CN104277224A - Special-type reinforcing silicon resin for 3D printing and preparation method thereof - Google Patents
Special-type reinforcing silicon resin for 3D printing and preparation method thereof Download PDFInfo
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- CN104277224A CN104277224A CN201410524009.2A CN201410524009A CN104277224A CN 104277224 A CN104277224 A CN 104277224A CN 201410524009 A CN201410524009 A CN 201410524009A CN 104277224 A CN104277224 A CN 104277224A
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Abstract
The invention discloses a special-type reinforcing silicon resin for 3D printing and a preparation method thereof. The special-type reinforcing silicon resin is prepared from an organic silicon resin and an epoxy resin in a mass ratio of 1:(10-100), wherein the organic silicon resin is prepared from hydroxyl-terminated vinyl polysiloxane and amino-terminated siloxane which accounts for not more than 5 wt% of the hydroxyl-terminated vinyl polysiloxane; and the hydroxyl-terminated vinyl polysiloxane is prepared from alkoxy siloxane and vinyl-terminated siloxane which accounts for 20-40 wt% of the alkoxy siloxane. The alkoxy siloxane and vinyl-terminated siloxane are subjected to polycondensation reaction to obtain the hydroxyl-terminated vinyl polysiloxane, the hydroxyl-terminated vinyl polysiloxane reacts with the amino-terminated siloxane to obtain the organic silicon resin, and the organic silicon resin is active amino-terminated polysiloxane and can be completely crosslinked with the epoxy resin, thereby obtaining the reinforcing silicon resin modified epoxy resin composite material. The composite material has the advantages of higher curing rate, lower shrinkage and higher mechanical strength.
Description
Technical field
The present invention relates to the technical field of silicone material, particularly relate to extraordinary reinforcement silicone resin of a kind of 3D printing and preparation method thereof.
Background technology
It is a kind of interdisciplinary interleaving techniques that 3D prints manufacturing technology, and primarily of equipment, software, material three part composition, wherein printed material is indispensable link.And now industry mainly studies is equipment and software, investigation of materials is paid attention to not enough.Material bottleneck has become the matter of utmost importance that restriction 3D prints development.3D printed material mainly comprises metallic substance, ceramic and organic polymer material, and this project mainly studies organic polymer material.Existing 3D prints macromolecular material, there is insufficient strength, the shortcoming of toughness deficiency after shaping.Thus, the whole world especially developed country be engaged in the company of 3D printing technique and university all to research and develop purposes energetically more extensive, the novel high polymer material that performance is more excellent.
3D prints and comprises numerous technology, and Stereolithography occurs the earliest in the world and realizes commercial a kind of Quick-forming (Rapid Prototyping, RP) technology, is also study the most deep, most widely used a kind of Rapid Prototyping technique.Its technique is the photopolymerization principle work based on liquid photosensitive resin.Usually adopt urethane acrylate, oxypropylene acid esters, unsaturated polyester resin etc. in prior art, these resin ubiquity solidification rates be slow, defect that mechanical strength after the large and solidification of yield is low.
Summary of the invention
In view of this, the extraordinary reinforcement silicone resin that one aspect of the present invention provides a kind of 3D to print, this matrix material has higher solidification rate, less shrinkability and higher physical strength.
The raw material packet of extraordinary reinforcement silicone resin is silicone resin and the epoxy resin of 1:10 ~ 100 containing mass ratio, the raw material packet hydroxyl end-blocking vinyl polysiloxane of described silicone resin and account for the Amino End Group siloxanes that hydroxy-end capped vinyl polysiloxane quality is no more than 5%, the raw material packet of described hydroxy-end capped vinyl polysiloxane is containing oxyalkylsiloxane and the end-vinyl siloxanes accounting for oxyalkylsiloxane quality 20 ~ 40%.
Here term " oxyalkylsiloxane " refers to that molecular structure is
r
1, R
2, R
3, R
4can identical also can not be identical, all can comprise other any substituted radical of hydrogen atom, such as tetraethoxy silica alkane, a methoxyl group triethoxy silica alkane etc.
