CN104961881A - Dynamic bond-containing polyurethane material for 3D printing and its preparation method and use - Google Patents
Dynamic bond-containing polyurethane material for 3D printing and its preparation method and use Download PDFInfo
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- CN104961881A CN104961881A CN201510299301.3A CN201510299301A CN104961881A CN 104961881 A CN104961881 A CN 104961881A CN 201510299301 A CN201510299301 A CN 201510299301A CN 104961881 A CN104961881 A CN 104961881A
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- 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
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- C08G18/48—Polyethers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
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Abstract
The invention discloses a dynamic bond-containing polyurethane material for 3D printing and its preparation method and use. The preparation method utilizes, by mole, 100 parts of diisocyanate, 50-75 parts of polyester polyol or polyether polyol, 50-125 parts of a Diels-Alder bond-containing dihydric alcohol chain extender, 0-50 parts of a diisocyanate trimer cross-linking agent, 50-100 parts of a ligand-containing dihydric alcohol chain extender and 0-50 parts of a metal salt cross-linking agent. The Diels-Alder bond-containing dihydric alcohol chain extender and the diisocyanate trimer cross-linking agent are matched and are used for preparation of a Diels-Alder bond-containing polyurethane material. The ligand-containing dihydric alcohol chain extender and the metal salt cross-linking agent are matched and are used for preparation of a metal ligand-containing polyurethane material. Molecular structures of the prepared polyurethane materials contain a dynamic medical bond Diels-Alder bond and a metal ligand bond. The Diels-Alder bond-containing or metal ligand-containing polyurethane material has functions of self-restoration and self-bonding.
Description
Technical field
The present invention relates to and print for 3D, containing the polyurethane material and its production and use of dynamic key, belong to polymeric material field.
Background technology
Over nearly 20 years, 3D printing technique, as emerging rapid shaping technique, development is very rapid, obtains utilization at present in fields such as aerospace, defence and military, biomedicines.3D printing technique, based on digital model, uses metal, and pottery and polymer materials etc., construct object by the mode successively printed.Its type comprises fusion sediment technology, Selective Laser Sintering, Stereolithography technology and layer separated growth technology.
Selective laser sintering technique is the 3D printing technique be most widely used.C.R.Dechard etc. propose selective laser sintering thought first and successfully developed laser sintering process in 1989 in patent US4863538.Briefly, laser beam sinters selectively according to layering cross section information under the control of the computer, carries out lower one deck sintering again after one deck completes, and removes unnecessary powder, then can obtain the part sintered after all having sintered.Can be used in laser sintered material, polymer materials receives much concern because of the performance of its excellence, but the polymkeric substance that can be used for selective laser sintering process is very limited.Heinz Scholten etc. proposes PA-12 to be used in laser sintered process in patent US6245281B1.At present, PA-12 accounts for laser sintered polymer materials more than 95%, and many polymer materialss with excellent properties can't be used for, in laser sintered process, greatly limit its range of application.
Medical field is that 3D prints utilization one of utilization field comparatively widely, and urethane has excellent mechanical property, have excellent water-resistance, it has good biocompatibility, anticoagulant property, has no side effect, easily processing simultaneously, there is larger molecular designing degree of freedom, medical particularly extensive at medical field.Urethane is used for 3D printing and but rarely has report.A kind of polyurethane material that can be used for 3D and print is disclosed in blue green alive patent CN104177815, tolylene diisocyanate mixes with acetone by the method, add tetraethylammonium bromide, add azo diisobutyl amidine hydrochloride, 3-aminopropyl trimethoxysilane, polyurethane particles after stirring at room temperature successively, last heated and stirred obtains compound polyurethane material.This material has the low advantage of processing temperature, is expected for the manufacture of artificial organ.But acetone is volatile organic solvent, easily human body is damaged in the course of processing.Meanwhile, to print through 3D the goods mechanical strength obtained not high yet for this material.
The introducing of functional groups is to polymer performance, and especially use properties, plays a decisive role.Such as Diels-Alder dynamic key, metal ligand etc., it has environment correspondence, can stimulation to external world make corresponding, imparts material selfreparing and autoadhesion performance.But, also do not see the application of band functional group polymkeric substance in 3D printing at present.
Summary of the invention
This bright object is printing for 3D, containing the polyurethane material and its production and use of dynamic key of developing for the deficiencies in the prior art, be characterized in that this polyurethane material has the corresponding Diels-Alder dynamic key of environment or metal ligand, in 3D print procedure, when temperature rises to critical temperature, Diels-Alder dynamic key or metal ligand fracture are separated crosslinked, system viscosity reduces rapidly, is conducive to laser sintered process; When the temperature decreases, Diels-Alder dynamic key or metal ligand are formed again, and system is cross-linked, and enhance the mechanical property of goods, and Diels-Alder dynamic key or metal ligand impart material selfreparing and autoadhesion performance simultaneously.
Object of the present invention is realized by following technical measures, and wherein said raw material number, except specified otherwise, is molfraction:
Print for 3D, be made up of following component containing the starting raw material of the polyurethane material of dynamic key,
Wherein, to mate with diisocyanate trimer linking agent containing Diels-Alder key glycol chain extender and prepare containing Diels-Alder key polyurethane material; To mate with metal salt crosslinking agent containing the glycol chain extender of part and prepare containing metal part polyurethane material; Containing dynamic chemical key Diels-Alder key and metal ligand key in the molecular structure of the polyurethane material made respectively, the polyurethane material containing Diels-Alder key or metal ligand key all has the function of selfreparing and autoadhesion.
