CN108912280A - A kind of radical cation hybrid UV-curing resin and its preparation method and application - Google Patents
A kind of radical cation hybrid UV-curing resin and its preparation method and application Download PDFInfo
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- CN108912280A CN108912280A CN201810629735.9A CN201810629735A CN108912280A CN 108912280 A CN108912280 A CN 108912280A CN 201810629735 A CN201810629735 A CN 201810629735A CN 108912280 A CN108912280 A CN 108912280A
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- curing resin
- radical
- radical cation
- curing
- cation hybrid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
It the invention discloses a kind of radical cation hybrid UV-curing resin and preparation method thereof, solves the problems, such as that current photocurable resin material photocuring reaction rate is slow, surface is imperfect, can satisfy the demand in manufacturing to working efficiency and product intensity.The preparation method of light-cured resin of the invention is simple, and raw material is cheap and easy to get, has the characteristics that curing rate is fast, shrinking percentage is low, intensity is high, viscosity is low, good toughness, surface are smooth, easy overlay film, the consistency of product can be improved while reducing product cost.
Description
Technical field
The present invention relates to photocurable resin material technical field more particularly to a kind of radical cation hybrid UV-curing trees
Rouge and preparation method and application.
Background technique
3D printing technique, also known as increases material manufacturing technology are a kind of threedimensional models that object is established using computer, and with this
It is the friendship of multiple subjects such as bioengineering, material processing and forming, automation control, computer modeling to rely on molding technology
Fork, compared with conventional molding techniques, it does not need traditional stage property, fixture and multi-step process, can lead on one device
Process control is crossed, various parts automatically, are accurately produced, 3D printing technique greatly reduces manufacturing procedure, hence it is evident that shortens
The R&D cycle of new product reduces research and development cost, is one of modern popular new and high technology.
Photo-curing material is obtained using photopolymerization reaction, and photopolymerization reaction refers to photo-curing monomer or copolymer in purple
Addition reaction occurs under the technical method of outer light or visible light, the liquid of free-flowing is sent out and receiving ultraviolet radioactive energy
Biochemical polymerization and reaction are changed into the phase transition process of solid non-stick.3D printing photo-curing material is exactly photosensitive resin in light
Solidify and occurs what such photopolymerization reaction obtained under the irradiation of rapid three dimensional printing forming equipment laser.
Current existing photo-curing material is mainly free radical type ray curing type resin, but the curing rate of the type material
It is relatively slow, applied to needing to expend longer time in 3D printing work, and after solidifying resin contraction it is larger.In industry
Interior, for 3D printing photo-curing material there is also a series of problems, specific manifestation is as follows：
（1）Curing rate is slow.Currently, many product curing rates are not fast enough, it is imperfect to will cause film forming, occurs after lamination residual
It lacks, the problem that displacement or laminated striation are deeper；
（2）Yellowing resistance is bad.Light-cured resin is easy to produce xanthochromia group, colour changed into yellow, along with solidification in film forming procedure
Imperfect, over time, constantly absorption ultraviolet light, product yellowing are further aggravated；
（3）Shrinking percentage is big, precision is not high enough.The light-cured resin now used is mostly radically curing or free radical-cation
Solidification, the bigger or curing rate of contraction is slow, causes Product Precision not high enough, influences on the production of some finings
It is bigger；
（4）Intensity is not high enough, and toughness is not good enough.
Photocuring 3D printing needs to guarantee at a certain temperature that printed material flowing is equal to the more demanding of material property
It is even, it is as fast as possible on curing time.In addition, also needing to meet other correlations for many functional 3D printing materials
Can requirement, and most domestic formula in the basic demand of material property there is also many problems, lead to not advise greatly
Mould produces and uses, to cause the result that photocuring 3D printing technique remains where one is.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide it is a kind of prepare it is simple, cheap and easy to get,
It is fast with curing rate, shrinking percentage is low, intensity is high, viscosity is low, the radical cation of good toughness, smooth, the easy overlay film in surface is mixed
Veiling glare solidified resin improves the consistency of product, solves photocurable resin material in the prior art while reducing product cost
Photocuring reaction rate is slow, not good etc. enough the technical problems in surface.
To achieve the goals above or other purposes, the present invention is achieved by the following technical solutions：
A kind of radical cation hybrid UV-curing resin, including following component：
Cation photocuring part 50%-70%
Radical UV curing part 10%-35%
Cation light initiator 4%-6%
Free radical photo-initiation 1%-3%
Toughener 5%-10%
Filler surplus
The above summation is 100%
Preferably, the mass fraction of the cation photocuring part is 50%-60%.
Preferably, the mass fraction of the radical UV curing part is 20%-35%；Most preferably, the free radical light
The mass fraction of cured portion is 23%-35%.
