CN111690096A - Preparation method of 3D printing photosensitive resin material - Google Patents
Preparation method of 3D printing photosensitive resin material Download PDFInfo
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- CN111690096A CN111690096A CN202010423835.3A CN202010423835A CN111690096A CN 111690096 A CN111690096 A CN 111690096A CN 202010423835 A CN202010423835 A CN 202010423835A CN 111690096 A CN111690096 A CN 111690096A
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- 229920005989 resin Polymers 0.000 title claims abstract description 64
- 239000011347 resin Substances 0.000 title claims abstract description 64
- 238000010146 3D printing Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 31
- -1 acrylic ester Chemical class 0.000 claims abstract description 19
- 239000003085 diluting agent Substances 0.000 claims abstract description 19
- 150000003254 radicals Chemical class 0.000 claims abstract description 19
- 239000012952 cationic photoinitiator Substances 0.000 claims abstract description 17
- 239000012949 free radical photoinitiator Substances 0.000 claims abstract description 16
- 238000001723 curing Methods 0.000 claims abstract description 14
- 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 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 11
- 229920002635 polyurethane Polymers 0.000 claims abstract description 11
- 150000005839 radical cations Chemical class 0.000 claims abstract description 7
- 238000000016 photochemical curing Methods 0.000 claims abstract description 5
- 239000003607 modifier Substances 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 16
- 238000007639 printing Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 238000003760 magnetic stirring Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical group C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 3
- ZXUJYIQZKNWLQN-UHFFFAOYSA-N [3-(7-oxabicyclo[4.1.0]heptan-3-ylmethyl)-7-oxabicyclo[4.1.0]heptan-3-yl] formate Chemical compound C(=O)OC1(CC2C(CC1)O2)CC1CC2C(CC1)O2 ZXUJYIQZKNWLQN-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 239000004925 Acrylic resin Substances 0.000 abstract 1
- 229920000178 Acrylic resin Polymers 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000001739 density measurement Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VUXKVKAHWOVIDN-UHFFFAOYSA-N Cyclohexyl formate Chemical compound O=COC1CCCCC1 VUXKVKAHWOVIDN-UHFFFAOYSA-N 0.000 description 1
- 241001411320 Eriogonum inflatum Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- C08F283/006—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
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of a free radical-cation hybrid curing type 3D printing photocuring resin. The polyurethane acrylic resin is mainly prepared by taking acrylic ester and epoxy resin as prepolymers and taking polyurethane acrylic ester (PUA) as a modifier. The light-cured resin is prepared from the following raw materials in parts by mass: acrylate ester: 20-60 parts of epoxy resin: 20-60 parts of urethane acrylate: 5.3-40 parts of free radical reactive diluent: 8-32 parts of cationic photoinitiator: 1.2-4 parts of free radical photoinitiator: 1.2-4 parts. The invention adopts acrylic ester as a free radical type prepolymer, 3, 4-epoxy cyclohexyl methyl-3, 4 epoxy cyclohexyl formic ether as a cationic prepolymer, and adds an active diluent and a photoinitiator to prepare the free radical-cationic hybrid curing type photosensitive resin, the tensile strength is improved by 50.22 percent (as shown in an abstract figure), the gel fraction is improved by about 2 percent, the thermal stability is improved, the viscosity is moderate, and the shrinkage rate meets the requirements. The preparation method is simple, and the use of the urethane acrylate solves the problems that the 3D printing material is relatively single in material type, has performance which does not meet the requirements of large-scale industrial production and is high in cost. And the development of 3D printing photocuring materials in China can be promoted.
Description
Technical Field
The invention belongs to the technical field of 3D printing material preparation, and particularly relates to a preparation method of a photosensitive resin material suitable for 3D printing.
Background
3D printing is a rapid prototyping additive manufacturing technology. The technical principle is dispersion and accumulation. Compared with the traditional material reducing manufacturing process, the 3D printing technology digitalizes the entity structure by means of the digital modeling technology, and then drives the printing equipment to perform refined processing through the electromechanical control technology, and a mold is not needed during production, so that high-precision and high-difficulty products can be manufactured conveniently, the forming speed is high, the manufacturing period is short, small-batch and personalized production on demand can be realized, the production cost and time are saved, the production efficiency is improved, the production waste is reduced, and the environment is protected. Therefore, the 3D printing technology has been rapidly developed since the 20 th century and the 80 th era, has been widely applied to various fields such as industrial design, aerospace, biomedical, food and the like, and is considered as one of the core technologies of the third industrial revolution. The global 3D printing industry is expected to remain a rapidly growing momentum in the future. According to the data disclosed by the China industry information network, the China 3D printing industry market can keep a higher growth rate, and is expected to get away from the global 3D printing market.
