CN104945574A - Preparation method of elastomer material - Google Patents
Preparation method of elastomer material Download PDFInfo
- Publication number
- CN104945574A CN104945574A CN201510254782.6A CN201510254782A CN104945574A CN 104945574 A CN104945574 A CN 104945574A CN 201510254782 A CN201510254782 A CN 201510254782A CN 104945574 A CN104945574 A CN 104945574A
- Authority
- CN
- China
- Prior art keywords
- rubber
- adds
- double bond
- thinner
- preparation
- 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.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of an elastomer material, relates to a light curing formula and a preparation method of a high polymer material and in particular relates to active anionic polymerization and free radical photopolymerization. The raw materials include liquid rubber having a two-terminal C-C double bond structure and a diluent; the diluent is a methacrylate or an acrylate or dithione; in the presence of or in absence of an initiator, light curing can be completed within 10s-300s under ultraviolet irradiation. The rubber phase is introduced in the light curing system to reduce volume shrinkage during curing and guarantee the dimensional stability of the product; in addition, the high polymer material obtained after lighting curing is endowed with the characteristics of the elastomer and has excellent mechanical properties without being reinforced by use of an inorganic filler.
Description
Technical field
The present invention relates to a kind of photocurable formulation and preparation method of macromolecular material, wherein in particular to anionic polymerization and radical photopolymerization.
Background technology
Ultraviolet photocureable material is as a kind of environmental friendliness, Economical energy-saving type product, and more and more by extensive concern and research, traditional Application Areas mainly contains coating, ink, sizing agent etc.In recent years rapid shaping field especially 3D printing technique be also applied to the printing that ultraviolet light polymerization principle carries out three-dimensional objects.
3DP material mainly contains metal, pottery, polymkeric substance etc.Wherein polymer class mainly engineering plastics, rubber type of material and photosensitive resin, principle that engineering plastics and rubber type of material mainly adopt " successively sintering ", need to provide heat, macromolecular material can give off a peculiar smell when laser sintered fusing, the easy buckling deformation of product surface after cooling, when printing accurate smallclothes, precision is poor, and surface is more coarse.Photosensitive resin can react solidification at once under ultraviolet lighting, and toxicity is little, pollution-free, drastically increase print speed and precision, its product has the accurate and rakish advantage of size, and its using value is high, therefore the development trend that development of new photo-curing material will be 3DP technology.
According to technical characteristic, 3DP technical requirements photosensitive system viscosity is low, good fluidity, and curing speed is fast, cure shrinkage is little, and product meets certain intensity and thermostability.At present, light-cured resin raw material mainly esters of acrylic acid and the epoxy resin of 3DP, this series products has class engineering plastics characteristic, and mainly rely on import, cost is higher, is not suitable for popular product.The common trade mark has the Somos series of DSM N. V., the Tango series etc. of Object company.Photo-curing material kind on market is relatively single, needs to develop abundanter category, broadened application market.
System of the present invention by the fluid rubber with photosensitive structure, (methyl) esters of acrylic acid or esters of acrylic acid, the component such as light trigger and mineral filler.Based on rubber phase, the product after light is solid has elastomer material feature, requires field that is anti-skidding or soft-surface, as electronic product, medical treatment, footwear, handle and automotive trim, tire etc. by being highly suitable for.
Summary of the invention
The present invention designs a kind of photocuring system, by the fluid rubber with photosensitive structure, and (methyl) esters of acrylic acid/esters of acrylic acid or dithiol, and light trigger composition.
Object is to introduce in photocuring system volumetric shrinkage when rubber phase can reduce solidification, ensures product size stability.
The macromolecular material that another object obtains after being to make photocuring has elastomeric characteristic, carries out without the need to adding mineral filler the mechanical property that namely reinforcement has excellence.
A kind of preparation method of elastomer material, it is characterized in that: raw material comprises the fluid rubber and thinner with both-end carbon-to-carbon double bond structure, thinner is methyl acrylic ester or esters of acrylic acid or dithiol, under the condition having initiator or no initiator, under UV-irradiation, in 10s-300s, complete photocuring.