Preferably, the mass fraction of the cation light initiator is 4%-5%.
Preferably, the mass fraction of the free radical photo-initiation is 2%-3%.
Preferably, the mass fraction of the filler is 1%-2%.
Further, the cation photocuring component is by glycidyl ether type epoxy resin, glycidol esters epoxy
Resin, cycloaliphatic epoxy resin, vinyl ethers monomer composition.
Preferably, the cation photocuring part is selected from standard type bisphenol A type epoxy resin, low viscosity liquid bisphenol A
Type epoxy resin, -3,4 epoxycyclohexyl formic acid esters of 3,4 epoxycyclohexyl-methyl, bis- ((3,4 epoxycyclohexyl) methyl) oneself two
One of acid esters, 3- ethyl -3- oxa- fourth ring methanol are a variety of.
Preferably, the cation photocuring part is selected from standard type bisphenol A type epoxy resin, low viscosity liquid bisphenol A
Type epoxy resin, -3,4 epoxycyclohexyl formic acid esters of 3,4 epoxycyclohexyl-methyl, bis- ((3,4 epoxycyclohexyl) methyl) oneself two
At least three kinds in acid esters, 3- ethyl -3- oxa- fourth ring methanol.
Preferably, the cation photocuring part is selected from standard type bisphenol A type epoxy resin, low viscosity liquid bisphenol A
Type epoxy resin, -3,4 epoxycyclohexyl formic acid esters of 3,4 epoxycyclohexyl-methyl, bis- ((3,4 epoxycyclohexyl) methyl) oneself two
Three kinds, four kinds or five kinds in acid esters, 3- ethyl -3- oxa- fourth ring methanol.
Most preferably, the cation photocuring part is standard type bisphenol A type epoxy resin, low viscosity liquid bisphenol A
Type epoxy resin, -3,4 epoxycyclohexyl formic acid esters of 3,4 epoxycyclohexyl-methyl, bis- ((3,4 epoxycyclohexyl) methyl) oneself two
Acid esters and 3- ethyl -3- oxa- fourth ring methanol.
Further, the radical UV curing part is made of acrylic monomers and prepolymer.
Preferably, the radical UV curing part is made of acrylic monomers and prepolymer, selected from epoxy acrylate,
Aliphatic polyamines ester acrylate, ethoxylated bisphenol A diacrylate, trimethylolpropane trimethacrylate, dipentaerythritol
One of six acrylate are a variety of.
Preferably, the radical UV curing part is made of acrylic monomers and prepolymer, selected from epoxy acrylate,
Aliphatic polyamines ester acrylate, ethoxylated bisphenol A diacrylate, trimethylolpropane trimethacrylate, dipentaerythritol
At least three kinds in six acrylate.
Preferably, the radical UV curing part is epoxy acrylate, aliphatic polyamines ester acrylate, ethoxyquin
Bisphenol a diacrylate, trimethylolpropane trimethacrylate and dipentaerythritol hexaacrylate.
Further, the cation light initiator is selected from 50% 2 [4- diphenyl sulfur phenenyl] thioether, two hexafluoro antimonate
Carbonic allyl ester solution, one or both of liquid hexafluorophosphate.
Preferably, the cation light initiator is selected from 50% 2 [4- diphenyl sulfur phenenyl] thioether, two hexafluoro antimonate
Carbonic allyl ester solution.
Further, the free radical photo-initiation is selected from 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxyl-ring
Hexyl-phenyl ketone, diphenyl（2,4,6- trimethylbenzoyl) one of phosphorous oxide or a variety of.
Preferably, the free radical photo-initiation is selected from 2- hydroxy-2-methyl -1- phenyl -1- acetone.
Further, the toughener is selected from carboxyl-terminated liguid nitrile rubber, hydroxyl terminated butyl nitrile (HTBN) rubber, Amino End Group liquid
One of body nitrile rubber, acrylate copolymer core-shell structure, organosilicon core-shell particles are a variety of.
Preferably, the toughener is organosilicon core-shell particles.
Further, the filler is modified Nano ceramic solution.The preparation method of the modified Nano ceramic solution is：
First nano-ceramic powder is added in resin, dispersing agent is added later and is ground uniformly with grinder, ultrasound after ammonium hydroxide is then added
The 1 hour extra ammonium hydroxide of removal is finally heated in wave processing at 100 DEG C.
Further, the preparation method of the modified Nano ceramic solution is：By the nano-ceramic powder of partial size 5-50nm
It is added in resin, stirs evenly, dispersing agent is added later, ground with grinder uniform.Then ammonium hydroxide, ultrasonic oscillation is added
1 hour, the 1 hour extra ammonium hydroxide of removal is heated at 100 DEG C later.
Preferably, the resin is selected from one of epoxy resin, amino resins, acrylic resin or a variety of.
