CN109354849A - It can be used for the unsaturated polyester resin and preparation method thereof of rapid three dimensional printing forming - Google Patents
It can be used for the unsaturated polyester resin and preparation method thereof of rapid three dimensional printing forming Download PDFInfo
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- CN109354849A CN109354849A CN201811063062.1A CN201811063062A CN109354849A CN 109354849 A CN109354849 A CN 109354849A CN 201811063062 A CN201811063062 A CN 201811063062A CN 109354849 A CN109354849 A CN 109354849A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
Present invention offer can be used for unsaturated polyester resin of rapid three dimensional printing forming and preparation method thereof, it is grouped as by each group of following mass fraction: 50 ~ 100 parts of unsaturated polyester resin, 10 ~ 50 parts of epoxy resin, 10 ~ 50 parts of toughener, 0.5 ~ 2 part of photoinitiator, 0.05 ~ 1 part of cobalt naphthenate, 10 ~ 30 parts of filler, 30 ~ 50 parts of diluent, 1) preparation method is the following steps are included: mix 0.5 ~ 2h of stirring for unsaturated polyester resin, epoxy resin and diluent, then toughener is added, stirring 1 ~ 2 hour, obtains resin mixture liquor；2) photoinitiator and filler are sequentially added into above-mentioned resin mixture liquor, cobalt naphthenate is added in stirring after a certain period of time, vacuum defoamation processing is carried out after continuing stirring, obtain product, the unsaturated polyester resin that this method is prepared has the quick-setting effect under action of ultraviolet light, and can preferably be applied to 3 D-printing field.The unsaturated polyester resin that the present invention can be used for rapid three dimensional printing forming has the features such as good, extremely low cure shrinkage of intensity, at low cost.
Description
Technical field
The present invention relates to unsaturated polyester resins to process preparation technical field, more particularly to can be used for 3 D-printing rapid-result fastly
Unsaturated polyester resin of type and preparation method thereof.
Background technique
Unsaturated polyester resin, by dihydric alcohol and unsaturated dicarboxylic acid anhydride or unsaturated dicarboxylic acid, monounsaturated dicarboxylic acid
Line style prepolymer made of acid anhydride or saturated dicarboxylic acid melt polycondensation, heating, illumination, radiation and photoinitiator effect under with
Vinyl monomer copolymerization, crosslinking curing are the thermosetting resin of network structure.Unsaturated polyester resin is due to excellent mouldability
It is concerned by people for a long time with good comprehensive service performance, is widely used in the fields such as building, ship, automobile, electronic apparatus,
It is the maximum resinoid of field of compound material dosage.
Three-dimensional printing technology is also known as increases material manufacturing technology, actually a kind of emerging technology of rapid shaping, with number
Based on simulation, successively printing is carried out using materials such as plastics, powdered-metals and realizes three-dimensional structure.Currently, 3 D-printing
It is mainly used for the fields such as product prototype, mold manufacture, jewelry-making, to substitute the field that tradition relies on retrofit.In addition, three
Dimension printing is gradually applied to the fields such as medicine, bioengineering, aviation, has biggish developing space.
The resin material of Stereolithography is mainly unsaturated polyester (UP), but the insatiable hunger currently used for 3 D-printing photocuring
That there are curing rates is slow, solidifies the disadvantages of photoinitiator additional amount used is big with polyester resin.It is therefore desirable to develop a kind of letter
Single easily unsaturated polyester resin three dimensional printing forming material.The advantages of such method, is that production technology is simpler
It is single, cheap, therefore application is also relatively broad.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide the unsaturation that can be used for rapid three dimensional printing forming is poly-
Ester resin and preparation method thereof, the unsaturated polyester resin prepared have the quick-setting effect under action of ultraviolet light, and
3 D-printing field can be preferably applied to.The unsaturated polyester resin that the present invention can be used for rapid three dimensional printing forming has strong
Spend, extremely low cure shrinkage, it is at low cost the features such as.
The present invention to solve above-mentioned technical problem the technical solution adopted is that: can be used for the insatiable hunger of rapid three dimensional printing forming
And polyester resin, it is to be grouped as by each group of following mass fraction: 50 ~ 100 parts of unsaturated polyester resin, epoxy resin 10 ~
50 parts, 10 ~ 50 parts of toughener, 0.5 ~ 2 part of photoinitiator, 0.05 ~ 1 part of cobalt naphthenate, 10 ~ 30 parts of filler, diluent 30 ~ 50
Part.
