CN114014986A - Highly elastic photosensitive resin composition - Google Patents
Highly elastic photosensitive resin composition Download PDFInfo
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- CN114014986A CN114014986A CN202111502326.0A CN202111502326A CN114014986A CN 114014986 A CN114014986 A CN 114014986A CN 202111502326 A CN202111502326 A CN 202111502326A CN 114014986 A CN114014986 A CN 114014986A
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- monomer
- photosensitive resin
- resin composition
- urethane acrylate
- polyether urethane
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- 239000011342 resin composition Substances 0.000 title claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 115
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 66
- 229920000570 polyether Polymers 0.000 claims abstract description 66
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 33
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 33
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 claims abstract description 24
- AKVUWTYSNLGBJY-UHFFFAOYSA-N 2-methyl-1-morpholin-4-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCOCC1 AKVUWTYSNLGBJY-UHFFFAOYSA-N 0.000 claims abstract description 8
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 claims abstract description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 4
- GZZGHWKDEIPWEB-UHFFFAOYSA-N n-(2,2,2-trihydroxyethyl)prop-2-enamide Chemical compound OC(O)(O)CNC(=O)C=C GZZGHWKDEIPWEB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 241001077419 Damas Species 0.000 claims description 16
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 37
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 229920006247 high-performance elastomer Polymers 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 38
- 229910052739 hydrogen Inorganic materials 0.000 description 25
- 239000001257 hydrogen Substances 0.000 description 25
- 239000010410 layer Substances 0.000 description 23
- 238000010146 3D printing Methods 0.000 description 19
- 238000009472 formulation Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 238000000016 photochemical curing Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001723 curing Methods 0.000 description 7
- 239000000370 acceptor Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- NOQGZXFMHARMLW-UHFFFAOYSA-N Daminozide Chemical compound CN(C)NC(=O)CCC(O)=O NOQGZXFMHARMLW-UHFFFAOYSA-N 0.000 description 5
- 241001397104 Dima Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000013013 elastic material Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000010606 normalization Methods 0.000 description 4
- 238000001029 thermal curing Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NSFGOWGWLHAJPC-UHFFFAOYSA-N COCOC.C(C=C)(=O)O Chemical compound COCOC.C(C=C)(=O)O NSFGOWGWLHAJPC-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Images
Classifications
-
- 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
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
Abstract
The invention provides a high-elasticity photosensitive resin composition which comprises a polyether urethane acrylate oligomer, a monomer and a photoinitiator, wherein the first monomer is selected from one or more of dimethyl glyceryl diacrylate, dimethylamino propyl acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate and N-acryloyl (trihydroxymethyl) aminomethane, and the second monomer is selected from one or more of acryloyl morpholine, methacryloyl morpholine, tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate. The photosensitive resin composition can effectively improve the vertical elasticity of the polymer, reduce the viscosity of a system, reduce the hardness of the polymer, keep higher tensile strength and elongation at break and be beneficial to preparing soft and elastic high-performance elastomer materials.
Description
Technical Field
The invention belongs to the field of photosensitive resin, and particularly relates to a high-elasticity photosensitive resin composition.
Background
Elasticity is the property of a material to recover its original shape quickly after undergoing a deformation. The elastic body is a high polymer material which has obvious deformation under weak stress and can be quickly recovered to be close to the original state and size after the stress is relaxed. The macromolecular elastomer material requires that macromolecular chains have enough flexibility to ensure that the material can generate larger deformation, and the material can be deformed and recovered under the drive of entropy increase after the external force is removed.
In order to ensure sufficient flexibility, the elastomer is often prepared by using an oligomer with a long flexible chain segment in a macromolecular chain, but the viscosity of the oligomer is high due to the long flexible chain segment, the molecular acting force between the flexible chain segments is weak, the diluting capability is poor, the 3D printing is not facilitated, and the mechanical property is poor. Viscosity can be reduced by adding short chain monomers as reactive diluents, but if more short chain monomers are added, the elasticity and flexibility of the cured material are affected, and the combination of low viscosity, high elasticity, high flexibility and high tensile strength properties is difficult to achieve simultaneously.
In order to solve the above problems, most of high-performance elastic materials used in 3D printing are dual-cured materials of photo-curing and thermal curing, and the performance is further improved by thermal curing after photo-curing. However, dual curing has some disadvantages, such as high energy consumption, long thermosetting time, difficult material storage, increased difficulty of 3D printing process, and the like.
Therefore, there is a need in the art for a photosensitive resin composition capable of simultaneously achieving low viscosity, high elasticity, high flexibility and high tensile strength properties without resorting to a dual curing manner of photocuring and thermal curing.
