Disclosure of Invention
In view of at least one of the above problems, the present invention provides a photosensitive resin composition for additive manufacturing modified with black talc and a method for preparing the same.
The aim of the invention is realized by adopting the following technical scheme:
the black talc modified photosensitive resin composition for additive manufacturing comprises, by weight, 100 parts of acrylate resin raw materials, 2-18 parts of fillers, 0.5-2 parts of photoinitiators, 0.01-0.1 part of catalysts, 1-3 parts of crosslinking agents, 0.01-0.05 part of light absorbers and 0-5 parts of auxiliary agents; wherein:
the acrylic ester resin raw material consists of an acrylic ester monomer, polyester modified epoxy acrylic ester and aliphatic polyurethane acrylic ester, wherein the acrylic ester monomer comprises 2-acrylic acid-2-hydroxy-3-phenoxypropyl ester;
the filler is modified black talcum.
Preferably, the mass percentages of the polyester modified epoxy acrylate, the aliphatic polyurethane acrylate and the 2-acrylic acid-2-hydroxy-3-phenoxy propyl ester in the acrylic ester resin raw materials are 18-26wt%, 12-18wt% and 10-22wt%, respectively.
Preferably, the preparation method of the modified black talc comprises the following steps:
(1) Pretreatment of
Pulverizing black talc into micropowder with particle diameter of 1-100 μm, adding into anhydrous alcohol solvent, stirring, soaking overnight, filtering, washing with deionized water, and drying;
(2) Modification treatment
Respectively weighing methyl methacrylate monomer, acrylic acid monomer and styrene monomer, dissolving in ammonium bicarbonate buffer solution, adding pretreated black talcum powder, adding sodium dodecyl benzene sulfonate, heating to 60-70 ℃ and reacting at a temperature of 30-60min, adding ammonium persulfate, reacting at a temperature of 70-80 ℃ under stirring for 1-10min, separating precipitate, and washing to obtain the product;
wherein the molar ratio of the methyl methacrylate monomer to the acrylic acid monomer to the styrene monomer is (3-4) to 10; the mass ratio of the monomer to the black talcum powder, the sodium dodecyl benzene sulfonate and the ammonium persulfate is (1-4) to (40-50) to (0.1-0.5) to (0.01-0.03).
Preferably, the photoinitiator is modified TPO, and the preparation method comprises the following steps:
weighing 2,4, 6-trimethylbenzoyl phosphorus dioxide, dissolving in a mixed solvent of butyl acetate and isopropanol, adding sodium dodecyl sulfate and polyvinylpyrrolidone, stirring and mixing overnight at normal temperature to obtain an oil phase solution, adding deionized water accounting for 40-60% of the volume of the oil phase solution, stirring and mixing overnight at normal temperature to obtain a microemulsion, and freeze-drying the microemulsion to obtain the modified TPO;
wherein the mass ratio of the 2,4, 6-trimethylbenzoyl phosphorus oxide to the butyl acetate, the isopropanol, the sodium dodecyl sulfate and the polyvinylpyrrolidone is 1:10-12:8-10:0.3-0.4:0.3-0.4.
Preferably, the catalyst is zinc acetylacetonate hydrate.
Preferably, the cross-linking agent is bisphenol a glyceride diacrylate.
Preferably, the light absorber is 2, 4-dihydroxyazobenzene.
Preferably, the auxiliary agent is one or more of pigment, polymerization inhibitor, thixotropic agent, flatting agent, defoamer, plasticizer and stabilizer.
Another aspect of the present invention is to provide a method for preparing the photosensitive resin composition for additive manufacturing modified with black talc, comprising the steps of:
s1, weighing the raw materials according to the ratio for standby;
s2, mixing the acrylic ester resin raw materials, adding the catalyst, heating to 60-70 ℃, fully mixing until the materials are uniform, and cooling;
and S3, adding the filler, the photoinitiator and the light absorber, fully mixing until the components are uniform, and adding the auxiliary agent according to the requirement to prepare the photosensitive resin composition.
