CN111690224A - Novel photosensitive resin suitable for photocuring forming 3D printing technology - Google Patents
Novel photosensitive resin suitable for photocuring forming 3D printing technology Download PDFInfo
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- CN111690224A CN111690224A CN202010425891.0A CN202010425891A CN111690224A CN 111690224 A CN111690224 A CN 111690224A CN 202010425891 A CN202010425891 A CN 202010425891A CN 111690224 A CN111690224 A CN 111690224A
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- 239000011347 resin Substances 0.000 title claims abstract description 92
- 229920005989 resin Polymers 0.000 title claims abstract description 92
- 238000010146 3D printing Methods 0.000 title claims abstract description 21
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 14
- 238000005516 engineering process Methods 0.000 title claims abstract description 12
- 238000001723 curing Methods 0.000 claims abstract description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 34
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims abstract description 34
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920002635 polyurethane Polymers 0.000 claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 17
- 239000002699 waste material Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 11
- DBYQGTLFSQKPCA-UHFFFAOYSA-N 4-hydroxy-5-methyl-2-propylfuran-3-one Chemical compound CCCC1OC(C)=C(O)C1=O DBYQGTLFSQKPCA-UHFFFAOYSA-N 0.000 claims abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 35
- 240000003183 Manihot esculenta Species 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000004042 decolorization Methods 0.000 claims description 7
- 239000003814 drug Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000007781 pre-processing Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims 2
- 239000003517 fume Substances 0.000 claims 1
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 239000004925 Acrylic resin Substances 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 241000658379 Manihot esculenta subsp. esculenta Species 0.000 abstract 1
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 238000009423 ventilation Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 206010040880 Skin irritation Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 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
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2399/00—Characterised by the use of natural macromolecular compounds or of derivatives thereof not provided for in groups C08J2301/00 - C08J2307/00 or C08J2389/00 - C08J2397/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2499/00—Characterised by the use of natural macromolecular compounds or of derivatives thereof not provided for in groups C08J2401/00 - C08J2407/00 or C08J2489/00 - C08J2497/00
Abstract
The invention discloses a novel photosensitive resin suitable for a photocuring molding 3D printing technology, which is prepared from the following raw materials in parts by weight: 10-20 parts of difunctional acrylate oligomer (JAZO-401), 10-20 parts of hexafunctional polyurethane acrylate (JAZO-303), 20-40 parts of tripropylene glycol diacrylate (TPGDA), 0.5-2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 10-40 parts of waste cassava residue. The free radical polymerization type photosensitive resin containing two oligomers is synthesized by the scheme, the mechanical property of the resin is greatly improved compared with that of pure acrylate resin with a single component, the cost can be reduced, and another way is provided for high-valued utilization of wastes; the waste fiber reinforced photosensitive resin has the characteristics of high reactivity, high gel rate (the gel content reaches 99.22%), good mechanical properties (the elongation at break is 4.97%, the tensile strength is 28.98 MPa, the elastic modulus is 841.11 MPa), low requirements on curing equipment and environment and the like.
Description
Technical Field
The invention belongs to the technical field of 3D printing, and particularly relates to preparation of novel photosensitive resin suitable for a photocuring forming 3D printing technology.
Background
The photocuring molding 3D printing technology takes a computer three-dimensional design model as a blueprint, and by means of a software layering dispersion and numerical control molding system, photosensitive resin materials are irradiated by ultraviolet light to cause photosensitive resin to be polymerized in a radiation mode to form cross-linked polymers, so that solid entity products are manufactured. The photosensitive resin has the characteristics of economy, high efficiency, environmental protection, energy conservation, strong adaptability and the like, and has wide application and wide market in the fields of packaging printing, automobile industry, medical health, aerospace, electronic communication and the like.
