CN112442147B - Low-viscosity 3D fluororesin and preparation method and application thereof - Google Patents
Low-viscosity 3D fluororesin and preparation method and application thereof Download PDFInfo
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- CN112442147B CN112442147B CN202011350597.4A CN202011350597A CN112442147B CN 112442147 B CN112442147 B CN 112442147B CN 202011350597 A CN202011350597 A CN 202011350597A CN 112442147 B CN112442147 B CN 112442147B
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- 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
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- 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
- B33Y80/00—Products made by additive manufacturing
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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
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
Abstract
The embodiment of the application discloses a low-viscosity 3D (three-dimensional) fluororesin, a preparation method and application thereof, wherein the fluororesin has a structure shown in a formula (1), and the preparation method of the modified fluororesin comprises the following steps: (a) Reacting the fluorocarbon resin represented by the formula (4) with the isocyanate represented by the formula (5), and (b) adding an acrylic diluent monomer to obtain a modified fluororesin. The 3D printing photo-curing composition adopting the modified fluororesin has good heat resistance. In addition, the photo-curing composition has good mechanical strength, and can be used in the technical field of photo-curing 3D printing.
Description
Technical Field
The embodiment of the application relates to the technical field of photo-curing 3D printing, in particular to a low-viscosity 3D fluororesin, a preparation method and application thereof.
Background
The photo-curing 3D printing technology is a rapid prototyping technology for curing and bonding materials layer by layer to construct a three-dimensional object by irradiating photosensitive resin with ultraviolet rays of a certain wavelength to perform polymerization reaction. The basic principle of the technology is that objects are printed and accumulated in layers, a digital three-dimensional model of the required objects is input into a computer, computer software processes the three-dimensional model and is divided into a plurality of thin layers, ultraviolet light with a certain wavelength is irradiated on photosensitive resin through a 3D printer, and the solidified resin is stacked layer by layer to form the three-dimensional object finally. The photo-curing 3D printing operation is simple, the object printing time is short, various complex three-dimensional object models can be printed, the precision is high, the mechanical properties of the objects are good, and the environmental pollution is small.
Materials currently developed for photo-curable 3D printing mainly include acrylic, and after photo-curing, these photosensitive resins can polymerize to form solid polymer parts. Thus, although photo-curing 3D printing provides a powerful manufacturing means, the uniqueness of the material still limits its application in more fields. Particularly, the characteristics of the polymer material formed after 3D printing, such as low heat resistance, low strength and the like, enable the 3D printing component to have single functions, and enable the photo-curing 3D printing technology to not realize printing of the multifunctional material, thereby limiting further development and application of the multifunctional material.
Disclosure of Invention
In order to solve the defects in the prior art, the application provides a modified fluororesin, a preparation method thereof, a photocuring composition containing the modified fluororesin, photocuring 3D printing ink, photocuring 3D printing device, photocuring 3D printing method and 3D printing forming body.
According to one aspect of the present application, a modified fluororesin has a structure as shown in formula (1):
wherein R is 1 、R 2 、R 3 And R is 4 The same or different, are independently selected from any one of hydrogen atom, fluorine atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C10-C40 condensed aryl, and R 1 、R 2 、R 3 And R is 4 At least one of which is a fluorine atom;
R 5 any one selected from a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C10-C40 condensed aryl group;
R 6 any one selected from a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C10-C40 condensed aryl group;
R 7 any one selected from a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C10-C40 condensed aryl group;
R 10 is a substituted or unsubstituted C1-C30 alkyl group, R 11 Is a hydrogen atom or a methyl group;
m is an integer of 1 to 100, n is an integer of 0 to 110, p is an integer of 0 to 110, n and p are not simultaneously 0, and n+p=1 to 110.
Preferably R 10 Is any one of the groups represented by the formula (2):
R 12 and R is 13 Independently selected from H, substituted or unsubstituted C1-C10 alkyl;
preferably, R 10 Is ethyl or a group of formula (3):
wherein, the liquid crystal display device comprises a liquid crystal display device,represents the position linked to-NH-in formula (1).