The beneficial effects of the invention are as follows:
the shrinkage of the material is reduced by adding inorganic mineral powder, the black talcum is a magnesium-rich silicate mineral, the main mineral component is talcum, the content of the talcum is more than 95%, and the main chemical component is MgO is more than or equal to 26% and SiO 2 More than or equal to 65 percent, and about 1 to 5 percent of organic matters, carbonic acid matters, sulfuric acid matters and other impurities, has excellent electrical insulation, heat resistance, acid and alkali resistance, soft texture and good plasticity, takes the black talcum as a filler, improves the compatibility of the black talcum in a resin system based on the characteristic that the surface of the black talcum contains natural organic matters, and further takes the styrene as the fillerThe preparation method is characterized in that the preparation method is a hydrophobic material, colloid particles distributed on the surface of the black talcum are formed in a buffer solution, hydrogen bonds formed between carboxyl groups on the surface of the colloid particles and amino groups of a monomer acrylamide enable the monomer to be uniformly distributed on the surface of the black talcum, and the existence of the hydrogen bonds enables the colloid particles to be uniformly distributed in a gradually contracted polymer framework in the solidification process, so that the contraction rate is further reduced; furthermore, the invention takes 2-acrylic acid-2-hydroxy-3-phenoxypropyl ester as a curing monomer, bisphenol A glyceride diacrylate as a cross-linking agent, hydroxyl and ester groups are introduced outside ultraviolet photosensitivity of acrylic ester, and the reprocessability of the printing structure is endowed by utilizing transesterification reaction which occurs at high temperature, so that the independent grid structure has adhesiveness and is endowed with remolding.
Detailed Description
The invention will be further described with reference to the following examples.
Example 1
The black talc modified photosensitive resin composition for additive manufacturing comprises, by weight, 100 parts of an acrylate resin raw material, 13 parts of a filler, 0.5 part of a photoinitiator, 0.04 part of a catalyst, 1.2 parts of a cross-linking agent, 0.03 part of a light absorber and 2 parts of an auxiliary agent; wherein:
the acrylic ester type resin raw material consists of methyl methacrylate, 2-acrylic acid-2-hydroxy-3-phenoxypropyl ester, polyester modified epoxy acrylic ester (CM 3225, functionality 2, viscosity 5500cps (60 ℃) and trifunctional aliphatic polyurethane acrylic ester (SW 3673, functionality 3, viscosity 20000cps (25 ℃)), wherein the mass ratio of the acrylic ester type resin raw material to the trifunctional aliphatic polyurethane acrylic ester is 45%, 18%, 22% and 15% respectively;
the filler is modified black talc, and the preparation method of the modified black talc comprises the following steps:
(1) Pretreatment of
Pulverizing black talc into micropowder with particle diameter of 1-100 μm, adding into absolute ethanol, stirring and soaking overnight, filtering, washing with deionized water, and drying;
(2) Modification treatment
Respectively weighing 1 part of methyl methacrylate monomer, 1 part of acrylic acid monomer and 3 parts of styrene monomer according to mole parts, dissolving in an ammonium bicarbonate buffer solution, adding 55 parts of pretreated black talcum powder, adding 0.3 part of sodium dodecyl benzene sulfonate, heating to 60-70 ℃ and reacting for 45min, adding 0.02 part of ammonium persulfate, reacting for 5min at 70-80 ℃ under heat preservation and stirring, separating precipitate, and washing to obtain the product;
the photoinitiator is modified TPO, and the preparation method comprises the following steps:
weighing 1 part by weight of 2,4, 6-trimethylbenzoyl phosphorus oxide, 12 parts by weight of butyl acetate and 9 parts by weight of isopropanol, mixing and dissolving, adding 0.3 part by weight of sodium dodecyl sulfate and 0.4 part by weight of polyvinylpyrrolidone, mixing and stirring overnight at normal temperature to obtain an oil phase solution, adding 50% by volume of deionized water into the oil phase solution, mixing and stirring overnight again at normal temperature to obtain a microemulsion, and freeze-drying the microemulsion to obtain the modified TPO;
the catalyst is zinc acetylacetonate hydrate;
the cross-linking agent is bisphenol A glyceride diacrylate;
the light absorber is 2, 4-dihydroxyazobenzene;
the auxiliary agent is a polymerization inhibitor, a defoaming agent and a stabilizer, the polymerization inhibitor is hydroquinone, the defoaming agent is polyether polysiloxane, and the temperature stabilizer is a hindered amine compound UV622;
the preparation method of the photosensitive resin composition comprises the following steps:
s1, weighing the raw materials according to the ratio for standby;
s2, mixing the acrylic ester resin raw materials, adding the catalyst, heating to 60-70 ℃, fully mixing until the materials are uniform, and cooling;
and S3, adding the filler, the photoinitiator and the light absorber, fully mixing until the components are uniform, and adding the auxiliary agent to prepare the photosensitive resin composition.