Further, the unsaturated polyester resin is O-phthalic acid type, M-phthalic acid type, bisphenol A-type and ethylene
One of fundamental mode unsaturated polyester resin or more than one mixture.
Further, the epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin
With one of acrylic acid epoxy resin or more than one mixture.
Further, toughener preparation method the following steps are included: (1), in terms of mass fraction, by styrene monomer 15
~ 35 parts, 2 ~ 5 parts of poly-methyl pyrrole alkanone, 5 ~ 10 parts of dodecyl benzene sulfonic acid be dissolved in 30 ~ 50 parts of deionized water, be in temperature
50 ~ 60 DEG C, mixing speed stirs 5 ~ 6h under conditions of being 500 ~ 650r/min, obtains white emulsion；(2), it is obtained in step (1)
White emulsion in be added 250 ~ 300 parts of dehydrated alcohol, be stirring evenly and then adding into ammonium hydroxide adjust pH to 9.5 ~ 10.5, positive silicon is added
5~10 parts of acetoacetic ester, be 35~45 DEG C in temperature, and mixing speed stirs 16~20h under conditions of being 250~300r/min, will
Obtained product is centrifuged, is washed, is dried, and polystyrene/silica dioxide core-shell structure microballoon toughener is obtained.
Further, the photoinitiator be Irgacure-2959, Irgacure-MBF, Irgacure-784,
One or more kinds of mixtures of Irgacure-TPO.
Further, the filler is one of carbon fiber, carbon nanotube and graphene or more than one mixture.
Further, the diluent be one of styrene, methyl methacrylate, acrylate or more than one
Mixture.
It can be used for the preparation method of the unsaturated polyester resin of rapid three dimensional printing forming, comprising the following steps:
It 1) is 10 ~ 50 DEG C in temperature by 50-100 parts of unsaturated polyester resin, 10 ~ 50 parts of epoxy resin, 30 ~ 50 parts of diluent
Under the conditions of stir 0.5 ~ 2h, then add 10 ~ 50 parts of toughener, temperature be 10 ~ 50 DEG C under conditions of stir 1 ~ 2 hour,
Obtain resin mixture liquor；
2) 0.5 ~ 2 part of photoinitiator is added into above-mentioned resin mixture liquor, after stirring 10 ~ 30min at being 50 ~ 60 DEG C in temperature
10 ~ 30 parts of filler are added, is added 0.05 ~ 1 part of cobalt naphthenate after continuing 0.5 ~ 1h of stirring under conditions of temperature is 50 ~ 60 DEG C,
Vacuum defoamation processing is carried out after continuing stirring 1 ~ 2 hour, obtains the unsaturated polyester resin that can be used for rapid three dimensional printing forming.
Beneficial effects of the present invention mainly show as follows: toughener-nucleocapsid knot is directly added into unsaturated polyester resin
Structure microballoon has preferable compatibility with unsaturated polyester resin system, overcomes directly due to containing polystyrene in microballoon
Be added nano silica dispersibility it is poor and the shortcomings that influence unsaturated polyester resin using effect, photoinitiator of the present invention is
German BASF photoinitiator Irgacure series, has the quick-setting effect under action of ultraviolet light, makes the insatiable hunger of preparation
3 D-printing field can be preferably applied to polyester resin.In addition, the present invention can reinforce this not by the way that some fillers are added
The mechanical strength of saturated polyester resin, the unsaturated polyester resin that the present invention can be used for rapid three dimensional printing forming have intensity
Good, extremely low cure shrinkage, it is at low cost the features such as, can satisfy industrial production demand, can be used for automobile, wind-powered electricity generation, high-speed rail, trip
The fields such as ship, building, shipbuilding, chemical industry equipment, electronic apparatus.
Specific embodiment
The present invention is described in detail in conjunction with the embodiments, the present embodiment based on the technical solution of the present invention, gives
Detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.It below will be right
The embodiment of technical solution of the present invention is described in detail.Following embodiment is only used for more clearly illustrating skill of the invention
Art scheme, therefore it is only used as example, and not intended to limit the protection scope of the present invention.Experiment side in following embodiments
Method is unless otherwise specified conventional method.Test material as used in the following examples is unless otherwise specified from often
Rule reagent shop is commercially available.Quantitative test in following embodiment, is respectively provided with three repeated experiments, and data are to repeat three times
The average value or mean+SD of experiment.