According to another aspect of the present application, the method for preparing a modified fluororesin comprises the steps of:
(a) Reacting the fluorocarbon resin represented by the formula (4) with the isocyanate represented by the formula (5), and
(b) Adding an acrylic diluent monomer to obtain modified fluororesin;
the fluorocarbon resin has a structure represented by formula (4):
wherein R is 1 、R 2 、R 3 And R is 4 The same or different, are independently selected from hydrogen atoms, fluorine atoms, substituted or unsubstituted C1-C30 alkyl groups, substituted or unsubstituted C1-C30 alkoxy groups, and substitutionsOr any one of unsubstituted C6-C40 aryl, substituted or unsubstituted C10-C40 condensed aryl, and R 1 、R 2 、R 3 And R is 4 At least one of which is a fluorine atom;
R 5 any one selected from a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C10-C40 condensed aryl group;
R 6 any one selected from a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C10-C40 condensed aryl group;
R 7 any one selected from a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C10-C40 condensed aryl group;
m is an integer of 1 to 100, n is an integer of 0 to 110, p is an integer of 0 to 110, n and p are not simultaneously 0, and n+p=1 to 110;
R 10 is a substituted or unsubstituted C1-C30 alkyl group, R 11 Is a hydrogen atom or a methyl group.
Preferably, R 10 Is any one of the groups represented by the formula (2):
R 12 and R is 13 Independently selected from H, substituted or unsubstituted C1-C10 alkyl;
preferably, R 10 Is ethyl or a group of formula (3):
wherein, the liquid crystal display device comprises a liquid crystal display device,represents the position to which-NCO in formula (5) is attached.
Preferably, the isocyanate represented by the formula (5) is selected from any one of isocyanate ethyl acrylate, isocyanatoethyl methacrylate, 2-isocyanato-2-methylpropane-1, 3-diyl diacrylate or 2- (2-methacryloyloxyethoxy isocyanatoethyl).
Preferably, the fluorocarbon resin has a hydroxyl value of 30 to 150mgKOH/g, preferably 63mgKOH/g;
preferably, the diluent monomer is an acrylic diluent monomer, preferably any one of HDDA, TPGDA, PETA or 3EOTM or a combination of at least two;
preferably, the isocyanate represented by formula (5) is added in an amount of 5 to 20 parts by weight and the diluent monomer is added in an amount of 10 to 35 parts by weight based on 100 parts by weight of the fluorocarbon resin;
preferably, the isocyanate represented by formula (5) is added in an amount of 10 parts by weight and the diluent monomer is added in an amount of 20 parts by weight based on 100 parts by weight of the fluorocarbon resin;
preferably, the process comprises the step of (b) adding a diluent monomer followed by a step of removing the solvent;
preferably, step (a) comprises: reacting a fluorocarbon resin represented by formula (4) with an isocyanate represented by formula (5) in the presence of a catalyst and a polymerization inhibitor under a protective atmosphere;
preferably, step (a) is carried out by reacting the fluorocarbon resin represented by formula (4) with the isocyanate represented by formula (5) at 45 to 90℃for 3 to 6 hours, preferably at 75℃for 4 hours;
preferably, the step (b) adds a diluent monomer and a polymerization inhibitor at 50-70 ℃ and then removes the solvent to obtain the modified fluororesin.
According to another aspect of the present application, a photocurable composition comprising the modified fluororesin as described above.
Preferably, the photocurable composition comprises:
(a) The modified fluororesin as described above,
(b) The acrylic acid ester is used for preparing the acrylic acid ester,
(c) A photoinitiator, and
(d) A thermal initiator;
preferably, the weight of component (a) is 20 to 70wt%, preferably 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt% or 60wt%, further preferably 35wt%, 40wt%, 45wt% or 50wt%, based on 100wt% of the weight of the photocurable composition;
preferably, the weight of component (b) is 10 to 60wt%, preferably 25wt%, 30wt%, 35wt%, 40wt% or 45wt%, further preferably 30wt%, 35wt% or 40wt%, based on 100wt% of the weight of the photocurable composition;
preferably, the weight of component (c) is 5 to 15wt%, preferably 6 to 12wt%, further preferably 8 to 10wt%, based on 100wt% of the weight of the photocurable composition;
preferably, the weight of component (d) is 0 to 2wt%, preferably 0.4 to 1.5wt%, further preferably 0.5 to 1.2wt%, based on 100wt% of the weight of the photocurable composition;
preferably, the photocurable composition further comprises the following components: component (f) defoamer and component (g) leveling agent;
preferably, the photocurable composition further comprises, based on 100wt% of the weight of the photocurable composition:
0.01 to 0.05 weight percent of component (f) defoamer and 0.02 to 0.8 weight percent of component (g) flatting agent;
preferably, the composition comprises the following components in 100wt% based on the weight of the photocurable composition:
(a) 20 to 70wt% of the modified fluororesin as described above,
(b) 10 to 60 weight percent of acrylic ester,
(c) 5-15 wt% of photoinitiator,
(d) 0 to 2 weight percent of thermal initiator,
(f) 0.01 to 0.05wt% of defoaming agent, and
(g) 0.02 to 0.8 weight percent of leveling agent.