At present, the existing photosensitive resin has high cost, and has the problems of low hardness, poor heat resistance, poor mechanical property and the like after photocuring a formed part, and the inherent defects cause that the formed part can not be directly used as a functional part, thereby limiting the application range of photocuring forming materials. The cassava residue contains cellulose, and the cellulose has good toughness, dispersibility and chemical stability and can serve as a reinforcing agent in photosensitive resin modification. In view of the insufficient research on photosensitive resin at present in China, the photosensitive resin is still in the exploration stage in some aspects
Therefore, the photosensitive resin with better performance is prepared by utilizing the existing raw materials, a novel photosensitive resin formula and a preparation process thereof are explored, and the experiences are accumulated for the related research of the photocuring resin in China.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a formula and a preparation process of a novel photosensitive resin suitable for a photocuring molding 3D printing technology, the scheme synthesizes a free radical polymerization type photosensitive resin containing two oligomers, the performance of the photosensitive resin is greatly improved compared with that of a pure acrylate resin with a single component, the cost can be reduced, and another way is provided for high-valued utilization of wastes; the waste fiber reinforced photosensitive resin has the characteristics of high reactivity, high gel rate, good mechanical property, low requirements on curing equipment and environment and the like.
The invention solves the technical problems by the following technical scheme:
the invention relates to a novel photosensitive resin suitable for a photocuring molding 3D printing technology, which is prepared from the following raw materials in parts by weight: 10-20 parts of difunctional acrylate oligomer (JAZO-401), 10-20 parts of hexafunctional polyurethane acrylate (JAZO-303), 20-40 parts of tripropylene glycol diacrylate (TPGDA), 0.5-2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 10-40 parts of waste cassava residue.
The preparation method comprises the following operation steps:
s1, preprocessing: adding the purchased industrial cassava residue into 10-15% hydrogen peroxide, cleaning in an ultrasonic cleaner with ultrasonic power of 60W and temperature of 50-60 deg.C for 30-40min, performing auxiliary decolorization, washing with distilled water, vacuum filtering, and repeating twice. Then putting the mixture into an oven to be dried to constant weight at 105 ℃, crushing the mixture and sieving the crushed mixture with a 60-mesh sieve for later use;
s2, weighing: accurately weighing 1173-5% photoinitiator, pure acrylate oligomer (JAZO-401), polyurethane acrylate (JAZO-303) and TPGDA (reactive diluent) in a ventilated kitchen by using an analytical balance, and placing in a container to be protected from light and sealed for later use;
s3, mixing: placing the resin mixture weighed in the step S2 on a digital display constant temperature magnetic stirrer, stirring for 30-60min at a constant temperature of 60 ℃ and a speed of 200 plus materials and 300rpm, adding the pretreated cassava residues, continuously stirring for 30-60min at a normal temperature and a speed of 300 plus materials and 400rpm, wherein the obtained colorless transparent liquid is the prepared liquid photosensitive resin, placing a medicine bottle containing the liquid photosensitive resin in an ultrasonic cleaner for ultrasonic treatment for 30-40min, removing bubbles, and placing in a dark place for later use;
s4, film formation: adding the resin mixed in the step S3 into a polytetrafluoroethylene mold, wherein the height of the liquid resin is about half of the depth of the mold, the mold is placed on a horizontal table, and a few bubbles in the mixed resin can be blown through by a aurilave;
s5, curing: curing the mold filled with the liquid photosensitive resin under an ultraviolet lamp with power of 80W and peak wavelength of 365nm for 3-5min, wherein the curing irradiation height of the ultraviolet lamp is 10cm, and the resin sheet in the mold is taken out after the curing is finished;
the invention has the following beneficial effects:
(1) the 3D printing photosensitive resin comprises the following components: the oligomer, the photoinitiator, the reactive diluent and the like have low skin irritation, low toxicity and low price, protect the human health to the maximum extent and save the cost;
(2) the invention aims to fully utilize waste cellulose resources and improve the solid loading capacity of cellulose in the 3D printing photosensitive resin;
(2) the 3D printing photosensitive resin contains cellulose components of cassava residues, can improve the mechanical property of a formed part, and obviously improves the tensile strength and Young modulus.