Here term " end-vinyl siloxanes " refers to that molecular structure is
r
1, R
2, R
3can identical also can not be identical, it can be any group comprising hydrogen atom, such as vinyl triethoxyl siloxanes and vinyl double-seal head.The structural formula of vinyl double-seal head is
Here term " Amino End Group siloxanes " refers to that molecular structure is
r
1, R
2, R
3can identical also can not be identical.Amino End Group siloxanes can be γ-aminopropyl triethoxysilane (KH550) or its derivative.
Wherein, extraordinary reinforcement silicone resin also comprises solvent and catalyzer further.Catalyzer is can be organic tin or titanate ester catalyzer.Organotin catalysts is that tin and carbon directly combine formed organometallics.General formula R
ns
nx4-(n=1-4, R are alkyl or aromatic base), specific examples has dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tin and dibutyltin diacetate etc.The specific examples of titanate ester catalyzer comprises tetrabutyl titanate and sequestering lactic acid titanate etc., its consumption can adopt this this area the consumption commonly used to implement the solution of the present invention.
Solvent can be toluene, and other solvent is also applicable to the present invention certainly.Select toluene in the present invention, itself and organosilyl mass ratio are preferably 1:1.
Wherein, described silicone resin also comprises in oxyalkylsiloxane quality 10 ~ 20 parts of deionized waters.
Wherein, the solid content of described epoxy resin is 50%.Epoxy resin is bisphenol A epoxide resin, and described bisphenol A epoxide resin is one in E20, E44, E51 and E54 or at least two kinds.The physicochemical property of E20, E44, E51 and E54 are known in the art, are not described in detail in this.
The preparation method of the extraordinary reinforcement silicone resin that the present invention provides a kind of 3D to print on the other hand, the extraordinary reinforcement silicone resin adopting this preparation method to obtain has higher solidification rate, less shrinkability and higher physical strength.
Prepare a method for above-mentioned extraordinary reinforcement silicone resin, comprise the following steps:
(1) by oxyalkylsiloxane and account for the end-vinyl siloxanes of oxyalkylsiloxane quality 20 ~ 40%, the deionized water of 10 ~ 20% carries out polycondensation, obtains hydroxy-end capped vinyl polysiloxane;
(2) add to hydroxy-end capped vinyl polysiloxane and account for the Amino End Group siloxanes that hydroxy-end capped vinyl polysiloxane quality is no more than 5%, make both that condensation reaction occur, obtain silicone resin;
(3) described silicone resin and epoxy resin are made it polycondensation occurs according to the mass ratio of 1:10 ~ 100, obtain extraordinary reinforcement silicone resin.
Wherein, described in step (1), the temperature of polycondensation is 8 ~ 12 DEG C, and the time of polycondensation is 0.5 ~ 12h.
Wherein, described in step (3), the temperature of polycondensation is 90 ~ 110 DEG C, and polycondensation reaction time is 4 ~ 8 hours.
What deserves to be explained is, the temperature range that the temperature of the condensation reaction in step (2) and the time of reaction can adopt this area usual and time, the present invention does not relate to the specific setting to this temperature and time.
Take tetraethoxysilane as oxyalkylsiloxane, be end-vinyl siloxanes with vinyl double-seal head, be that Amino End Group siloxanes is as follows so that the reaction principle of above-mentioned preparation process to be described with KH550:
First the present invention carries out polycondensation by oxyalkylsiloxane and end-vinyl siloxanes and obtains hydroxy-end capped vinyl polysiloxane, silicone resin is obtained again with Amino End Group siloxanes, this silicone resin is the polysiloxane containing active amino end-blocking, can be completely crosslinked with epoxy resin, thus obtaining the silicone-modified epoxy resin composite material of reinforcement, this matrix material has higher solidification rate, less shrinkability and higher physical strength.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
By tetraethoxysilane, vinyl double-seal head and water according to proportion by weight (i.e. 100 parts of tetraethoxysilanes, 20 parts of vinyl double-seal heads and 10 parts of deionized waters), under acid or alkaline catalysts effect, at 8 DEG C, be polymerized 12h, remove catalyzer after polymerization and obtain hydroxy-end capped vinyl polysiloxane.Then, add the KH550 accounting for hydroxy-end capped vinyl polysiloxane quality 0.5% to hydroxy-end capped vinyl polysiloxane, make it that polycondensation occurs and obtain silicone resin.Finally, the catalyzer of organic tin or titanate ester is added in silicone resin, after stirring, slow dropping bisphenol A epoxide resin (one or more mixtures in E20, E44, E51, E54) toluene solution (epoxy solid content 50%, organosilicon, epoxy resin and toluene solution quality are 1:10:1), react 8 hours at 90 DEG C, obtain for extraordinary reinforcement silicone resin.
