CN115819711A - 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
- Publication number
- CN115819711A CN115819711A CN202211485564.XA CN202211485564A CN115819711A CN 115819711 A CN115819711 A CN 115819711A CN 202211485564 A CN202211485564 A CN 202211485564A CN 115819711 A CN115819711 A CN 115819711A
- Authority
- CN
- China
- Prior art keywords
- printing
- silicone rubber
- polyurea
- polyurea material
- reactive extrusion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 42
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 39
- 238000010146 3D printing Methods 0.000 title claims abstract description 32
- 238000001125 extrusion Methods 0.000 title claims abstract description 25
- -1 polysiloxane, diisocyanate Polymers 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000007639 printing Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000009257 reactivity Effects 0.000 claims abstract description 4
- 239000003566 sealing material Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 150000003141 primary amines Chemical class 0.000 claims description 6
- 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
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 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
- 230000035939 shock Effects 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 125000003277 amino group Chemical group 0.000 abstract description 7
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 238000013016 damping Methods 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
- 238000010017 direct printing Methods 0.000 abstract 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 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
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 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
- 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
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 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
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations 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
- ODZZIKZQNODXFS-UHFFFAOYSA-N n,n'-dimethyl-n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCN(C)CCNC ODZZIKZQNODXFS-UHFFFAOYSA-N 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
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Images
Landscapes
- Polyurethanes Or Polyureas (AREA)
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 (2) blending and extruding the amino-terminated polysiloxane, diisocyanate and a reactive catalyst for direct printing, and cooling to room temperature to obtain the product, wherein the printing temperature is 120-200 ℃, and the printing speed is controlled at 0.5-2mm/s. Wherein the molar ratio of amino groups and isocyanate groups in the amino-terminated polysiloxane to diisocyanate and in the reactivity rate modifier is 1.05 to 1.3. The silicone rubber-polyurea material printed by the method has good rebound resilience, toughness, hydrophobicity and antifouling performance, and the mechanical performance of the product is not obviously changed after the product 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 in the production and application of 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 the 3D printing technology has the advantages of designable structure, personal customization and the like. The materials for preparing the shoe upper or the shoe sole by adopting the 3D printing technology are polyurethane elastomers or light-cured resin materials. Polyureas and polyurethanes have similar molecular structures, except that polyurethanes are prepared by reacting hydroxyl groups with isocyanates and polyureas are prepared by reacting amino groups with isocyanates. The polyurea material has excellent elasticity and can be used as a material for shoes. The disadvantages are 1) the reaction rate of amino and isocyanate is extremely fast, difficult to control, difficult to process and difficult to prepare products with specific structures; 2) The urea bond in polyurea can make the material absorb water, and is usually solved by introducing aromatic rigid group and increasing the crosslinking degree, but the elasticity and toughness of the material are lost.
The most common processing method for polyureas is spray coating, which is suitable for producing protective coatings on a variety of substrates. In addition, the reaction extrusion molding method can also be used for spraying construction of polyurea. Spray coating and conventional reactive extrusion processes do not produce articles having specific structures and functions. The polyurea material with a special structure is constructed by using a 3D printing technology, so that the performances of vibration reduction, resilience and the like of the polyurea material can be improved, and the polyurea material has important application in the field of shoe materials. There are few reports on the polyurea 3D printing technology, and the technology is generally a photocuring 3D technology.
Application No.: 2019107906039 provides a photosensitive resin comprising an acrylate oligomer containing a urea bond and having a functionality of 2 or more, and a method of 3D printing polyurea; the acrylate oligomer containing urea bonds and having double bond functionality of more than or equal to 2 is obtained by reacting an isocyanate group-terminated compound having functionality of more than or equal to 2 with an amino-containing acrylate or methacrylate compound. The invention also provides a 3D polyurea printing method. After the photosensitive resin provided by the invention is photocured or 3D printed to form a polymer, the molecular structure, 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 polymer can be adjusted through the post-treatment. This patent adopts photocuring technique to carry out 3D and prints, and it is difficult to print the surperficial monomer of goods and clear away, and environmental pollution is serious, and printable monomer kind is limited, is not suitable for reaction to extrude 3D and prints silicon rubber-polyurea material.