Described vulcabond is any one in tolylene diisocyanate, diphenylmethanediisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate.
Described polyester polyol is any one in polyethylene glycol adipate, poly-adipate glycol propylene glycol ester, poly-adipate glycol butanediol ester, poly-hexanodioic acid hexylene glycol ester, poly-epsilon-caprolactone, and polyether glycol is any one in polyether glycol-2000, polyether glycol-3000, polyether glycol-4000, polyether glycol-5000, polyether glycol-6000, polyether glycol-7000 or polyether glycol-8000.
Described diisocyanate trimer linking agent is any one in hexamethylene diisocyanate trimer, toluene diisocyanate trimer, diphenylmethanediisocyanate tripolymer.
The preparation method containing Diels-Alder key polyurethane material printed for 3D comprises the following steps:
1) containing the preparation of Diels-Alder key dibasic alcohol
Furans and maleic anhydride equimolar amount are dissolved in excessive Isosorbide-5-Nitrae-dioxane, at room temperature reaction 12 ~ 36h, throw out are smashed to pieces, through suction filtration, washed with diethylether, oven dry, obtain product III; Product III and hydramine equimolar amount, temperature 65 ~ 80 DEG C, react 12 ~ 36h, reaction mixture are put into refrigerator crystallisation by cooling, then through suction filtration, washed with diethylether, oven dry, obtain product IV in excessive methanol; Product IV is joined in excessive toluene, at temperature 100 ~ 125 DEG C of back flow reaction 10 ~ 20h, put into refrigerator crystallisation by cooling after then being filtered by solution, through suction filtration, washed with diethylether, oven dry, obtain product V; The product V of equimolar amount temperature 70 ~ 85 DEG C with furfuryl alcohol, reacts 12 ~ 36h, is smashed to pieces by throw out, through suction filtration, washed with diethylether, oven dry, obtain product VI, be the dibasic alcohol containing Diels-Alder key in excess toluene;
2) containing the preparation of Diels-Alder key urethane
By 100 parts of vulcabond and 50 ~ 75 parts of polyester polyols or polyether glycol, performed polymer is obtained at temperature 70 ~ 100 DEG C of frit reaction 1 ~ 3h, adding isocyanate trimer 0 ~ 50 part is again linking agent, dibasic alcohol 50 ~ 125 parts containing Diels-Alder key is chainextender, continue at temperature 70 ~ 90 DEG C reaction 48 ~ 120h, obtain containing Diels-Alder key urethane, and be prepared into the powder that particle diameter is 10 ~ 100 μm.
Described hydramine is any one in carbinolamine, thanomin, n-propyl alcohol amine, α-amino isopropyl alcohol, the amino propyl carbinol of 4-, the amino n-hexyl alcohol of 6-and diglycolamine.
Preparation method for the containing metal part polyurethane material of 3D printing comprises the following steps:
1) preparation of containing metal part dibasic alcohol
By 3-pyrazole carboxylic acid methyl esters, 1,6-dihalopyridine and sodium hydride are dissolved in N, dinethylformamide, at temperature 90 ~ 110 DEG C reaction 10 ~ 15h, add deionized water precipitation, obtain product 3-carboxylate methyl ester-2, two (pyrazoles) pyridine of 6-, again with sodium borohydride in dehydrated alcohol, temperature 40 ~ 60 DEG C reaction 4 ~ 8h, neutralize with hydrochloric acid except after desolventizing, be extracted with ethyl acetate, after drying, obtain the dibasic alcohol containing part;
2) preparation of containing metal part polyurethane material
By 100 parts of vulcabond and 50 ~ 75 parts of polyester polyols or polyether glycol, performed polymer is obtained at temperature 70 ~ 100 DEG C of frit reaction 1 ~ 3h, add 1 again, 4-dioxane is solvent, the dibasic alcohol 50 ~ 100 parts added containing part is chainextender, after room temperature reaction 24 ~ 72h, use methanol extraction.Throw out is dissolved in methylene dichloride, then to add metal-salt 0 ~ 50 part be linking agent, after drying the polyurethane material of containing metal part, and be prepared into the powder that particle diameter is 10 ~ 100 μm.
Described 1,6-dihalopyridine is any one in 1,6-difluoro pyridine, 1,6-dichloropyridine, 1,6-dibromo pyridine and 1,6-diiodopyridine, and described metal salt crosslinking agent is for containing Co
2+, Zn
2+, La
3+, Eu
3+, Ru
2+, Fe
2+, Fe
3+, Al
3+, Cu
2+, Cd
2+in any one.
The described method preparing polyurethane material powder is any one in mechanical milling method, freezing and pulverizing method, solvent precipitation or spray-drying process.
The described polyurethane material containing dynamic key is used for Selective Laser Sintering, fusion sediment technology, Stereolithography technology or layer separated growth technology in 3D printing technique.