Photosensitive resins are used as raw materials for photocuring techniques, and their properties have a direct and important influence on the printing process and the properties of the cured product. The photosensitive resin consists of prepolymer, reactive diluent, photoinitiator and additive. The photoinitiator in the photosensitive resin generates free radicals or cation active centers under the irradiation of ultraviolet light, so that the prepolymer is activated and undergoes chain polymerization reaction to be cured. The photosensitive resin does not need to be heated in the curing process, and no solvent is volatilized, so that the utilization rate is close to 100 percent, and the photosensitive resin is an energy-saving and environment-friendly material. However, the mechanical property and heat resistance of the hybrid curing photosensitive resin need to be improved, and the shrinkage rate of the product cannot meet the requirement. The urethane acrylate molecule contains acrylate functional group and urethane bond, and has the advantages of both urethane and acrylate, the cured product has good flexibility, high adhesive force and good compatibility with other resins, and because the urethane acrylate has slow curing speed and relatively high price, the urethane acrylate is generally used as auxiliary functional resin.
Therefore, on the basis of the current research situation and development prospect of 3D printing photosensitive resin at home and abroad, according to the characteristics and requirements of 3D printing technology forming, practical photosensitive resin with higher tensile strength and hardness and lower shrinkage is developed, so that the import dependence of 3D printing materials is reduced, the quality of 3D printing formed products is improved, and the development trend of 3D printing photosensitive resin at home and abroad is reached.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a hybrid curing type photosensitive resin material suitable for 3D printing, and the preparation process is simple. The tensile strength of the photosensitive resin can be obviously improved by adding the urethane acrylate; the gel rate of the photosensitive resin prepared by the invention is high; the viscosity is moderate, the fluidity is stable, 3D printing is more convenient, and the forming is easier; the shrinkage rate meets the requirement, and the thermal stability is also obviously improved, so that the quality of the 3D printing formed product is improved.
The invention solves the technical problems by the following technical scheme:
the invention relates to a preparation method of a photosensitive resin material suitable for 3D printing, which is mainly prepared from acrylate, 3, 4-epoxy cyclohexyl methyl-3, 4 epoxy cyclohexyl formate and urethane acrylate. During preparation, the components with certain mass are weighed in a beaker by using an analytical balance, stirred for 30 minutes by magnetic force, defoamed for 30 minutes by ultrasonic vibration, and stored in a dark place for later use.
The preparation method of the free radical-cation hybrid photosensitive resin comprises the following steps: acrylate ester: 20-60 parts of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate: 20-60 parts of free radical reactive diluent: 8-32 parts of cationic photoinitiator: 1.2-4 parts of free radical photoinitiator: 1.2-4 parts.
The preparation method of the modifier comprises the following steps: urethane acrylate: 5.3 to 40 portions of
The preparation process comprises the following steps:
s1, weighing: weighing a certain mass of acrylate, epoxy resin, polyurethane acrylate, a free radical reactive diluent, a cationic photoinitiator and a free radical photoinitiator on an analytical balance in a 500ml beaker;
s2, blending: blending the raw materials in the step 1 by adopting magnetic stirring, wrapping a beaker by using tinfoil during stirring, and performing magnetic stirring for 30 minutes at a rotating speed of 300 revolutions per minute to obtain blended raw materials;
s3, ultrasound: carrying out ultrasonic treatment on the uniformly mixed raw materials in the step 2 in an ice bath for 30 min;
s4, storage: and (4) storing the uniform mixture subjected to ultrasonic treatment in the step (3) at normal temperature in a dark place.
S5, printing and forming of products: and (3) precisely printing the high-quality photosensitive resin in the step (2) under the control of a pre-designed digital three-dimensional model of a real object, and cooling to obtain a finished product.
The free radical active diluent is tripropylene glycol diacrylate, the cationic photoinitiator is triarylsulfonium salt, and the free radical photoinitiator is 2, 2-dimethyl-alpha-hydroxyacetophenone.