Disclosure of Invention
In view of the above problems, the present invention provides a photosensitive resin composition capable of simultaneously achieving low viscosity, high elasticity, high flexibility and high tensile strength properties without resorting to a dual curing system of photocuring and thermosetting. According to the invention, the first monomer and the second monomer are added into the polyether urethane acrylate oligomer, and the synergistic effect among the first monomer, the second monomer and the polyether urethane acrylate oligomer on the aspects of reducing viscosity, improving elasticity and reducing hardness is utilized to obtain the high-elasticity photosensitive resin composition. The photosensitive resin composition disclosed by the invention is low in viscosity, is beneficial to 3D printing, and can be used for forming a material with high elasticity, high flexibility and high tensile strength through single photocuring.
Specifically, the present invention provides an elastic photosensitive resin composition comprising a polyether urethane acrylate oligomer, a monomer and a photoinitiator;
wherein the mass ratio of the polyether urethane acrylate oligomer to the monomer is 2:3 to 3: 2;
the monomers comprise a first monomer and a second monomer, the molar ratio of the first monomer to the second monomer is 1:1 to 2:1, the first monomer is selected from one or more of dimethyl glyceryl diacrylate, dimethylamino propyl acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate and N-acryloyl (trihydroxymethyl) aminomethane, and the second monomer is selected from one or more of acryloyl morpholine, methacryloyl morpholine, tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate;
the mass of the photoinitiator is 1-5% of the total mass of the polyether urethane acrylate oligomer and the monomer.
In one or more embodiments, the polyether urethane acrylate oligomer has an elongation at break of 150% or more.
In one or more embodiments, the polyether urethane acrylate oligomer has a weight average molecular weight of 1000 to 20000.
In one or more embodiments, the polyether urethane acrylate oligomer has a glass transition temperature of ≦ -10 ℃.
In one or more embodiments, the polyether urethane acrylate oligomer is selected from one or more of Sadoma CN8888, Sadoma CN966J75 NS, Sadoma CN9782, Demas BR-543, Demas BR-374, Demas BR-744, Demas BR-345 and Demas BR-344.
In one or more embodiments, the polyether urethane acrylate oligomer is selected from one or both of Demas BR-374 and Demas BR-344.
In one or more embodiments, the first monomer is selected from one or both of dimethylaminopropyl acrylamide and hydroxyethyl methacrylate.
In one or more embodiments, the second monomer is selected from one or both of acryloyl morpholine and tetrahydrofurfuryl methacrylate.
In one or more embodiments, the first monomer is dimethylaminopropyl acrylamide and the second monomer is selected from one or both of acryloylmorpholine and methacryloylmorpholine.
In one or more embodiments, the first monomer is dimethylaminopropyl acrylamide and the second monomer is acryloylmorpholine.
In one or more embodiments, the first monomer is hydroxyethyl methacrylate and the second monomer is selected from one or both of tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate.
In one or more embodiments, the first monomer is hydroxyethyl methacrylate and the second monomer is tetrahydrofurfuryl methacrylate.
In one or more embodiments, the initiator is phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
In one or more embodiments, the polyether urethane acrylate oligomer is damass BR-374 and the monomers include dimethylaminopropyl acrylamide and acryloylmorpholine in a molar ratio of 1:1 to 2: 1.
In one or more embodiments, the polyether urethane acrylate oligomer is damass BR-344 and the monomers comprise hydroxyethyl methacrylate and tetrahydrofurfuryl methacrylate in a molar ratio of 1:1 to 2: 1.
The present invention also provides a resin material or a resin article obtained by curing the elastic photosensitive resin composition according to any one of the embodiments herein.
Drawings
FIG. 1 is a graph comparing the performance data of Table 2 after normalization.
Fig. 2 is a graph comparing the performance data in table 4 after normalization.
FIG. 3 is a comparison of the performance data in Table 6 after normalization.
Detailed Description
To make the features and effects of the present invention obvious to those skilled in the art, the terms and words used in the specification and claims are generally described and defined below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as numbers, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
In the present invention, the photosensitive resin composition has a meaning conventional in the art, and is a resin composition capable of being cured under ultraviolet irradiation. The high elasticity means that the photosensitive resin composition can be remarkably deformed under the action of external force and can be quickly restored to be close to the original state and size after the external force is removed.
The photosensitive resin composition of the present invention includes a polyether urethane acrylate oligomer, a monomer and a photoinitiator.
The polyether urethane acrylate oligomer is an acrylate oligomer with high elongation at break and containing polyether and polyurethane structural units, has a weight average molecular weight of generally 1000 to 20000, contains longer flexible segments and is good in flexibility, but has higher viscosity due to longer molecular chains. The polyether urethane acrylate oligomer suitable for the present invention preferably has an elongation at break of not less than 150% and a glass transition temperature of not more than-10 ℃.