Application No.: 2018800638856 discloses a method of additive layer manufacturing using co-reactive components. Thermosetting compositions for use in additive manufacturing are also disclosed. The invention provides a reactive lamination manufacturing method, which comprises the following steps: providing a first component comprising a first compound to a first pump; providing a second component comprising a second compound into a second pump, wherein the first compound is reactive with the second compound. Amino compounds and isocyanate compounds are suitable for this method, but this invention does not mention how to control the reaction rate of the amino compound and the isocyanate compound to ensure high-precision printing, mechanical properties, antifouling properties, and hydrophobic properties of printed products, and specific printing parameters such as printing speed, printing temperature, and the like. In addition, the technology needs mold support, and the preparation of a complex structure is difficult. Although the above-mentioned problem of determining the reaction rate and optimum temperature can be solved by a limited number of experiments, the effect is limited.
Based on this, the speed regulator is specially added to solve the technical problems, but part of the system may have too high viscosity, so that a printing sample cannot be obtained, and layer-by-layer obstacles including selection of raw materials, determination of reaction temperature, determination of monomer proportion, selection of molecular weight and catalyst type and the like are overcome, so that the direct-writing 3D printing of the silicone rubber-polyurea product with a special complex structure is finally realized.
Disclosure of Invention
In view of the above disadvantages, the present invention provides a reactive extrusion 3D printing silicone rubber-polyurea material and applications thereof, and the technical solution is realized by the following method:
a method of reactive extrusion 3D printing a silicone rubber-polyurea material, comprising:
and (3) blending the monomer A, the monomer B and the reactive catalyst, extruding, directly printing, and cooling to room temperature to obtain the ink.
Further, the monomer A is primary amine terminated polysiloxane or secondary amine terminated 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 600-5000g/mol.
Further, the monomer B is one or a mixture of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.
Further, the reactive catalyst is one or a mixture of several of N-methyl-2,2 ' -diaminodiethylamine, aminoethylpiperazine, N ' -trimethyldiethylenetriamine and N, N ' -trimethylbis (hexamethylene) triamine.
Further, the printing temperature is 120-200 ℃
Further, the molar ratio of the amino group to the isocyanate in the monomer A and the monomer B and the reactivity rate regulator is 1.05 to 1.3.
Further, the printing speed is 0.5-2mm/s.
The invention also discloses a silicone rubber-polyurea material prepared by any one of the reactive extrusion 3D printing methods.
The invention also discloses an application of the silicone rubber-polyurea material in the production and preparation of shoe products, sealing materials, toys for children, artware and damping materials.
Further, the production of the footwear comprises the production of an upper material and the production of a midsole material.
The technical scheme of the invention has the following beneficial effects:
1) The monomer A, the monomer B and the reactivity rate regulator 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 mixing, the amino compound reacts with the isocyanate compound to effect curing, ensuring that the printed article retains its shape on the substrate. The reactive catalyst is a triamine compound, one amino group is tertiary amine and plays a role in catalysis, the other two amino groups are primary amine or secondary amine and can react on the main chain of the silicone rubber-polyurea elastomer material, and different from the traditional catalyst, the catalyst can react on the main chain of a polymer, so that the phenomenon that the overflow of the catalyst is generated to influence the performance and the service life of the material is avoided. The tertiary amine group in the reactive catalyst can catalyze the urea bond to be dissociated at high temperature, so that amino and isocyanate are regenerated, 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 group generated by dissociation and isocyanate to form a urea bond again at low temperature, so that the material printed on the substrate is quickly cured, 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 the printed product is soaked in water for 3 days. The printed article may be used to make shoe uppers, shoe soles, children's toys, artwork, and the like.
Drawings
FIG. 1 is a stress-strain curve of a printed article of example 1;
FIG. 2 is an optical photograph of a printed article of example 2;
FIG. 3 is a static contact angle photomicrograph of a printed article of example 3;
FIG. 4 is an infrared spectrum of a printed article of example 4;
FIG. 5 is a stress-strain curve of the original printed article of example 5 and after 72 hours of immersion in water;
FIG. 6 is an optical photograph of example 5 at the needle during printing extrusion;
FIG. 7 is an optical photograph of example 6 printed at the needle during extrusion.
