CN115819711B - Reactive extrusion 3D printing silicone rubber-polyurea material and application thereof - Google Patents
Reactive extrusion 3D printing silicone rubber-polyurea material and application thereof Download PDFInfo
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 40
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 37
- 238000010146 3D printing Methods 0.000 title claims abstract description 27
- 238000001125 extrusion Methods 0.000 title claims abstract description 22
- -1 polysiloxane, diisocyanate Polymers 0.000 claims abstract description 28
- 238000007639 printing Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- 125000003277 amino group Chemical group 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000003566 sealing material Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 150000003141 primary amines Chemical class 0.000 claims description 8
- 150000003335 secondary amines Chemical class 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- HYSQEYLBJYFNMH-UHFFFAOYSA-N n'-(2-aminoethyl)-n'-methylethane-1,2-diamine Chemical compound NCCN(C)CCN HYSQEYLBJYFNMH-UHFFFAOYSA-N 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 239000011359 shock absorbing material Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 238000013016 damping Methods 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 230000000172 allergic effect Effects 0.000 abstract description 2
- 208000010668 atopic eczema Diseases 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 239000000806 elastomer Substances 0.000 abstract description 2
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Abstract
The invention discloses a reactive extrusion 3D printing silicone rubber-polyurea material and application thereof, wherein the silicone rubber-polyurea elastomer material is prepared by the following steps: and (3) blending and extruding the amino-terminated polysiloxane, diisocyanate and an allergic catalyst, directly printing, and cooling to room temperature to obtain the polyurethane printing ink, wherein the printing temperature is 120-200 ℃, and the printing speed is controlled to be 0.5-2mm/s. Wherein the molar ratio of amino groups to isocyanate in the amino-terminated polysiloxane to diisocyanate and the reactivity rate modifier is 1.05-1.3:1. The silicone rubber-polyurea material printed by the invention has good rebound resilience, toughness, hydrophobicity and antifouling property, and the mechanical property of the product is not obviously changed after being soaked in water for 3 days. The printed material has good performance and long service life, and the transparency of the printed product can be adjusted. Can be used for producing soles, vamps, sealing materials, children toys, artware, damping products and the like.
Description
Technical Field
The invention belongs to the technical field of 3D printing, and particularly relates to a reactive extrusion 3D printing silicone rubber-polyurea material and application thereof.
Background
The vamp or sole material prepared by using the 3D printing technology has the advantages of being designable in structure, customized in private and the like. The materials commonly used at present for preparing shoe uppers or shoe soles by adopting a 3D printing technology are polyurethane elastomer or photo-curing resin materials. Polyureas and polyurethanes have similar molecular structures, except that the polyurethane is prepared by reacting hydroxyl groups with isocyanate and the polyurea is prepared by reacting amino groups with isocyanate. The polyurea material has excellent elasticity and can be used as a shoe material. The defects are that 1) the reaction rate of amino and isocyanate is extremely high, the control is difficult, the processing is difficult, and the preparation of products with specific structures is difficult; 2) Urea linkages in polyureas can cause the material to absorb water, and are typically addressed by introducing aromatic rigid groups and increasing the degree of crosslinking, but can lose the elasticity and toughness of the material.
The most common processing method for polyureas is spraying, which is suitable for preparing protective coatings on a variety of substrates. In addition, the reactive extrusion molding method can also be used for spraying construction of polyurea. Spray coating and conventional reactive extrusion processes are not capable of producing articles having specific structures and functions. The polyurea material with a special structure is constructed by utilizing the 3D printing technology, so that the vibration reduction, rebound and other performances of the polyurea material can be improved, and the polyurea material has important application in the field of shoe materials. Few reports are currently made on polyurea 3D printing techniques, typically photo-curing 3D techniques.