According to another aspect of the present application there is provided the use of a photocurable composition as described above in photocured 3D printing.
According to another aspect of the present application, a photocurable 3D printing ink comprises the modified fluororesin or the photocurable composition as described above.
According to another aspect of the present application, there is provided a method of photo-curing 3D printing using the modified fluororesin, photo-curing composition or ink as described above.
According to another aspect of the present application, there is provided a photo-curable 3D printing device comprising the modified fluororesin, the photo-curable composition or the ink as described above.
According to another aspect of the present application, there is provided a 3D printed molded body obtained by photo-curing 3D printed molding from the photo-curing composition as described above.
The beneficial effects are that: the 3D printing photo-curing composition adopting the modified fluororesin has good heat resistance. In addition, the photocurable composition has good mechanical strength.
Detailed Description
The present application will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are for purposes of illustration and not of limitation.
In order to solve the defects in the prior art, the application provides a modified fluororesin, a preparation method thereof, a photocuring composition containing the modified fluororesin, photocuring 3D printing ink, photocuring 3D printing device, photocuring 3D printing method and 3D printing forming body. The 3D printing photo-curing composition adopting the modified fluororesin has good heat resistance. In addition, the photocurable composition has good mechanical strength.
The inventors have unexpectedly found that: the modified fluororesin is modified by adopting allyl monofunctional isocyanate, so that the modified fluororesin can keep the performance of polyurethane, and the 3D printing light-cured composition containing the modified fluororesin has good heat resistance. In addition, the photocurable composition has also good mechanical strength, and thus the present application has been completed.
According to an aspect of the present application, there is provided a modified fluororesin having a structure as shown in formula (1):
wherein R is 1 、R 2 、R 3 And R is 4 The same or different, are independently selected from any one of hydrogen atom, fluorine atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C10-C40 condensed aryl, and R 1 、R 2 、R 3 And R is 4 At least one of which is a fluorine atom;
R 5 any one selected from a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C10-C40 condensed aryl group;
R 6 any one selected from a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C10-C40 condensed aryl group;
R 7 any one selected from a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C10-C40 condensed aryl group;
R 10 is a substituted or unsubstituted C1-C30 alkyl group, R 11 Is a hydrogen atom or a methyl group;
m is an integer of 1 to 100, n is an integer of 0 to 110, p is an integer of 0 to 110, n and p are not simultaneously 0, and n+p=1 to 110.
Preferably, R 10 Is any one of the groups represented by the formula (2):
R 12 and R is 13 Independently selected from H, substituted or unsubstituted C1-C10 alkyl;
preferably, R 10 Is ethyl or a group of formula (3):
wherein, the liquid crystal display device comprises a liquid crystal display device,represents the position linked to-NH-in formula (1).
According to another aspect of the present application, there is provided a method for producing the modified fluororesin as described above, comprising the steps of:
(a) Reacting the fluorocarbon resin represented by the formula (4) with the isocyanate represented by the formula (5), and
(b) Adding an acrylic diluent monomer to obtain modified fluororesin;
the fluorocarbon resin has a structure represented by formula (2):
wherein R is 1 、R 2 、R 3 And R is 4 The same or different, are independently selected from any one of hydrogen atom, fluorine atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C10-C40 condensed aryl, and R 1 、R 2 、R 3 And R is 4 At least one of which is a fluorine atom;
R 5 selected from any of a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C40 aryl group, and a substituted or unsubstituted C10-C40 condensed aryl groupOne of the two;
R 6 any one selected from a hydrogen atom, a fluorine atom, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C40 aryl group and a substituted or unsubstituted C10-C40 condensed aryl group;
R 7 any one selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl and substituted or unsubstituted C10-C40 condensed aryl;
m is an integer of 1 to 100, n is an integer of 0 to 110, p is an integer of 0 to 110, n and p are not simultaneously 0, and n+p=1 to 110;
R 10 is a substituted or unsubstituted C1-C30 alkyl group, R 11 Is a hydrogen atom or a methyl group.
In the present application, in order to achieve photocuring (i.e., grafting acrylate groups) of fluorocarbon resins, it is generally possible to: (A) Direct esterification, but this approach involves a water removal process, which is relatively complex; (B) Forming a semi-adduct with a difunctional isocyanate such as IPDI and hydroxyethyl acrylate, and reacting with a fluorocarbon resin; although urethane groups can be effectively introduced in this way, gel is easily formed in the synthesis process or chain extension reaction is caused, so that the viscosity of the resin becomes high, which is not beneficial to subsequent use. Because of the physical property advantage of polyurethane, namely a carbamate group, the application utilizes good reaction selectivity of monofunctional isocyanate to carry out structural design of resin in order to effectively introduce the group and not cause side reaction, on one hand, excellent physical property of polyurethane is reserved, on the other hand, low-viscosity solvent-free acrylic carbamate fluororesin is obtained, and the application is applied to the field of 3D printing.