Embodiment 2
By tetraethoxysilane, vinyl double-seal head and water according to proportion by weight (i.e. 100 parts of tetraethoxysilanes, 40 parts of vinyl double-seal heads and 20 parts of deionized waters), under acid or alkaline catalysts effect, at 12 DEG C, be polymerized 12h, remove catalyzer after polymerization and obtain hydroxy-end capped vinyl polysiloxane.Then, add the KH550 accounting for hydroxy-end capped vinyl polysiloxane quality 5% to hydroxy-end capped vinyl polysiloxane, make it that polycondensation occurs and obtain silicone resin.Finally, the catalyzer of organic tin or titanate ester is added in silicone resin, after stirring, slow dropping bisphenol A epoxide resin (E20, E44, E51, one or more mixtures in E54) toluene solution slowly drips bisphenol A epoxide resin (one or more mixtures in E20, E44, E51, E54) toluene solution (epoxy solid content 50%, organosilicon, epoxy resin and toluene solution quality are 1:100:1), react 4 hours at 110 DEG C, obtain for extraordinary reinforcement silicone resin.
Embodiment 3
By tetraethoxysilane, vinyl double-seal head and water according to proportion by weight (i.e. 100 parts of tetraethoxysilanes, 30 parts of vinyl double-seal heads and 15 parts of deionized waters), under acid or alkaline catalysts effect, at 10 DEG C, be polymerized 6h, remove catalyzer after polymerization and obtain hydroxy-end capped vinyl polysiloxane.Then, add the KH550 accounting for hydroxy-end capped vinyl polysiloxane quality 2.5% to hydroxy-end capped vinyl polysiloxane, make it that polycondensation occurs and obtain silicone resin.Finally, the catalyzer of organic tin or titanate ester is added in silicone resin, after stirring, slow dropping bisphenol A epoxide resin (E20, E44, E51, one or more mixtures in E54) toluene solution (epoxy solid content 50%, organosilicon is 1:55:1 with the ratio of epoxy), react 6 hours at 100 DEG C, obtain for extraordinary reinforcement silicone resin.
Embodiment 4
By tetraethoxysilane, vinyl double-seal head and water according to proportion by weight (i.e. 100 parts of tetraethoxysilanes, 25 parts of vinyl double-seal heads and 15 parts of deionized waters), under acid or alkaline catalysts effect, at 10 DEG C, polymerase 17 h, removes catalyzer after polymerization and obtains hydroxy-end capped vinyl polysiloxane.Then, add the KH550 accounting for hydroxy-end capped vinyl polysiloxane quality 1.5% to hydroxy-end capped vinyl polysiloxane, make it that polycondensation occurs and obtain silicone resin.Finally, the catalyzer of organic tin or titanate ester is added in silicone resin, after stirring, slow dropping bisphenol A epoxide resin (E20, E44, E51, one or more mixtures in E54) toluene solution (epoxy solid content 50%, organosilicon is 1:40:1 with the ratio of epoxy), react 5 hours at 95 DEG C, obtain for extraordinary reinforcement silicone resin.
Embodiment 5
By tetraethoxysilane, vinyl double-seal head and water according to proportion by weight (i.e. 100 parts of tetraethoxysilanes, 30 parts of vinyl double-seal heads and 15 parts of deionized waters), under acid or alkaline catalysts effect, at 10 DEG C, be polymerized 6h, remove catalyzer after polymerization and obtain hydroxy-end capped vinyl polysiloxane.Then, add the KH550 accounting for hydroxy-end capped vinyl polysiloxane quality 4% to hydroxy-end capped vinyl polysiloxane, make it that polycondensation occurs and obtain silicone resin.Finally, the catalyzer of organic tin or titanate ester is added in silicone resin, after stirring, slow dropping bisphenol A epoxide resin (E20, E44, E51, one or more mixtures in E54) toluene solution (epoxy solid content 50%, organosilicon is 1:60:1 with the ratio of epoxy), react 6 hours at 100 DEG C, obtain for extraordinary reinforcement silicone resin.