Performance test:
Mechanics Performance Testing is carried out to Application Example 1 gained sample, obtains corresponding tensile strength, elongation at break, Young's modulus, as shown in table 1;
Cut-out process is carried out to Application Example 1 gained sample, then two sections is fit together, it is heated, UV-irradiation or after supersound process for some time, surface of fracture bonds.Mechanics Performance Testing is carried out to the sample after bonding, obtains corresponding tensile strength, elongation at break, Young's modulus, as shown in table 2;
The present invention has the following advantages:
1, in 3D print procedure, when temperature rises to more than critical temperature, Diels-Alder dynamic key or metal ligand rupture, and system viscosity reduces, and is conducive to 3D print procedure;
2, Diels-Alder dynamic key or metal ligand are recombinated lower than during critical temperature in temperature, material system are occurred crosslinked, improve the mechanical property of goods;
3, Diels-Alder dynamic key or metal ligand have environment correspondence, impart 3D and print goods selfreparing and autoadhesion performance;
4, body material is urethane, and it has good snappiness;
5, this material can be used for the preparation of artificial skin, artificial blood vessel, artificial cartilage.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary that again this is pointed out that the present embodiment is only for further illustrating of carrying out the present invention; can not be interpreted as limiting the scope of the invention, person skilled in art can make some nonessential improvement and adjustment according to the content of foregoing invention.Molfraction is without the following number of specified otherwise.
Embodiment 1
Furans and maleic anhydride equimolar amount are dissolved in excessive Isosorbide-5-Nitrae-dioxane, at room temperature reaction 12h, throw out are smashed to pieces, through suction filtration, washed with diethylether, oven dry, obtain product III; Product III and carbinolamine equimolar amount, temperature 65 DEG C, react 12h, reaction mixture are put into refrigerator crystallisation by cooling, then through suction filtration, washed with diethylether, oven dry, obtain product IV in excessive methanol; Product IV is joined in excessive toluene, at temperature 100 DEG C of back flow reaction 10h, put into refrigerator crystallisation by cooling after then being filtered by solution, through suction filtration, washed with diethylether, oven dry, obtain product V; The product V of equimolar amount at temperature 70 C with furfuryl alcohol, reacts 12h, is smashed to pieces by throw out, through suction filtration, washed with diethylether, oven dry, obtain product VI, be the dibasic alcohol containing Diels-Alder key in excess toluene;
By 100 parts of tolylene diisocyanates and 50 parts of polyethylene glycol adipate polyvalent alcohols, performed polymer is obtained at temperature 70 C frit reaction 1h, the dibasic alcohol 50 parts added again containing Diels-Alder key is chainextender, continue at temperature 70 C reaction 48h, obtain containing Diels-Alder key urethane, and make with mechanical milling method the powder that median size is 10 μm.
Embodiment 2
Furans and maleic anhydride equimolar amount are dissolved in excessive Isosorbide-5-Nitrae-dioxane, at room temperature reaction 18h, throw out are smashed to pieces, through suction filtration, washed with diethylether, oven dry, obtain product III; Product III and thanomin equimolar amount, temperature 68 DEG C, react 18h, reaction mixture are put into refrigerator crystallisation by cooling, then through suction filtration, washed with diethylether, oven dry, obtain product IV in excessive methanol; Product IV is joined in excessive toluene, at temperature 105 DEG C of back flow reaction 12h, put into refrigerator crystallisation by cooling after then being filtered by solution, through suction filtration, washed with diethylether, oven dry, obtain product V; The product V of equimolar amount temperature 73 DEG C with furfuryl alcohol, reacts 18h, is smashed to pieces by throw out, through suction filtration, washed with diethylether, oven dry, obtain product VI, be the dibasic alcohol containing Diels-Alder key in excess toluene;
By 100 parts of tolylene diisocyanates and 55 parts of polyethylene glycol adipate polyvalent alcohols, performed polymer is obtained at temperature 75 DEG C of frit reaction 1.5h, adding hexamethylene diisocyanate trimer 10 parts is again linking agent, dibasic alcohol 65 parts containing Diels-Alder key is chainextender, continue at temperature 75 DEG C reaction 60h, obtain containing Diels-Alder key urethane, and make with mechanical milling method the powder that median size is 20 μm.
Embodiment 3
Furans and maleic anhydride equimolar amount are dissolved in excessive Isosorbide-5-Nitrae-dioxane, at room temperature reaction 24h, throw out are smashed to pieces, through suction filtration, washed with diethylether, oven dry, obtain product III; Product III and Propanolamine equimolar amount, temperature 71 DEG C, react 24h, reaction mixture are put into refrigerator crystallisation by cooling, then through suction filtration, washed with diethylether, oven dry, obtain product IV in excessive methanol; Product IV is joined in excessive toluene, at temperature 110 DEG C of back flow reaction 14h, put into refrigerator crystallisation by cooling after then being filtered by solution, through suction filtration, washed with diethylether, oven dry, obtain product V; The product V of equimolar amount temperature 76 DEG C with furfuryl alcohol, reacts 24h, is smashed to pieces by throw out, through suction filtration, washed with diethylether, oven dry, obtain product VI, be the dibasic alcohol containing Diels-Alder key in excess toluene;
By 100 parts of diphenylmethanediisocyanates and 60 parts of polyethylene glycol adipate polyvalent alcohols, performed polymer is obtained at temperature 80 DEG C of frit reaction 2h, carry that to add toluene diisocyanate trimer 20 parts be linking agent, dibasic alcohol 80 parts containing Diels-Alder key is chainextender, continue at temperature 80 DEG C reaction 72h, obtain containing Diels-Alder key urethane, and make with mechanical milling method the powder that median size is 30 μm.