Examples of the polyether urethane acrylate oligomer suitable for the present invention include CN8888, CN966J75 NS, CN9782 and the like of Saedoma, and BR-543, BR-374, BR-744, BR-345, BR-344 and the like of Damass, and satisfy the requirements of low glass transition temperature and high elongation at break. In some embodiments, the polyether urethane acrylate oligomer used in the present invention is selected from one or both of the group consisting of Damas BR-374 and Damas BR-344.
The monomers used in the present invention include a first monomer and a second monomer. The invention discovers that after a first monomer and a second monomer are simultaneously added into a polyether urethane acrylate oligomer, the first monomer and the second monomer have synergistic effect on reducing system viscosity and improving polymer elasticity and flexibility, so that 3D printing is facilitated, and a material with high elasticity, high flexibility and high tensile strength can be formed through single photocuring.
In the present invention, the monomer refers to a small molecule reactive diluent capable of photo-initiated polymerization, such as acrylate monomers and acrylamide monomers. The photosensitive resin composition of the present invention is characterized by containing a polyether urethane acrylate oligomer, and the monomers contained therein include a first monomer and a second monomer. In some embodiments, the photosensitive resin composition of the present invention contains monomers consisting of a first monomer and a second monomer.
In the present invention, the first monomer is selected from one or more of glycerol dimethyldiacrylate, dimethylaminopropylacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate and N-acryloyl (trihydroxymethyl) aminomethane. The first monomer used in the present invention contains a hydrogen bond donor. The first monomer is preferably one or two selected from dimethylamino propyl acrylamide and hydroxyethyl methacrylate, which is beneficial to produce better synergy between the polyether urethane acrylate oligomer and the second monomer in reducing the viscosity of the system, improving the elasticity and flexibility of the polymer.
In the present invention, the hydrogen bond donor and the hydrogen bond acceptor refer to groups capable of forming a hydrogen bond contained in a molecule, wherein a group providing a hydrogen atom in the hydrogen bond is the hydrogen bond donor, and a group receiving the hydrogen atom in the hydrogen bond is the hydrogen bond acceptor. In the present invention, the first monomer may contain one or more hydrogen bond donors. In some embodiments, the first monomer is a monomer containing a hydrogen bond donor, such as dimethylaminopropyl acrylamide and hydroxyethyl methacrylate.
In the present invention, the second monomer is selected from one or more of acryloyl morpholine (i.e. 4-acryloyl morpholine), methacryloyl morpholine, tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate. The second monomer used in the present invention contains a hydrogen bond acceptor. The present invention has surprisingly found that the use of acryloyl morpholine, methacryloyl morpholine, tetrahydrofurfuryl acrylate, and tetrahydrofurfuryl methacrylate as the second monomer ensures that the second monomer, when compounded with the polyether urethane acrylate oligomer and the first monomer, achieves a synergistic effect in reducing the system viscosity and increasing the elasticity and flexibility of the polymer, whereas the use of other monomers containing hydrogen bond acceptors (e.g., cyclotrimethylolpropane formal acrylate) does not ensure that the above synergistic effect is achieved.
In some specific embodiments, the present invention uses dimethylaminopropyl acrylamide as a first monomer and one or two selected from acryloyl morpholine and methacryloyl morpholine, in particular acryloyl morpholine, as a second monomer. In other specific embodiments, the present invention uses hydroxyethyl methacrylate as the first monomer and one or two selected from tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate, particularly tetrahydrofurfuryl methacrylate, as the second monomer. With these embodiments, a synergistic effect in reducing the viscosity of the system, increasing the elasticity and flexibility of the polymer can be achieved.
In order to obtain better synergy among the polyether urethane acrylate oligomer, the hydrogen bond donor-containing monomer, and the hydrogen bond acceptor-containing monomer in reducing the viscosity of the system, increasing the elasticity and flexibility of the polymer, the molar ratio of the first monomer to the second monomer in the photosensitive resin composition is preferably 1:1 to 2: 1.
In the present invention, the photosensitive resin composition contains the monomers mainly of the first monomer and the second monomer. The total mass of the first monomer and the second monomer accounts for 80% or more, preferably 90% or more, 95% or more, 99% or more, or 100% of the total mass of the monomers contained in the photosensitive resin composition. In some embodiments, the photosensitive resin composition of the present invention contains monomers consisting of a first monomer and a second monomer.
The mass ratio of the polyether urethane acrylate oligomer to the monomer in the invention is preferably 2:3 to 3:2, so as to effectively reduce the viscosity of the system and obtain the comprehensive properties of high elasticity, high flexibility and higher tensile strength.