The present invention adopts extraordinary silicone resin as supporting material, achieves complete crosslinking reaction, and material property reaches best; This compound resin curing speed is fast, has higher absorption and response speed to the light at 355nm place; Cure shrinkage is little, and this compound resin precalculated volume shrinking percentage controls about 5.7%, and in addition, cost is lower, and starting material are easy to get, and is applicable to large-scale production.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. the extraordinary reinforcement silicone resin of a 3D printing, it is characterized in that, its raw material packet is silicone resin and the epoxy resin of 1:10 ~ 100 containing mass ratio, the raw material packet hydroxyl end-blocking vinyl polysiloxane of described silicone resin and account for the Amino End Group siloxanes that hydroxy-end capped vinyl polysiloxane quality is no more than 5%, the raw material packet of described hydroxy-end capped vinyl polysiloxane is containing oxyalkylsiloxane and the end-vinyl siloxanes accounting for oxyalkylsiloxane quality 20 ~ 40%.
2. extraordinary reinforcement silicone resin according to claim 1, is characterized in that, also comprise solvent and catalyzer, and described catalyzer is organic tin or titanate ester catalyzer.
3. extraordinary reinforcement silicone resin according to claim 1, is characterized in that, described hydroxy-end capped vinyl polysiloxane also comprises the deionized water accounting for oxyalkylsiloxane quality 10 ~ 20%.
4. extraordinary reinforcement silicone resin according to claim 1, is characterized in that, the solid content of described epoxy resin is 50%.
5. extraordinary reinforcement silicone resin according to claim 1, is characterized in that, described epoxy resin is bisphenol A epoxide resin, and described bisphenol A epoxide resin is one in E20, E44, E51 and E54 or at least two kinds.
6. extraordinary reinforcement silicone resin according to claim 1, is characterized in that, described oxyalkylsiloxane is tetraethoxysilane; Described end-vinyl siloxanes is vinyl double-seal head; Described Amino End Group siloxanes is γ-aminopropyl triethoxysilane.
7. extraordinary reinforcement silicone resin according to claim 2, is characterized in that, described solvent is toluene, and the mass ratio of described toluene and silicone resin is 1:1.
8. prepare a method for extraordinary reinforcement silicone resin as claimed in claim 1, it is characterized in that, comprise the following steps:
(1) by oxyalkylsiloxane and account for the end-vinyl siloxanes of oxyalkylsiloxane quality 20 ~ 40%, the deionized water of 10 ~ 20% carries out polycondensation, obtains hydroxy-end capped vinyl polysiloxane;
(2) add to hydroxy-end capped vinyl polysiloxane and account for the Amino End Group siloxanes that hydroxy-end capped vinyl polysiloxane quality is no more than 5%, make both that condensation reaction occur, obtain silicone resin;
(3) described silicone resin and epoxy resin are made it polycondensation occurs according to the mass ratio of 1:10 ~ 100, obtain extraordinary reinforcement silicone resin.
9. method according to claim 8, is characterized in that, described in step (1), the temperature of polycondensation is 8 ~ 12 DEG C, and the time of polycondensation is 0.5 ~ 12h.
10. method according to claim 8, is characterized in that, described in step (3), the temperature of polycondensation is 90 ~ 110 DEG C, and polycondensation reaction time is 4 ~ 8 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746576A (en) * | 2019-09-20 | 2020-02-04 | 宏昌电子材料股份有限公司 | Modified epoxy resin and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746576A (en) * | 2019-09-20 | 2020-02-04 | 宏昌电子材料股份有限公司 | Modified epoxy resin and preparation method thereof |
| CN110746576B (en) * | 2019-09-20 | 2022-10-28 | 宏昌电子材料股份有限公司 | Modified epoxy resin and preparation method thereof |
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Application publication date: 20150114 |