Further, when thinner is methyl acrylic ester or esters of acrylic acid, the initiator of fluid rubber quality 0.1%-10% is added; Thinner add-on is that 1g fluid rubber adds 0.1-10ml;
When thinner is dithiol, add the initiator of fluid rubber quality 0%-10%; Thinner add-on is that 1mol fluid rubber adds 0.5-2mol.
Further, when thinner is methyl acrylic ester or esters of acrylic acid, cure times is 10s-100s;
When thinner is methyl acrylic ester or esters of acrylic acid, cure times is 30s-300s.
More specifically:
A kind of photocuring system provided of the present invention is composed as follows:
Fluid rubber provided by the invention comprises two parts, and one is polymer A; Two is end-group structure B, is specifically expressed as follows:
A kind of route of synthesis is:
A uses both-end active initiator, and adopt the synthesis of active anionic polymerization method, rubber has both-end activity.It can be polyhutadiene (PB), polyisoprene (PI), polyisoprene-butadiene block polymkeric substance (PIB), polyisoprene-styrene block polymer (PIS), polystyrene-butadiene block polymkeric substance (SB, SBS, SEBS) etc. fluid rubber, there is diversity.
B adopts the successively end-blocking acquisition of oxyethane and acrylate chloride.
Another kind of approach is:
A uses own method synthesis, can be the fluid rubbers such as fourth hydroxyl glue (HTPB), end hydroxy styrene-butadiene rubber (HTBS), hydroxyl terminated polyisoprene (HTPI), have diversity.
B adopts acrylate chloride to obtain terminal double bond structure to making it after its blocking modification.
The acrylic ester monomer that system one uses, can comprise methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, isopropyl acrylate etc.(methyl) acrylic ester monomer of a kind of use of system, can comprise (methyl) methyl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate etc.
According to system one, by above-mentioned formula rate obtain solution, mix under lucifuge condition.Under UV-light (250 ~ 420nm) is irradiated, complete photocuring rapidly in 10s-100s, obtain the solid transparent material with elastomeric characteristic.
Detailed process is as follows:
According to system one, the both-end carbon-to-carbon double bond structure of fluid rubber tool provided by the invention, with esters of acrylic acid and (methyl) acrylic ester monomer structural similitude, two components have good consistency, and solidifying product is homogeneous.Owing to being both-end functionalized structure, macromole chain extension can occur rapidly after illumination and be cross-linked, laser curing velocity is fast.The material obtained is translucent and smooth surface, has excellent elasticity.
According to system two, by above-mentioned formula rate obtain solution, mix under lucifuge condition.Under UV-light (250 ~ 420nm) is irradiated, complete photocuring rapidly in 30-300s, obtain the solid transparent material with elastomeric characteristic.
Detailed process is as follows:
According to system two, the both-end carbon-to-carbon double bond structure of fluid rubber tool provided by the invention, part has chain medium vinyl double bond structure.After adding dithiol, according to mercaptan-alkene " click chemistry " principle, can open in chain and chain terminal double bond occurs crosslinked, process is simply without the need to initiator.Obtain ganoid transparent sheet-like material, there is excellent elasticity.
Photo-curing material prepared by the present invention has excellent mechanical property, and when not adding mineral filler reinforcement, Shao A hardness can reach 40-95, and tensile strength reaches 8-20Mpa, and elongation at break reaches 148-589%.
Embodiment
Example is below selected to further illustrate method of the present invention, only illustrates in order to explain, but should not be so limited in actual applications.
The present invention designs a kind of photocuring macromolecular material with elastomeric characteristic, and it is as follows to test concrete technical scheme:
Wherein fluid rubber molecular weight < 10000, has end both-end carbon-to-carbon double bond structure;
According to system one, take reagent by above-mentioned formula, be mixed with solution in proportion, mix under lucifuge condition.Fluent material completes photocuring under UV-irradiation, obtains transparent elastomer material.