Example 2
The black talc modified photosensitive resin composition for additive manufacturing comprises, by weight, 100 parts of an acrylate resin raw material, 13 parts of a filler, 0.5 part of a photoinitiator, 0.04 part of a catalyst, 1.2 parts of a cross-linking agent, 0.03 part of a light absorber and 2 parts of an auxiliary agent; wherein:
the acrylic ester type resin raw material consists of methyl methacrylate, 2-acrylic acid-2-hydroxy-3-phenoxypropyl ester, polyester modified epoxy acrylic ester (CM 3225, functionality 2, viscosity 5500cps (60 ℃) and trifunctional aliphatic polyurethane acrylic ester (SW 3673, functionality 3, viscosity 20000cps (25 ℃)), wherein the mass ratio of the acrylic ester type resin raw material to the trifunctional aliphatic polyurethane acrylic ester is 45%, 18%, 22% and 15% respectively;
the filler is modified black talc, and the preparation method of the modified black talc is the same as that of example 1;
the photoinitiator is TPO;
the catalyst is zinc acetylacetonate hydrate;
the cross-linking agent is bisphenol A glyceride diacrylate;
the light absorber is 2, 4-dihydroxyazobenzene;
the auxiliary agent is a polymerization inhibitor, a defoaming agent and a stabilizer, the polymerization inhibitor is hydroquinone, the defoaming agent is polyether polysiloxane, and the temperature stabilizer is a hindered amine compound UV622;
the photosensitive resin composition was prepared in the same manner as in example 1.
Example 3
The black talc modified photosensitive resin composition for additive manufacturing comprises, by weight, 100 parts of an acrylate resin raw material, 13 parts of a filler, 0.5 part of a photoinitiator, 0.04 part of a catalyst, 1.2 parts of a cross-linking agent, 0.03 part of a light absorber and 2 parts of an auxiliary agent; wherein:
the acrylic ester type resin raw material consists of methyl methacrylate, polyester modified epoxy acrylic ester (CM 3225, functionality 2, viscosity 5500cps (60 ℃) and trifunctional aliphatic polyurethane acrylic ester (SW 3673, functionality 3, viscosity 20000cps (25 ℃)), wherein the mass ratio of the acrylic ester type resin raw material to the trifunctional aliphatic polyurethane acrylic ester is 63%, 22% and 15% respectively;
the filler is modified black talc, and the preparation method of the modified black talc is the same as that of example 1;
the photoinitiator is modified TPO, and the preparation method is the same as that of the example 1;
the catalyst is zinc acetylacetonate hydrate;
the cross-linking agent is bisphenol A glyceride diacrylate;
the light absorber is 2, 4-dihydroxyazobenzene;
the auxiliary agent is a polymerization inhibitor, a defoaming agent and a stabilizer, the polymerization inhibitor is hydroquinone, the defoaming agent is polyether polysiloxane, and the temperature stabilizer is a hindered amine compound UV622;
the photosensitive resin composition was prepared in the same manner as in example 1.
