CN108148355A - It is a kind of for nylon micro-sphere composite material of Stereolithography and preparation method thereof - Google Patents
It is a kind of for nylon micro-sphere composite material of Stereolithography and preparation method thereof Download PDFInfo
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- CN108148355A CN108148355A CN201611105220.6A CN201611105220A CN108148355A CN 108148355 A CN108148355 A CN 108148355A CN 201611105220 A CN201611105220 A CN 201611105220A CN 108148355 A CN108148355 A CN 108148355A
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/004—Additives being defined by their length
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- 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
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Abstract
The present invention provides a kind of for nylon micro-sphere composite material of Stereolithography and preparation method thereof, belong to photosensitive resin and be modified field.It is made of following raw material in mass ratio：1~5 part of 25~45 parts of acrylate, 25~45 parts of epoxy resin, 5~25 parts of nylon micro-sphere, 5~25 parts of ultrashort glass, 0.2~1 part of coupling agent, 0.02~0.1 part of the steady agent of light, 5~25 parts of diluent, 0.5~2.5 part of antifoaming agent, 0.5~2.5 part of levelling agent, 0.02~0.1 part of antioxidant, 1~5 part of cationic initiators and free radical type Photoepolymerizationinitiater initiater are prepared.The present invention is innovatively with ultrashort glass modification of nylon microballoon material, it is prepared for the nylon micro-sphere composite material for Stereolithography, prepared composite material has the strong and excellent shaping speed of big mechanical strength, good stability of the dimension, wearability, composite material synthesis cost is cut down simultaneously, in addition production equipment according to the present invention and Product Process are simple, and composite material can be directly used for photocureable rapid shaping field.
Description
Technical field
The present invention provides a kind of for nylon micro-sphere composite material of Stereolithography and preparation method thereof, belong to photosensitive
Field of resin modification.
Background technology
Stereolithography be one kind using oligomer or prepolymer as raw material, will be in raw material using ultraviolet light or laser as the energy
Carbon-carbon single bond destroy after form free radical, and a kind of rapid shaping of polymerizing curable is completed under initiator and catalyst action
Mode.Photocuring is often prepolymer and the liquid photosensitive resin of monomer composition with raw material, and often there are curing efficiency is low, size is steady
The deficiencies of qualitative difference and poor mechanical strength.
Photosensitive resin is usually made of monomer, performed polymer or prepolymer, and type is less, and there is speed in material building process
The deficiencies of spending slow, poor toughness and poor dimensional stability, and pure resin wearability is poor.The present invention is using microballoons such as nylon micro-spheres
The pure photosensitive resin of class material modification, can improve product size stability and mechanical strength to a certain extent, and the present invention is innovative
With ultrashort glass and the composite modified liquid photosensitive resin of nylon micro-sphere, be prepared for compound for the nylon micro-sphere of Stereolithography
Material, prepared composite material have the strong and excellent shaping speed of big mechanical strength, good stability of the dimension, wearability,
Composite material synthesis cost is cut down simultaneously, and production equipment according to the present invention and Product Process are simple in addition, composite wood
Material can be directly used for photocureable rapid shaping field.
Invention content
The present invention provides a kind of for nylon micro-sphere composite material of Stereolithography and preparation method thereof, belong to photosensitive
Field of resin modification.Innovatively with ultrashort glass modification of nylon microballoon photosensitive resin composite material, it is prepared for for photocuring
Molding nylon micro-sphere composite material, prepared composite material have mechanical strength is big, good stability of the dimension, wearability by force with
And excellent shaping speed, while composite material synthesis cost is cut down, production equipment according to the present invention and production in addition
Product are simple for process, and composite material can be directly used for photocureable rapid shaping field.
To achieve the above object, the present invention uses following technical scheme：
A kind of nylon micro-sphere composite material for Stereolithography is prepared by weight by following components：
25~45 parts of acrylate,
25~45 parts of epoxy resin,
5~25 parts of nylon micro-sphere,
Ultrashort 5~25 parts of glass,
0.2~1 part of coupling agent,
0.02~0.1 part of the steady agent of light,
5~25 parts of diluent,
0.5~2.5 part of antifoaming agent,
0.5~2.5 part of levelling agent,
0.02~0.1 part of antioxidant,
1~5 part of cationic initiators,
1~5 part of free radical type Photoepolymerizationinitiater initiater.
The acrylate is epoxy monoacrylate or polyester acrylate；The epoxy resin is four phenolic group rings
Oxygen resin or glycerol epoxy resin.
The nylon micro-sphere is 6 microballoon of nylon 4 or nylon, and grain size is 0.1~500 μm.
The ultrashort Length of Glass Fiber is 50~100 μm.
The coupling agent is gamma-aminopropyl-triethoxy-silane or γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicon
Alkane.
The steady agent of the light is 2-hydroxy-4-n-octoxybenzophenone or chlorination benzotriazole.
The diluent is ethylene glycol diglycidylether or tripropyleneglycol diglycidyl ether；The antifoaming agent is
Dimethyl polysiloxane or polyether silicone；The levelling agent is organosilicon-epoxide ethane copolymer or organosilicon-epoxide third
Alkyl copolymer.
Described is a kind of for nylon micro-sphere composite material of Stereolithography and preparation method thereof, it is characterised in that：Institute
The antioxidant stated is four (3,5- di-t-butyl -4- hydroxyls) benzenpropanoic acid pentaerythritol esters, three (2,4- di-t-butyls) phosphorous acid benzene
Ester or N, N'- it is bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine.
The cationic initiators are diphenyl iodnium or diaryl sulfonium salt；The free radical type photopolymerization
Initiator is dimethoxybenzoin or benzophenone.
A kind of preparation method of nylon micro-sphere composite material for Stereolithography, includes the following steps：
(1) 25~45 parts of acrylate, 25~45 parts of epoxy resin, nylon micro-sphere 5 are sequentially added by proportioning in a reservoir
~25 parts, 5~25 parts of diluent, 0.5~2.5 part of antifoaming agent, 0.5~2.5 part of levelling agent, 1~5 part of cationic initiators and
1~5 part of free radical type Photoepolymerizationinitiater initiater is simultaneously kept stirring；
(2) added in aforesaid liquid ultrashort 5~25 parts of glass, 0.2~1 part of coupling agent, 0.02~0.1 part of the steady agent of light and
Above-mentioned mixed liquor is warming up to 45 DEG C~85 DEG C and controls condensation, ultrasonic disperse 10min~30min by 0.02~0.1 part of antioxidant
To uniform state, a kind of nylon micro-sphere composite material for Stereolithography is obtained.
It is of the invention innovative with ultrashort glass and the composite modified liquid photosensitive resin of nylon micro-sphere, be prepared for consolidating for light
Change molding nylon micro-sphere composite material, have the advantages that：
1st, buffering and energy-absorbing function are played in the introducing of nylon micro-sphere in the composite, play toughening effect, significantly improve
The impact strength of composite material；
2nd, glass fiber material has greater advantage compared with the dimensional stability of photosensitive resin, and composite material is significantly reduced after introducing
Shrinking percentage improves dimensional stability；
3rd, nylon micro-sphere and glass fiber material play the role of wear-resisting jointly, improve the wearability of composite material；
4th, microballoon and fibre structure play the role of support and frame in liquid phase solidification process, can effectively improve composite wood
The curing efficiency of material accelerates speed of embarking on journey；
5th, first Matrix Solution is stirred evenly in preparation process, the resin solidification effect in solidification process can be effectively ensured
Rate；After add in ultrashort glass and coupling agent and continue to stir, the uniform distribution of forces of dispersed phase in the base can be improved, formed
Preferable homogeneous phase ensure that the stability of composite property.
Therefore the composite material prepared by the present invention has mechanical strength big, good stability of the dimension, the wearability strong and excellent
Different shaping speed, while composite material synthesis cost is cut down, production equipment according to the present invention and product work in addition
Skill is simple, and composite material can be directly used for photocureable rapid shaping field.
Specific implementation method
The content of present invention is further detailed with reference to specific example, but it is to this hair that the embodiment, which is not,
The simple restriction of bright connotation, any simple change or equivalent replacement based on made by true spirit should all belong to
Within scope of the present invention.Unless otherwise instructed, number described in each example is parts by weight.
After the sample of preparation is adjusted under 23 DEG C, 50% humidity environment, be respectively adopted ASTM D6110, ASTM D955 and
ASTM D1242 detect impact strength, shrinking percentage and the wearability of composite material, while the shaping speed of recording materials.
Specific embodiments of the present invention are as follows：
Embodiment 1
(1) it is equipped with raw material in the following proportions：
25 parts of epoxy monoacrylate,
Four 45 parts of phenolic group epoxy resin,
5 parts of 4 microballoon of nylon,
Ultrashort 25 parts of glass,
0.2 part of coupling agent gamma-aminopropyl-triethoxy-silane,
0.02 part of the steady agent 2-hydroxy-4-n-octoxybenzophenone of light,
5 parts of diluent ethylene glycol diglycidylether,
0.5 part of antifoaming agent dimethyl polysiloxane,
0.5 part of levelling agent organosilicon-epoxide ethane copolymer,
Antioxidant four (3,5- di-t-butyl -4- hydroxyls) 0.008 part of benzenpropanoic acid pentaerythritol ester,
0.012 part of antioxidant three (2,4- di-t-butyl) phenyl-phosphite,
1 part of cationic initiators diphenyl iodnium,
1 part of free radical type Photoepolymerizationinitiater initiater dimethoxybenzoin.
(2) acrylate, epoxy resin, nylon micro-sphere, diluent, antifoaming agent, stream are sequentially added by proportioning in a reservoir
Flat agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater are simultaneously kept stirring；
(3) the steady agent of ultrashort glass, coupling agent, light and antioxidant are added in aforesaid liquid, above-mentioned mixed liquor is warming up to
45 DEG C and condensation is controlled, it is compound to obtain a kind of nylon micro-sphere for Stereolithography by ultrasonic disperse 10min to uniform state
Material；
(4) detection performance after Stereolithography of composite material obtained by.
It is prepared a kind of to be shown in Table one for the nylon micro-sphere composite property of Stereolithography.
Embodiment 2
(1) it is equipped with raw material in the following proportions：
30 parts of epoxy monoacrylate,
Four 40 parts of phenolic group epoxy resin,
10 parts of 4 microballoon of nylon,
Ultrashort 20 parts of glass,
0.4 part of coupling agent gamma-aminopropyl-triethoxy-silane,
0.04 part of the steady agent 2-hydroxy-4-n-octoxybenzophenone of light,
10 parts of diluent ethylene glycol diglycidylether,
1 part of antifoaming agent dimethyl polysiloxane,
Levelling agent organosilicon-epoxide ethane copolymer 1 part,
Antioxidant four (3,5- di-t-butyl -4- hydroxyls) 0.016 part of benzenpropanoic acid pentaerythritol ester,
0.024 part of antioxidant three (2,4- di-t-butyl) phenyl-phosphite,
2 parts of cationic initiators diphenyl iodnium,
2 parts of free radical type Photoepolymerizationinitiater initiater dimethoxybenzoin.
(2) acrylate, epoxy resin, nylon micro-sphere, diluent, antifoaming agent, stream are sequentially added by proportioning in a reservoir
Flat agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater are simultaneously kept stirring；
(3) the steady agent of ultrashort glass, coupling agent, light and antioxidant are added in aforesaid liquid, above-mentioned mixed liquor is warming up to
55 DEG C and condensation is controlled, it is compound to obtain a kind of nylon micro-sphere for Stereolithography by ultrasonic disperse 15min to uniform state
Material；
(4) detection performance after Stereolithography of composite material obtained by.
It is prepared a kind of to be shown in Table one for the nylon micro-sphere composite property of Stereolithography.
Embodiment 3
(1) it is equipped with raw material in the following proportions：
35 parts of epoxy monoacrylate,
Four 35 parts of phenolic group epoxy resin,
15 parts of 4 microballoon of nylon,
Ultrashort 15 parts of glass,
0.6 part of coupling agent gamma-aminopropyl-triethoxy-silane,
0.06 part of the steady agent 2-hydroxy-4-n-octoxybenzophenone of light,
15 parts of diluent ethylene glycol diglycidylether,
1.5 parts of antifoaming agent dimethyl polysiloxane,
.5 parts of levelling agent organosilicon-epoxide ethane copolymer 1,
Antioxidant four (3,5- di-t-butyl -4- hydroxyls) 0.024 part of benzenpropanoic acid pentaerythritol ester,
0.048 part of antioxidant three (2,4- di-t-butyl) phenyl-phosphite,
3 parts of cationic initiators diphenyl iodnium,
3 parts of free radical type Photoepolymerizationinitiater initiater dimethoxybenzoin.
(2) acrylate, epoxy resin, nylon micro-sphere, diluent, antifoaming agent, stream are sequentially added by proportioning in a reservoir
Flat agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater are simultaneously kept stirring；
(3) the steady agent of ultrashort glass, coupling agent, light and antioxidant are added in aforesaid liquid, above-mentioned mixed liquor is warming up to
65 DEG C and condensation is controlled, it is compound to obtain a kind of nylon micro-sphere for Stereolithography by ultrasonic disperse 20min to uniform state
Material；
(4) detection performance after Stereolithography of composite material obtained by.
It is prepared a kind of to be shown in Table one for the nylon micro-sphere composite property of Stereolithography.
Embodiment 4
(1) it is equipped with raw material in the following proportions：
40 parts of epoxy monoacrylate,
Four 30 parts of phenolic group epoxy resin,
20 parts of 4 microballoon of nylon,
Ultrashort 10 parts of glass,
0.8 part of coupling agent gamma-aminopropyl-triethoxy-silane,
0.08 part of the steady agent 2-hydroxy-4-n-octoxybenzophenone of light,
20 parts of diluent ethylene glycol diglycidylether,
2 parts of antifoaming agent dimethyl polysiloxane,
2 parts of levelling agent organosilicon-epoxide ethane copolymer,
Antioxidant four (3,5- di-t-butyl -4- hydroxyls) 0.032 part of benzenpropanoic acid pentaerythritol ester,
0.05 part of antioxidant three (2,4- di-t-butyl) phenyl-phosphite,
4 parts of cationic initiators diphenyl iodnium,
4 parts of free radical type Photoepolymerizationinitiater initiater dimethoxybenzoin.
(2) acrylate, epoxy resin, nylon micro-sphere, diluent, antifoaming agent, stream are sequentially added by proportioning in a reservoir
Flat agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater are simultaneously kept stirring；
(3) the steady agent of ultrashort glass, coupling agent, light and antioxidant are added in aforesaid liquid, above-mentioned mixed liquor is warming up to
75 DEG C and condensation is controlled, it is compound to obtain a kind of nylon micro-sphere for Stereolithography by ultrasonic disperse 25min to uniform state
Material；
(4) detection performance after Stereolithography of composite material obtained by.
It is prepared a kind of to be shown in Table one for the nylon micro-sphere composite property of Stereolithography.
Embodiment 5
(1) it is equipped with raw material in the following proportions：
45 parts of epoxy monoacrylate,
Four 25 parts of phenolic group epoxy resin,
25 parts of 4 microballoon of nylon,
Ultrashort 5 parts of glass,
1 part of coupling agent gamma-aminopropyl-triethoxy-silane,
0.1 part of the steady agent 2-hydroxy-4-n-octoxybenzophenone of light,
25 parts of diluent ethylene glycol diglycidylether,
2.5 parts of antifoaming agent dimethyl polysiloxane,
2.5 parts of levelling agent organosilicon-epoxide ethane copolymer,
Antioxidant four (3,5- di-t-butyl -4- hydroxyls) 0.04 part of benzenpropanoic acid pentaerythritol ester,
0.06 part of antioxidant three (2,4- di-t-butyl) phenyl-phosphite,
5 parts of cationic initiators diphenyl iodnium,
5 parts of free radical type Photoepolymerizationinitiater initiater dimethoxybenzoin.
(2) acrylate, epoxy resin, nylon micro-sphere, diluent, antifoaming agent, stream are sequentially added by proportioning in a reservoir
Flat agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater are simultaneously kept stirring；
(3) the steady agent of ultrashort glass, coupling agent, light and antioxidant are added in aforesaid liquid, above-mentioned mixed liquor is warming up to
85 DEG C and condensation is controlled, it is compound to obtain a kind of nylon micro-sphere for Stereolithography by ultrasonic disperse 30min to uniform state
Material；
(4) detection performance after Stereolithography of composite material obtained by.
It is prepared a kind of to be shown in Table one for the nylon micro-sphere composite property of Stereolithography.
Embodiment 6
(1) it is equipped with raw material in the following proportions：
25 parts of polyester acrylate,
45 parts of glycerol epoxy resin,
5 parts of 6 microballoon of nylon,
Ultrashort 25 parts of glass,
Coupling agent γ-(2,3- the third oxygen of epoxy) 0.2 part of propyl trimethoxy silicane,
0.02 part of the steady agent chlorination benzotriazole of light,
5 parts of diluent tripropyleneglycol diglycidyl ether,
0.5 part of antifoaming agent polyether silicone,
0.5 part of levelling agent organosilicon-epoxide propane copolymer,
Antioxidant four (3,5- di-t-butyl -4- hydroxyls) 0.008 part of benzenpropanoic acid pentaerythritol ester,
Antioxidant N, N'- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) 0.012 part of hexamethylene diamine,
1 part of cationic initiators diaryl sulfonium salt,
1 part of free radical type Photoepolymerizationinitiater initiater benzophenone.
(2) acrylate, epoxy resin, nylon micro-sphere, diluent, antifoaming agent, stream are sequentially added by proportioning in a reservoir
Flat agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater are simultaneously kept stirring；
(3) the steady agent of ultrashort glass, coupling agent, light and antioxidant are added in aforesaid liquid, above-mentioned mixed liquor is warming up to
45 DEG C and condensation is controlled, it is compound to obtain a kind of nylon micro-sphere for Stereolithography by ultrasonic disperse 10min to uniform state
Material；
(4) detection performance after Stereolithography of composite material obtained by.
It is prepared a kind of to be shown in Table one for the nylon micro-sphere composite property of Stereolithography.
Embodiment 7
(1) it is equipped with raw material in the following proportions：
30 parts of polyester acrylate,
40 parts of glycerol epoxy resin,
10 parts of 6 microballoon of nylon,
Ultrashort 20 parts of glass,
Coupling agent γ-(2,3- the third oxygen of epoxy) 0.4 part of propyl trimethoxy silicane,
0.04 part of the steady agent chlorination benzotriazole of light,
10 parts of diluent tripropyleneglycol diglycidyl ether,
1 part of antifoaming agent polyether silicone,
Levelling agent organosilicon-epoxide propane copolymer 1 part,
Antioxidant four (3,5- di-t-butyl -4- hydroxyls) 0.016 part of benzenpropanoic acid pentaerythritol ester,
Antioxidant N, N'- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) 0.024 part of hexamethylene diamine,
2 parts of cationic initiators diaryl sulfonium salt,
2 parts of free radical type Photoepolymerizationinitiater initiater benzophenone.
(2) acrylate, epoxy resin, nylon micro-sphere, diluent, antifoaming agent, stream are sequentially added by proportioning in a reservoir
Flat agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater are simultaneously kept stirring；
(3) the steady agent of ultrashort glass, coupling agent, light and antioxidant are added in aforesaid liquid, above-mentioned mixed liquor is warming up to
55 DEG C and condensation is controlled, it is compound to obtain a kind of nylon micro-sphere for Stereolithography by ultrasonic disperse 15min to uniform state
Material；
(4) detection performance after Stereolithography of composite material obtained by.
It is prepared a kind of to be shown in Table one for the nylon micro-sphere composite property of Stereolithography.
Embodiment 8
(1) it is equipped with raw material in the following proportions：
35 parts of polyester acrylate,
35 parts of glycerol epoxy resin,
15 parts of 6 microballoon of nylon,
Ultrashort 15 parts of glass,
Coupling agent γ-(2,3- the third oxygen of epoxy) 0.6 part of propyl trimethoxy silicane,
0.06 part of the steady agent chlorination benzotriazole of light,
15 parts of diluent tripropyleneglycol diglycidyl ether,
1.5 parts of antifoaming agent polyether silicone,
.5 parts of levelling agent organosilicon-epoxide propane copolymer 1,
Antioxidant four (3,5- di-t-butyl -4- hydroxyls) 0.024 part of benzenpropanoic acid pentaerythritol ester,
Antioxidant N, N'- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) 0.048 part of hexamethylene diamine,
3 parts of cationic initiators diaryl sulfonium salt,
3 parts of free radical type Photoepolymerizationinitiater initiater benzophenone.
(2) acrylate, epoxy resin, nylon micro-sphere, diluent, antifoaming agent, stream are sequentially added by proportioning in a reservoir
Flat agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater are simultaneously kept stirring；
(3) the steady agent of ultrashort glass, coupling agent, light and antioxidant are added in aforesaid liquid, above-mentioned mixed liquor is warming up to
65 DEG C and condensation is controlled, it is compound to obtain a kind of nylon micro-sphere for Stereolithography by ultrasonic disperse 20min to uniform state
Material；
(4) detection performance after Stereolithography of composite material obtained by.
It is prepared a kind of to be shown in Table one for the nylon micro-sphere composite property of Stereolithography.
Embodiment 9
(1) it is equipped with raw material in the following proportions：
40 parts of polyester acrylate,
30 parts of glycerol epoxy resin,
20 parts of 6 microballoon of nylon,
Ultrashort 10 parts of glass,
Coupling agent γ-(2,3- the third oxygen of epoxy) 0.8 part of propyl trimethoxy silicane,
0.08 part of the steady agent chlorination benzotriazole of light,
20 parts of diluent tripropyleneglycol diglycidyl ether,
2 parts of antifoaming agent polyether silicone,
2 parts of levelling agent organosilicon-epoxide propane copolymer,
Antioxidant four (3,5- di-t-butyl -4- hydroxyls) 0.032 part of benzenpropanoic acid pentaerythritol ester,
Antioxidant N, N'- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) 0.05 part of hexamethylene diamine,
4 parts of cationic initiators diaryl sulfonium salt,
4 parts of free radical type Photoepolymerizationinitiater initiater benzophenone.
(2) acrylate, epoxy resin, nylon micro-sphere, diluent, antifoaming agent, stream are sequentially added by proportioning in a reservoir
Flat agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater are simultaneously kept stirring；
(3) the steady agent of ultrashort glass, coupling agent, light and antioxidant are added in aforesaid liquid, above-mentioned mixed liquor is warming up to
75 DEG C and condensation is controlled, it is compound to obtain a kind of nylon micro-sphere for Stereolithography by ultrasonic disperse 25min to uniform state
Material；
(4) detection performance after Stereolithography of composite material obtained by.
It is prepared a kind of to be shown in Table one for the nylon micro-sphere composite property of Stereolithography.
Embodiment 10
(1) it is equipped with raw material in the following proportions：
45 parts of polyester acrylate,
25 parts of glycerol epoxy resin,
25 parts of 6 microballoon of nylon,
Ultrashort 5 parts of glass,
Coupling agent γ-(2,3- the third oxygen of epoxy) 1 part of propyl trimethoxy silicane,
0.1 part of the steady agent chlorination benzotriazole of light,
25 parts of diluent tripropyleneglycol diglycidyl ether,
2.5 parts of antifoaming agent polyether silicone,
2.5 parts of levelling agent organosilicon-epoxide propane copolymer,
Antioxidant four (3,5- di-t-butyl -4- hydroxyls) 0.04 part of benzenpropanoic acid pentaerythritol ester,
Antioxidant N, N'- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) 0.06 part of hexamethylene diamine,
5 parts of cationic initiators diaryl sulfonium salt,
5 parts of free radical type Photoepolymerizationinitiater initiater benzophenone.
(2) acrylate, epoxy resin, nylon micro-sphere, diluent, antifoaming agent, stream are sequentially added by proportioning in a reservoir
Flat agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater are simultaneously kept stirring；
(3) the steady agent of ultrashort glass, coupling agent, light and antioxidant are added in aforesaid liquid, above-mentioned mixed liquor is warming up to
85 DEG C and condensation is controlled, it is compound to obtain a kind of nylon micro-sphere for Stereolithography by ultrasonic disperse 30min to uniform state
Material；
(4) detection performance after Stereolithography of composite material obtained by.
It is prepared a kind of to be shown in Table one for the nylon micro-sphere composite property of Stereolithography.
Comparative example 1
(1) it is equipped with raw material in the following proportions：
25 parts of epoxy monoacrylate,
Four 45 parts of phenolic group epoxy resin,
Ultrashort 25 parts of glass,
0.2 part of coupling agent gamma-aminopropyl-triethoxy-silane,
0.02 part of the steady agent 2-hydroxy-4-n-octoxybenzophenone of light,
5 parts of diluent ethylene glycol diglycidylether,
0.5 part of antifoaming agent dimethyl polysiloxane,
0.5 part of levelling agent organosilicon-epoxide ethane copolymer,
Antioxidant four (3,5- di-t-butyl -4- hydroxyls) 0.008 part of benzenpropanoic acid pentaerythritol ester,
0.012 part of antioxidant three (2,4- di-t-butyl) phenyl-phosphite,
1 part of cationic initiators diphenyl iodnium,
1 part of free radical type Photoepolymerizationinitiater initiater dimethoxybenzoin.
(2) in a reservoir by proportioning sequentially add acrylate, epoxy resin, diluent, antifoaming agent, levelling agent, sun from
Subtype initiator and free radical type Photoepolymerizationinitiater initiater are simultaneously kept stirring；
(3) the steady agent of ultrashort glass, coupling agent, light and antioxidant are added in aforesaid liquid, above-mentioned mixed liquor is warming up to
45 DEG C and condensation is controlled, it is compound to obtain a kind of nylon micro-sphere for Stereolithography by ultrasonic disperse 10min to uniform state
Material；
(4) detection performance after Stereolithography of composite material obtained by.
Prepared ultrashort glass modified light-sensitive resin composite materials performance is shown in Table one.
Comparative example 2
(1) it is equipped with raw material in the following proportions：
25 parts of epoxy monoacrylate,
Four 45 parts of phenolic group epoxy resin,
5 parts of 4 microballoon of nylon,
0.02 part of the steady agent 2-hydroxy-4-n-octoxybenzophenone of light,
5 parts of diluent ethylene glycol diglycidylether,
0.5 part of antifoaming agent dimethyl polysiloxane,
0.5 part of levelling agent organosilicon-epoxide ethane copolymer,
Antioxidant four (3,5- di-t-butyl -4- hydroxyls) 0.008 part of benzenpropanoic acid pentaerythritol ester,
0.012 part of antioxidant three (2,4- di-t-butyl) phenyl-phosphite,
1 part of cationic initiators diphenyl iodnium,
1 part of free radical type Photoepolymerizationinitiater initiater dimethoxybenzoin.
(2) acrylate, epoxy resin, nylon micro-sphere, diluent, antifoaming agent, stream are sequentially added by proportioning in a reservoir
Flat agent, cationic initiators and free radical type Photoepolymerizationinitiater initiater are simultaneously kept stirring；
(3) the steady agent of light and antioxidant are added in aforesaid liquid, above-mentioned mixed liquor is warming up to 45 DEG C and controls condensation, is surpassed
Sound disperses 10min to uniform state, obtains a kind of nylon micro-sphere composite material for Stereolithography；
(4) detection performance after Stereolithography of composite material obtained by.
Prepared nylon micro-sphere modified light-sensitive resin composite materials performance is shown in Table one.
Table one：
| Performance | Impact strength (J/m) | Shrinking percentage (%) | Taber Abrasion (mg/1000 times) | Shaping speed (cm3/h) |
| Embodiment 1 | 39 | 0.78 | 24 | 34 |
| Embodiment 2 | 41 | 0.75 | 22 | 35 |
| Embodiment 3 | 43 | 0.72 | 21 | 36 |
| Embodiment 4 | 46 | 0.71 | 19 | 38 |
| Embodiment 5 | 45 | 0.73 | 20 | 37 |
| Embodiment 6 | 37 | 0.79 | 25 | 33 |
| Embodiment 7 | 40 | 0.76 | 23 | 34 |
| Embodiment 8 | 42 | 0.74 | 22 | 35 |
| Embodiment 9 | 45 | 0.73 | 20 | 37 |
| Embodiment 10 | 44 | 0.75 | 21 | 36 |
| Comparative example 1 | 33 | 1.00 | 32 | 31 |
| Comparative example 2 | 29 | 1.10 | 35 | 25 |
Composite material prepared by the present invention have mechanical strength big, good stability of the dimension, wearability it is strong and it is excellent into
The features such as type speed.By data in table one it is found that the nylon micro-sphere composite material for Stereolithography for preparing of the present invention,
Impact strength is up to 46J/m, and more ultrashort glass modified light-sensitive resin material (comparative example 1) improves 39.4%, compared with nylon micro-sphere
Modified light-sensitive resin material (comparative example 2) improves 58.6%；Shrinking percentage minimum 0.71%, more ultrashort glass modified light-sensitive resin
Material (comparative example 1) reduces by 29.0%, and 35.5% is reduced compared with nylon micro-sphere modified light-sensitive resin material (comparative example 2)；Taibo is ground
Consume 19mg/1000 times minimum, more ultrashort glass modified light-sensitive resin material (comparative example 1) reduction by 40.6%, compared with nylon micro-sphere
Modified light-sensitive resin material (comparative example 2) reduces by 45.7%；It embarks on journey fastest for 38cm3/ h, more ultrashort glass modified light-sensitive
Resin material (comparative example 1) improves 22.6%, and 52.0% is improved compared with nylon micro-sphere modified light-sensitive resin material (comparative example 2).This
Composite material synthesis cost prepared by the outer present invention is cut down, and involved production equipment and Product Process are simple, compound
Material can be directly used for photocureable rapid shaping field.
It is understood that the above description of the embodiments is intended to facilitate those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make various modifications, and described herein to these embodiments
General Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to implementations here
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (10)
1. a kind of nylon micro-sphere composite material for Stereolithography, it is characterised in that：It is prepared by weight by following components
It forms：
25~45 parts of acrylate,
25~45 parts of epoxy resin,
5~25 parts of nylon micro-sphere,
Ultrashort 5~25 parts of glass,
0.2~1 part of coupling agent,
0.02~0.1 part of the steady agent of light,
5~25 parts of diluent,
0.5~2.5 part of antifoaming agent,
0.5~2.5 part of levelling agent,
0.02~0.1 part of antioxidant,
1~5 part of cationic initiators,
1~5 part of free radical type Photoepolymerizationinitiater initiater.
2. a kind of nylon micro-sphere composite material for Stereolithography according to claim 1, it is characterised in that：It is described
Acrylate be epoxy monoacrylate or polyester acrylate；The epoxy resin is four phenolic group epoxy resin or the third three
Alcohol epoxy resin.
3. a kind of nylon micro-sphere composite material for Stereolithography according to claim 1, it is characterised in that：It is described
Nylon micro-sphere for 6 microballoon of nylon 4 or nylon, grain size is 0.1~500 μm.
4. a kind of nylon micro-sphere composite material for Stereolithography according to claim 1, it is characterised in that：It is described
Ultrashort Length of Glass Fiber be 50~100 μm.
5. a kind of nylon micro-sphere composite material for Stereolithography according to claim 1, it is characterised in that：It is described
Coupling agent be gamma-aminopropyl-triethoxy-silane or γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy silicane.
6. a kind of nylon micro-sphere composite material for Stereolithography according to claim 1, it is characterised in that：It is described
The steady agent of light be 2-hydroxy-4-n-octoxybenzophenone or chlorination benzotriazole.
7. a kind of nylon micro-sphere composite material for Stereolithography according to claim 1, it is characterised in that：It is described
Diluent be ethylene glycol diglycidylether or tripropyleneglycol diglycidyl ether；The antifoaming agent is the poly- silica of dimethyl
Alkane or polyether silicone；The levelling agent is organosilicon-epoxide ethane copolymer or organosilicon-epoxide propane copolymer.
8. a kind of nylon micro-sphere composite material for Stereolithography according to claim 1, it is characterised in that：It is described
Antioxidant for four (3,5- di-t-butyl -4- hydroxyls) benzenpropanoic acid pentaerythritol esters, three (2,4- di-t-butyls) phenyl-phosphites
Or N, N'- it is bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine.
9. a kind of nylon micro-sphere composite material for Stereolithography according to claim 1, it is characterised in that：It is described
Cationic initiators be diphenyl iodnium or diaryl sulfonium salt；The free radical type Photoepolymerizationinitiater initiater is rests in peace
Fragrant dimethyl ether or benzophenone.
10. preparing a kind of method of nylon micro-sphere composite material for Stereolithography described in claim 1, feature exists
In including the following steps：
（1）In a reservoir 25~45 parts of acrylate, 25~45 parts of epoxy resin, nylon micro-sphere 5~25 are sequentially added by proportioning
Part, 5~25 parts of diluent, 0.5~2.5 part of antifoaming agent, 0.5~2.5 part of levelling agent, 1~5 part of cationic initiators and freedom
1~5 part of fundamental mode Photoepolymerizationinitiater initiater is simultaneously kept stirring；
（2）Ultrashort 5~25 parts of glass, 0.2~1 part of coupling agent, 0.02~0.1 part of the steady agent of light and antioxygen are added in aforesaid liquid
Above-mentioned mixed liquor is warming up to 45 DEG C~85 DEG C and controls condensation by 0.02~0.1 part of agent, and ultrasonic disperse 10min~30min is to equal
One state obtains a kind of nylon micro-sphere composite material for Stereolithography.
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| CN113185653A (en) * | 2021-06-17 | 2021-07-30 | 江西金石三维智能制造科技有限公司 | High-strength high-toughness three-dimensional photo-molding resin and preparation method thereof |
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| CN104250436A (en) * | 2013-06-26 | 2014-12-31 | 合肥杰事杰新材料股份有限公司 | Nylon microsphere modified photosensitive resin, its preparation method, and its application in 3D printing |
| CN105646795A (en) * | 2014-11-10 | 2016-06-08 | 合肥杰事杰新材料股份有限公司 | Resin for three-dimensional light-cured forming technology and preparation method therefor |
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| CN104250436A (en) * | 2013-06-26 | 2014-12-31 | 合肥杰事杰新材料股份有限公司 | Nylon microsphere modified photosensitive resin, its preparation method, and its application in 3D printing |
| CN105646795A (en) * | 2014-11-10 | 2016-06-08 | 合肥杰事杰新材料股份有限公司 | Resin for three-dimensional light-cured forming technology and preparation method therefor |
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| CN110845814A (en) * | 2018-07-24 | 2020-02-28 | 上海杰事杰新材料(集团)股份有限公司 | Nylon microsphere modified photocuring resin composite material for 3D printing and preparation method thereof |
| CN113185653A (en) * | 2021-06-17 | 2021-07-30 | 江西金石三维智能制造科技有限公司 | High-strength high-toughness three-dimensional photo-molding resin and preparation method thereof |
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