The invention has the following beneficial effects:
(1) the 3D printing photosensitive resin material contains pure acrylate, and has very good adhesive force and flexibility.
(2) The 3D printing photosensitive resin material contains 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl formic ether, so that the fluidity can be obviously improved, and the use of organic solvents can be reduced; the finished product has good weather resistance, water resistance and alkali resistance; the curing shrinkage rate of the product can be reduced; the thermal stability is good, and the prepared finished product has excellent stability. Therefore, the stability of the surface shape of the 3D printing photosensitive resin material can be improved, and the appearance is more stable, unique and attractive.
(3) The 3D printing photosensitive resin material contains urethane acrylate, and can remarkably improve the mechanical property, flexibility, chemical resistance and high and low temperature resistance of a cured product. Thereby widening the application range of the product.
(4) According to the invention, 3D printing can be directly carried out by defoaming treatment after all components are fully and uniformly mixed.
(5) According to the invention, after the raw materials are fully and uniformly mixed, defoaming treatment is carried out, and the printing ink can be directly used for 3D printing. The process is very simple. The prepared 3D printing photosensitive resin material has high gel rate; the viscosity is moderate, the fluidity is stable, 3D printing is more convenient, and the forming is easier; the shrinkage rate meets the requirement, and the thermal stability is also obviously improved. Therefore, the invention can improve the quality of 3D printing and forming products, the printed products are not easy to turn yellow and whitish, the 3D printing products with diversified creative manufacture, high precision, complex curved surfaces and unique modeling can be realized, the traditional mould pouring mode is overturned, the mould constraint is completely eliminated, and the personalized customization market of people is satisfied.
Drawings
FIG. 1 is a graph of the effect of the mass fraction of PUA on viscosity; FIG. 2 is the effect of the mass fraction of PUA on the gel fraction; FIG. 3 is the effect of mass fraction of PUA on shrinkage; FIG. 4 is a graph of the effect of mass fraction of PUA on Shore hardness; FIG. 5 is the effect of the mass fraction of PUA on the tensile Strength
Detailed Description
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
The free radical reactive diluent described in the examples below is tripropylene glycol diacrylate, the cationic photoinitiator is a triarylsulfonium salt, and the free radical photoinitiator is 2, 2-dimethyl-alpha-hydroxyacetophenone.
Example 1:
the raw materials required by the 3D printing photosensitive resin material of the embodiment are as follows in parts by weight: acrylate ester: 28 parts of epoxy resin: 28 parts, urethane acrylate: 5.6 parts, free radical reactive diluent: 9 parts, cationic photoinitiator: 1.3 parts, free radical photoinitiator: 1.3 parts.
The preparation method comprises the following steps:
s1, weighing: weighing a certain mass of acrylate, epoxy resin, polyurethane acrylate, a free radical reactive diluent, a cationic photoinitiator and a free radical photoinitiator on an analytical balance in a 500ml beaker;
s2, blending: blending the raw materials in the step 1 by adopting magnetic stirring, wrapping a beaker by using tinfoil during stirring, and performing magnetic stirring for 30 minutes at a rotating speed of 300 revolutions per minute to obtain blended raw materials;
s3, ultrasound: carrying out ultrasonic treatment on the uniformly mixed raw materials in the step 2 in an ice bath for 30 min;
s4, storage: and (4) storing the uniform mixture subjected to ultrasonic treatment in the step (3) at normal temperature in a dark place.
S5, printing and forming of products: and (3) precisely printing the high-quality photosensitive resin in the step (2) in 3D under the control of a digital three-dimensional model of a predesigned real object, and cooling to obtain a finished product with the tensile strength of 23.63MPa, the volume shrinkage of 4.26% and the gel fraction of 89.7%.
Example 2:
the raw materials required by the 3D printing photosensitive resin material of the embodiment are as follows in parts by weight: the raw materials required by the 3D printing photosensitive resin material of the embodiment are as follows in parts by weight: acrylate ester: 37 parts of epoxy resin: 37 parts, urethane acrylate: 11.1 parts, free radical reactive diluent: 15 parts, cationic photoinitiator: 1.85 parts, free radical photoinitiator: 1.85 parts.