In a particularly preferred embodiment, in the photosensitive resin composition of the present invention, the mass ratio of the polyether urethane acrylate oligomer to the monomer is 2:3 to 3:2, the first monomer is one or two selected from dimethylaminopropyl acrylamide and hydroxyethyl methacrylate, and the second monomer is one or two selected from 4-acryloylmorpholine and tetrahydrofurfuryl methacrylate. In these embodiments, the polyether urethane acrylate oligomer is preferably selected from one or two of the group consisting of Damas BR-374 and Damas BR-344, and the molar ratio of the first monomer to the second monomer is preferably 1:1 to 2: 1.
In some specific embodiments, the polyether urethane acrylate oligomer is damass BR-374, the mass ratio of polyether urethane acrylate oligomer to monomer is from 2:3 to 3:2, e.g., 2:3, and the monomers are dimethylaminopropyl acrylamide and 4-acryloylmorpholine in a mass ratio of from 1:1 to 2:1, e.g., 2: 1. In other specific embodiments, the polyether urethane acrylate oligomer is damass BR-344, the polyether urethane acrylate oligomer and monomer are present in a mass ratio of 2:3 to 3:2, e.g., 2:3, and the monomer is hydroxyethyl methacrylate and tetrahydrofurfuryl methacrylate in a mass ratio of 1:1 to 2:1, e.g., 2:1, 1.5:1, or 1:1.
Photoinitiators suitable for use in the present invention include one or more selected from the group consisting of 2-hydroxy-2-methyl-phenyl-propanone-1, 1-hydroxycyclohexyl phenyl ketone, alpha-hydroxyisobutyrophenone, methyl benzoylformate, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, and the like. Preferably, the photoinitiator is phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (i.e., photoinitiator 819), which facilitates a better synergy between the polyether urethane acrylate oligomer, the monomer containing a hydrogen bond donor, and the monomer containing a hydrogen bond acceptor in reducing the viscosity of the system, increasing the elasticity and flexibility of the polymer. In the photosensitive resin composition, the mass of the photoinitiator may be 1 to 5 wt%, for example, 2 wt%, 3 wt%, 4 wt%, etc., of the total mass of the polyether urethane acrylate oligomer and the monomer.
The photosensitive resin composition of the present invention may optionally include an auxiliary. The auxiliary may be an auxiliary commonly used in the art for photosensitive resin compositions, including but not limited to, a colorant, a leveling agent, a defoaming agent, a light absorbing agent, a dispersing agent, an anti-aging agent, and the like. The amounts of auxiliaries may be conventional in the art. In some embodiments, the photosensitive resin composition of the present invention is composed of a polyether urethane acrylate oligomer, a monomer, a photoinitiator, and optionally an auxiliary. In some embodiments, the photosensitive resin composition of the present invention consists of a polyether urethane acrylate oligomer, a monomer and a photoinitiator.
The photosensitive resin composition can effectively improve the vertical elasticity of a polymer, reduce the hardness of the polymer, keep higher tensile strength and elongation at break, is beneficial to preparing soft and elastic high-performance elastomer materials, can reduce the viscosity of a system, does not need thermal curing, and is beneficial to 3D printing.
The invention includes curing the photosensitive resin composition of the inventionThe curing is photocuring. The light intensity can be 1-50mW/cm during photocuring2E.g. 2-20mW/cm2、6±1mW/cm2The wavelength may be 280-480nm, for example 405 + -5 nm. Photocuring can be performed by means of 3D printing. The monolayer film thickness may be 10-150 μm, such as 20-120 μm, 70 + -10 μm, for 3D printing, and the monolayer exposure time may be 1-100s, such as 2-20s, 10 + -2 s. The photosensitive resin composition of the present invention can be made into a resin material or a resin article by the following method: and (3) feeding the uniformly mixed photosensitive resin composition into a 3D printer, and performing layer-by-layer printing and exposure curing by using the 3D printer to obtain the resin material or the resin product. The photosensitive resin composition is suitable for preparing products such as flexible conduits, sealing materials and the like.
The photosensitive resin composition and the material cured by the same can achieve one or more or all of the following properties:
the photosensitive resin composition has a viscosity of 500MPa · s or less at 30 ℃ measured in accordance with ASTM D4212-93;
the vertical elasticity of the photosensitive resin material measured according to ASTM D2632 is more than or equal to 45 percent;
the Shore hardness of the photosensitive resin material is less than or equal to 85A measured according to ASTM D2240-05:
the tensile strength of the photosensitive resin material measured according to ASTM D638-14 is not less than 7 MPa:
the photosensitive resin material has an elongation at break of 250% or more as measured in accordance with ASTM D638-14.
The present invention will be illustrated below by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples and comparative examples are those conventional in the art unless otherwise indicated. The starting materials in the examples and comparative examples were all commercially available.