Wherein fluid rubber molecular weight < 10000, has end both-end carbon-to-carbon double bond structure.
According to system two, take reagent by above-mentioned formula, be mixed with solution in proportion, mix under lucifuge condition.Fluent material completes photocuring under UV-irradiation, obtains transparent elastomer material.
Now have terminated polybutadiene liquid rubber and the polyisoprene fluid rubber of carbon-to-carbon double bond for the both-end obtained by two kinds of route of synthesis described in this patent, but be not limited to this type of rubber, the fluid rubber with same double-ended structure all can be implemented.Enumerate embodiment as follows:
Embodiment 1
As system one, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds 0.1ml methyl acrylate, adds the light trigger TPO relative to rubber quality mark 3%.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 30s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 2
As system one, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds 3ml methyl acrylate, adds the light trigger TPO relative to rubber quality mark 3%.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 60s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 3
As system one, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds 10ml methyl acrylate, adds the light trigger TPO relative to rubber quality mark 3%.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 80s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 4
As system one, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds 3ml methyl acrylate, adds the light trigger TPO relative to rubber quality mark 0.1%.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 120s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 5
As system one, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds 3ml methyl acrylate, adds the light trigger TPO relative to rubber quality mark 10%.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 30s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 6
As system one, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds 0.1ml methacrylic ester, adds the light trigger TPO relative to rubber quality mark 3%.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 30s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 7
As system one, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds 3ml methacrylic ester, adds the light trigger TPO relative to rubber quality mark 3%.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 60s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 8
As system one, get the styrene-butadiene rubber(SBR) that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds 3ml methyl acrylate, adds the light trigger TPO relative to rubber quality mark 3%.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 80s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 9
As system one, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds 3ml methyl acrylate, adds the light trigger 651 relative to rubber quality mark 3%.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 60s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 10
As system one, get the polyisoprene fluid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds 0.1ml methyl acrylate, adds the light trigger TPO relative to rubber quality mark 3%.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 30s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 11
As system one, get the polyisoprene fluid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds 3ml methyl acrylate, adds the light trigger TPO relative to rubber quality mark 3%.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 60s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 12
As system two, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds two decyl mercaptan, do not add light trigger by rubber and dithiol mol ratio 1:1.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 300s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 13
As system two, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds two decyl mercaptan, add the light trigger TPO relative to rubber quality mark 1% by rubber and dithiol mol ratio 1:1.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 180s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 14
As system two, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds two decyl mercaptan, add the light trigger TPO relative to rubber quality mark 3% by rubber and dithiol mol ratio 1:1.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 120s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 15
As system two, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds two decyl mercaptan, add the light trigger TPO relative to rubber quality mark 10% by rubber and dithiol mol ratio 1:1.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 100s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 16
As system two, get the terminated polybutadiene liquid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds two decyl mercaptan, add the light trigger TPO relative to rubber quality mark 3% by rubber and dithiol mol ratio 1:0.5.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 120s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 17
As system two, get the polyisoprene fluid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds two decyl mercaptan, add the light trigger TPO relative to rubber quality mark 3% by rubber and dithiol mol ratio 1:2.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 120s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 17
As system two, get the styrene-butadiene rubber(SBR) that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds two decyl mercaptan, do not add light trigger by rubber and dithiol mol ratio 1:1.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 300s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Embodiment 18
As system two, get the polyisoprene fluid rubber that 1g has both-end carbon-to-carbon double bond, molecular weight is 5000, adds two decyl mercaptan, do not add light trigger by rubber and dithiol mol ratio 1:1.It is made fully to dissolve and mix, in pale yellow transparent under lucifuge condition.