Detailed Description
The specific technical scheme of the invention is described by combining the embodiment.
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 0.2g of N-methyl-2,2' -diaminodiethylamine were mixed, subjected to reaction extrusion 3D printing at 140 ℃ at a speed of 1mm/s, and cooled to room temperature to obtain a printed article.
As shown in FIG. 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 a primary amine-terminated polysiloxane having a molecular weight of 1000g/mol, 5.2g of dicyclohexylmethane diisocyanate and 0.3g of aminoethylpiperazine were subjected to reaction extrusion 3D printing at 160 ℃ at a speed of 1mm/s and cooled to room temperature to give a printed article.
As shown in FIG. 2, the 3D printing method can be used for preparing the silicone rubber-polyurea product with a special complex structure and higher printing precision.
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, subjected to reaction extrusion 3D printing at 120 ℃ at a speed of 1.5mm/s, and cooled to room temperature to obtain a printed article.
As shown in fig. 3, the contact angle of the printed article obtained in example 3 is 111 °, which illustrates that the article with hydrophobic and anti-fouling surface can be obtained by the 3D printing technology.
Example 4
6g of a primary amine-terminated polysiloxane having a molecular weight of 600g/mol, 14g of a secondary amine-terminated polysiloxane having a molecular weight of 1000g/mol, 6g of diphenylmethane diisocyanate and 0.5g of N, N' -trimethyldiethylenetriamine were subjected to reaction extrusion 3D printing at a speed of 1mm/s at 160 ℃ and cooled to room temperature to obtain a printed article.
FIG. 4 is an infrared spectrum of example 4 from which 2250cm-1 shows no significant absorption peak, demonstrating complete reaction of the amino group and isocyanate.
Example 5
10g of primary amine terminated polysiloxane with the molecular weight of 1000g/mol, 10g of secondary amine terminated polysiloxane with the molecular weight of 1000g/mol, 5g of diphenylmethane diisocyanate and 0.5g of N, N' -trimethyldiethylenetriamine are subjected to reaction extrusion 3D printing at the speed of 1.5mm/s at 160 ℃, cooled to room temperature to obtain a printed product, and the printed product is placed in deionized water to be soaked for 3 days to test the mechanical property of the printed product.
Fig. 5 is a tensile curve of example 5, from which it can be derived that the mechanical properties of the printed article do not change significantly after being soaked in deionized water for 7 days, demonstrating that the printed article has excellent water resistance.
FIG. 6 is an optical photograph of the printer tip 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 a primary amine-terminated polysiloxane having a molecular weight of 1000g/mol, 10g of a secondary amine-terminated polysiloxane having a molecular weight of 1000g/mol, 5g of diphenylmethane diisocyanate were subjected to reaction extrusion 3D printing at a speed of 1.5mm/s at 160-200 ℃.
Fig. 7 is an optical photograph of the printer needle in the printing process of example 6, from which it can be seen that the sample without the reactive catalyst N, N', N ″ -trimethyldiethylenetriamine is difficult to print, and the temperature is raised to 200 ℃ in time, so that the sample is still difficult to print smoothly, and aggregation occurs at the nozzle.
In conclusion, the silicone rubber-polyurea material printed by the method has good rebound resilience, toughness, hydrophobicity and antifouling performance, and the mechanical properties of the product are not obviously changed after the product 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 the production and application of soles, vamps, sealing materials, children toys, artware, shock absorption products and the like.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of reactive extrusion 3D printing of a 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 ink.
2. The method of reactive extrusion 3D printing of silicone rubber-polyurea material according to claim 1, wherein:
the monomer A is primary amine terminated polysiloxane or secondary amine terminated 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 600-5000g/mol.
3. The method of reactive extrusion 3D printing of silicone rubber-polyurea material according to claim 1, wherein:
the monomer B is one or a mixture of more of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate.
4. The method of reactive extrusion 3D printing of silicone rubber-polyurea material according to claim 1, wherein:
the reactive catalyst is one or a mixture of more of N-methyl-2,2 ' -diaminodiethylamine, aminoethylpiperazine, N ' -trimethyldiethylenetriamine and N, N ' -trimethylbis (hexamethylene) triamine.