The polymer samples in the examples and comparative examples were tested for their performance according to the following criteria:
tensile strength: ASTM D638-14;
elongation at break: ASTM D638-14;
shore hardness: ASTM D2240-05;
viscosity: ASTM D4212-93;
vertical elasticity: ASTM D2632.
Example 1
According to the formulation shown in table 1, 40 parts by mass of a polyether urethane acrylate oligomer (dimass, BR-374), 18.7 parts by mass of 4-acryloylmorpholine, 41.3 parts by mass of dimethylaminopropylacrylamide (the molar ratio of 4-acryloylmorpholine to dimethylaminopropylacrylamide is 1:2), and 3 parts by mass of a photoinitiator 819 were uniformly stirred to obtain a photosensitive resin composition. Using a 3D printer at a wavelength of 405nm, a layer thickness of 70 μm, a light intensity of 6mW/cm2And exposure time of 10s per layer to 3D printing to produce polymer samples. The polymer samples were tested for viscosity (30 ℃), tensile strength, elongation at break, vertical elasticity, and shore hardness. The test results are shown in table 2 and fig. 1.
Comparative example 1
The photosensitive resin composition was obtained by uniformly stirring 40 parts by mass of a polyether urethane acrylate oligomer (damas, BR-374), 60 parts by mass of 4-acryloylmorpholine and 3 parts by mass of a photoinitiator 819 according to the formulation shown in table 1. Using the same 3D printer as in example 1, a wavelength of 405nm, a layer thickness of 70 μm and a light intensity of 6mW/cm2And exposure time of 10s per layer to 3D printing to produce polymer samples. The polymer samples were tested for viscosity (30 ℃), tensile strength, elongation at break, vertical elasticity, and shore hardness. The test results are shown in table 2 and fig. 1.
Comparative example 2
The photosensitive resin composition was obtained by uniformly stirring 40 parts by mass of a polyether urethane acrylate oligomer (damas, BR-374), 60 parts by mass of dimethylaminopropylacrylamide, and 3 parts by mass of a photoinitiator 819 according to the formulation shown in table 1. Using the same 3D printer as in example 1, a wavelength of 405nm, a layer thickness of 70 μm and a light intensity of 6mW/cm2And exposure time of 10s per layer to 3D printing to produce polymer samples. Test Polymer samples for viscosity (30 ℃), tensile Strength, elongation at BreakRate, vertical elasticity, and shore hardness. The test results are shown in table 2 and fig. 1.
Table 1: photosensitive resin formulations of example 1 and comparative examples 1 to 2 (unit: parts by mass)
Table 2: comparison of Properties of photosensitive resins of example 1 and comparative examples 1 to 2
In table 2, "theoretical value" means a property value calculated by proportioning the properties of comparative example 1 and comparative example 2 according to the formulation of example 1.
As shown in table 2, in terms of viscosity, example 1 has a viscosity lower than the theoretical value, probably because 4-acryloylmorpholine has a poor compatibility with polyether urethane acrylate, resulting in a higher viscosity in comparative example 1, and after dimethylaminopropylacrylamide is added to form a hydrogen bond, although the intermolecular interaction is increased, the compatibility among dimethylaminopropylacrylamide, 4-acryloylmorpholine and polyether urethane acrylate is improved, and thus the effect of reducing viscosity is finally exhibited.
In terms of vertical elasticity, example 1 shows higher elasticity than comparative example 1 and comparative example 2, probably because the cross-linking network density of the polyether urethane acrylate oligomer itself is lower, and the hydrogen bonding structure between dimethylaminopropyl acrylamide, 4-acryloylmorpholine and the polyether urethane acrylate oligomer increases the cross-linking network density, so that the cross-linking network density is in a proper range, and the elasticity is effectively improved.
In terms of hardness, example 1 exhibited lower hardness than comparative example 1 and comparative example 2, i.e., exhibited softer properties, probably due to the increase in elasticity while lowering the material hardness.
In summary, comparative example 1 has both high tensile strength and elongation at break and high elasticity, but the hardness is too high, indicating that the addition of only 4-acryloylmorpholine makes the formulation unsuitable for application to elastic materials; comparative example 2, however, had lower elasticity, lower tensile strength, and higher hardness, indicating that the formulation was not suitable for use in elastic materials with only dimethylaminopropyl acrylamide; however, when 4-acryloylmorpholine and dimethylaminopropylacrylamide were added simultaneously, example 1 exhibited higher elasticity and lower hardness than both comparative example 1 and comparative example 2, i.e., exhibited softer and more elastic, and maintained higher tensile strength and elongation at break, and was of high value in the direction of application of elastic materials.