Furthermore, in the present application, fluorocarbon resins (FEVE) contain hydroxyl groups which contain a solvent, typically but not limited to toluene, which, once volatilized, gives very good crystallization properties. The present application first employs fluorocarbon resins reacted with monofunctional isocyanates to graft acryloxy groups. Furthermore, the purpose of adding the diluent monomer is: the fluorocarbon resin is difficult to be redissolved after desolvation, so that the monomer is added to ensure the solubility of the fluorocarbon resin. In addition, if the solvent is not contained, the reaction product can be crystallized quickly, the diluent monomer can be prevented from crystallizing immediately after the reaction is finished, and meanwhile, the added diluent monomer can be cured in the photo-curing process. The modified fluororesin is crystallized during the photo-curing process, and thus, the heat resistance of the photo-curing composition can be remarkably improved. In addition, the crystallization property of the modified fluororesin can also obviously improve the mechanical property of the photo-curing composition.
Preferably, R 10 Is any one of the groups represented by the formula (2):
R 12 and R is 13 Independently selected from H, substituted or unsubstituted C1-C10 alkyl;
preferably, R 10 Is ethyl or a group of formula (3):
wherein, the liquid crystal display device comprises a liquid crystal display device,represents the position to which-NCO in formula (5) is attached.
In the present application, the C1-C30 label represents the number of carbon atoms of the continuous substituent herein, and C1-C30 represents 1-30 carbon atoms.
In a preferred embodiment of the application, in R 1 、R 2 、R 3 And R is 4 、R 5 、R 6 And R is 7 Wherein each substituted or unsubstituted C1-C30 alkyl independently comprises a substituted or unsubstituted C1-C30 straight or branched alkyl, preferably unsubstituted C1-C30Straight or branched alkyl groups, alternative examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-dimethylbutyl and the like.
In a preferred embodiment of the application, in R 1 、R 2 、R 3 And R is 4 、R 5 、R 6 And R is 7 In (2), the substituted or unsubstituted C1-C30 alkoxy groups each independently include a substituted or unsubstituted C1-C30 straight or branched chain alkoxy group, preferably an unsubstituted C1-C30 straight or branched chain alkoxy group, and alternative examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy, and the like.
In a preferred embodiment of the application, in R 1 、R 2 、R 3 And R is 4 、R 5 、R 6 And R is 7 The substituted or unsubstituted C6-C40 aryl group may be selected from any one of aromatic hydrocarbon groups such as phenyl, biphenyl, 9-fluorenyl, and terphenyl. The above-mentioned C6-C40 aryl group may have a substituent or may not have a substituent.
In a preferred embodiment of the application, in R 1 、R 2 、R 3 And R is 4 、R 5 、R 6 And R is 7 The substituted or unsubstituted C6-C40 condensed aryl group may be selected from any one of, for example, naphthyl, anthryl, phenanthryl, 9, 10-benzophenanthryl, 1, 2-benzophenanthryl, acenaphthylenyl, perylenyl, pyrenyl, indenyl and the like. The C6-C40 condensed aryl group may have a substituent or may not have a substituent.
The same is to be understood as the above for the substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C10-C40 condensed aryl mentioned elsewhere in the present application.
In a preferred embodiment of the present application, the substituted or unsubstituted C1-C10 alkyl groups mentioned anywhere above, alternative examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and the like.
In a preferred embodiment of the present application, the isocyanate represented by formula (5) is selected from any one of isocyanate ethyl acrylate, isocyanatoethyl methacrylate, 2-isocyanato-2-methylpropan-1, 3-diyl diacrylate or 2- (2-methacryloyloxyethoxy isocyanatoethyl).
In a preferred embodiment of the present application, the fluorocarbon resin has a hydroxyl value of 30 to 150mgKOH/g, preferably 63mgKOH/g.
In a preferred embodiment of the present application, the diluent monomer is an acrylic monomer, preferably any one or a combination of at least two of HDDA (1, 6-hexanediol diacrylate), TPGDA (tripropylene glycol diacrylate), PETA (pentaerythritol triacrylate) or 3EOTM (ethoxylated trimethylolpropane triacrylate).