The preparation method comprises the following steps:
s1, weighing: weighing a certain mass of acrylate, epoxy resin, polyurethane acrylate, a free radical reactive diluent, a cationic photoinitiator and a free radical photoinitiator on an analytical balance in a 500ml beaker;
s2, blending: blending the raw materials in the step 1 by adopting magnetic stirring, wrapping a beaker by using tinfoil during stirring, and performing magnetic stirring for 30 minutes at a rotating speed of 300 revolutions per minute to obtain blended raw materials;
s3, ultrasound: carrying out ultrasonic treatment on the uniformly mixed raw materials in the step 2 in an ice bath for 30 min;
s4, storage: and (4) storing the uniform mixture subjected to ultrasonic treatment in the step (3) at normal temperature in a dark place.
S5, printing and forming of products: and (3) precisely printing the high-quality photosensitive resin in the step (2) in 3D under the control of a digital three-dimensional model of a predesigned real object, and cooling to obtain a finished product with the stretching lightness of 24.99MPa, the volume shrinkage of 5.19 percent and the gel fraction of 91.22 percent.
Example 3:
the raw materials required by the 3D printing photosensitive resin material of the embodiment are as follows in parts by weight: the raw materials required by the 3D printing photosensitive resin material of the embodiment are as follows in parts by weight: acrylate ester: 43 parts of epoxy resin: 43 parts, urethane acrylate: 17.2 parts, free radical reactive diluent: 18 parts, cationic photoinitiator: 2.15 parts, free radical photoinitiator: 2.15 parts.
The preparation method comprises the following steps:
s1, weighing: weighing a certain mass of acrylate, epoxy resin, polyurethane acrylate, a free radical reactive diluent, a cationic photoinitiator and a free radical photoinitiator on an analytical balance in a 500ml beaker;
s2, blending: blending the raw materials in the step 1 by adopting magnetic stirring, wrapping a beaker by using tinfoil during stirring, and performing magnetic stirring for 30 minutes at a rotating speed of 300 revolutions per minute to obtain blended raw materials;
s3, ultrasound: carrying out ultrasonic treatment on the uniformly mixed raw materials in the step 2 in an ice bath for 30 min;
s4, storage: and (4) storing the uniform mixture subjected to ultrasonic treatment in the step (3) at normal temperature in a dark place.
S5, printing and forming of products: and (3) precisely printing the high-quality photosensitive resin in the step (2) in 3D under the control of a digital three-dimensional model of a predesigned real object, and cooling to obtain a finished product with the tensile strength of 26.80MPa, the volume shrinkage of 5.43 percent and the gel fraction of 94.67 percent.
Example 4:
the raw materials required by the 3D printing photosensitive resin material of the embodiment are as follows in parts by weight: the raw materials required by the 3D printing photosensitive resin material of the embodiment are as follows in parts by weight: the raw materials required by the 3D printing photosensitive resin material of the embodiment are as follows in parts by weight: acrylate ester: 58 parts of epoxy resin: 58 parts of polyurethane acrylate: 29 parts, free radical reactive diluent: 18 parts, cationic photoinitiator: 2.15 parts, free radical photoinitiator: 2.15 parts.
The preparation method comprises the following steps:
s1, weighing: weighing a certain mass of acrylate, epoxy resin, polyurethane acrylate, a free radical reactive diluent, a cationic photoinitiator and a free radical photoinitiator on an analytical balance in a 500ml beaker;
s2, blending: blending the raw materials in the step 1 by adopting magnetic stirring, wrapping a beaker by using tinfoil during stirring, and performing magnetic stirring for 30 minutes at a rotating speed of 300 revolutions per minute to obtain blended raw materials;
s3, ultrasound: carrying out ultrasonic treatment on the uniformly mixed raw materials in the step 2 in an ice bath for 30 min;
s4, storage: and (4) storing the uniform mixture subjected to ultrasonic treatment in the step (3) at normal temperature in a dark place.
S5, printing and forming of products: and (3) precisely printing the high-quality photosensitive resin in the step (2) in 3D under the control of a digital three-dimensional model of a predesigned real object, and cooling to obtain a finished product with the tensile strength of 16.04MPa, the volume shrinkage of 5.71 percent and the gel fraction of 95.16 percent.
The above description should not be taken as limiting the invention to the embodiments, but rather, as will be apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which shall be deemed to fall within the scope of the invention as defined by the claims appended hereto.