Embodiment 4
Furans and maleic anhydride equimolar amount are dissolved in excessive Isosorbide-5-Nitrae-dioxane, at room temperature reaction 30h, throw out are smashed to pieces, through suction filtration, washed with diethylether, oven dry, obtain product III; Product III and α-amino isopropyl alcohol equimolar amount, temperature 74 DEG C, react 30h, reaction mixture are put into refrigerator crystallisation by cooling, then through suction filtration, washed with diethylether, oven dry, obtain product IV in excessive methanol; Product IV is joined in excessive toluene, at temperature 115 DEG C of back flow reaction 16h, put into refrigerator crystallisation by cooling after then being filtered by solution, through suction filtration, washed with diethylether, oven dry, obtain product V; The product V of equimolar amount temperature 79 DEG C with furfuryl alcohol, reacts 30h, is smashed to pieces by throw out, through suction filtration, washed with diethylether, oven dry, obtain product VI, be the dibasic alcohol containing Diels-Alder key in excess toluene;
By 100 parts of diphenylmethanediisocyanates and 65 parts of poly-adipate glycol propylene glycol ester polyvalent alcohols, performed polymer is obtained at temperature 85 DEG C of frit reaction 2.5h, adding toluene diisocyanate trimer 30 parts is again linking agent, dibasic alcohol 95 parts containing Diels-Alder key is chainextender, continue at temperature 85 DEG C reaction 84h, obtain containing Diels-Alder key urethane, and make with mechanical milling method the powder that median size is 40 μm.
Embodiment 5
Furans and maleic anhydride equimolar amount are dissolved in excessive Isosorbide-5-Nitrae-dioxane, at room temperature reaction 36h, throw out are smashed to pieces, through suction filtration, washed with diethylether, oven dry, obtain product III; Product III and the amino propyl carbinol equimolar amount of 4-, temperature 77 DEG C, react 36h, reaction mixture are put into refrigerator crystallisation by cooling, then through suction filtration, washed with diethylether, oven dry, obtain product IV in excessive methanol; Product IV is joined in excessive toluene, at temperature 120 DEG C of back flow reaction 18h, put into refrigerator crystallisation by cooling after then being filtered by solution, through suction filtration, washed with diethylether, oven dry, obtain product V; The product V of equimolar amount temperature 82 DEG C with furfuryl alcohol, reacts 36h, is smashed to pieces by throw out, through suction filtration, washed with diethylether, oven dry, obtain product VI, be the dibasic alcohol containing Diels-Alder key in excess toluene;
By 100 parts of tolylene diisocyanates and 70 parts, poly-adipate glycol butanediol ester polyvalent alcohol, performed polymer is obtained at temperature 90 DEG C of frit reaction 3h, adding part diphenylmethanediisocyanate tripolymer 40 parts is again linking agent, dibasic alcohol 110 parts containing Diels-Alder key is chainextender, continue at temperature 90 DEG C reaction 96h, obtain containing Diels-Alder key urethane, and make by freezing and pulverizing method the powder that median size is 50 μm.
Embodiment 6
Furans and maleic anhydride equimolar amount are dissolved in excessive Isosorbide-5-Nitrae-dioxane, at room temperature reaction 24h, throw out are smashed to pieces, through suction filtration, washed with diethylether, oven dry, obtain product III; Product III and the amino n-hexyl alcohol equimolar amount of 6-, temperature 80 DEG C, react 24h, reaction mixture are put into refrigerator crystallisation by cooling, then through suction filtration, washed with diethylether, oven dry, obtain product IV in excessive methanol; Product IV is joined in excessive toluene, at temperature 125 DEG C of back flow reaction 20h, put into refrigerator crystallisation by cooling after then being filtered by solution, through suction filtration, washed with diethylether, oven dry, obtain product V; The product V of equimolar amount temperature 85 DEG C with furfuryl alcohol, reacts 24h, is smashed to pieces by throw out, through suction filtration, washed with diethylether, oven dry, obtain product VI, be the dibasic alcohol containing Diels-Alder key in excess toluene;
By 100 parts of diphenylmethanediisocyanates and 75 parts of poly-hexanodioic acid hexylene glycol ester polyols, performed polymer is obtained at temperature 100 DEG C of frit reaction 2h, adding part diphenylmethanediisocyanate tripolymer 50 parts is again linking agent, dibasic alcohol containing Diels-Alder key is 125 parts of chainextenders, continue at temperature 70 C reaction 108h, obtain containing Diels-Alder key urethane, and make by freezing and pulverizing method the powder that median size is 60 μm.
Embodiment 7
Furans and maleic anhydride equimolar amount are dissolved in excessive Isosorbide-5-Nitrae-dioxane, at room temperature reaction 24h, throw out are smashed to pieces, through suction filtration, washed with diethylether, oven dry, obtain product III; Product III and diglycolamine equimolar amount, temperature 75 DEG C, react 24h, reaction mixture are put into refrigerator crystallisation by cooling, then through suction filtration, washed with diethylether, oven dry, obtain product IV in excessive methanol; Product IV is joined in excessive toluene, at temperature 110 DEG C of back flow reaction 15h, put into refrigerator crystallisation by cooling after then being filtered by solution, through suction filtration, washed with diethylether, oven dry, obtain product V; The product V of equimolar amount temperature 75 DEG C with furfuryl alcohol, reacts 24h, is smashed to pieces by throw out, through suction filtration, washed with diethylether, oven dry, obtain product VI, be the dibasic alcohol containing Diels-Alder key in excess toluene;
By 100 parts of diphenylmethanediisocyanates and 75 parts of poly-epsilon-caprolactone polyvalent alcohols, performed polymer is obtained at temperature 80 DEG C of frit reaction 2h, adding diphenylmethanediisocyanate tripolymer 50 parts is again linking agent, dibasic alcohol 125 parts containing Diels-Alder key is chainextender, continue at temperature 80 DEG C reaction 120h, obtain containing Diels-Alder key urethane, and make by freezing and pulverizing method the powder that median size is 70 μm.