Detailed Description
In the preparation raw materials, difunctional acrylate oligomer (JAZO-401), hexafunctional polyurethane acrylate (JAZO-303) and tripropylene glycol diacrylate (TPGDA) are adopted as main materials, 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and waste cassava residue are adopted as auxiliary agents, and the main materials and the auxiliary agents are prepared from the following raw materials in parts by weight: 10-20 parts of difunctional acrylate oligomer (JAZO-401), 10-20 parts of hexafunctional polyurethane acrylate (JAZO-303), 20-40 parts of tripropylene glycol diacrylate (TPGDA), 0.5-2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 10-40 parts of waste cassava residue.
The following are specific embodiments of the present invention:
example 1
The raw materials are as follows according to the weight portion: 10 parts of difunctional acrylate oligomer (JAZO-401), 10 parts of hexafunctional polyurethane acrylate (JAZO-303), 40 parts of tripropylene glycol diacrylate (TPGDA), 1 part of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 39 parts of waste cassava residues;
the preparation method of the 3D printing photosensitive resin of the embodiment includes the following steps:
s1, preprocessing: adding the purchased industrial cassava residues into prepared hydrogen peroxide with the concentration of 10%, then putting the industrial cassava residues into an ultrasonic cleaner with the ultrasonic power of 60W and the temperature of 50-60 ℃ for cleaning for 30min, carrying out auxiliary decolorization, then washing with distilled water, carrying out suction filtration, and repeating twice. Then putting the mixture into an oven to be dried to constant weight at 105 ℃, crushing the mixture and sieving the crushed mixture with a 60-mesh sieve for later use;
s2, weighing: accurately weighing 1173% photoinitiator, pure acrylate oligomer (JAZO-401), polyurethane acrylate (JAZO-303) and reactive diluent TPGDA in a ventilated kitchen by using an analytical balance, and storing in a container in a dark place and in a sealed manner for later use;
s3, mixing: placing the resin mixture weighed in the step S2 on a digital display constant temperature magnetic stirrer, stirring for 30min at a constant temperature of 60 ℃ and a speed of 200rpm, adding the pretreated cassava residue, continuing stirring for 30min at a speed of 300rpm at a normal temperature, obtaining colorless transparent liquid which is the prepared liquid photosensitive resin, placing a medicine bottle containing the liquid photosensitive resin in an ultrasonic cleaner, carrying out ultrasonic treatment for 30min, removing bubbles, and placing in a dark place for later use;
s4, film formation: adding the resin mixed in the step S3 into a polytetrafluoroethylene mold, wherein the height of the liquid resin is about half of the depth of the mold, the mold is placed on a horizontal table, and a few bubbles in the mixed resin can be blown through by a aurilave;
s5, curing: curing the mold filled with the liquid photosensitive resin under an ultraviolet lamp with the power of 80W and the peak wavelength of 365nm, the curing irradiation height of the ultraviolet lamp being 10cm, and the curing time being 3min, turning off the ultraviolet lamp after curing is completed, and taking out the resin sheet in the mold;
example 2
The raw materials are as follows according to the weight portion: 20 parts of difunctional acrylate oligomer (JAZO-401), 20 parts of hexafunctional polyurethane acrylate (JAZO-303), 20 parts of tripropylene glycol diacrylate (TPGDA), 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 38 parts of waste cassava residues;
the preparation method of the 3D printing photosensitive resin of the embodiment includes the following steps:
s1, preprocessing: adding the purchased industrial cassava residues into prepared hydrogen peroxide with the concentration of 15%, then putting the industrial cassava residues into an ultrasonic cleaner with the ultrasonic power of 60W and the temperature of 50-60 ℃ for cleaning for 40min, carrying out auxiliary decolorization, then washing with distilled water, carrying out suction filtration, and repeating twice. Then putting the mixture into an oven to be dried to constant weight at 105 ℃, crushing the mixture and sieving the crushed mixture with a 60-mesh sieve for later use;