Example 2
A photosensitive resin composition was obtained by uniformly stirring 40 parts by mass of a polyether urethane acrylate oligomer (dimas, BR-344), 23.7 parts by mass of tetrahydrofurfuryl methacrylate, 36.3 parts by mass of hydroxyethyl methacrylate (the molar ratio of tetrahydrofurfuryl methacrylate to hydroxyethyl methacrylate is 1:2), and 3 parts by mass of a photoinitiator 819 according to the formulation shown in table 3. Using a 3D printer at a wavelength of 405nm, a layer thickness of 70 μm, a light intensity of 6mW/cm2And exposure time of 10s per layer to 3D printing to produce polymer samples. The polymer samples were tested for viscosity (30 ℃), tensile strength, elongation at break, vertical elasticity, and shore hardness. The test results are shown in table 4 and fig. 2.
Example 3
After 40 parts by mass of a polyether urethane acrylate oligomer (demass, BR-344), 27.9 parts by mass of tetrahydrofurfuryl methacrylate, 32.1 parts by mass of hydroxyethyl methacrylate (the molar ratio of tetrahydrofurfuryl methacrylate to hydroxyethyl methacrylate is 1:1.5) and 3 parts by mass of a photoinitiator 819 were uniformly stirred in accordance with the formulation shown in table 3, a photosensitive resin composition was obtained. Using the same 3D printer of example 2, a wavelength of 405nm, a layer thickness of 70 μm and a light intensity of 6mW/cm2And exposure time of 10s per layer to 3D printing to produce polymer samples. The polymer samples were tested for viscosity (30 ℃), tensile strength, elongation at break, vertical elasticity, and shore hardness. The test results are shown in Table 4.
Example 4
A photosensitive resin composition was obtained by uniformly stirring 40 parts by mass of a polyether urethane acrylate oligomer (dimas, BR-344), 34.0 parts by mass of tetrahydrofurfuryl methacrylate, 26.0 parts by mass of hydroxyethyl methacrylate (the molar ratio of tetrahydrofurfuryl methacrylate to hydroxyethyl methacrylate is 1:1), and 3 parts by mass of a photoinitiator 819 according to the formulation shown in table 3. Using the same 3D printer of example 2, a wavelength of 405nm, a layer thickness of 70 μm and a light intensity of 6mW/cm2And exposure time of 10s per layer to 3D printing to produce polymer samples. The polymer samples were tested for viscosity (30 ℃), tensile strength, elongation at break, vertical elasticity, and shore hardness. The test results are shown in Table 4.
Comparative example 3
A photosensitive resin composition was obtained by uniformly stirring 40 parts by mass of a polyether urethane acrylate oligomer (dimas, BR-344), 60 parts by mass of tetrahydrofurfuryl methacrylate, and 3 parts by mass of a photoinitiator 819 according to the formulation shown in table 3. Using the same 3D printer of example 2, a wavelength of 405nm, a layer thickness of 70 μm and a light intensity of 6mW/cm2And exposure time of 10s per layer to 3D printing to produce polymer samples. The polymer samples were tested for viscosity (30 ℃), tensile strength, elongation at break, vertical elasticity, and shore hardness. The test results are shown in table 4 and fig. 2.
Comparative example 4
The photosensitive resin composition was obtained by uniformly stirring 40 parts by mass of a polyether urethane acrylate oligomer (damas, BR-344), 60 parts by mass of hydroxyethyl methacrylate, and 3 parts by mass of a photoinitiator 819 according to the formulation shown in table 3. Using the same 3D printer of example 2, a wavelength of 405nm, a layer thickness of 70 μm and a light intensity of 6mW/cm2And exposure time of 10s per layer to 3D printing to produce polymer samples. TestingViscosity (30 ℃), tensile strength, elongation at break, vertical elasticity, and shore hardness of the polymer samples. The test results are shown in table 4 and fig. 2.
Table 3: photosensitive resin formulations of example 2 and comparative examples 3 to 4 (unit: parts by mass)
Table 4: comparison of Properties of photosensitive resins of example 2 and comparative examples 3 to 4
In Table 4, "theoretical value" means a value of property obtained by calculating the value of property of comparative example 3 and comparative example 4 in the proportion of the formulation of example 2.
As shown in table 4, in the case of example 2 having a viscosity lower than the theoretical value, it is possible that the viscosity of comparative example 4 is high because the compatibility of hydroxyethyl methacrylate with polyether urethane acrylate is not good enough, and the compatibility among tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate and polyether urethane acrylate oligomer is improved although the intermolecular interaction is increased after tetrahydrofurfuryl methacrylate is added to form hydrogen bonds, and thus the effect of reducing the viscosity is finally exhibited.
In terms of vertical elasticity, example 2 showed higher elasticity than comparative example 3 and comparative example 4, probably due to the lower crosslink network density of the polyether urethane acrylate oligomer itself, while the hydrogen bonding structure between tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate and the polyether urethane acrylate oligomer increased the crosslink network density, making the crosslink network density in a suitable range, effectively increasing the elasticity.
