the present invention, in the ken that art those of ordinary skill possesses, can also make a variety of changes under the prerequisite not departing from present inventive concept.
Claims (4)
1. 3D prints a thermoplastic polyurethane material, and it is characterized in that, it is composed as follows, by weight:
2. 3D according to claim 1 prints thermoplastic polyurethane material, it is characterized in that, the PTMG of described macromolecular polyol to be molecular weight be 500 ~ 5000g/mol, polyoxypropyleneglycol, tetrahydrofuran (THF)-propylene oxide copolyether glycol, polyoxytetramethylene ether glycol, polycarbonate diol, polycaprolactone glycol, polyethylene glycol adipate glycol, polybutylene glyool adipate, poly-adipate glycol propylene glycol ester glycol, poly-adipate glycol butanediol ester glycol one or more combination wherein;
Described fluorine-containing polyvalent alcohol is one or more combinations wherein of tetrafluoro Resorcinol, phenyl-hexafluoride hexafluoro pentanediol, hexafluoro pentamethylene adipic acid ester, hexafluoro pentamethylene malonic ester;
Described small molecule chain extender is ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 2, one or more the combination wherein of 2-dimethyl-penten glycol, 1,6-hexylene glycol, cyclohexanedimethanol, glycol ether, glycerol, quadrol, trolamine, tri-isopropanolamine, diethyl toluene diamine, N methyldiethanol amine;
Described fluorine-containing chainextender is one or more combination of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexylene glycol, light cured fluorine carbon resin;
Described isocyanic ester is one or more combination of diphenylmethanediisocyanate, tolylene diisocyanate, isofoer diisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, PPDI, dimethyl diphenyl vulcabond, hexamethylene diisocyanate;
Described hydrolysis stabilizer is one or more the combination in carbodiimide, 2-oxazoline compound, phenyl glycidyl ether, dihydroxyphenyl propane bisglycidyl ether, tetraphenyl glycidyl ether ethane, γ-glycidyl ether oxygen propyl trimethoxy silicane;
Other auxiliary agents described are one or more combinations of look mother, static inhibitor, enhancing inorganic particulate.
3. 3D according to claim 2 prints thermoplastic polyurethane material, and it is characterized in that, described look mother is one or more combination of cadmium red, cadmium yellow, titanium dioxide, carbon black, red iron oxide, iron oxide yellow; Described static inhibitor is one or more combination of oxygen base aliphatic alkylamine, alkylsulphonic acid an alkali metal salt, phosphoric acid alkali metal salt, dithiocarbamic acid an alkali metal salt; One or more combination of described enhancing inorganic particulate nano silver, nano silicon, polynite, calcium carbonate, carbon nanotube.
4. 3D prints a thermoplastic polyurethane material's preparation method, and it is characterized in that, it comprises the following steps:
Step one, takes macromolecular polyol 35-75 part, fluorine-containing polyvalent alcohol 0-10 part, small molecule chain extender 2-25 part, fluorine-containing chainextender 0-7 part, hydrolysis stabilizer 0-8 part, other auxiliary agents 0-10 part, is positioned over melting dehydration 2 ~ 4h under 30 ~ 150 DEG C of conditions respectively;
Step 2, added in double screw rod extruder by 5-60 part isocyanic ester of melting at macromolecular polyol, fluorine-containing polyvalent alcohol, small molecule chain extender, hydrolysis stabilizer and other auxiliary agents after melting dehydration and 50 ~ 120 DEG C simultaneously and react, extrusion temperature is 130 ~ 250 DEG C and obtains Thermoplastic polyurethane composite material particle through underwater cutpellet;
Step 3, is placed in 60 ~ 200 DEG C of baking ovens oven dry, slaking 4 ~ 72h, obtains required 3D and print thermoplastic polyurethane material by gained Thermoplastic polyurethane composite material particle.
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| DE102018003274A1 (en) | 2018-04-23 | 2019-10-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymer blend with shape memory and / or with thermoresponsive properties |
| CN114057971A (en) * | 2020-08-05 | 2022-02-18 | 北京化工大学 | Thermoplastic polyurethane elastomer and preparation method thereof |
| CN114891179A (en) * | 2022-05-06 | 2022-08-12 | 中国科学院宁波材料技术与工程研究所 | Biocompatible degradable polyurethane and preparation method and application thereof |
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| CN109890595A (en) * | 2016-10-25 | 2019-06-14 | 科思创德国股份有限公司 | Handle at least part of method on the surface of 3D printing object |
| TWI655915B (en) * | 2017-04-07 | 2019-04-11 | 艾索特克控股有限公司 | Upper surface of polyurethane three-dimensional decorative pattern and its preparation method and shoes made |
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| CN109320950A (en) * | 2018-03-09 | 2019-02-12 | 苏州诺普再生医学有限公司 | A kind of degradable composite material and preparation method thereof for biological 3D printing |
| DE102018003274A1 (en) | 2018-04-23 | 2019-10-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymer blend with shape memory and / or with thermoresponsive properties |
| DE102018003274B4 (en) | 2018-04-23 | 2022-08-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymer blend with shape memory and/or thermoresponsive properties based on thermoplastic polyurethanes and polyolefins, polymer molding and method for programming the polymer blend of such a molding |
| CN108559050A (en) * | 2018-05-11 | 2018-09-21 | 美瑞新材料股份有限公司 | A kind of antistatic, conductive thermoplastic polyurethane elastomer and preparation method thereof |
| CN109177360A (en) * | 2018-07-27 | 2019-01-11 | 江苏贝格丽新材料科技有限公司 | A kind of paper-plastic stick ornament materials and its manufacturing method |
| CN109280361A (en) * | 2018-09-30 | 2019-01-29 | 嘉兴学院 | A kind of thermoplastic elastic material and preparation method thereof |
| CN109280361B (en) * | 2018-09-30 | 2021-02-26 | 嘉兴学院 | Thermoplastic elastomer material and preparation method thereof |
| CN114057971A (en) * | 2020-08-05 | 2022-02-18 | 北京化工大学 | Thermoplastic polyurethane elastomer and preparation method thereof |
| CN115044003A (en) * | 2022-02-22 | 2022-09-13 | 合肥柔性科天机器人材料有限公司 | Preparation method of fluorine-containing self-healing waterborne polyurethane artificial skin material |
| CN115044003B (en) * | 2022-02-22 | 2023-12-05 | 合肥柔性科天机器人材料有限公司 | Preparation method of fluorine-containing self-healing aqueous polyurethane artificial skin material |
| CN114891179A (en) * | 2022-05-06 | 2022-08-12 | 中国科学院宁波材料技术与工程研究所 | Biocompatible degradable polyurethane and preparation method and application thereof |
| CN117186313A (en) * | 2023-07-24 | 2023-12-08 | 明澈生物科技(苏州)有限公司 | 3D printing material and magnetic control micro-nano robot |
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