Preferably, the dispersing agent is macromolecule dispersing agent, is selected from polyacrylamide, polyacrylic acid and its sodium salt, hydroxyl first
One of base cellulose, polyvinyl alcohol are a variety of.
Most preferably, the dispersing agent is polyacrylamide.
The present invention also provides the preparation methods of above-mentioned radical cation hybrid UV-curing resin.
A kind of preparation method of radical cation hybrid UV-curing resin, mainly includes the following steps that：
（1）Cation photocuring part and filler are uniformly dispersed by dispersion machine；
（2）By step（1）Obtained scattered material and toughener stirs 1 hour at 60 DEG C in proportion；
（3）Other materials is stirred in proportion and is added thereto, is stirred 2 hours under room temperature；
（4）It vacuumizes 0.5 hour, obtains radical cation hybrid UV-curing resin.
Further, step（2）Middle stirring rate is 100-1000rpm.
Further, step（3）In stirring rate be 100-1000rpm.
Further, step（4）In, it is vacuumized under 0.05-0.2 atmospheric pressure.
The present invention also provides above-mentioned radical cation hybrid UV-curing resin 3D printing technique field purposes.
In summary, the present invention has the following technical effect that：
（1）It has excellent performance, for light-cured resin of the invention by addition inorganic filler, the light-cured resin being prepared has both height
The advantages of molecular material and inorganic material, has faster photocuring reaction rate, higher mechanical strength and preferable table
Face effect can satisfy the requirement in manufacturing to working efficiency and product intensity.
（2）Preparation process is environmentally protective, does not add other hazardous solvents, to no damage to human body, no pollution to the environment.
（3）With short production cycle, simple process effectively shortens the product manufacturing period, improves production efficiency.
Specific embodiment
Illustrate embodiments of the present invention below by way of particular specific embodiment, those skilled in the art can be by this explanation
Other advantages and efficacy of the present invention can be easily understood for content disclosed by book.The present invention can also be by addition different specific
Embodiment is embodied or practiced, and the various details in this specification can also not carried on the back based on different viewpoints and application
From carrying out various modifications or alterations under spirit of the invention.
It should be noted that in the absence of conflict, the feature in following embodiment and embodiment can be combined with each other.Also
It should be appreciated that term used in the embodiment of the present invention is in order to describe specific specific embodiment, rather than in order to limit
Protection scope of the present invention.The test method of actual conditions is not specified in the following example, usually according to normal condition, or presses
According to condition proposed by each manufacturer.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, the present invention used in all technologies and
The grasp and record of the invention of scientific term and those skilled in the art to the prior art, can also use and this hair
Any method, equipment and the material of the similar or equivalent prior art of bright method as described in the examples, equipment, material is realized
The present invention.
One, test material
Test material used in the embodiment of the present invention is as shown in table 1.
The test material of table 1, embodiment A-L.
Two, the preparation of light-cured resin
According to test material, the light-cured resin of different component is set, the group of each embodiment A-L is grouped as shown in table 2.
The content of each ingredient in 2 embodiment A-L of table
It feeds intake according to the raw material components and mass fraction listed in table 2, prepares light-cured resin in accordance with the following methods：
（1）Cation photocuring part and filler are uniformly dispersed by dispersion machine；
（2）By step（1）Obtained scattered material and toughener stirs 1 hour at 60 DEG C in proportion；
（3）Other materials is stirred in proportion and is added thereto, is stirred 2 hours under room temperature；
（4）It vacuumizes 0.5 hour, obtains radical cation hybrid UV-curing resin.
Performance test
Obtained light-cured resin prepared by A-L of the embodiment of the present invention carries out critical phototonus energy, curing depth, work filling
Sweep speed, tensile strength, stretch modulus, shore hardness and the test of overarm arm notch impact strength, can buy in the market
Obtained conventional solidified resin（Comparative example 1-4）It is tested for control.Wherein, the test method of each performance indicator is as follows：
（1）The test of critical phototonus energy Ec and curing depth Dp：Using SLA 3D printer, in known laser power P L,
In the case of the h s of laser scanning interval, using different laser scan rate V s, Single Slice Mode solidification is carried out, different thickness are obtained
The exemplar of degree C d draws corresponding straight line according to formula C d=D p ln [P L/(V s * h s)]-D p lnE c,
Curing depth D p and critical phototonus energy E c wherein can be acquired by the intersection point of the slope of straight line and axis of abscissas.
（2）Work filling sweep speed：Using SLA 3D printer, in the case where constant power P L=300mW, into
Row scanning solidification, fluent material curing molding can wherein be made by taking, and can take out the maximum filling sweep speed cleaned
Sweep speed is filled for the work of the material.The index directly reflects the solidification rate of the light-sensitive material, wherein the work of material
Work filling sweep speed is higher, and the shaping efficiency of the material is higher.