The 3D printing photosensitive resin materials prepared in examples 1-4 were subjected to performance testing as follows:
measurement of viscosity:
the viscosity (mPas) of the resin solution at 25 ℃ was measured using a rotary viscometer model NDJ-79. And injecting the resin liquid to be tested into the container until the rotor can be completely immersed in the liquid, reading the stable pointer to be tested, and multiplying the stable pointer to be tested by the coefficient of the sub-meter to obtain the viscosity of the resin liquid. Triplicate experiments were performed and the arithmetic mean was taken as the final viscosity.
Testing of gel fraction:
the gel fraction can be used to measure the curing degree of the photosensitive resin in the same time of ultraviolet irradiation. Casting a quantity of photosensitive resin onto the polytetrafluoroethyleneAnd (3) curing the mixture in an olefin mold for 2 minutes under an ultraviolet light source. The mass M of the cured sample is weighed on an analytical balance1And g. Soaking the sample in sufficient acetone to remove uncured resin liquid, taking out the sample after 24 hours, drying in a 45 ℃ forced air drying oven for 4 hours, and weighing the mass M of the dried resin solid2And g. The gel fraction is calculated as follows:
measurement of linear shrinkage:
a certain amount of photosensitive resin is cast in a polytetrafluoroethylene mold with the thickness of 80mm multiplied by 10mm multiplied by 4mm, the polytetrafluoroethylene mold is placed under an ultraviolet light source for curing for 3 minutes, and the length L and mm of a cured product are measured by an electronic digital display caliper. The calculation formula of the linear shrinkage is as follows:
measurement of volume shrinkage:
according to the method such as Ponzenzhen et al, distilled water is selected as a reference substance, and the density of the resin before and after curing is measured by a pycnometer method, thereby obtaining the volume shrinkage.
(1) Liquid density measurement
The mass m, g of the dry pycnometer was weighed on an analytical balance. Taking out the bottle, injecting distilled water, placing in a 25 deg.C constant temperature water bath, plugging the bottle plug after the liquid temperature in the bottle is stabilized at 25 deg.C, wiping off water overflowing from the capillary tube with filter paper while keeping the outside of the bottle body dry, placing in an analytical balance, and weighing to obtain a mass m0And g. Pouring distilled water in the empty bottle, drying the pycnometer, filling the pycnometer with the resin liquid to be measured, and weighing the mass m of the pycnometer and the resin liquid by the same method1And g. Density of resin liquid rho1Is represented by the formula (2-3), p0＝0.97705g/cm3The density of water at 25 ℃.
(2) Solid density measurement
The mass m of the cured product was weighed out with an analytical balance2And g. Then placing the condensate into a pycnometer, filling with 25 deg.C distilled water, plugging a bottle stopper, wiping the outside of the bottle body with filter paper to dry, placing into an analytical balance, and weighing to obtain a mass m3And g. Density of cured product [ rho ]2The formula of (2) is as follows:
from this, the volume shrinkage can be determined:
testing of Shore hardness:
according to GB/T2411-2008, a cured product with the thickness of 6mm is placed on a firm plane, and a pressing pin of a Shore durometer is vertically pressed into a test sample until the pressing pin completely contacts the test sample for 1s, and the reading is carried out. Each measuring point is at least 6mm away, the hardness values are measured for 5 times at different positions, and the arithmetic mean value is taken as the final hardness, and the unit is HD.
Testing of tensile properties:
the cured article was tested for tensile strength, elongation at break and Young's modulus using a universal material tester at 25 ℃. Casting a certain amount of photosensitive resin in a polytetrafluoroethylene mould with the thickness of 100mm multiplied by 10mm, placing the solidified photosensitive resin in a forced air drying oven with the temperature of 45 ℃ for drying for 24 hours, taking out the solidified photosensitive resin, and polishing the sample by using sand paper to be smooth so as to ensure that the surfaces of all samples have no cracks or other defects. And measuring the thickness of the sample in the gauge length by using a digital caliper, wherein the gauge length is set to be 50mm, and the speed is set to be 10 mm/min. Each group was tested in parallel 5 times and the average was taken as the final result.
Tensile Strength is the maximum stress that a specimen can withstand in the direction of stretching during stretching, expressed as σb(MPa) is calculated as follows. In the formula: f-breaking load, N; b-width of sample, mm; d-testSample thickness, mm.