In a preferred embodiment of the present application, the isocyanate represented by formula (5) is added in an amount of 5 to 20 parts by weight and the diluent monomer is added in an amount of 10 to 35 parts by weight based on 100 parts by weight of the fluorocarbon resin.
If the amount of the isocyanate represented by the formula (5) added is less than 5 parts by weight, the modified fluororesin has few UV-curing active groups, is too slow to cure or causes incompatibility with the existing acrylate system upon polymerization curing, and if the amount of the isocyanate represented by the formula (5) added is more than 20 parts by weight, the isocyanate groups are too large, resulting in residues of the groups, which causes instability of the modified fluororesin.
If the addition amount of the diluent monomer is less than 10 parts by weight, the diluent monomer cannot be used as a replacement solvent to well dissolve and disperse the modified fluororesin, so that the resin phase is separated, and if the addition amount is more than 35 parts by weight, the proportion of the diluent monomer is too high, the physical properties of the fluororesin per se are greatly influenced, and the formula adjustability of the later-stage resin is also influenced.
In a preferred embodiment of the present application, the isocyanate represented by formula (5) is added in an amount of 10 parts by weight and the diluent monomer is added in an amount of 20 parts by weight based on 100 parts by weight of the fluorocarbon resin.
In a preferred embodiment of the application, the process comprises a step (b) of adding a diluent monomer followed by a step of removing the solvent. Typical but non-limiting methods of solvent removal according to the present application are distillation under reduced pressure, preferably for 2 hours.
In a preferred embodiment of the present application, step (a) comprises: reacting the fluorocarbon resin represented by formula (4) with the isocyanate represented by formula (5) in the presence of a catalyst and a polymerization inhibitor under a protective atmosphere. The protective gas may be, for example, nitrogen, carbon dioxide, or argon, and nitrogen is preferable from an economical point of view.
In a preferred embodiment of the present application, the protective atmosphere may be, for example, nitrogen protection.
In a preferred embodiment of the present application, the catalyst is, for example, dibutyl tin laurate, organic bismuth, dioctyl di-neodecanoyl tin oxide or bismuth chelate (KRBI-6), etc., and the polymerization inhibitor is a substituted phenol, for example, p-methoxyphenol.
In a preferred embodiment of the present application, step (a) reacts the fluorocarbon resin represented by formula (4) with the isocyanate represented by formula (5) at 45 to 90℃for 3 to 6 hours, preferably at 75℃for 4 hours.
Typically, but not by way of limitation, step (a) may be carried out under the following conditions: 100 parts of fluorocarbon resin, 0.001-0.01 part of catalyst dibutyl tin laurate, 0.001-0.01 part of polymerization inhibitor p-methoxyphenol and 5-20 parts of isocyanate ethyl acrylate are put into a reactor with a stirrer and a thermometer, stirred and heated to 75 ℃ under the protection of nitrogen, and the temperature is kept for 4.0 hours for reaction.
In a preferred embodiment of the present application, step (b) adds a diluting monomer and a polymerization inhibitor at 50-70℃and then removes the solvent to obtain a modified fluororesin. The polymerization inhibitor added in step (b) may be the same as or different from that added in step (a). Typical but non-limiting such inhibitors are substituted phenols, such as p-methoxyphenol.
According to another aspect of the present application, there is provided a photocurable composition comprising the modified fluororesin as described above.
Because the modified fluororesin is adopted, the obtained photo-curing composition has good heat resistance (200-300 ℃) and mechanical property.
In a preferred embodiment of the present application, the photocurable composition comprises:
(a) The modified fluororesin as described above,
(b) The acrylic acid ester is used for preparing the acrylic acid ester,
(c) A photoinitiator, and
(d) A thermal initiator.
In the preferred embodiment, the modified fluororesin contains a double bond and a diluent monomer, and an acrylic ester is added thereto, whereby radical curing occurs by the action of a photoinitiator.
In a preferred embodiment of the present application, the acrylate comprises CTFA (cyclic trimethylol propane methylacrylate), ACMO (acryloylmorpholine), methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-hexyl acrylate, isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, methyl- α -chloroacrylate, phenyl- α -bromoacrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, 1-phenyl ethyl methacrylate, 2-phenyl ethyl methacrylate, bran methacrylate, diphenyl methyl methacrylate, pentachlorophenyl methacrylate, naphthalene methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, or a combination of at least one of two of the foregoing.
The photoinitiator in the photocurable composition is not particularly limited as long as it can polymerize the modified fluororesin, the acrylic acid ester and the other photopolymerizable compound optionally added in the present application as described above, but a photoinitiator that generates radicals by ultraviolet rays or visible rays is preferable.