s2, weighing: accurately weighing 1173 photoinitiator with the concentration of 5%, pure acrylate oligomer (JAZO-401), polyurethane acrylate (JAZO-303) and reactive diluent TPGDA by using an analytical balance in a ventilation kitchen, and placing into a container to be protected from light and sealed for later use;
s3, mixing: placing the resin mixture weighed in the step S2 on a digital display constant temperature magnetic stirrer, stirring for 60min at a constant temperature of 60 ℃ and a speed of 300rpm, adding the pretreated cassava residue, continuing stirring for 60min at a speed of 400rpm at a normal temperature, obtaining colorless transparent liquid which is the prepared liquid photosensitive resin, placing a medicine bottle containing the liquid photosensitive resin in an ultrasonic cleaner, carrying out ultrasonic treatment for 40min, removing bubbles, and placing in a dark place for later use;
s4, film formation: adding the resin mixed in the step S3 into a polytetrafluoroethylene mold, wherein the height of the liquid resin is about half of the depth of the mold, the mold is placed on a horizontal table, and a few bubbles in the mixed resin can be blown through by a aurilave;
s5, curing: curing the mold filled with the liquid photosensitive resin under an ultraviolet lamp with the power of 80W and the peak wavelength of 365nm, the curing irradiation height of the ultraviolet lamp being 10cm, the curing time being 5min, turning off the ultraviolet lamp after curing is finished, and taking out the resin sheet in the mold;
example 3
The raw materials are as follows according to the weight portion: 20 parts of difunctional acrylate oligomer (JAZO-401), 20 parts of hexafunctional polyurethane acrylate (JAZO-303), 40 parts of tripropylene glycol diacrylate (TPGDA), 0.5 part of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 19.5 parts of waste cassava residues;
the preparation method of the 3D printing photosensitive resin of the embodiment includes the following steps:
s1, preprocessing: adding the purchased industrial cassava residues into prepared hydrogen peroxide with the concentration of 10%, then putting the industrial cassava residues into an ultrasonic cleaner with the ultrasonic power of 60W and the temperature of 60 ℃ for cleaning for 30min, carrying out auxiliary decolorization, then washing with distilled water, carrying out suction filtration, and repeating twice. Then putting the mixture into an oven to be dried to constant weight at 105 ℃, crushing the mixture and sieving the crushed mixture with a 60-mesh sieve for later use;
s2, weighing: accurately weighing 1173% photoinitiator, pure acrylate oligomer (JAZO-401), polyurethane acrylate (JAZO-303) and reactive diluent TPGDA in a ventilated kitchen by using an analytical balance, and storing in a container in a dark place and in a sealed manner for later use;
s3, mixing: placing the resin mixture weighed in the step S2 on a digital display constant temperature magnetic stirrer, stirring for 60min at a constant temperature of 60 ℃ and a speed of 300rpm, adding the pretreated cassava residues, continuing stirring for 60min at a speed of 300 plus 400rpm at a normal temperature, wherein the obtained colorless transparent liquid is the prepared liquid photosensitive resin, placing a medicine bottle containing the liquid photosensitive resin in an ultrasonic cleaner for ultrasonic treatment for 30min, removing bubbles, and placing in a dark place for later use;
s4, film formation: adding the resin mixed in the step S3 into a polytetrafluoroethylene mold, wherein the height of the liquid resin is about half of the depth of the mold, the mold is placed on a horizontal table, and a few bubbles in the mixed resin can be blown through by a aurilave;
s5, curing: curing the mold filled with the liquid photosensitive resin under an ultraviolet lamp with the power of 80W and the peak wavelength of 365nm, the curing irradiation height of the ultraviolet lamp being 10cm, the curing time being 5min, turning off the ultraviolet lamp after curing is finished, and taking out the resin sheet in the mold;
example 4
The raw materials are as follows according to the weight portion: 15 parts of difunctional acrylate oligomer (JAZO-401), 15 parts of hexafunctional polyurethane acrylate (JAZO-303), 30 parts of tripropylene glycol diacrylate (TPGDA), 1 part of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 39 parts of waste cassava residues.