5. The method of reactive extrusion 3D printing of silicone rubber-polyurea material according to claim 1, wherein:
the printing temperature is 120-200 ℃.
6. The method of reactive extrusion 3D printing of silicone rubber-polyurea material according to claim 1, wherein:
the molar ratio of amino and isocyanate in the monomer A to the monomer B and in the reactivity rate regulator is 1.05-1.3.
7. The method of reactive extrusion 3D printing of silicone rubber-polyurea material according to claim 1, wherein:
the printing speed is 0.5-2mm/s.
8. A silicone rubber-polyurea material made according to any one of the reactive extrusion 3D printing methods of claims 1-7.
9. Use of the silicone rubber-polyurea material according to claim 8 for the production of footwear, sealing materials, toys for children, crafts, shock absorbers.
10. The use according to claim 9, wherein:
the production of the footwear comprises the production of an upper material and the production of a midsole material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211485564.XA CN115819711B (en) | 2022-11-24 | 2022-11-24 | Reactive extrusion 3D printing silicone rubber-polyurea material and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211485564.XA CN115819711B (en) | 2022-11-24 | 2022-11-24 | Reactive extrusion 3D printing silicone rubber-polyurea material and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115819711A true CN115819711A (en) | 2023-03-21 |
| CN115819711B CN115819711B (en) | 2024-04-05 |
Family
ID=85531327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211485564.XA Active CN115819711B (en) | 2022-11-24 | 2022-11-24 | Reactive extrusion 3D printing silicone rubber-polyurea material and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115819711B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181764A (en) * | 1995-04-25 | 1998-05-13 | 美国3M公司 | Polydiorganosiloxane polyurea segmented copolymers and methods of making the same |
| CN103360562A (en) * | 2013-03-21 | 2013-10-23 | 哈尔滨工程大学 | Polysiloxane-polyurea-polyurethane gel material and preparation method thereof |
| CN105400405A (en) * | 2015-10-30 | 2016-03-16 | 华南理工大学 | Self-repairing organic silicon polyurethane/polyurea anti-pollution material as well as method and application thereof |
| CN108559045A (en) * | 2018-04-23 | 2018-09-21 | 四川大学 | The polyurea materials and preparation method and application of the repeatable processing of selfreparing |
| CN108610466A (en) * | 2018-05-17 | 2018-10-02 | 山东大学 | A kind of polyurea elastomer and preparation method thereof substituting polyethers completely with polysiloxanes |
| CN111148631A (en) * | 2017-08-18 | 2020-05-12 | Ppg工业俄亥俄公司 | Additive manufacturing using reactive compositions |
| US20210037908A1 (en) * | 2017-02-27 | 2021-02-11 | Voxel8, Inc. | Articles of footwear and apparel having a three-dimensionally printed feature |
| CN113045728A (en) * | 2021-03-23 | 2021-06-29 | 中国工程物理研究院化工材料研究所 | Hot-melt low-temperature-resistant organic silicon-polyurea copolymer adhesive containing steric urea bond and preparation and application methods thereof |
| CN113929869A (en) * | 2021-11-29 | 2022-01-14 | 四川大学 | Two-component polyurea material for 3D printing and method for 3D printing of polyurea product |
| WO2022129359A1 (en) * | 2020-12-18 | 2022-06-23 | SETUP Performance SAS | Silicone-based thermoplastic materials for 3d-printing |
-
2022
- 2022-11-24 CN CN202211485564.XA patent/CN115819711B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181764A (en) * | 1995-04-25 | 1998-05-13 | 美国3M公司 | Polydiorganosiloxane polyurea segmented copolymers and methods of making the same |
| CN103360562A (en) * | 2013-03-21 | 2013-10-23 | 哈尔滨工程大学 | Polysiloxane-polyurea-polyurethane gel material and preparation method thereof |
| CN105400405A (en) * | 2015-10-30 | 2016-03-16 | 华南理工大学 | Self-repairing organic silicon polyurethane/polyurea anti-pollution material as well as method and application thereof |
| US20210037908A1 (en) * | 2017-02-27 | 2021-02-11 | Voxel8, Inc. | Articles of footwear and apparel having a three-dimensionally printed feature |