Examples of such a photoinitiator include benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin phenyl ether, benzophenones such as benzophenone, N-tetramethyl-4, 4-diaminobenzophenone (michler's ketone), benzophenones such as N, N-tetraethyl-4, 4-diaminobenzophenone, benzyl ketals such as benzyl dimethyl ketal and benzyl diethyl ketal, acetophenones such as 2, 2-dimethoxy-2-phenylacetophenone, p-t-butyldichloroacetophenone and p-dimethylaminoacetophenone, xanthones such as 2, 4-dimethylthioxanthone and 2, 4-diisopropylthioxanthone, and xanthones such as hydroxycyclohexyl benzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-dimethoxy-1, 2-diphenylethane-1-one, and the like, and these can be used singly or in combination of two or more.
Thermal initiators generate free radicals due to heat, causing thermal crosslinking to proceed. The thermal initiator becomes the starting point for the crosslinking reaction. As the thermal initiator, they may be used alone or in combination. In some preferred embodiments, the thermal initiator comprises a peroxide or a non-peroxide radical initiator. Examples of useful peroxide initiators include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl benzene hydroperoxide, t-butyl peroctoate, 2, 5-dimethylhexane-2, 5-dihydro peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -hex-3-yne, di-t-butyl peroxide, t-butyl cumyl peroxide, α -bis (t-butylperoxy-m-isopropyl) benzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, di (t-butylperoxy) isophthalate, t-butyl peroxybenzoate, 2-bis (t-butylperoxy) butane, 2-bis (t-butylperoxy) octane, 2, 5-dimethyl-2, 5-bis (benzoyl peroxy) hexane, bis (trimethylsilyl) peroxide, trimethylsilylphenyl triphenylsilyl peroxide and the like, and mixtures thereof. Suitable non-peroxide initiators include 2, 3-dimethyl-2, 3-diphenylbutane, 2, 3-trimethylsiloxy-23-diphenylbutane, and the like, and mixtures thereof.
The content of the components (a), (b), (c) and (d) is preferably such that the weight of the component (a) is 20 to 70% by weight, for example 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight or 65% by weight, preferably 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, more preferably 35% by weight, 40% by weight, 45% by weight, 50% by weight, based on 100% by weight of the photocurable composition.
If the content of the component (a) is less than 20% by weight, the physical properties of the fluorocarbon resin are not reflected in the molded article, and if it exceeds 70% by weight, the fluorocarbon resin is too much, and the curing is not ideal, but the viscosity of the final product is too high to perform 3D molding well.
The weight of component (b) is 10 to 60wt%, for example 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt% or 55wt%, preferably 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, further preferably 30wt%, 35wt%, 40wt%, based on 100wt% of the weight of the photocurable composition.
If the content of the component (b) is less than 10% by weight, the overall curing speed is too slow or even impossible to cure, and if it exceeds 60% by weight, the fluorine content is too low, the properties are not exhibited or shrinkage is liable to be excessive, resulting in unstable overall dimensions.
The weight of component (c) is 5 to 15wt%, for example, 2.5wt%, 3wt%, 3.5wt%, 4wt% or 4.5wt%, preferably 6 to 12wt%, and more preferably 8 to 10wt%, based on 100wt% of the weight of the photocurable composition.
If the content of the component (c) is less than 5% by weight, the curing speed is too low to be molded or the accuracy is poor. If it exceeds 15wt%, the curing molecular weight is too low, the strength of the molded article is lowered, and the surface accuracy is lowered.
The weight of component (d) is 0 to 2wt%, for example 0.2wt%, 0.5wt%, 0.8wt%, 1.1wt%, 1.4wt% or 1.8wt%, preferably 0.4 to 1.5wt%, further preferably 0.5 to 1.2wt%, based on 100wt% of the weight of the photocurable composition.
If the content of the component (d) exceeds 2wt%, the resin itself is liable to be unstable and the heat release is too great in the subsequent heat curing to damage the molded article.
In some preferred embodiments, as the components other than the components (a), (b), (c) and (d), the following components may be contained as required: plasticizers, pigments, fillers, defoamers, flame retardants, stabilizers, tackifiers, leveling agents, antioxidants, and the like. These may be used alone or in combination of 2 or more, and preferably contain the following components together: component (f) defoamer and component (g) leveling agent.
In a further preferred embodiment, the following components are preferably also present in the light-curable composition in an amount of 100% by weight: 0.01 to 0.05 weight percent of component (f) defoamer and 0.02 to 0.8 weight percent of component (g) flatting agent.