（3）The test of tensile strength and stretch modulus：According to standard ASTM D638, electronic universal material testing machine is used
It measures.
（4）The test of shore hardness D：According to standard ASTM D2240, measured using Shore durometer D type 0-100HD.
（5）The test of overarm arm notch impact strength：According to standard ASTM D256, digital display balance weight impact testing machine is used
It measures.
Performance testing index is as shown in table 3：
Table 3, embodiment A-L and comparative example 1-4 light-cured resin testing performance index
The light-cured resin of the embodiment of the present invention A-L is in terms of shaping efficiency compared to city it can be seen from 3 performance indicator of table
Purchase light-cured resin is greatly improved, and is applied in SLA 3D printer, builds same product, required time
It greatly shortens, greatly improves working efficiency, reduce time cost；In addition, being also greatly improved in terms of mechanical strength.
The above performance indicator shows that light-cured resin of the invention is greatly improved compared with the existing technology, is worthy of popularization.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (9)
1. a kind of radical cation hybrid UV-curing resin, which is characterized in that contain including following raw material components and quality percentage
Amount：
Cation photocuring part 50%-70%
Radical UV curing part 10%-30%
Cation light initiator 4%-6%
Free radical photo-initiation 1%-3%
Toughener 5%-10%
Filler surplus
The above summation is 100%.
2. a kind of radical cation hybrid UV-curing resin according to claim 1, which is characterized in that the filler is
Modified Nano ceramic solution.
3. a kind of radical cation hybrid UV-curing resin according to claim 2, which is characterized in that the modification is received
The preparation method of rice ceramic solution mainly includes the following steps that：First nano-ceramic powder is dissolved in resin, dispersing agent is added, with grinding
Grinding machine grinding uniformly, ultrasonication after ammonium hydroxide is then added wherein, it is extra that removal in 1 hour is finally heated at 100 DEG C
Ammonium hydroxide.
4. a kind of radical cation hybrid UV-curing resin according to claim 1, which is characterized in that the addition of filler
Amount is 1-2%.
5. radical cation hybrid UV-curing resin according to claim 1, which is characterized in that the cationic photopolymerization is solid
Change component by glycidyl ether type epoxy resin, glycidyl ester epoxy resin, cycloaliphatic epoxy resin, vinyl ethers list
Body composition.
6. radical cation hybrid UV-curing resin according to claim 1, which is characterized in that the free radical light is solid
Change component to be made of acrylic monomers and prepolymer.
7. radical cation hybrid UV-curing resin according to claim 1, which is characterized in that the toughener is selected from
Carboxyl-terminated liguid nitrile rubber, hydroxyl terminated butyl nitrile (HTBN) rubber, amino terminated liquid nitrile rubber, acrylate copolymer nucleocapsid knot
One of structure, organosilicon core-shell particles are a variety of.
8. a kind of preparation method of radical cation hybrid UV-curing resin as claimed in claim 1 to 7, feature exist
In mainly including the following steps that：
（1）Cation photocuring part and filler are uniformly dispersed by dispersion machine；
（2）By step（1）Obtained scattered material and toughener stirs 1 hour at 60 DEG C in proportion；
（3）Other materials is stirred in proportion and is added to step（2）In obtained mixing material, stirred 2 hours under room temperature；
（4）It vacuumizes 0.5 hour, obtains radical cation hybrid UV-curing resin.
9. radical cation hybrid UV-curing resin as claimed in claim 1 to 7 is in the application of 3D printing technique field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810629735.9A CN108912280A (en) | 2018-06-19 | 2018-06-19 | A kind of radical cation hybrid UV-curing resin and its preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810629735.9A CN108912280A (en) | 2018-06-19 | 2018-06-19 | A kind of radical cation hybrid UV-curing resin and its preparation method and application |
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| CN108912280A true CN108912280A (en) | 2018-11-30 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6283997B1 (en) * | 1998-11-13 | 2001-09-04 | The Trustees Of Princeton University | Controlled architecture ceramic composites by stereolithography |
| CN106749986A (en) * | 2016-12-12 | 2017-05-31 | 中山大简高分子材料有限公司 | A kind of epoxy phenolic resin composition for photocuring rapid prototyping |
-
2018
- 2018-06-19 CN CN201810629735.9A patent/CN108912280A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6283997B1 (en) * | 1998-11-13 | 2001-09-04 | The Trustees Of Princeton University | Controlled architecture ceramic composites by stereolithography |
| CN106749986A (en) * | 2016-12-12 | 2017-05-31 | 中山大简高分子材料有限公司 | A kind of epoxy phenolic resin composition for photocuring rapid prototyping |
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Application publication date: 20181130 |