Embodiment 1
The unsaturated polyester resin that can be used for rapid three dimensional printing forming is grouped as by each group of following mass fraction: adjacent
50 parts of benzene-type unsaturated polyester resin, 10 parts of bisphenol A type epoxy resin, 10 parts of toughener, 0.5 part of Irgacure-2959, ring
0.05 part of alkanoic acid cobalt, 10 parts of carbon fiber, 30 parts of styrene.
It can be used for the preparation method of the unsaturated polyester resin of rapid three dimensional printing forming, comprising the following steps:
It 1) is 20 DEG C in temperature by 50 parts of m-phthalate unsaturated polyester resin, 10 parts of bisphenol A type epoxy resin, 30 parts of styrene
Under the conditions of stir 0.5 ~ 2h, then add 10 parts of toughener, temperature be 10 ~ 50 DEG C under conditions of stir 1 ~ 2 hour, must set
Rouge mixed liquor；
2) into above-mentioned resin mixture liquor be added 0.5 part of Irgacure-2959, temperature be 50 ~ 60 DEG C at stirring 10 ~
10 parts of carbon fiber are added after 30min, cobalt naphthenate 0.05 is added after continuing 0.5 ~ 1h of stirring under conditions of temperature is 50 ~ 60 DEG C
Part, vacuum defoamation processing is carried out after continuing stirring 1 ~ 2 hour, obtains the unsaturated polyester (UP) tree that can be used for rapid three dimensional printing forming
Rouge.
The preparation method of toughener the following steps are included: (1), in terms of mass fraction, by 15 ~ 35 parts of styrene monomer, poly-
2 ~ 5 parts of methyl pyrrolidone, 5 ~ 10 parts of dodecyl benzene sulfonic acid be dissolved in 30 ~ 50 parts of deionized water, temperature be 50 ~ 60 DEG C,
Mixing speed stirs 5 ~ 6h under conditions of being 500 ~ 650r/min, obtains white emulsion；(2), the white cream obtained in step (1)
250 ~ 300 parts of dehydrated alcohol are added in liquid, is stirring evenly and then adding into ammonium hydroxide and adjusts pH to 9.5 ~ 10.5, ethyl orthosilicate 5 is added
~10 parts, be 35~45 DEG C in temperature, mixing speed stirs 16~20h, the production that will be obtained under conditions of being 250~300r/min
Object is centrifuged, is washed, is dried, and the polystyrene/silica dioxide core-shell structure microballoon toughening that partial size is 50nm ~ 10 μm is obtained
Agent.
Embodiment 2
The unsaturated polyester resin that can be used for rapid three dimensional printing forming is grouped as by each group of following mass fraction:
60 parts of benzene-type unsaturated polyester resin, 20 parts of bisphenol f type epoxy resin, 20 parts of toughener, 0.8 part of Irgacure-MBF, cycloalkanes
0.08 part of sour cobalt, 12 parts of carbon nanotube, 32 parts of methyl methacrylate.
It can be used for the preparation method of the unsaturated polyester resin of rapid three dimensional printing forming, comprising the following steps:
1) by 60 parts of metaphenylene unsaturated polyester resin, 20 parts of bisphenol f type epoxy resin, 32 parts of methyl methacrylate in temperature
2h is stirred under conditions of being 30 DEG C, then adds 20 parts of toughener, is stirred 1 ~ 2 hour under conditions of temperature is 10 ~ 50 DEG C,
Obtain resin mixture liquor；
2) 0.8 part of Irgacure-MBF is added into above-mentioned resin mixture liquor, stirs 10 ~ 30min at being 50 ~ 60 DEG C in temperature
12 parts of carbon nanotube are added afterwards, cobalt naphthenate 0.05 ~ 1 is added after continuing 0.5 ~ 1h of stirring under conditions of temperature is 50 ~ 60 DEG C
Part, vacuum defoamation processing is carried out after continuing stirring 1 ~ 2 hour, obtains the unsaturated polyester (UP) tree that can be used for rapid three dimensional printing forming
Rouge.
Further, toughener preparation method the following steps are included: (1), in terms of mass fraction, by styrene monomer 15
~ 35 parts, 2 ~ 5 parts of poly-methyl pyrrole alkanone, 5 ~ 10 parts of dodecyl benzene sulfonic acid be dissolved in 30 ~ 50 parts of deionized water, be in temperature
50 ~ 60 DEG C, mixing speed stirs 5 ~ 6h under conditions of being 500 ~ 650r/min, obtains white emulsion；(2), it is obtained in step (1)
White emulsion in be added 250 ~ 300 parts of dehydrated alcohol, be stirring evenly and then adding into ammonium hydroxide adjust pH to 9.5 ~ 10.5, positive silicon is added
5~10 parts of acetoacetic ester, be 35~45 DEG C in temperature, and mixing speed stirs 16~20h under conditions of being 250~300r/min, will
Obtained product is centrifuged, is washed, is dried, and polystyrene/silica dioxide core-shell structure microballoon toughener is obtained.
Embodiment 3
The unsaturated polyester resin that can be used for rapid three dimensional printing forming is to be grouped as by each group of following mass fraction: double
70 parts of phenol A type unsaturated polyester resin, 30 parts of phenol aldehyde type epoxy resin, 30 parts of toughener, 1 part of Irgacure-784, aphthenic acids
0.05 ~ 1 part of cobalt, 15 parts of graphene, 36 parts of acrylate.
It can be used for the preparation method of the unsaturated polyester resin of rapid three dimensional printing forming, comprising the following steps:
It 1) is 40 in temperature by 70 parts of Bisphenol a unsaturated polyester resin, 30 parts of phenol aldehyde type epoxy resin, 36 parts of acrylate
0.5 ~ 2h is stirred under conditions of DEG C, then adds 30 parts of toughener, is stirred 1 ~ 2 hour under conditions of temperature is 10 ~ 50 DEG C,
Obtain resin mixture liquor；
2) 1 part of Irgacure-784 is added into above-mentioned resin mixture liquor, after stirring 10 ~ 30min at being 50 ~ 60 DEG C in temperature
15 parts of graphene are added, is added 0.05 ~ 1 part of cobalt naphthenate after continuing 0.5 ~ 1h of stirring under conditions of temperature is 50 ~ 60 DEG C, after
Continuous stirring carried out vacuum defoamation processing after 1 ~ 2 hour, obtained the unsaturated polyester resin that can be used for rapid three dimensional printing forming.
The preparation method of toughener the following steps are included: (1), in terms of mass fraction, by 15 ~ 35 parts of styrene monomer, poly-
2 ~ 5 parts of methyl pyrrolidone, 5 ~ 10 parts of dodecyl benzene sulfonic acid be dissolved in 30 ~ 50 parts of deionized water, temperature be 50 ~ 60 DEG C,
Mixing speed stirs 5 ~ 6h under conditions of being 500 ~ 650r/min, obtains white emulsion；(2), the white cream obtained in step (1)
250 ~ 300 parts of dehydrated alcohol are added in liquid, is stirring evenly and then adding into ammonium hydroxide and adjusts pH to 9.5 ~ 10.5, ethyl orthosilicate 5 is added
~10 parts, be 35~45 DEG C in temperature, mixing speed stirs 16~20h, the production that will be obtained under conditions of being 250~300r/min
Object is centrifuged, is washed, is dried, and polystyrene/silica dioxide core-shell structure microballoon toughener is obtained.
Embodiment 4
The unsaturated polyester resin that can be used for rapid three dimensional printing forming is to be grouped as by each group of following mass fraction: second
60 parts of alkenyl type unsaturated polyester resin, 20 parts of acrylic acid epoxy resin, 20 parts of toughener, 0.9 part of Irgacure-TPO, ring
0.06 part of alkanoic acid cobalt, 15 parts of carbon fiber, 40 parts of styrene.
It can be used for the preparation method of the unsaturated polyester resin of rapid three dimensional printing forming, comprising the following steps:
It 1) is 50 DEG C in temperature by 60 parts of vinyl-type unsaturated polyester resin, 20 parts of acrylic acid epoxy resin, 40 parts of styrene
Under conditions of stir 0.5 ~ 2h, then add 20 parts of toughener, temperature be 10 ~ 50 DEG C under conditions of stir 1 ~ 2 hour, obtain
Resin mixture liquor；
2) 0.9 part of Irgacure-TPO is added into above-mentioned resin mixture liquor, stirs 10 ~ 30min at being 50 ~ 60 DEG C in temperature
15 parts of carbon fiber are added afterwards, is added 0.06 part of cobalt naphthenate after continuing 0.5 ~ 1h of stirring under conditions of temperature is 50 ~ 60 DEG C,
Vacuum defoamation processing is carried out after continuing stirring 1 ~ 2 hour, obtains the unsaturated polyester resin that can be used for rapid three dimensional printing forming.
Further, toughener preparation method the following steps are included: (1), in terms of mass fraction, by styrene monomer 15
~ 35 parts, 2 ~ 5 parts of poly-methyl pyrrole alkanone, 5 ~ 10 parts of dodecyl benzene sulfonic acid be dissolved in 30 ~ 50 parts of deionized water, be in temperature
50 ~ 60 DEG C, mixing speed stirs 5 ~ 6h under conditions of being 500 ~ 650r/min, obtains white emulsion；(2), it is obtained in step (1)
White emulsion in be added 250 ~ 300 parts of dehydrated alcohol, be stirring evenly and then adding into ammonium hydroxide adjust pH to 9.5 ~ 10.5, positive silicon is added
5~10 parts of acetoacetic ester, be 35~45 DEG C in temperature, and mixing speed stirs 16~20h under conditions of being 250~300r/min, will
Obtained product is centrifuged, is washed, is dried, and polystyrene/silica dioxide core-shell structure microballoon toughener is obtained.
Embodiment 5
The unsaturated polyester resin that can be used for rapid three dimensional printing forming is grouped as by each group of following mass fraction: adjacent
80 parts of benzene-type unsaturated polyester resin, 30 parts of bisphenol A type epoxy resin, 30 parts of toughener, 1.4 parts of Irgacure-MBF, ring
0.08 part of alkanoic acid cobalt, 18 parts of carbon nanotube, 40 parts of methyl methacrylate.
It can be used for the preparation method of the unsaturated polyester resin of rapid three dimensional printing forming, comprising the following steps:
1) 80 parts of m-phthalate unsaturated polyester resin, 30 parts of bisphenol A type epoxy resin, 40 parts of methyl methacrylate are existed
Temperature stirs 0.5 ~ 2h under conditions of being 20 DEG C, then adds 30 parts of toughener, stirs under conditions of temperature is 10 ~ 50 DEG C
1 ~ 2 hour, obtain resin mixture liquor；
2) 1.4 parts of Irgacure-MBF are added into above-mentioned resin mixture liquor, stirs 10 ~ 30min at being 50 ~ 60 DEG C in temperature
18 parts of carbon nanotube are added afterwards, cobalt naphthenate 0.08 is added after continuing 0.5 ~ 1h of stirring under conditions of temperature is 50 ~ 60 DEG C
Part, vacuum defoamation processing is carried out after continuing stirring 1 ~ 2 hour, obtains the unsaturated polyester (UP) tree that can be used for rapid three dimensional printing forming
Rouge.
Further, toughener preparation method the following steps are included: (1), in terms of mass fraction, by styrene monomer 15
~ 35 parts, 2 ~ 5 parts of poly-methyl pyrrole alkanone, 5 ~ 10 parts of dodecyl benzene sulfonic acid be dissolved in 30 ~ 50 parts of deionized water, be in temperature
50 ~ 60 DEG C, mixing speed stirs 5 ~ 6h under conditions of being 500 ~ 650r/min, obtains white emulsion；(2), it is obtained in step (1)
White emulsion in be added 250 ~ 300 parts of dehydrated alcohol, be stirring evenly and then adding into ammonium hydroxide adjust pH to 9.5 ~ 10.5, positive silicon is added
5~10 parts of acetoacetic ester, be 35~45 DEG C in temperature, and mixing speed stirs 16~20h under conditions of being 250~300r/min, will
Obtained product is centrifuged, is washed, is dried, and polystyrene/silica dioxide core-shell structure microballoon toughener is obtained.
Embodiment 6
The unsaturated polyester resin that can be used for rapid three dimensional printing forming is to be grouped as by each group of following mass fraction: second
75 parts of alkenyl type unsaturated polyester resin, 25 parts of bisphenol f type epoxy resin, 25 parts of toughener, 1.2 parts of Irgacure-TPO,
0.075 part of cobalt naphthenate, 18 parts of graphene, 45 parts of acrylate.
It can be used for the preparation method of the unsaturated polyester resin of rapid three dimensional printing forming, comprising the following steps:
1) it is in temperature by 75 parts of vinyl-type unsaturated polyester resin, 25 parts of bisphenol f type epoxy resin, 45 parts of acrylate
0.5 ~ 2h is stirred under conditions of 30 DEG C, then adds 25 parts of toughener, and stirring 1 ~ 2 is small under conditions of temperature is 10 ~ 50 DEG C
When, obtain resin mixture liquor；
2) 1.2 parts of Irgacure-TPO are added into above-mentioned resin mixture liquor, stirs 10 ~ 30min at being 50 ~ 60 DEG C in temperature
18 parts of graphene are added afterwards, is added 0.075 part of cobalt naphthenate after continuing 0.5 ~ 1h of stirring under conditions of temperature is 50 ~ 60 DEG C,
Vacuum defoamation processing is carried out after continuing stirring 1 ~ 2 hour, obtains the unsaturated polyester resin that can be used for rapid three dimensional printing forming.
Further, toughener preparation method the following steps are included: (1), in terms of mass fraction, by styrene monomer 15
~ 35 parts, 2 ~ 5 parts of poly-methyl pyrrole alkanone, 5 ~ 10 parts of dodecyl benzene sulfonic acid be dissolved in 30 ~ 50 parts of deionized water, be in temperature
50 ~ 60 DEG C, mixing speed stirs 5 ~ 6h under conditions of being 500 ~ 650r/min, obtains white emulsion；(2), it is obtained in step (1)
White emulsion in be added 250 ~ 300 parts of dehydrated alcohol, be stirring evenly and then adding into ammonium hydroxide adjust pH to 9.5 ~ 10.5, positive silicon is added
5~10 parts of acetoacetic ester, be 35~45 DEG C in temperature, and mixing speed stirs 16~20h under conditions of being 250~300r/min, will
Obtained product is centrifuged, is washed, is dried, and polystyrene/silica dioxide core-shell structure microballoon toughener is obtained.
Measuring mechanical property is carried out to unsaturated polyester resin material made from Examples 1 to 6,
Tensile strength is tested by standard GBT1040, and bending strength is tested by standard GBT9341, and impact strength is by mark
Quasi- GBT1043 is tested, and test result is as shown in table 1.
Table 1
Toughener-core-shell structure microballoon is directly added into unsaturated polyester resin, since nano silica partial size is small, compares table
Area is larger, and adsorption ability is stronger, and chemical purity is high, is widely used in more multi-field.But nano silica is easy to reunite,
Dispersibility is poor, significantly impacts its service performance, due to containing polystyrene in microballoon, has with unsaturated polyester resin system
Have preferable compatibility, overcome be directly added into nano silica dispersibility it is poor and influence unsaturated polyester resin using effect
The shortcomings that fruit, it can effectively improve the toughness and tensile strength of the unsaturated polyester resin, photoinitiator of the present invention is Germany bar
This husband's photoinitiator Irgacure series, has the quick-setting effect under action of ultraviolet light, makes the unsaturated polyester (UP) of preparation
Resin can preferably be applied to 3 D-printing field.In addition, it is poly- can to reinforce the unsaturation by the way that some fillers are added by the present invention
The mechanical strength of ester resin, the unsaturated polyester resin that the present invention can be used for rapid three dimensional printing forming has intensity good, extremely low
Cure shrinkage, it is at low cost the features such as, can satisfy industrial production demand, can be used for automobile, wind-powered electricity generation, high-speed rail, yacht, build
It builds, shipbuilding, chemical industry equipment, the fields such as electronic apparatus.
Certainly, the case where being enumerated in addition to embodiment one to embodiment six, in the proportions of other raw material components, preparation process
Each condition and parameter etc. are also possible.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (8)
1. can be used for the unsaturated polyester resin of rapid three dimensional printing forming, it is characterised in that: it is by following mass fraction
Each group is grouped as: 50 ~ 100 parts of unsaturated polyester resin, 10 ~ 50 parts of epoxy resin, 10 ~ 50 parts of toughener, photoinitiator 0.5 ~ 2
Part, 0.05 ~ 1 part of cobalt naphthenate, 10 ~ 30 parts of filler, 30 ~ 50 parts of diluent.
2. the unsaturated polyester resin according to claim 1 that can be used for rapid three dimensional printing forming, it is characterised in that: institute
Stating unsaturated polyester resin is in O-phthalic acid type, M-phthalic acid type, bisphenol A-type and vinyl-type unsaturated polyester resin
One or more kinds of mixtures.
3. the unsaturated polyester resin according to claim 1 that can be used for rapid three dimensional printing forming, it is characterised in that: institute
Stating epoxy resin is in bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin and acrylic acid epoxy resin
One or more kinds of mixtures.
4. the unsaturated polyester resin according to claim 1 that can be used for rapid three dimensional printing forming, it is characterised in that: increase
Tough dose of preparation method the following steps are included: (1), in terms of mass fraction, by 15 ~ 35 parts of styrene monomer, poly-methyl pyrrole alkane
2 ~ 5 parts of ketone, 5 ~ 10 parts of dodecyl benzene sulfonic acid be dissolved in 30 ~ 50 parts of deionized water, be 50 ~ 60 DEG C in temperature, mixing speed is
5 ~ 6h is stirred under conditions of 500 ~ 650r/min, obtains white emulsion；(2), nothing is added in the white emulsion that step (1) obtains
It 250 ~ 300 parts of water-ethanol, is stirring evenly and then adding into ammonium hydroxide and adjusts pH to 9.5 ~ 10.5,5~10 parts of ethyl orthosilicate are added, in temperature
Degree is 35~45 DEG C, and mixing speed stirs 16~20h under conditions of being 250~300r/min, obtained product is centrifuged,
Washing, drying, obtain polystyrene/silica dioxide core-shell structure microballoon toughener.
5. the unsaturated polyester resin according to claim 1 that can be used for rapid three dimensional printing forming, it is characterised in that: institute
State one kind or one kind that photoinitiator is Irgacure-2959, Irgacure-MBF, Irgacure-784, Irgacure-TPO
Above mixture.
6. the unsaturated polyester resin according to claim 1 that can be used for rapid three dimensional printing forming, it is characterised in that: institute
Stating filler is one of carbon fiber, carbon nanotube and graphene or more than one mixture.
7. the unsaturated polyester resin according to claim 1 that can be used for rapid three dimensional printing forming, it is characterised in that: institute
Stating diluent is one of styrene, methyl methacrylate, acrylate or more than one mixture.
8. the preparation of described in any item unsaturated polyester resins that can be used for rapid three dimensional printing forming according to claim 1 ~ 7
Method, it is characterised in that: the following steps are included:
It 1) is 10 ~ 50 DEG C in temperature by 50-100 parts of unsaturated polyester resin, 10 ~ 50 parts of epoxy resin, 30 ~ 50 parts of diluent
Under the conditions of stir 0.5 ~ 2h, then add 10 ~ 50 parts of toughener, temperature be 10 ~ 50 DEG C under conditions of stir 1 ~ 2 hour,
Obtain resin mixture liquor；
2) 0.5 ~ 2 part of photoinitiator is added into above-mentioned resin mixture liquor, after stirring 10 ~ 30min at being 50 ~ 60 DEG C in temperature
10 ~ 30 parts of filler are added, is added 0.05 ~ 1 part of cobalt naphthenate after continuing 0.5 ~ 1h of stirring under conditions of temperature is 50 ~ 60 DEG C,
Vacuum defoamation processing is carried out after continuing stirring 1 ~ 2 hour, obtains the unsaturated polyester resin that can be used for rapid three dimensional printing forming.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811063062.1A CN109354849A (en) | 2018-09-12 | 2018-09-12 | It can be used for the unsaturated polyester resin and preparation method thereof of rapid three dimensional printing forming |
Applications Claiming Priority (1)
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| CN113150496B (en) * | 2021-04-09 | 2023-09-05 | 上纬新材料科技股份有限公司 | Epoxy resin reinforced material |
| CN114773788A (en) * | 2022-05-11 | 2022-07-22 | 泉州师范学院 | Photosensitive resin composition based on nano silicon rubber core-shell structure polymer toughened epoxy resin and application of photosensitive resin composition in 3D printing |
| CN114773788B (en) * | 2022-05-11 | 2023-09-19 | 泉州师范学院 | Photosensitive resin composition based on nano silicone rubber core-shell structure polymer toughened epoxy resin and application of photosensitive resin composition in 3D printing |
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Application publication date: 20190219 |