Embodiment 8
By 3-pyrazole carboxylic acid methyl esters, 1,6-difluoro pyridine and sodium hydride are dissolved in DMF, at temperature 90 DEG C reaction 10h, add deionized water precipitation, obtain two (pyrazoles) pyridine of product 3-carboxylate methyl ester-2,6-, then with sodium borohydride in dehydrated alcohol, at temperature 40 DEG C reaction 4h, neutralize with hydrochloric acid except after desolventizing, be extracted with ethyl acetate, after drying, obtain the dibasic alcohol containing part.
By 100 parts of xylylene diisocyanates, 50 parts of polyether glycols-8000, obtain performed polymer at temperature 70 C frit reaction 1h, then add 1,4-dioxane is solvent, the dibasic alcohol 50 parts added containing part is chainextender, after room temperature reaction 24h, uses methanol extraction.Throw out is dissolved in methylene dichloride, obtains the polyurethane material of containing metal part after drying, and make by freezing and pulverizing method the powder that median size is 80 μm.
Embodiment 9
By 3-pyrazole carboxylic acid methyl esters, 1,6-difluoro pyridine and sodium hydride are dissolved in DMF, at temperature 92 DEG C reaction 10.5h, add deionized water precipitation, obtain two (pyrazoles) pyridine of product 3-carboxylate methyl ester-2,6-, then with sodium borohydride in dehydrated alcohol, at temperature 42 DEG C reaction 4.4h, neutralize with hydrochloric acid except after desolventizing, be extracted with ethyl acetate, after drying, obtain the dibasic alcohol containing part.
By 100 parts of xylylene diisocyanates, 50 parts of polyether glycols-8000, obtain performed polymer at temperature 73 DEG C of frit reaction 1.2h, then add 1,4-dioxane is solvent, the dibasic alcohol 55 parts added containing part is chainextender, after room temperature reaction 32h, uses methanol extraction.Throw out is dissolved in methylene dichloride, adds Zn
2+5 parts is linking agent, obtains the polyurethane material of containing metal part, and make with solvent precipitation the powder that median size is 90 μm after drying.
Embodiment 10
By 3-pyrazole carboxylic acid methyl esters, 1,6-difluoro pyridine and sodium hydride are dissolved in DMF, at temperature 94 DEG C reaction 11h, add deionized water precipitation, obtain two (pyrazoles) pyridine of product 3-carboxylate methyl ester-2,6-, then with sodium borohydride in dehydrated alcohol, at temperature 44 DEG C reaction 4.8h, neutralize with hydrochloric acid except after desolventizing, be extracted with ethyl acetate, after drying, obtain the dibasic alcohol containing part.
By 100 parts of xylylene diisocyanates, 55 parts of polyether glycols-8000, obtain performed polymer at temperature 76 DEG C of frit reaction 1.4h, then add 1,4-dioxane is solvent, the dibasic alcohol 60 parts added containing part is chainextender, after room temperature reaction 40h, uses methanol extraction.Throw out is dissolved in methylene dichloride, adds La
3+10 parts is linking agent, obtains the polyurethane material of containing metal part, and make with solvent precipitation the powder that median size is 100 μm after drying.
Embodiment 11
By 3-pyrazole carboxylic acid methyl esters, 1,6-dichloropyridine and sodium hydride are dissolved in DMF, at temperature 96 DEG C reaction 11.5h, add deionized water precipitation, obtain two (pyrazoles) pyridine of product 3-carboxylate methyl ester-2,6-, then with sodium borohydride in dehydrated alcohol, at temperature 46 DEG C reaction 5.2h, neutralize with hydrochloric acid except after desolventizing, be extracted with ethyl acetate, after drying, obtain the dibasic alcohol containing part.
By 100 parts of hexamethylene diisocyanates and 55 parts of polyether glycols-7000, obtain performed polymer at temperature 80 DEG C of frit reaction 1.6h, then add 1,4-dioxane is solvent, the dibasic alcohol 65 parts added containing part is chainextender, after room temperature reaction 48h, uses methanol extraction.Throw out is dissolved in methylene dichloride, adds Eu
3+15 parts is linking agent, obtains the polyurethane material of containing metal part, and make with solvent precipitation the powder that median size is 10 μm after drying.
Embodiment 12
By 3-pyrazole carboxylic acid methyl esters, 1,6-dichloropyridine and sodium hydride are dissolved in DMF, at temperature 98 DEG C reaction 12h, add deionized water precipitation, obtain two (pyrazoles) pyridine of product 3-carboxylate methyl ester-2,6-, then with sodium borohydride in dehydrated alcohol, at temperature 48 DEG C reaction 5.6h, neutralize with hydrochloric acid except after desolventizing, be extracted with ethyl acetate, after drying, obtain the dibasic alcohol containing part.