Be coated on slide glass by aforesaid liquid material, be placed in 500w ultraviolet lamp box, lamp, apart from 20cm, illumination 300s, obtains translucent solid sheet material.Print smooth surface, evenly, have resilient material feature, Main Mechanical is as follows in solidification:
Claims (3)
1. the preparation method of an elastomer material, it is characterized in that: raw material comprises the fluid rubber and thinner with both-end carbon-to-carbon double bond structure, thinner is methyl acrylic ester or esters of acrylic acid or dithiol, under the condition having initiator or no initiator, under UV-irradiation, in 10s-300s, complete photocuring.
2. the preparation method of a kind of elastomer material according to claim 1, is characterized in that: when thinner is methyl acrylic ester or esters of acrylic acid, add the initiator of fluid rubber quality 0.1%-10%; Thinner add-on is that 1g fluid rubber adds 0.1-10ml;
When thinner is dithiol, add the initiator of fluid rubber quality 0%-10%; Thinner add-on is that 1mol fluid rubber adds 0.5-2mol.
3. the preparation method of a kind of elastomer material according to claim 1, is characterized in that: when thinner is methyl acrylic ester or esters of acrylic acid, cure times is 10s-100s;
When thinner is methyl acrylic ester or esters of acrylic acid, cure times is 30s-300s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510254782.6A CN104945574A (en) | 2015-05-19 | 2015-05-19 | Preparation method of elastomer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510254782.6A CN104945574A (en) | 2015-05-19 | 2015-05-19 | Preparation method of elastomer material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104945574A true CN104945574A (en) | 2015-09-30 |
Family
ID=54160682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510254782.6A Pending CN104945574A (en) | 2015-05-19 | 2015-05-19 | Preparation method of elastomer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104945574A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107998447A (en) * | 2017-12-21 | 2018-05-08 | 无锡市第四人民医院 | Conformal performance radiotherapy tissue equivalent compensation glue and its preparation method and application |
| CN110845679A (en) * | 2019-11-19 | 2020-02-28 | 珠海格力绿色再生资源有限公司 | Modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material and preparation method thereof |
| CN111163922A (en) * | 2017-09-28 | 2020-05-15 | 国家科学技术发展局 | Natural rubber mould-free manufacturing method |
| CN111704805A (en) * | 2020-07-02 | 2020-09-25 | 成都东软学院 | Printing liquid for 3D printing soft supplies, preparation method, method for preparing 3D printing soft supplies by using printing liquid and application |
| CN114874360A (en) * | 2022-04-14 | 2022-08-09 | 北京化工大学 | Aromatic ring-free thiol initiator and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6453960B1 (en) * | 1999-02-22 | 2002-09-24 | Toray Industries, Inc. | Prepreg and fiber-reinforced rubber materials |
| CN101415769A (en) * | 2006-03-29 | 2009-04-22 | 国家淀粉及化学投资控股公司 | Radiation solidified rubberized adhesive/sealant |
| CN101642682A (en) * | 2009-06-30 | 2010-02-10 | 清华大学 | Film material for desulfuration of liquefied gas and preparation method thereof |
| CN103289580A (en) * | 2013-05-30 | 2013-09-11 | 深圳市友联亨达光电有限公司 | Twice-cured liquid optical cement and preparation method thereof |
-
2015
- 2015-05-19 CN CN201510254782.6A patent/CN104945574A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6453960B1 (en) * | 1999-02-22 | 2002-09-24 | Toray Industries, Inc. | Prepreg and fiber-reinforced rubber materials |
| CN101415769A (en) * | 2006-03-29 | 2009-04-22 | 国家淀粉及化学投资控股公司 | Radiation solidified rubberized adhesive/sealant |
| CN101642682A (en) * | 2009-06-30 | 2010-02-10 | 清华大学 | Film material for desulfuration of liquefied gas and preparation method thereof |
| CN103289580A (en) * | 2013-05-30 | 2013-09-11 | 深圳市友联亨达光电有限公司 | Twice-cured liquid optical cement and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| TUNG-PING LIAO,等: "New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents(inifers)", 《JOURNAL OR POLYMER SCIENCE》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111163922A (en) * | 2017-09-28 | 2020-05-15 | 国家科学技术发展局 | Natural rubber mould-free manufacturing method |