As a preferred embodiment of the present application, the composition comprises the following components, based on 100wt% of the weight of the photocurable composition:
(a) 20 to 70wt% of the modified fluororesin as described above,
(b) 10 to 60 weight percent of acrylic ester,
(c) 5-15 wt% of photoinitiator,
(d) 0 to 2 weight percent of thermal initiator,
(f) 0.01 to 0.05wt% of defoaming agent, and
(g) 0.02 to 0.8 weight percent of leveling agent.
According to another aspect of the present application there is provided the use of a photocurable composition as described above in photocured 3D printing.
According to another aspect of the present application, a photocurable 3D printing ink comprises the modified fluororesin or the photocurable composition as described above.
According to another aspect of the present application, there is provided a method of photo-curing 3D printing using the modified fluororesin, photo-curing composition or ink as described above.
According to another aspect of the present application, there is provided a photo-curable 3D printing device comprising the modified fluororesin, the photo-curable composition or the ink as described above.
According to another aspect of the present application, there is provided a 3D printed molded body obtained by photo-curing 3D printed molding from the photo-curing composition as described above.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
1. Preparation of modified fluororesin
Synthesis example 1
100 parts by weight of fluorocarbon resin, 0.001 part by weight of catalyst dibutyl tin laurate, 0.001 part by weight of polymerization inhibitor p-methoxyphenol and 10 parts by weight of isocyanate ethyl acrylate are put into a reactor with a stirrer and a thermometer, stirred and heated to 75 ℃ under the protection of nitrogen, and the temperature is kept for 4.0 hours for reaction; cooling to 70 ℃, adding 20 parts by weight of diluted monomer HDDA and 0.001 part by weight of polymerization inhibitor p-methoxyphenol, and carrying out reduced pressure distillation for 2 hours to obtain the solvent-free acrylic urethane fluororesin, namely the modified fluororesin.
Synthesis examples 2 to 5 are given in Table 1, wherein the viscosity test standard is (GB/T2794-2013)
TABLE 1
2. Photocurable composition
Example 1
The modified fluororesin of synthesis example 1, an acrylic acid ester, a photoinitiator, a thermal initiator, a defoaming agent, and a leveling agent were mixed to obtain a photocurable composition.
Examples 1 to 5 are shown in Table 2
TABLE 2
| Examples | Modified fluororesin | Acrylic esters | Photoinitiator | Thermal initiator | Defoaming agent | Leveling agent |
| Example 1 | Synthesis examples 1 and 20 | IBOA,63.9 | 819，15 | BPO,1 | 0.05,BYK066 | 0.05BYK333 |
| Example 2 | Synthesis example 2 and 40 | IBOA,50.9 | 819，8 | BPO,1 | 0.05,BYK066 | 0.05BYK333 |
| Example 3 | Synthesis examples 3 and 40 | IBOA,48.9 | 819，10 | BPO,1 | 0.05,BYK066 | 0.05BYK333 |
| Example 4 | Synthesis example 4,60 | IBOA,29.4 | 819，10 | BPO,0.5 | 0.05,BYK066 | 0.05BYK333 |
| Example 5 | Synthesis examples 5 and 60 | IBOA，29.4 | 819，10 | BPO,0.5 | 0.05,BYK066 | 0.05BYK333 |
The photocurable compositions of examples 1 to 5 were evaluated for heat resistance and weather resistance, and the heat resistance was measured according to GB1699-2003 and the weather resistance was measured according to GBT3511-2008, and the results are shown in Table 3 below.
TABLE 3 Table 3
| Heat resistant temperature DEG C | Weather resistance | |
| Example 1 | 142 | No pulverization and little crack |
| Example 2 | 187 | No pulverization and no cracking |
| Example 3 | 203 | No pulverization and no cracking |
| Example 4 | 277 | No pulverization and no cracking |
| Example 5 | 279 | No pulverization and no cracking |
Note that the above is only a preferred embodiment of the present application and the technical principle applied. It will be understood by those skilled in the art that the present application is not limited to the particular embodiments described herein, but is capable of various obvious changes, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the application. Therefore, while the application has been described in connection with the above embodiments, the application is not limited to the embodiments, but may be embodied in many other equivalent forms without departing from the spirit or scope of the application, which is set forth in the following claims.