By 100 parts of hexamethylene diisocyanates and 60 parts of polyether glycols-6000, obtain performed polymer at temperature 84 DEG C of frit reaction 1.8h, then add 1,4-dioxane is solvent, the dibasic alcohol 70 parts added containing part is chainextender, after room temperature reaction 56h, uses methanol extraction.Throw out is dissolved in methylene dichloride, adds Ru
2+20 parts is linking agent, obtains the polyurethane material of containing metal part, and make with solvent precipitation the powder that median size is 20 μm after drying.
Embodiment 13
By 3-pyrazole carboxylic acid methyl esters, 1,6-dichloropyridine and sodium hydride are dissolved in DMF, at temperature 100 DEG C reaction 12.5h, add deionized water precipitation, obtain two (pyrazoles) pyridine of product 3-carboxylate methyl ester-2,6-, then with sodium borohydride in dehydrated alcohol, at temperature 50 C reaction 6h, neutralize with hydrochloric acid except after desolventizing, be extracted with ethyl acetate, after drying, obtain the dibasic alcohol containing part.
By 100 parts of hexamethylene diisocyanates and 60 parts of polyether glycols-5000, obtain performed polymer at temperature 87 DEG C of frit reaction 2h, then add 1,4-dioxane is solvent, the dibasic alcohol 75 parts added containing part is chainextender, after room temperature reaction 64h, uses methanol extraction.Throw out is dissolved in methylene dichloride, adds Fe
2+25 parts is linking agent, obtains the polyurethane material of containing metal part, and make by spray-drying process the powder that median size is 30 μm after drying.
Embodiment 14
By 3-pyrazole carboxylic acid methyl esters, 1,6-dibromo pyridine and sodium hydride are dissolved in DMF, at temperature 102 DEG C reaction 13h, add deionized water precipitation, obtain two (pyrazoles) pyridine of product 3-carboxylate methyl ester-2,6-, then with sodium borohydride in dehydrated alcohol, at temperature 52 DEG C reaction 6.4h, neutralize with hydrochloric acid except after desolventizing, be extracted with ethyl acetate, after drying, obtain the dibasic alcohol containing part.
By 100 parts of dicyclohexyl methane diisocyanates and 65 parts of polyether glycols-4000, obtain performed polymer at temperature 90 DEG C of frit reaction 2.2h, then add 1,4-dioxane is solvent, the dibasic alcohol 80 parts added containing part is chainextender, after room temperature reaction 72h, uses methanol extraction.Throw out is dissolved in methylene dichloride, adds Fe
3+30 parts is linking agent, obtains the polyurethane material of containing metal part, and make by spray-drying process the powder that median size is 40 μm after drying.
Embodiment 15
By 3-pyrazole carboxylic acid methyl esters, 1,6-dibromo pyridine and sodium hydride are dissolved in DMF, at temperature 106 DEG C reaction 14h, add deionized water precipitation, obtain two (pyrazoles) pyridine of product 3-carboxylate methyl ester-2,6-, then with sodium borohydride in dehydrated alcohol, at temperature 54 DEG C reaction 6.8h, neutralize with hydrochloric acid except after desolventizing, be extracted with ethyl acetate, after drying, obtain the dibasic alcohol containing part.
By 100 parts of dicyclohexyl methane diisocyanates and 65 parts of polyether glycols-3000, obtain performed polymer at temperature 93 DEG C of frit reaction 2.4h, then add 1,4-dioxane is solvent, the dibasic alcohol 85 parts added containing part is chainextender, after room temperature reaction 64h, uses methanol extraction.Throw out is dissolved in methylene dichloride, adds Al
3+35 parts is linking agent, obtains the polyurethane material of containing metal part, and make by spray-drying process the powder that median size is 50 μm after drying.
Embodiment 16
By 3-pyrazole carboxylic acid methyl esters, 1,6-diiodopyridine and sodium hydride are dissolved in DMF, at temperature 108 DEG C reaction 14.5h, add deionized water precipitation, obtain two (pyrazoles) pyridine of product 3-carboxylate methyl ester-2,6-, then with sodium borohydride in dehydrated alcohol, at temperature 56 DEG C reaction 7.2h, neutralize with hydrochloric acid except after desolventizing, be extracted with ethyl acetate, after drying, obtain the dibasic alcohol containing part.
By 100 parts of dicyclohexyl methane diisocyanates and 70 parts of polyether glycols-3000, obtain performed polymer at temperature 96 DEG C of frit reaction 2.6h, then add 1,4-dioxane is solvent, the dibasic alcohol 90 parts added containing part is chainextender, after room temperature reaction 56h, uses methanol extraction.Throw out is dissolved in methylene dichloride, adds Cu
2+40 parts is linking agent, obtains the polyurethane material of containing metal part, and make by spray-drying process the powder that median size is 60 μm after drying.
Embodiment 17
By 3-pyrazole carboxylic acid methyl esters, 1,6-diiodopyridine and sodium hydride are dissolved in DMF, at temperature 110 DEG C reaction 15h, add deionized water precipitation, obtain two (pyrazoles) pyridine of product 3-carboxylate methyl ester-2,6-, then with sodium borohydride in dehydrated alcohol, at temperature 60 C reaction 8h, neutralize with hydrochloric acid except after desolventizing, be extracted with ethyl acetate, after drying, obtain the dibasic alcohol containing part.
By 100 parts of dicyclohexyl methane diisocyanates and 75 parts of polyether glycols-2000, obtain performed polymer at temperature 100 DEG C of frit reaction 3h, then add 1,4-dioxane is solvent, the dibasic alcohol 100 parts added containing part is chainextender, after room temperature reaction 48h, uses methanol extraction.Throw out is dissolved in methylene dichloride, adds Cd
2+50 parts is linking agent, obtains the polyurethane material of containing metal part, and make by spray-drying process the powder that median size is 70 μm after drying.
Application example 1
The polyurethane powder powder material containing Diels-Alder dynamic key obtained for embodiment 1 ~ 3 is laid on the worktable of 3D printer, it is 95 DEG C that cylinder temperature is built in setting, and laser power is 60w, sweep span 0.2mm, paving powder thickness 0.15mm, sweep velocity is 7.6m/s;
Laser, under the control of computer dependent program, vertically carries out the cross-section data of hierarchy slicing according to three-dimensional stl file, scan and sinter selectively to the described polyurethane material powder containing Diels-Alder dynamic key;
Be heated by the polyurethane material powder containing Diels-Alder dynamic key described in the region that laser is inswept, melt, Diels-Alder dynamic key ruptures simultaneously, and viscosity of material reduces greatly, bonds.After one deck has sintered, the height of working cylinder decline setting, then carry out paving powder and the sintering of lower one deck, and bond with front one deck, reprocessabilty like this is shaping.At laser sintered rear and cooling stages, material solidification Diels-Alder dynamic key restructuring simultaneously, makes material system occur crosslinked.Powder, the polyurethane product that can obtain containing Diels-Alder dynamic key of polishing clearly are carried out in final taking-up, and its good mechanical performance, has the performance of selfreparing and autoadhesion simultaneously.
Application example 2
Be laid on the worktable of 3D printer by the polyurethane powder powder material of containing metal part obtained for embodiment 8 ~ 10, it is 100 DEG C that cylinder temperature is built in setting, and laser power is 60w, sweep span 0.2mm, paving powder thickness 0.15mm, and sweep velocity is 7.6m/s;
Laser, under the control of computer dependent program, vertically carries out the cross-section data of hierarchy slicing according to three-dimensional stl file, scan and sinter selectively to described compound polyurethane material powder;
Be heated by the described containing metal part polyurethane material powder in the region that laser is inswept, melt, metal ligand ruptures simultaneously, and viscosity of material reduces greatly, bonds.After one deck has sintered, the height of working cylinder decline setting, then carry out paving powder and the sintering of lower one deck, and bond with front one deck, reprocessabilty like this is shaping.At laser sintered rear and cooling stages, material solidification metal ligand restructuring simultaneously, makes material system occur crosslinked.The polyurethane product that powder is clearly carried out in final taking-up, polishing can obtain containing metal part, its good mechanical performance, has the performance of selfreparing and autoadhesion simultaneously.
Table 1. embodiment 1 ~ 3 resulting materials is through 3D printed sample mechanical property
| Elongation at break/% | Tensile strength/MPa | Tensile modulus/ GPa | |
| Embodiment 1 | 307.31 | 6.50 | 0.02 |
| Embodiment 2 | 362.59 | 10.55 | 0.02 |
| Embodiment 3 | 413.35 | 13.02 | 0.03 |
As shown in Table 1, the sample that this urethane prints preparation through 3D has excellent mechanical property.It has excellent mechanical property, and tensile strength 13.02MPa, can reach elongation at break and can reach 413.35%, illustrates that this material has good snappiness
Table 2. embodiment 1 ~ 3 resulting materials is through the mechanical property of 3D printed sample after cutting off, bonding
| Elongation at break/% | Tensile strength/MPa | Tensile modulus/ GPa | |
| Embodiment 1 | 301.25 | 6.07 | 0.02 |
| Embodiment 2 | 353.40 | 10.23 | 0.02 |
| Embodiment 3 | 399.08 | 12.56 | 0.03 |
As shown in Table 2, this polyurethane material prints the sample that obtains through cutting off, after autoadhesion process through 3D, and mechanical property still can remain on higher level, illustrates that this material has good autoadhesion, self-healing properties.
Claims (10)
1. print for 3D, containing the polyurethane material of dynamic key, it is characterized in that the starting raw material of this polyurethane material is made up of following component, count by molfraction:
Wherein, to mate with diisocyanate trimer linking agent containing Diels-Alder key glycol chain extender and prepare containing Diels-Alder key polyurethane material; To mate with metal salt crosslinking agent containing the glycol chain extender of part and prepare containing metal part polyurethane material; Containing dynamic chemical key Diels-Alder key and metal ligand key in the molecular structure of the polyurethane material made respectively, the polyurethane material containing Diels-Alder key or metal ligand key all has the function of selfreparing and autoadhesion.
2. print for 3D according to claim 1, containing the polyurethane material of dynamic key, it is characterized in that vulcabond is any one in tolylene diisocyanate, diphenylmethanediisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate.
3. print for 3D according to claim 1, containing the polyurethane material of dynamic key, it is characterized in that polyester polyol is any one in polyethylene glycol adipate, poly-adipate glycol propylene glycol ester, poly-adipate glycol butanediol ester, poly-hexanodioic acid hexylene glycol ester, poly-epsilon-caprolactone; Polyether glycol is any one in polyether glycol-2000, polyether glycol-3000, polyether glycol-4000, polyether glycol-5000, polyether glycol-6000, polyether glycol-7000, polyether glycol-8000.
4. print for 3D according to claim 1, containing the polyurethane material of dynamic key, it is characterized in that diisocyanate trimer linking agent is any one in hexamethylene diisocyanate trimer, toluene diisocyanate trimer, diphenylmethanediisocyanate tripolymer.
5. print for 3D according to claim 1, containing the preparation method of the polyurethane material of dynamic key, it is characterized in that the described preparation method containing Diels-Alder key polyurethane material comprises the following steps:
1) containing the preparation of Diels-Alder key dibasic alcohol
Furans and maleic anhydride equimolar amount are dissolved in excessive Isosorbide-5-Nitrae-dioxane, at room temperature reaction 12 ~ 36h, throw out are smashed to pieces, through suction filtration, washed with diethylether, oven dry, obtain product III; Product III and hydramine equimolar amount, temperature 65 ~ 80 DEG C, react 12 ~ 36h, reaction mixture are put into refrigerator crystallisation by cooling, then through suction filtration, washed with diethylether, oven dry, obtain product IV in excessive methanol; Product IV is joined in excessive toluene, at temperature 100 ~ 125 DEG C of back flow reaction 10 ~ 20h, put into refrigerator crystallisation by cooling after then being filtered by solution, through suction filtration, washed with diethylether, oven dry, obtain product V; The product V of equimolar amount temperature 70 ~ 85 DEG C with furfuryl alcohol, reacts 12 ~ 36h, is smashed to pieces by throw out, through suction filtration, washed with diethylether, oven dry, obtain product VI, be the dibasic alcohol containing Diels-Alder key in excess toluene;
2) containing the preparation of Diels-Alder key urethane
By 100 parts of vulcabond and 50 ~ 75 parts of polyester polyols or polyether glycol, performed polymer is obtained at temperature 70 ~ 100 DEG C of frit reaction 1 ~ 3h, adding isocyanate trimer 0 ~ 50 part is again linking agent, dibasic alcohol 50 ~ 125 parts containing Diels-Alder key is chainextender, continue at temperature 70 ~ 90 DEG C reaction 48 ~ 120h, obtain containing Diels-Alder key urethane, and be prepared into the powder that particle diameter is 10 ~ 100 μm.
6. print for 3D according to claim 4, containing the preparation method of the polyurethane material of dynamic key, it is characterized in that hydramine is any one in carbinolamine, thanomin, n-propyl alcohol amine, α-amino isopropyl alcohol, the amino propyl carbinol of 4-, the amino n-hexyl alcohol of 6-and diglycolamine.
7. print for 3D according to claim 1, containing the preparation method of the polyurethane material of dynamic key, it is characterized in that the preparation method of described containing metal part key polyurethane material comprises the following steps:
1) preparation of containing metal part dibasic alcohol
By 3-pyrazole carboxylic acid methyl esters, 1,6-dihalopyridine and sodium hydride are dissolved in N, dinethylformamide, at temperature 90 ~ 110 DEG C reaction 10 ~ 15h, add deionized water precipitation, obtain product 3-carboxylate methyl ester-2, two (pyrazoles) pyridine of 6-, again with sodium borohydride in dehydrated alcohol, temperature 40 ~ 60 DEG C reaction 4 ~ 8h, neutralize with hydrochloric acid except after desolventizing, be extracted with ethyl acetate, after drying, obtain the dibasic alcohol containing part;
2) preparation of containing metal part polyurethane material
By 100 parts of vulcabond and 50 ~ 75 parts of polyester polyols or polyether glycol, performed polymer is obtained at temperature 70 ~ 100 DEG C of frit reaction 1 ~ 3h, adding Isosorbide-5-Nitrae-dioxane is again solvent, and the dibasic alcohol 50 ~ 100 parts added containing part is chainextender, after room temperature reaction 24 ~ 72h, with methanol extraction, throw out is dissolved in methylene dichloride, then to add metal-salt 0 ~ 50 part be linking agent, obtain the polyurethane material of containing metal part after drying, and be prepared into the powder that particle diameter is 10 ~ 100 μm.
8. print for 3D according to claim 7, containing the preparation method of the polyurethane material of dynamic key, it is characterized in that described 1,6-dihalopyridine is any one in 1,6-difluoro pyridine, 1,6-dichloropyridine, 1,6-dibromo pyridine and 1,6-diiodopyridine; Described metal salt crosslinking agent is for containing Co
2+, Zn
2+, La
3+, Eu
3+, Ru
2+, Fe
2+, Fe
3+, Al
3+, Cu
2+, Cd
2+in any one.
9. print for 3D according to claim 1, containing the polyurethane material of dynamic key, the method that it is characterized in that preparing described polyurethane material powder is any one in mechanical milling method, freezing and pulverizing method, solvent precipitation or spray-drying process.
10. according to claim 1ly to print for 3D, containing the purposes of the polyurethane material of dynamic key, it is characterized in that the described polyurethane material containing dynamic key is for any one in the Selective Laser Sintering in 3D printing technique, fusion sediment technology, Stereolithography technology or layer separated growth technology.
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