The elongation at break is the ratio of the length of the elongated portion of the specimen stretched during the stretching process to the original length of the specimen after the specimen was broken, and is represented by e (%), and is calculated by the following formula. In the formula: l is0-initial gauge length of the specimen, mm; l-the distance between lines at the time of sample breakage, mm; -tensile strain, dimension 1.
The tensile modulus of elasticity, i.e., Young's modulus, is expressed as E (MPa) and is calculated as follows. The young's modulus measures the degree of difficulty of the material in elastic deformation, and the larger the young's modulus is, the larger the stress for causing the material to elastically deform to a certain extent is, i.e., the higher the rigidity of the material is.
Claims (7)
1. A preparation method of a free radical-cation hybrid curing type 3D printing photosensitive resin suitable for a 3D printing photocuring technology is characterized by mainly preparing the photosensitive resin from acrylate, 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl formate and polyurethane acrylate.
2. When the preparation method is used, the free radical-cation hybrid photosensitive resin is firstly prepared, and then the polyurethane acrylate is added into the prepared hybrid photosensitive resin for blending modification.
3. The preparation method of the free radical-cation hybrid photosensitive resin comprises the following steps: acrylate ester: 20-60 parts of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate: 20-60 parts of free radical reactive diluent: 8-32 parts of cationic photoinitiator: 1.2-4 parts of free radical photoinitiator: 1.2-4 parts.
4. The preparation method of the modifier comprises the following steps: urethane acrylate: 5.3 to 40 portions of the raw materials,
the preparation process comprises the following steps:
the method comprises the following steps: weighing: weighing a certain mass of acrylate, epoxy resin, a free radical reactive diluent, polyurethane acrylate, a cationic photoinitiator and a free radical photoinitiator on an analytical balance in a 500ml beaker;
the preparation process comprises the following steps:
step two: blending: blending the raw materials in the step 1 by adopting magnetic stirring, wrapping the beaker by using tinfoil during stirring, and performing magnetic stirring for 35-35 minutes at the rotating speed of 200-400 revolutions per minute to obtain the blended raw materials;
preparation process
Step three: ultrasonic: carrying out ultrasonic treatment on the uniformly mixed raw materials in the step 2 in an ice bath for 30min under the power of 1000W;
the preparation process comprises the following steps:
step four: and (3) storage: and (4) storing the uniform mixture subjected to ultrasonic treatment in the step (3) at normal temperature in a dark place.
5. The preparation process comprises the following steps:
step five: printing and forming a product: and (5) accurately performing 3D printing on the uniformly mixed photosensitive resin in the step S2 under the control of a digital three-dimensional model of a pre-designed real object, and curing for 3-5 minutes under 405nm ultraviolet light to obtain a finished product.
6. The method for preparing the radical-cation hybrid curing type 3D printing photosensitive resin suitable for the 3D printing photocuring technology according to claim 1, wherein the radical-active diluent is tripropylene glycol diacrylate, the cationic photoinitiator is triarylsulfonium salt, and the radical photoinitiator is 2, 2-dimethyl-alpha-hydroxyacetophenone.
7. The radical-cation hybrid photosensitive resin according to claim 1, wherein the preferred ratio of the selected raw materials is as follows: acrylate ester: 43 parts of epoxy resin: 43 parts, urethane acrylate: 17.2 parts, free radical reactive diluent: 18 parts, cationic photoinitiator: 2.15 parts, free radical photoinitiator: 2.15 parts.
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| CN112174575A (en) * | 2020-09-27 | 2021-01-05 | 嘉兴饶稷科技有限公司 | Photocuring clay printing material and preparation method thereof |
| CN112480851A (en) * | 2020-11-23 | 2021-03-12 | 华南理工大学 | UV (ultraviolet) adhesive for reducing curing shrinkage and preparation method thereof |
| CN112608429A (en) * | 2020-12-03 | 2021-04-06 | 深圳市匠和新材料有限公司 | Pretreatment dual-curing 3D printing resin and pretreatment method thereof |
| CN116144134A (en) * | 2023-03-14 | 2023-05-23 | 吉林大学 | 3D printing polyether-ether-ketone-containing antibacterial fluid photosensitive resin and preparation method thereof |
| CN116144134B (en) * | 2023-03-14 | 2024-07-26 | 吉林大学 | 3D printing polyether-ether-ketone-containing antibacterial fluid photosensitive resin and preparation method thereof |
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