Claims (20)
1. A photocurable composition, characterized in that it comprises:
(a) A modified fluororesin, which is prepared by the following steps,
(b) The acrylic acid ester is used for preparing the acrylic acid ester,
(c) A photoinitiator, and
(d) A thermal initiator;
wherein the modified fluororesin is obtained by a preparation method comprising,
100 parts by weight of fluorocarbon resin GK570, 0.001 part by weight of catalyst dibutyl tin laurate, 0.001 part by weight of polymerization inhibitor 26-tert-butylphenol and 10 parts by weight of isocyanate ethyl acrylate are put into a reactor with a stirrer and a thermometer, stirred and heated to 75 ℃ under the protection of nitrogen, and the temperature is kept for 4.0 hours for reaction; cooling to 70 ℃, adding 20 parts by weight of diluted monomer trimethylolpropane triglycidyl ether and 0.001 part by weight of polymerization inhibitor 26-tertiary butyl phenol, and carrying out reduced pressure distillation for 2 hours to obtain solvent-free acrylic carbamate fluororesin, namely modified fluororesin; or alternatively, the first and second heat exchangers may be,
100 parts by weight of fluorocarbon resin GK570, 0.001 part by weight of catalyst dibutyl tin laurate, 0.001 part by weight of polymerization inhibitor p-methoxyphenol and 20 parts by weight of isocyanate ethyl acrylate are put into a reactor with a stirrer and a thermometer, stirred and heated to 75 ℃ under the protection of nitrogen, and the temperature is kept for 4.0 hours for reaction; cooling to 70 ℃, adding 30 parts by weight of diluted monomer trimethylolpropane triglycidyl ether and 0.001 part by weight of polymerization inhibitor p-methoxyphenol, and carrying out reduced pressure distillation for 2 hours to obtain the solvent-free acrylic urethane fluororesin, namely the modified fluororesin.
2. The photocurable composition according to claim 1, wherein the weight of component (a) is 20 to 70% by weight, based on 100% by weight of the photocurable composition.
3. The photocurable composition according to claim 2, characterized in that the weight of component (a) is 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt% or 60wt%, based on 100wt% of the photocurable composition.
4. A photocurable composition according to claim 3, characterized in that the weight of component (a) is 35wt%, 40wt%, 45wt% or 50wt%, based on 100wt% of the photocurable composition.
5. The photocurable composition according to claim 1, wherein the weight of component (b) is 10 to 60% by weight, based on 100% by weight of the photocurable composition.
6. The photocurable composition according to claim 5, wherein the weight of component (b) is 25wt%, 30wt%, 35wt%, 40wt% or 45wt%, based on 100wt% of the photocurable composition.
7. The photocurable composition according to claim 6, wherein the weight of component (b) is 30wt%, 35wt% or 40wt%, based on 100wt% of the photocurable composition.
8. The photocurable composition according to claim 1, wherein the weight of component (c) is from 5 to 15% by weight, based on 100% by weight of the photocurable composition.
9. The photocurable composition according to claim 8, wherein the weight of component (c) is 6 to 12% by weight, based on 100% by weight of the photocurable composition.
10. The photocurable composition according to claim 9, wherein the weight of component (c) is 8-10 wt%, based on 100wt% of the photocurable composition.
11. The photocurable composition according to claim 1, wherein the weight of component (d) is 0 to 2wt%, based on 100wt% of the photocurable composition.
12. The photocurable composition according to claim 11, wherein the weight of component (d) is 0.4-1.5% by weight, based on 100% by weight of the photocurable composition.
13. The photocurable composition according to claim 12, characterized in that the weight of component (d) is 0.5-1.2 wt%, based on 100wt% of the photocurable composition.
14. The photocurable composition according to claim 1, characterized in that it further comprises the following components: component (f) defoamer and component (g) leveling agent.
15. The photocurable composition according to claim 14, characterized in that it further comprises, based on 100% by weight of the photocurable composition:
0.01 to 0.05 weight percent of component (f) defoamer and 0.02 to 0.8 weight percent of component (g) flatting agent.
16. The photocurable composition according to claim 1, characterized in that it comprises the following components, based on 100% by weight of the photocurable composition:
(a) 20 to 70 weight percent of modified fluorine resin,
(b) 10 to 60 weight percent of acrylic ester,
(c) 5-15 wt% of photoinitiator,
(d) 0 to 2 weight percent of thermal initiator,
(f) 0.01 to 0.05wt% of defoaming agent, and
(g) 0.02 to 0.8 weight percent of leveling agent.
17. Use of a photocurable composition according to any one of claims 1-16 in photocured 3D printing.
18. A photocurable 3D printing ink comprising the photocurable composition of any one of claims 1-16.
19. A method of photo-curing 3D printing employing the photo-curing composition of any one of claims 1-16 or the ink of claim 18.
20. A 3D printed shaped body obtained from the photocurable composition according to any one of claims 1-16 by photocuring 3D printed shaping.
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