Example 4
The black talc modified photosensitive resin composition for additive manufacturing comprises, by weight, 100 parts of an acrylate resin raw material, 13 parts of a filler, 0.5 part of a photoinitiator, 0.04 part of a catalyst, 1.2 parts of a cross-linking agent, 0.03 part of a light absorber and 2 parts of an auxiliary agent; wherein:
the acrylic ester type resin raw material consists of methyl methacrylate, 2-acrylic acid-2-hydroxy-3-phenoxypropyl ester, polyester modified epoxy acrylic ester (CM 3225, functionality 2, viscosity 5500cps (60 ℃) and trifunctional aliphatic polyurethane acrylic ester (SW 3673, functionality 3, viscosity 20000cps (25 ℃)), wherein the mass ratio of the acrylic ester type resin raw material to the trifunctional aliphatic polyurethane acrylic ester is 45%, 18%, 22% and 15% respectively;
the filler is black talcum powder with the particle size of 1-100 mu m;
the photoinitiator is modified TPO, and the preparation method is the same as that of the example 1;
the catalyst is zinc acetylacetonate hydrate;
the cross-linking agent is bisphenol A glyceride diacrylate;
the light absorber is 2, 4-dihydroxyazobenzene;
the auxiliary agent is a polymerization inhibitor, a defoaming agent and a stabilizer, the polymerization inhibitor is hydroquinone, the defoaming agent is polyether polysiloxane, and the temperature stabilizer is a hindered amine compound UV622;
the photosensitive resin composition was prepared in the same manner as in example 1.
Comparative example
The photosensitive resin composition comprises, by weight, 100 parts of an acrylate resin raw material, 0.5 part of a photoinitiator, 0.04 part of a catalyst, 1.2 parts of a crosslinking agent, 0.03 part of a light absorber and 2 parts of an auxiliary agent; wherein:
the acrylic ester type resin raw material consists of methyl methacrylate, polyester modified epoxy acrylic ester (CM 3225, functionality 2, viscosity 5500cps (60 ℃) and trifunctional aliphatic polyurethane acrylic ester (SW 3673, functionality 3, viscosity 20000cps (25 ℃)), wherein the mass ratio of the acrylic ester type resin raw material to the trifunctional aliphatic polyurethane acrylic ester is 63%, 22% and 15% respectively;
the photoinitiator, catalyst, cross-linker, light absorber and auxiliary agent were the same as in example 1.
Experimental example
1. Cure volume shrinkage (%)
Placing the photosensitive resin composition in a polytetrafluoroethylene mould, placing the photosensitive resin composition in an oven at 80 ℃ for 1h after ultraviolet irradiation curing, measuring the length of a sample by using a caliper after the composition is completely cured, and calculating the curing volume shrinkage rate according to the following formula:
cure volume shrinkage (%) = (|c-d|/C) ×100%; wherein C is the length of the mold before curing, and D is the length of the sample after curing;
2. mechanical properties
Impact strength was tested according to GB/T1043.1-2008 standard; tensile strength and elongation at break were tested according to type I test specimens in GB/T1042-92;
3. reproplasticity
And (3) carrying out 3D printing on the sample by using the photosensitive resin composition, continuing to carry out secondary printing after the semi-finished sample is completely cured, and measuring the connection strength (tensile strength) between the secondary printing connection surfaces.
The results of the testing of the photosensitive resin compositions described in the examples are shown in the following table:
|
example 1
|
Example 2
|
Example 3
|
Example 4
|
Comparative example
|
Cure volume shrinkage (%)
|
0.27
|
0.48
|
0.55
|
1.09
|
1.91
|
Impact Strength (kJ.m) 2 )
|
54.2
|
49.1
|
48.0
|
32.4
|
24.2
|
Tensile Strength (MPa)
|
62
|
54
|
52
|
34
|
25
|
Elongation at break (%)
|
58.5
|
53.1
|
48.7
|
36.3
|
29.4
|
Connection strength (MPa)
|
41
|
39
|
-
|
38
|
- |
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.