The preparation method of the 3D printing photosensitive resin of the embodiment includes the following steps:
s1, preprocessing: adding the purchased industrial cassava residues into prepared hydrogen peroxide with the concentration of 15%, then putting the industrial cassava residues into an ultrasonic cleaner with the ultrasonic power of 60W and the temperature of 50-60 ℃ for cleaning for 40min, carrying out auxiliary decolorization, then washing with distilled water, carrying out suction filtration, and repeating twice. Then putting the mixture into an oven to be dried to constant weight at 105 ℃, crushing the mixture and sieving the crushed mixture with a 60-mesh sieve for later use;
s2, weighing: accurately weighing 1173 photoinitiator with the concentration of 5%, pure acrylate oligomer (JAZO-401), polyurethane acrylate (JAZO-303) and reactive diluent TPGDA by using an analytical balance in a ventilation kitchen, and placing into a container to be protected from light and sealed for later use;
s3, mixing: placing the resin mixture weighed in the step S2 on a digital display constant temperature magnetic stirrer, stirring for 60min at a constant temperature of 60 ℃ and a speed of 300rpm, adding the pretreated cassava residue, continuing stirring for 60min at a speed of 400rpm at a normal temperature, obtaining colorless transparent liquid which is the prepared liquid photosensitive resin, placing a medicine bottle containing the liquid photosensitive resin in an ultrasonic cleaner, carrying out ultrasonic treatment for 40min, removing bubbles, and placing in a dark place for later use;
s4, film formation: adding the resin mixed in the step S3 into a polytetrafluoroethylene mold, wherein the height of the liquid resin is about half of the depth of the mold, the mold is placed on a horizontal table, and a few bubbles in the mixed resin can be blown through by a aurilave;
s5, curing: curing the mold filled with the liquid photosensitive resin under an ultraviolet lamp with the power of 80W and the peak wavelength of 365nm, the curing irradiation height of the ultraviolet lamp being 10cm, the curing time being 5min, turning off the ultraviolet lamp after curing is finished, and taking out the resin sheet in the mold;
example 5
The raw materials are as follows according to the weight portion: 20 parts of difunctional acrylate oligomer (JAZO-401), 20 parts of hexafunctional polyurethane acrylate (JAZO-303), 38 parts of tripropylene glycol diacrylate (TPGDA), 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 20 parts of waste cassava residues.
The preparation method of the 3D printing photosensitive resin of the embodiment includes the following steps:
s1, preprocessing: adding the purchased industrial cassava residues into prepared hydrogen peroxide with the concentration of 12%, then putting the industrial cassava residues into an ultrasonic cleaner with the ultrasonic power of 60W and the temperature of 55 ℃ for cleaning for 35min, carrying out auxiliary decolorization, then washing with distilled water, carrying out suction filtration, and repeating twice. Then putting the mixture into an oven to be dried to constant weight at 105 ℃, crushing the mixture and sieving the crushed mixture with a 60-mesh sieve for later use;
s2, weighing: accurately weighing 1173 photoinitiator with the concentration of 4%, pure acrylate oligomer (JAZO-401), polyurethane acrylate (JAZO-303) and reactive diluent TPGDA by using an analytical balance in a ventilation kitchen, and placing into a container to be protected from light and sealed for later use;
s3, mixing: placing the resin mixture weighed in the step S2 on a digital display constant temperature magnetic stirrer, stirring for 50min at a constant temperature of 60 ℃ and a speed of 270rpm, adding the pretreated cassava residue, continuing stirring for 50min at a speed of 370rpm at a normal temperature, obtaining colorless transparent liquid which is the prepared liquid photosensitive resin, placing a medicine bottle containing the liquid photosensitive resin in an ultrasonic cleaner, carrying out ultrasonic treatment for 35min, removing bubbles, and placing in a dark place for later use;
s4, film formation: adding the resin mixed in the step S3 into a polytetrafluoroethylene mold, wherein the height of the liquid resin is about half of the depth of the mold, the mold is placed on a horizontal table, and a few bubbles in the mixed resin can be blown through by a aurilave;
s5, curing: curing the mold filled with the liquid photosensitive resin under an ultraviolet lamp with the power of 80W and the peak wavelength of 365nm, the curing irradiation height of the ultraviolet lamp being 10cm, and the curing time being 4min, turning off the ultraviolet lamp after curing is completed, and taking out the resin sheet in the mold;
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.