| US20200269493A1 (en) * | 2017-09-28 | 2020-08-27 | National Science And Technology Development Agency | A method for mold-free manufacturing of natural rubber articles |
| CN111163922B (en) * | 2017-09-28 | 2023-03-14 | 国家科学技术发展局 | Natural rubber mould-free manufacturing method |
| CN107998447A (en) * | 2017-12-21 | 2018-05-08 | 无锡市第四人民医院 | Conformal performance radiotherapy tissue equivalent compensation glue and its preparation method and application |
| CN107998447B (en) * | 2017-12-21 | 2020-12-15 | 无锡市第四人民医院 | Conformal radiotherapy tissue equivalent compensation glue and preparation method and application thereof |
| CN110845679A (en) * | 2019-11-19 | 2020-02-28 | 珠海格力绿色再生资源有限公司 | Modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material and preparation method thereof |
| CN111704805A (en) * | 2020-07-02 | 2020-09-25 | 成都东软学院 | Printing liquid for 3D printing soft supplies, preparation method, method for preparing 3D printing soft supplies by using printing liquid and application |
| CN114874360A (en) * | 2022-04-14 | 2022-08-09 | 北京化工大学 | Aromatic ring-free thiol initiator and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104945574A (en) | Preparation method of elastomer material | |
| CN107641200B (en) | Thiol-ene photocuring resin for 3D printing and preparation method thereof | |
| CN107325603B (en) | A kind of aqueous photochromic coating, nail polish and ornament materials | |
| CN102643591B (en) | Resin composition for thermal transfer protection layer, thermal transfer film using resin composition and thermal transfer method | |
| CN102504623B (en) | Peeling layer composition and preparation method and application thereof | |
| RU2007130772A (en) | RESISTANT TO UNFAVORABLE WEATHER CONDITIONS A FILM FOR PAINTING A RETURNING RETURNING FORMED PRODUCTS IN YELLOW | |
| CN109880024B (en) | Hydrogel for three-dimensional photocuring molding 3D printing and preparation method thereof | |
| CN102732119B (en) | Aqueous two-component baking type car coating varnish with improved acid etching resistance, and its preparation method | |
| KR101153864B1 (en) | Room temperature hardening paint composition for road line and construction method using the same | |
| CN112080241B (en) | Photo-curing adhesive and preparation method and application thereof | |
| EP3500608A1 (en) | Polymerization-induced phase-separating compositions for acrylate-based networks | |
| US20180016464A1 (en) | Method and appratus for manufacture of 3d objects | |
| CN104114593A (en) | Toughness modifier for curable resin, and curable resin composition | |
| CN107849188B (en) | Methacrylic resin, method for producing methacrylic resin, molded article, and automobile | |
| CN104804151A (en) | Preparation method of light-cured resin material for three-dimensional printing | |
| CN102516446A (en) | Aqueous acrylic resin, and preparation method and application thereof | |
| CN103246164A (en) | Photosensitive resin for stereo lithography forming and preparation method thereof | |
| CN103666171A (en) | Environmental protection type nanometer silica/polyacrylate composite-base aqueous varnish and preparation method thereof | |
| CN105278239A (en) | Stereo-lithography rapid-prototyping polysiloxane photosensitive resin composition and preparation method and application thereof | |
| CN106632895A (en) | 3D printing light-cured resin composition activated by epoxidized limonene | |
| CN102031055B (en) | Volatile organic solvent-free UV spraying finish coat | |
| CN105237689A (en) | Digital light procession photocuring material and preparing method thereof | |
| CN107739585A (en) | A kind of preparation method of LED solidifications PVB adhesives | |
| CN108192024A (en) | Liquid coumarone resin and preparation method thereof | |
| JP2003313489A (en) | Radiation curable resin composition for coating aluminum material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150930 |