In terms of hardness, example 2 exhibited lower hardness than comparative example 3 and comparative example 4, i.e., exhibited softer properties, probably due to the increase in elasticity, while lowering the material hardness.
In summary, when tetrahydrofurfuryl methacrylate and hydroxyethyl methacrylate are added simultaneously to form hydrogen bonds in the formulation, example 2 shows higher elasticity and lower hardness than both comparative example 3 and comparative example 4, i.e., shows softer and more elastic properties, and simultaneously maintains higher tensile strength and elongation at break, and is of high value in the direction of application of elastic materials.
Examples 3 and 4 are different from example 2 in the amount ratio of tetrahydrofurfuryl methacrylate to hydroxyethyl methacrylate. In examples 2 to 4, the molar ratios of tetrahydrofurfuryl methacrylate to hydroxyethyl methacrylate were 1:2, 1:1.5, and 1:1, respectively. As can be seen from Table 4, examples 2-4 have relatively similar properties, all with reduced system viscosity, increased vertical elasticity of the polymer, reduced hardness of the polymer, and maintained good tensile strength and elongation at break. Of these, example 3 shows the best vertical elasticity, probably due to steric hindrance, and the monomer molar ratio used in example 3 more efficiently forms hydrogen bonds, and better shows the effect of hydrogen bonds.
The experiment results show that the photosensitive resin formula based on the hydrogen bond structure can effectively improve the vertical elasticity of the polymer, reduce the system viscosity and the polymer hardness, simultaneously keep higher tensile strength and elongation at break, and is beneficial to preparing soft and elastic high-performance elastomer materials.
Comparative example 5
A photosensitive resin composition was obtained by uniformly stirring 40 parts by mass of a polyether urethane acrylate oligomer (dimas, BR-344), 26.1 parts by mass of cyclotrimethylolpropane formal acrylate, 33.9 parts by mass of hydroxyethyl methacrylate (the molar ratio of the cyclotrimethylolpropane formal acrylate to the hydroxyethyl methacrylate is 1:2) and 3 parts by mass of a photoinitiator 819 according to the formulation shown in table 5. Make itUsing a 3D printer at a wavelength of 405nm, a layer thickness of 70 μm, and a light intensity of 6mW/cm2And exposure time of 10s per layer to 3D printing to produce polymer samples. The polymer samples were tested for viscosity (30 ℃), tensile strength, elongation at break, vertical elasticity, and shore hardness. The test results are shown in table 6 and fig. 3.
Comparative example 6
A photosensitive resin composition was obtained by uniformly stirring 40 parts by mass of a polyether urethane acrylate oligomer (dimas, BR-344), 60 parts by mass of a cyclic trimethylolpropane formal acrylate and 3 parts by mass of a photoinitiator 819 according to the formulation shown in table 5. Using the same 3D printer as in comparative example 5 at a wavelength of 405nm, a layer thickness of 70 μm and a light intensity of 6mW/cm2And exposure time of 10s per layer to 3D printing to produce polymer samples. The polymer samples were tested for viscosity (30 ℃), tensile strength, elongation at break, vertical elasticity, and shore hardness. The test results are shown in table 6 and fig. 3.
Comparative example 7
The photosensitive resin composition was obtained by uniformly stirring 40 parts by mass of a polyether urethane acrylate oligomer (damas, BR-344), 60 parts by mass of hydroxyethyl methacrylate, and 3 parts by mass of a photoinitiator 819 according to the formulation shown in table 5. Using the same 3D printer as in comparative example 5 at a wavelength of 405nm, a layer thickness of 70 μm and a light intensity of 6mW/cm2And exposure time of 10s per layer to 3D printing to produce polymer samples. The polymer samples were tested for viscosity (30 ℃), tensile strength, elongation at break, vertical elasticity, and shore hardness. The test results are shown in table 6 and fig. 3.
Table 5: photosensitive resin formulations of comparative examples 5 to 7 (unit: parts by mass)
Table 6: comparison of Properties of photosensitive resins of comparative examples 5 to 7
Table 6 the data is shown in figure 3 after normalization. It can be seen that the effect of greatly improving the vertical elasticity is not generated after the cyclotrimethylolpropane methylal acrylate and the hydroxyethyl methacrylate are compounded as the combined monomer and the polyether urethane acrylate oligomer, and a strong hydrogen bond network is not formed possibly under the combination, so that the vertical elasticity of the material is not improved enough.