Claims (5)
1. A novel photosensitive resin suitable for a photocuring molding 3D printing technology is prepared from the following raw materials in parts by weight: 10-20 parts of difunctional acrylate oligomer (JAZO-401), 10-20 parts of hexafunctional polyurethane acrylate (JAZO-303), 20-40 parts of tripropylene glycol diacrylate (TPGDA), 0.5-2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 10-40 parts of waste cassava residue;
the preparation method comprises the following operation steps:
s1, preprocessing: adding purchased industrial cassava residue into prepared hydrogen peroxide, then putting into an ultrasonic cleaning instrument for cleaning for 30-40min, carrying out auxiliary decolorization, then washing with distilled water (the ratio of fiber to distilled water is 1:100(g/ml)), carrying out suction filtration, and repeating twice; then drying and sieving for later use;
s2, weighing: accurately weighing the diluted 1173 photoinitiator, the pure acrylate oligomer (JAZO-401), the polyurethane acrylate (JAZO-303) and the reactive diluent TPGDA in a fume hood by using an analytical balance, and placing the weighed materials into a container to be protected from light and sealed for later use;
s3, mixing: placing the resin mixture weighed in the step S2 on a digital display constant temperature magnetic stirrer for stirring at a constant temperature of 25 ℃, adding the cassava residue pretreated in the step S1, continuing stirring to obtain colorless transparent liquid, namely the prepared liquid photosensitive resin, placing a medicine bottle containing the liquid photosensitive resin in an ultrasonic cleaner for ultrasonic treatment, removing bubbles, and placing in a dark place for later use;
s4, film formation: adding the resin mixed in the step S3 into a polytetrafluoroethylene mold, wherein the height of the liquid resin is about half of the depth of the mold, the mold is placed on a horizontal table, and a few bubbles in the mixed resin can be blown through by a aurilave;
s5, curing: and (3) placing the mold filled with the liquid photosensitive resin under an ultraviolet lamp for curing, turning off the ultraviolet lamp after curing is finished, and taking out the resin sheet in the mold.
2. The novel photosensitive resin suitable for the photocuring molding 3D printing technology as claimed in claim 1, wherein in the step of pretreating the industrial cassava dregs, the concentration of hydrogen peroxide is 10-15%, the ultrasonic power of an ultrasonic cleaner is 60-150W, the temperature is 50-60 ℃, the drying temperature of an oven is set to 105 ℃, and the industrial cassava dregs are crushed and sieved by a 60-mesh sieve.
3. The novel photosensitive resin suitable for stereolithography 3D printing technology as claimed in claim 1, wherein the concentration of 1173 photoinitiator diluted in step S2 is 3-5%.
4. The novel photosensitive resin suitable for the photocuring molding 3D printing technology as claimed in claim 1, wherein the specific parameters of the step S3 for placing the resin mixture on the digital display constant-temperature magnetic stirrer are as follows: keeping the temperature at 60 ℃ at 200-300rpm, and stirring for 30-60 min; adding the pretreated cassava residues, and continuing stirring at normal temperature at 400rpm for 30-60min and ultrasonic in an ultrasonic cleaner for 30-40 min.
5. The novel photosensitive resin suitable for photocuring molding 3D printing technology as claimed in claim 1, wherein the power of an ultraviolet lamp is 60-80W, the peak wavelength is 310-400nm, the curing irradiation height of the ultraviolet lamp is 10cm, and the curing time is 3-5 min.
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