Application number: 2019107906039A photosensitive resin and a method of 3D printing polyurea, the photosensitive resin comprising an acrylate oligomer containing urea linkages and having a functionality of 2 or more; the acrylate oligomer containing urea bonds and having double bond functionality of 2 or more is obtained by reacting an isocyanate group-terminated compound having functionality of 2 or more with an amino group-containing acrylate or methacrylate compound. The invention also provides a method for 3D printing polyurea. After the photosensitive resin is photocured or 3D printed to form a polymer, the molecular structure, the crosslinking density and other network structure characteristics of the polymer can be changed through specific post-treatment, so that the thermal and mechanical properties of the photosensitive resin can be adjusted through the post-treatment. The 3D printing is carried out by adopting the photo-curing technology, the surface monomer of a printing product is difficult to clear, the environmental pollution is serious, the types of printable monomers are limited, and the method is not suitable for reactive extrusion of the 3D printing silicone rubber-polyurea material.
Application number: 2018800638856 discloses a method of build-up fabrication using co-reactive components. Thermosetting compositions for laminate manufacturing are also disclosed. The invention relates to a method for manufacturing a reactive lamination, which comprises the following steps: providing a first component comprising a first compound into a first pump; a second component comprising a second compound is provided to a second pump, wherein the first compound is reactive with the second compound. The amino compound and the isocyanate compound are suitable for the method, but how to control the reaction rate of the amino compound and the isocyanate compound to ensure high-precision printing is not mentioned in this invention, and mechanical properties, antifouling properties, and hydrophobic properties of printed matter are not mentioned, and specific printing parameters such as printing speed, printing temperature, and the like are not mentioned. In addition, the technology requires a mold support, and is difficult to prepare complex structures. Although the above reaction rate and the problem of certainty of the optimal temperature can be solved by a limited number of experiments, the effect is limited.
Based on the above, the present application specifically adds a rate regulator to solve the above technical problems, but part of the system may have excessive viscosity, and cannot obtain a printing sample, and by overcoming layer-by-layer hindrance, including selection of raw materials, determination of reaction temperature, determination of monomer proportion, selection of molecular weight and catalyst type, etc., direct-writing 3D printing of a silicone rubber-polyurea product with a special complex structure is finally achieved.
Disclosure of Invention
In view of the above-mentioned shortcomings, the invention provides a reactive extrusion 3D printing silicone rubber-polyurea material and application thereof, and the technical scheme is realized by the following method:
a method of reactive extrusion of 3D printed silicone rubber-polyurea material comprising:
and (3) blending and extruding the monomer A, the monomer B and the reactive catalyst, directly printing, and cooling to room temperature to obtain the catalyst.
Further, the monomer A is primary amine end-capped polysiloxane or secondary amine end-capped polysiloxane or a mixture of the two;
the molecular weight of the primary amine terminated polysiloxane is 600-5000g/mol;
the molecular weight of the secondary amine-terminated polysiloxane is 600 to 5000g/mol.
Further, the monomer B is one or a mixture of more of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.
Further, the reactive catalyst is one or a mixture of more of N-methyl-2, 2' -diamino diethylamine, amino ethyl piperazine, N ' -trimethyl diethylenetriamine and N, N ' -trimethyl di (hexamethylene) triamine.
Further, the printing temperature is 120-200 DEG C
Further, the molar ratio of the amino group to the isocyanate in the monomer A to the monomer B and the reaction catalyst is 1.05-1.3:1.
Further, the printing speed is 0.5-2mm/s.
The invention also discloses a silicone rubber-polyurea material prepared by the reactive extrusion 3D printing method.
The invention also discloses an application of the silicone rubber-polyurea material in production and preparation of shoes, sealing materials, children toys, artware and damping materials.
Further, the footwear production includes vamp material production and midsole material production.
The technical scheme of the invention has the beneficial effects that:
1) The monomer A, the monomer B and the allergic catalyst are mixed by a printer and extruded in the reaction process, so that direct-writing 3D printing is realized, and a silicone rubber-polyurea product with a special complex structure can be printed. During the mixing process, the amino compound reacts with the isocyanate compound to effect curing, ensuring that the printed article will remain in shape on the substrate. The reactive catalyst is a triamine compound, wherein one amino group is tertiary amine and plays a role in catalysis, and the other two amino groups are primary amine or secondary amine, so that the reactive catalyst can react on a main chain of a silicone rubber-polyurea elastomer material, and unlike the traditional catalyst, the reactive catalyst can react on a main chain of a polymer, so that the phenomenon that the catalyst overflows and the material performance and the service life are influenced is avoided. The tertiary amine group in the reactive catalyst can catalyze the dissociation of urea bond at high temperature to regenerate amino and isocyanate, so that the viscosity of the system is reduced, and smooth printing is ensured. The tertiary amine group in the reactive catalyst can promote the generated amino generated by dissociation to reform urea bond with isocyanate at low temperature, so that the rapid solidification of the material printed on the substrate is ensured, and the printing precision is ensured. By changing the monomer ratio, molecular weight and catalyst type, products with different mechanical properties can be obtained, and the transparency of the printed product can be adjusted.
2) The product printed by the invention has an antifouling function, and when the surface is polluted, pollutants are easy to remove. Meanwhile, the printed product has better hydrophobic property, and the mechanical property of the product is not obviously changed after being soaked in water for 3 days. The printed article may be used in making uppers, soles, children's toys, artwork, and the like.
Drawings
FIG. 1 is a stress-strain curve of the printed article of example 1;
FIG. 2 is an optical photograph of the printed article of example 2;
FIG. 3 is a static contact angle photomicrograph of the printed article of example 3;
FIG. 4 is an infrared spectrum of a printed article of example 4;
FIG. 5 is a plot of stress strain after 72 hours of immersion in water for the original printed article of example 5;
FIG. 6 is an optical photograph of example 5 at the needle during the printing extrusion process;
FIG. 7 is an optical photograph of example 6 at the needle during the printing extrusion process.
Detailed Description
The specific technical scheme of the invention is described by combining the embodiments.
Example 1
15g of a primary amine-terminated polysiloxane having a molecular weight of 1000g/mol, 5g of a secondary amine-terminated polysiloxane having a molecular weight of 1000g/mol, 4.5g of isophorone diisocyanate and 0.2. 0.2g N-methyl-2, 2' -diaminodiethylamine were mixed, and the mixture was subjected to reactive extrusion 3D printing at 140℃at a speed of 1mm/s, and cooled to room temperature to obtain a printed product.
As shown in figure 1, the elongation at break of the silicone rubber-polyurea prepared by the 3D printing method can reach 520%, and the silicone rubber-polyurea has good flexibility.
Example 2
20g of primary amine terminated polysiloxane with molecular weight of 1000g/mol, 5.2g of dicyclohexylmethane diisocyanate and 0.3g of aminoethylpiperazine are subjected to reactive extrusion 3D printing at 160 ℃ at a speed of 1mm/s, and cooled to room temperature to obtain a printed product.
As shown in fig. 2, a silicone rubber-polyurea product with a special complex structure and high printing precision can be prepared by the 3D printing method.
Example 3
13g of a primary amine-terminated polysiloxane having a molecular weight of 1000g/mol, 7g of a secondary amine-terminated polysiloxane having a molecular weight of 1000g/mol, 3.5g of toluene diisocyanate and 0.3g of N-methyl-2, 2' -diaminodiethylamine were mixed, and reactive extrusion 3D printing was performed at 120℃at a rate of 1.5mm/s, and cooled to room temperature to obtain a printed product.
As shown in fig. 3, the contact angle of the printed article obtained in example 3 was 111 °, indicating that a surface hydrophobic and antifouling article could be obtained by this 3D printing technique.
Example 4
6g of primary amine end-capped polysiloxane with molecular weight of 600g/mol, 14g of secondary amine end-capped polysiloxane with molecular weight of 1000g/mol, 6g of diphenylmethane diisocyanate and 0.5g of N, N' -trimethyldiethylenetriamine are subjected to reactive extrusion 3D printing at 160 ℃ at a speed of 1mm/s, and the mixture is cooled to room temperature to obtain a printed product.
FIG. 4 is an infrared spectrum of example 4, from which it can be seen that 2250cm-1 has no significant absorption peak, demonstrating complete reaction of amino groups and isocyanate.
Example 5
10g of primary amine end-capped polysiloxane with the molecular weight of 1000g/mol, 10g of secondary amine end-capped polysiloxane with the molecular weight of 1000g/mol, 5g of diphenylmethane diisocyanate and 0.5g of N, N' -trimethyldiethylenetriamine are subjected to reactive extrusion 3D printing at 160 ℃ at a speed of 1.5mm/s, the printing product is obtained after cooling to room temperature, and the printing product is placed in deionized water for soaking for 3 days, and the mechanical properties of the printing product are tested.
Fig. 5 is a drawing of example 5, from which it can be seen that the mechanical properties of the printed article were not significantly changed after being immersed in deionized water for 7 days, demonstrating that the printed article has excellent waterproof properties.
FIG. 6 is an optical photograph of the printer head during the printing process of example 5, from which it can be seen that the sample containing the reactive catalyst N, N' -trimethyldiethylenetriamine can be printed smoothly.
Example 6
10g of primary amine-terminated polysiloxane having a molecular weight of 1000g/mol, 10g of secondary amine-terminated polysiloxane having a molecular weight of 1000g/mol, and 5g of diphenylmethane diisocyanate were subjected to reactive extrusion 3D printing at a rate of 1.5mm/s at 160 to 200 ℃.
FIG. 7 is an optical photograph of the needle of the printer during the printing process of example 6, from which it can be seen that the sample without the reactive catalyst N, N' -trimethyldiethylenetriamine was difficult to print, and the sample was still difficult to print smoothly when the temperature was raised to 200℃in time, and aggregation occurred at the printing nozzle.
In conclusion, the silicone rubber-polyurea material printed by the method has good rebound resilience, toughness, hydrophobicity and antifouling property, and the mechanical property of the product is not obviously changed after the silicone rubber-polyurea material is soaked in water for 3 days. The printed material has good performance and long service life, and the transparency of the printed product can be adjusted. Can be used for producing soles, vamps, sealing materials, children toys, artware, damping products and the like.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A method of reactive extrusion of 3D printed silicone rubber-polyurea material comprising:
blending and extruding the monomer A, the monomer B and the reactive catalyst, directly printing, and cooling to room temperature to obtain the catalyst; wherein:
the monomer A is primary amine end-capped polysiloxane or secondary amine end-capped polysiloxane or a mixture of the two; the molecular weight of the primary amine terminated polysiloxane is 600-5000g/mol; the molecular weight of the secondary amine terminated polysiloxane is 600 to 5000g/mol;
the monomer B is one or a mixture of more of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate;
the reactive catalyst is one or a mixture of more of N-methyl-2, 2' -diamino diethylamine, amino ethyl piperazine, N ' N ' -trimethyl diethylenetriamine and N, N ' N ' -trimethyl di (hexamethylene) triamine;
the molar ratio of the amino group to the isocyanate in the monomer A to the monomer B and the reactive catalyst is 1.05-1.3:1.
2. The method of reactive extrusion of 3D printed silicone rubber-polyurea material of claim 1, wherein:
the printing temperature is 120-200 ℃.
3. The method of reactive extrusion of 3D printed silicone rubber-polyurea material of claim 1, wherein:
the printing speed is 0.5-2mm/s.
4. A silicone rubber-polyurea material prepared according to the method of reactive extrusion 3D printing of silicone rubber-polyurea materials of any one of claims 1-3.
5. Use of the silicone rubber-polyurea material according to claim 4 in the production and preparation of articles for footwear, sealing materials, toys for children, artwork, shock absorbing materials.
6. The use according to claim 5, wherein:
the production of the shoe product comprises the production of vamp materials and the production of midsole materials.
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| 聚氟硅氧烷—聚氨酯（脲）嵌段共聚物弹性体的制备、形态结构及性能研究;石振东;中国博士学位论文全文数据库 工程科技Ⅰ辑;20080615(第6期);B016-5 * |
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