Claims (10)
1. An elastic photosensitive resin composition, characterized in that it comprises a polyether urethane acrylate oligomer, a monomer and a photoinitiator;
wherein the mass ratio of the polyether urethane acrylate oligomer to the monomer is 2:3 to 3: 2;
the monomers comprise a first monomer and a second monomer, the molar ratio of the first monomer to the second monomer is 1:1 to 2:1, the first monomer is selected from one or more of dimethyl glyceryl diacrylate, dimethylamino propyl acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate and N-acryloyl (trihydroxymethyl) aminomethane, and the second monomer is selected from one or more of acryloyl morpholine, methacryloyl morpholine, tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate;
the mass of the photoinitiator is 1-5% of the total mass of the polyether urethane acrylate oligomer and the monomer.
2. The elastomeric photosensitive resin composition of claim 1, wherein said polyether urethane acrylate oligomer has one or more of the following characteristics:
the elongation at break of the polyether urethane acrylate oligomer is more than or equal to 150 percent;
the weight average molecular weight of the polyether urethane acrylate oligomer is 1000-20000;
the glass transition temperature of the polyether urethane acrylate oligomer is less than or equal to-10 ℃.
3. The elastomeric photosensitive resin composition of claim 1, wherein said polyether urethane acrylate oligomer is selected from one or more of sartomer CN8888, sartomer CN966J75 NS, sartomer CN9782, damass BR-543, damass BR-374, damass BR-744, damass BR-345, and damass BR-344.
4. The elastic photosensitive resin composition of claim 1, wherein said polyether urethane acrylate oligomer is one or two selected from the group consisting of damass BR-374 and damass BR-344.
5. The elastic photosensitive resin composition of claim 1, wherein said first monomer is one or two selected from the group consisting of dimethylaminopropyl acrylamide and hydroxyethyl methacrylate.
6. The elastic photosensitive resin composition of claim 1, wherein said second monomer is one or two selected from the group consisting of acryloyl morpholine and tetrahydrofurfuryl methacrylate.
7. The elastic photosensitive resin composition according to claim 1,
the first monomer is dimethylaminopropyl acrylamide and the second monomer is selected from one or two of acryloyl morpholine and methacryloyl morpholine, and preferably the second monomer is acryloyl morpholine; or
The first monomer is hydroxyethyl methacrylate and the second monomer is selected from one or two of tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate, and preferably the second monomer is tetrahydrofurfuryl methacrylate.
8. The elastic photosensitive resin composition of claim 1, wherein said initiator is phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
9. The elastic photosensitive resin composition according to claim 1,
the polyether urethane acrylate oligomer is Damas BR-374, and the monomer comprises dimethylamino propyl acrylamide and acryloyl morpholine in a molar ratio of 1:1 to 2: 1; or
The polyether urethane acrylate oligomer is Damas BR-344 and the monomers comprise hydroxyethyl methacrylate and tetrahydrofurfuryl methacrylate in a molar ratio of 1:1 to 2: 1.
10. A resin material or a resin article obtained by curing the elastic photosensitive resin composition according to any one of claims 1 to 9.
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| CN111040102A (en) * | 2019-12-02 | 2020-04-21 | 中国科学院福建物质结构研究所 | Photosensitive resin and preparation method and application thereof |
| CN113105590A (en) * | 2021-04-12 | 2021-07-13 | 泉州师范学院 | Photosensitive resin composition for photocuring 3D printing elastomer and preparation method thereof |
| CN113174016A (en) * | 2021-03-01 | 2021-07-27 | 广东工业大学 | Low-viscosity flexible photosensitive resin for 3D printing and preparation method and application thereof |
| CN113388073A (en) * | 2020-03-13 | 2021-09-14 | 中国石油化工股份有限公司 | Photocurable flexible photosensitive resin, preparation method of photocurable flexible photosensitive resin, 3D printing product and preparation method of 3D printing product |
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| JP6086358B1 (en) * | 2016-01-19 | 2017-03-01 | 東洋インキＳｃホールディングス株式会社 | Ultraviolet curable resin composition and laminate |
| CN108727550A (en) * | 2018-04-23 | 2018-11-02 | 浙江锐胜新材料有限公司 | A kind of photosensitive resin and its application |
| CN111040102A (en) * | 2019-12-02 | 2020-04-21 | 中国科学院福建物质结构研究所 | Photosensitive resin and preparation method and application thereof |
| CN113388073A (en) * | 2020-03-13 | 2021-09-14 | 中国石油化工股份有限公司 | Photocurable flexible photosensitive resin, preparation method of photocurable flexible photosensitive resin, 3D printing product and preparation method of 3D printing product |
| CN113174016A (en) * | 2021-03-01 | 2021-07-27 | 广东工业大学 | Low-viscosity flexible photosensitive resin for 3D printing and preparation method and application thereof |
| CN113105590A (en) * | 2021-04-12 | 2021-07-13 | 泉州师范学院 | Photosensitive resin composition for photocuring 3D printing elastomer and preparation method thereof |
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