| CN111148631A (en) * | 2017-08-18 | 2020-05-12 | Ppg工业俄亥俄公司 | Additive manufacturing using reactive compositions |
| CN108559045A (en) * | 2018-04-23 | 2018-09-21 | 四川大学 | The polyurea materials and preparation method and application of the repeatable processing of selfreparing |
| CN108610466A (en) * | 2018-05-17 | 2018-10-02 | 山东大学 | A kind of polyurea elastomer and preparation method thereof substituting polyethers completely with polysiloxanes |
| WO2022129359A1 (en) * | 2020-12-18 | 2022-06-23 | SETUP Performance SAS | Silicone-based thermoplastic materials for 3d-printing |
| CN113045728A (en) * | 2021-03-23 | 2021-06-29 | 中国工程物理研究院化工材料研究所 | Hot-melt low-temperature-resistant organic silicon-polyurea copolymer adhesive containing steric urea bond and preparation and application methods thereof |
| CN113929869A (en) * | 2021-11-29 | 2022-01-14 | 四川大学 | Two-component polyurea material for 3D printing and method for 3D printing of polyurea product |
Non-Patent Citations (2)
| Title |
|---|
| NAN SUN 等: "Synthesis of cellulose nanofiber/polysiloxane-polyurea composite materials with self-healing and reprocessing properties", INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES, vol. 227, 20 December 2022 (2022-12-20), pages 203 - 213, XP087244879, DOI: 10.1016/j.ijbiomac.2022.12.168 * |
| 石振东: "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", 中国博士学位论文全文数据库 工程科技Ⅰ辑, no. 6, 15 June 2008 (2008-06-15), pages 016 - 5 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115819711B (en) | 2024-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101974533B1 (en) | Polyurea resin waterproofing materials and manufacturing method thereof, the waterproof coating method using the same | |
| JP5674990B1 (en) | Eyewear materials, eyewear frames and lenses | |
| CA1150442A (en) | Process for producing polyurethane elastomer | |
| CN101033287A (en) | High solid content water polyurethane adhesive for non-absorbability base material and preparing method | |
| KR20100083140A (en) | Polyurethane resin | |
| CN1608089A (en) | Polyurethane composition | |
| CN1968984A (en) | Blocked polyurethane prepolymers useful in coating compositions | |
| KR101398113B1 (en) | Scratch self-healing polyol composition and polyurethane mouldings produced therefrom | |
| EP1707584A1 (en) | Novel polyurea isocyanates | |
| CN102040720A (en) | High-transparency polyurethane elastomer | |
| KR101854424B1 (en) | Polyurea waterproof agent improving crack resistant and manufacturing method thereof and waterproof method using thereof | |
| CN104072716A (en) | Polyurethane elastomer and sole made from same | |
| CN1751097A (en) | Polyurethane system and application thereof | |
| KR101924187B1 (en) | Polyurea waterproof agent with noflame property and manufacturing method thereof and waterproof method using thereof | |
| JP6069576B2 (en) | Process for producing spray polyurethane elastomer and elastomer produced by the process | |
| CN108070069A (en) | The high rebound low melting point thermoplastic polyurethane elastomer of soft and preparation method and application | |
| CN108883433A (en) | The three-dimensional deposition method of polymer material layer is formed on object | |
| CN115819711B (en) | Reactive extrusion 3D printing silicone rubber-polyurea material and application thereof | |
| JP5675011B1 (en) | 1,4-bis (isocyanatomethyl) cyclohexane, polyisocyanate composition, polyurethane resin and molded article | |
| CN113929869B (en) | Two-component polyurea material for 3D printing and method for 3D printing of polyurea product | |
| KR102091129B1 (en) | Composition of allophanate and hydrophobic resin | |
| TWI816882B (en) | Composition for polyurethane integral surface layer foaming, polyurethane integral surface layer foaming and manufacturing method thereof | |
| CN106674480B (en) | Preparation method of NDI (Newcastle disease) -modified MDI (diphenylmethane diisocyanate) -based polyurethane microporous elastomer | |
| JP2006506490A5 (en) | ||
| CN102140245A (en) | Polyurethane elastomer composition for embedding LED (Light-Emitting Diode) lamp strip |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |