CN105348514A - Polyamide composite material capable of being used for 3D printing and preparation method thereof - Google Patents
Polyamide composite material capable of being used for 3D printing and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polyamide composite material capable of being used for 3D printing and a preparation method thereof. The preparation method includes the preparation steps that firstly, aromatic dibasic acid monomers, aliphatic dibasic acid monomers, alicyclic dibasic acid monomers, polyamine monomers and additives are sequentially added into a high-pressure reaction kettle, temperature is raised to 200-220 DEG C in a segmented mode under protection of protective gas, constant temperature and constant pressure last for 0.5-3 h, then heating continues so that the temperature can be raised to 250-300 DEG C, pressure is controlled to be 1,5-3 MPa, a pressure-maintaining constant temperature reaction lasts for 1-5 h, then gas is slowly released, degassing is performed within 1-3 h till normal pressure is achieved, then vacuumizing is performed for 0.5-3 h, and high-liquidity transparent polyamide is obtained through pressing and discharging after reaction ends; secondly, water-soluble high-molecule and high-liquidity transparent nylon resin, bulking agents, nanometer particles, pigment and the like are subjected to melting blending and are placed in water to be dissolved, classification is performed after washing and vacuum drying, and nylon compound powder material for 3D printing is obtained.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of high-strength transparence polyamide compoiste material and preparation method thereof that can be used for 3D and print.
Background technology
3D prints, i.e. the one of rapid shaping technique, and it is a kind of based on digital model file, uses powdery metal or plastics etc. can jointing material, is carried out the technology of constructed object by the mode successively printed.3D prints and normally adopts digital technique file printing machine to realize.The field such as Making mold, industrial design of being everlasting is used to modeling, after gradually for the direct manufacture of some products, had the component using this technology to print.This technology is at jewelry, footwear, industrial design, building, engineering and construction (AEC), automobile, and aerospace, dentistry and medical industries, education, geographical information system(GIS), civil engineering work, gun and other field are applied all to some extent.
Can be used for the transparent polymer that 3D prints to be difficult to extrude, material binding intensity when successively piling up shaping, the performance such as high temperature resistant can be lost, and the 3D being applicable to consumption and industrial use prints engineering grade thermostable transparent material and there is very large blank.Nylon material has high temperature resistant, erosion resistance, wear-resisting, the advantage such as high strength and good stability, as the TR90 temperature resistant transparent nylon of EMS Company, Switzerland's exploitation, it is current international most popular ultralight picture frame material, but the melt processing temperature of PA powder is more than 260 DEG C, melt viscosity is very large, high to sinter molding conditional request, and PA sintered part exists that intensity is low, poor toughness, complex process, high in cost of production shortcoming, and require to use with private print coordinative composition of equipments, equipment and material price costliness.
Utilize nylon resin, ethanolic soln, high molecular polymer powder and antioxidant to prepare nylon in patent CN104191615A and cover high molecular polymer powdered material, this Composite Sintering excellent property, good fluidity, can be used for 3D and prints, indirect fabrication high molecular functional part.
Print with weather-proof nylon powder matrix material with the spray-dried 3D for preparing of nylon, hindered amine as light stabilizer, UV light absorber, hindered phenol antioxygen, phosphite antioxidant and other necessary auxiliary agents in patent CN104910613A, this material spherical particle narrowly distributing, good fluidity.
Polymkeric substance is obtained for the auxiliary agent of trifluoroacetic acid and necessity through polymerization with nylon 12, SL-AH, double-end amino ethylene glycol tritium in patent CN104910616A, drying, ball milling, oven dry obtain the low temperature nylon powder that can be used for selective laser sintering again, and its sphericity and mobility are all good.
In addition, the auxiliary agent that Zhongshan University Bai Peikang seminar, Shi Yusheng seminar of the Central China University of Science and Technology all utilize nylon 12 to add necessity after metal-powder is filled obtains the nylon powder that can be used for selective laser sintering.
The goods that the nylon powder that can be used for 3D printing of above patent and document announcement prints all cannot be transparent, limits its Application Areas.The transparent polymer that can be used for 3D printing is difficult to extrude, material binding intensity when successively piling up shaping, the performance such as high temperature resistant can be lost, the transparency printing goods as PET material is not high especially, although the high-strength high temperature-resistant special engineering plastics PPSF excellent performance that Stratasys company releases, but expensive, only there is application space in human body implantation and some high-end fields.The performance of current domestic 3D printed material does not reach requirement and kind is on the low side, and the engineering grade high-performance transparent material that can be used for 3D printing is more rare.By synthetic technology, optimize material property from molecular structure, exploitation is applicable to 3D and prints the thermostable transparent nylon required, significant for the commanding elevation seizing 3D printing science and technology.
On market, most 3D printed material tone is single, uses 3D printing technique to make practical colorful opaque products still more difficult.Nontransparent nylon is printed compared to the common engineering grade 3D being base material with PA12, PA6 etc., thermostable transparent nylon can not only be printed as the water white transparency products such as glasses, food product containers, medical facilities, or plant the porous material of easy coloring, can combine with black material and create art pattern and multiple translucent tone, mix with transparent coloured material and obtain beautiful transparent colored product as stained glass.The present invention adopts chemical synthesis and modified technique, intend on semi-aromatic nylon molecular chain, introduce alicyclic rigidity heterogeneous structure unit, destroy the regularity of nylon molecules chain, material is made to have high strength, high heat resistance the while of reducing material crystalline degree and obtain outstanding high transparent, introduce the flexible chain structural units such as functional polyamines, polyethers, preparation high workability, high tenacity low thermostable transparent nylon relative to processing temperature.Further functional modification nylon resin, improves the cohesive strength of printed product, thermotolerance and aesthetic effect, develops the engineering grade thermostable transparent nylon composite materials of applicable 3D printing technique.
Summary of the invention
The present invention aims to provide and a kind ofly can be used for 3D printing, good combination property, transparent polyamide based composites that transparency is high and preparation method thereof.
Can be used for a preparation method for the high-strength transparence polyamide compoiste material that 3D prints, it is characterized in that, comprise the following steps:
(1) by aromatic dicarboxylic acid mono, binary aliphatic acid mono, cycloalphatic diamine monomer and required auxiliary agent join in autoclave by a certain percentage successively, after substitution gas under the protection of shielding gas, be warming up to 200 ~ 220 DEG C stage by stage, constant temperature and pressure reaction 0.5 ~ 3 hour, then continue to be heated to 250 ~ 300 DEG C, control pressure is at 1.5 ~ 3MPa, pressurize isothermal reaction 1 ~ 5 hour, slowly exit afterwards, exitted in 1 ~ 3 hour to normal pressure, then 0.5 ~ 3 hour is vacuumized, reaction terminates, suppress, discharging obtains transparent polyamide.(2) water-soluble polymer and transparent nylon resin and expanding material, nanoparticle, colorant etc. are passed through melt blending, be placed in water dissolution filter, wash and after vacuum-drying, utilize ball mill and vibratory screening apparatus classification, obtaining homogeneous cladded type 3D and print nylon composite powder material.
Aromatic dicarboxylic acid mono of the present invention is one or more in m-phthalic acid, terephthalic acid and naphthalene diacid, preferred m-phthalic acid and terephthalic acid.
A kind of high-strength transparence polyamide compoiste material that can be used for 3D and print of the present invention, it is characterized in that, described binary aliphatic acid mono is one or more in pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, tetradecane diacid, pentadecane diacid, Thapsic acid, pentadecane dicarboxylic acid, octadecane diacid, nonadecen diacid, octadecane dicarboxylic acid, nonadecane dicarboxylic acid, preferred sebacic acid and dodecanedioic acid.
The mol ratio of aromatic dicarboxylic acid mono of the present invention and binary aliphatic acid mono is 1: 9 ~ 9: 1.
Cycloalphatic diamine monomer of the present invention is 4,4 '-diamino cyclohexyl-methane (PACM), 4,4 '-diamino cyclohexyl propane (PACP), 3,3 '-dimethyl-4,4 '-diamino cyclohexyl propane (MACM), 3,3 '-diethyl-4,4 '-diamino cyclohexyl propane (EACM), 3,3 ', 5, one or more in your ketone diamines (IPD) of 5 '-tetramethyl--4,4 '-diamino cyclohexyl propane (TMACM) and different fluorine.
Polyamine monomers of the present invention is triaminotriphenyl methylmethane, polymine, diethylenetriamine, triethylene tetramine, polyamide-amide and polyetheramine T403, preferably polyethylene imines and polyetheramine T403, content is the 0.1mol% ~ 15mol% of total monomer of polyamide amount.
Auxiliary agent of the present invention comprises end-capping reagent, oxidation inhibitor, catalyzer, whitening agent, thermo-stabilizer, softening agent, releasing agent and fire retardant etc., wherein end-capping reagent is phenylformic acid, acetic acid, propionic acid or Tetra hydro Phthalic anhydride, preferred phenylformic acid, addition is 0.01 ~ 1wt% of diacid and diamine monomer total mass, preferably 0.02 ~ 0.5wt%; Oxidation inhibitor is one or more mixing in stannous octoate, dibutyl tin laurate and tin protochloride, preferred tin protochloride, and addition is 0.01 ~ 1wt% of diprotic acid and diamine monomer total mass, preferably 0.02 ~ 0.5wt%; Catalyzer is sodium phosphate, phosphoric acid, calcium phosphate, sodium phosphite, phosphorous acid magnesium, Arizona bacilli, one or more in zinc phosphite, inferior sodium phosphate, ortho phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid zinc, preferred inferior sodium phosphate, addition is 0.01 ~ 0.5wt% of diprotic acid and diamine monomer total mass, preferably 0.02 ~ 0.2wt%; The content of other each auxiliary agents is 0.01 ~ 0.5wt%, preferably equal 0.01 ~ 0.1wt%.
Shielding gas of the present invention is the one in nitrogen, argon gas, helium and carbonic acid gas, preferred monomers and carbonic acid gas.
Nanoparticle of the present invention is one or more in lithium algae soil, polynite, Feldspar Powder, talcum powder, mica powder, vermiculite, montmorillonite and hectorite.
Water-soluble polymer of the present invention be one in polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyacrylamide (PAM), polyacrylic acid (PAA), polyvinylpyrrolidone (PVP) and polyamideepichlorohydrin (PAE) or a kind of more than one.
Can be used for the high-strength transparence polyamide compoiste material that 3D prints, obtained by transparent polyamide resin, water-soluble polymer, expanding material, nanoparticle and colorant;
Wherein, being synthesized by nanoparticle, aromatic dicarboxylic acid mono, binary aliphatic acid mono, cycloalphatic diamine monomer, polyamine monomers and auxiliary agent of described transparent polyamide resin; Described nanoparticle add-on is 1wt% ~ 30wt%; The mol ratio of aromatic dicarboxylic acid mono and binary aliphatic acid mono is 1: 9 ~ 9: 1; The content of polyamine monomers is the 0.1mol% ~ 15mol% of total monomer of polyamide amount.
The present invention compared with prior art, has following beneficial effect:
(1) from molecular structure level, introduce alicyclic structural elements strongthener thermotolerance, mechanical strength and obtain high-clarity, this resin has the advantage of transparent material and high temperature resistant nylon over-all properties concurrently.
(2) with production formula and controlling of production process molecular size range and distribution, functional polyamines structural unit is introduced, the thermostable transparent nylon resin of synthesis high workability, low processing temperature.
(3) on molecular chain, introduce the flexible chain structural units such as polyethers, ultra-tough transparent nylon is prepared in copolymerization, expands its range of application.
(4) " melt blending-water dissolution " technique is adopted, the characteristic cladded type nylon composite spherical powder materials such as preparation high strength, high-clarity, high-adhesion, size uniformity, develop the multi items engineering grade thermostable transparent nylon material of applicable 3D printing technique requirement.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the concrete embodiment of the present invention, but embodiments of the present invention are by the restriction of following embodiment.
Embodiment 1
(1) by terephthalic acid, dodecanedioic acid, 4,4 '-diamino cyclohexyl-methane (PACM), polymine and required auxiliary agent by a certain percentage (see table 1) join in autoclave successively, and wherein the content of polymine is the 5mol% of raw material monomer.With nitrogen replacement gas 6 times, then inflated with nitrogen to pressure is 0.2MPa, sealed reactor.Heat temperature raising, controls temperature rise rate, makes temperature rise to 210 DEG C stage by stage, constant temperature and pressure 1 hour, and wherein open 90 DEG C time and stir, stir speed (S.S.) is 60r/min, starts slow venting when pressure is at 1.8MPa; Then continue to be heated to 275 DEG C, control pressure is at 2.2MPa, pressurize isothermal reaction 2 hours, slowly exit afterwards, exitted in 2 hours to normal pressure, then 1 hour is vacuumized, reaction terminates, suppresses, discharging, transparent polyamide PACMT/PACM12 (2) can be obtained PAM and PACMT/PACM12 resin and expanding material, Feldspar Powder, colorant etc. are passed through melt blending, be placed in water dissolution filter, wash and after vacuum-drying, utilize ball mill and vibratory screening apparatus classification, obtaining homogeneous cladded type 3D and print nylon composite powder material.
Embodiment 2
(1) by m-phthalic acid, dodecanedioic acid, 4,4 '-diamino cyclohexyl-methane (PACM), polyetheramine T403 and required auxiliary agent by a certain percentage (see table 1) join in autoclave successively, and wherein the content of polyetheramine T403 is the 5m of raw material monomer
ol%.With nitrogen replacement gas 6 times, then inflated with nitrogen to pressure is 0.2MPa, sealed reactor.Heat temperature raising, controls temperature rise rate, makes temperature rise to 210 DEG C stage by stage, constant temperature and pressure 1 hour, and wherein open 90 DEG C time and stir, stir speed (S.S.) is 60r/min, starts slow venting when pressure is at 1.8MPa; Then continue to be heated to 275 DEG C, control pressure is at 2.2MPa, pressurize isothermal reaction 2 hours, slowly exit afterwards, exitted in 2 hours to normal pressure, then 1 hour is vacuumized, reaction terminates, suppresses, discharging, transparent polyamide PACMI/PACM12 (2) can be obtained PAA and PACMI/PACM12 resin and expanding material, talcum powder, colorant etc. are passed through melt blending, be placed in water dissolution filter, wash and after vacuum-drying, utilize ball mill and vibratory screening apparatus classification, obtaining homogeneous cladded type 3D and print nylon composite powder material.
Embodiment 3
(1) by terephthalic acid, dodecanedioic acid, 3,3 '-dimethyl-4,4 '-diamino cyclohexyl-methane (MACM), triethylene tetramine and required auxiliary agent by a certain percentage (see table 1) join in autoclave successively, and wherein the content of triethylene tetramine is the 5mol% of raw material monomer.With nitrogen replacement gas 6 times, then inflated with nitrogen to pressure is 0.2MPa, sealed reactor.Heat temperature raising, controls temperature rise rate, makes temperature rise to 210 DEG C stage by stage, constant temperature and pressure 1 hour, and wherein open 90 DEG C time and stir, stir speed (S.S.) is 60r/min, starts slow venting when pressure is at 1.8MPa; Then continue to be heated to 275 DEG C, control pressure is at 2.2MPa, pressurize isothermal reaction 2 hours, slowly exit afterwards, exitted in 2 hours to normal pressure, then 1 hour is vacuumized, reaction terminates, suppresses, discharging, transparent polyamide MACMT/MACM12 (2) can be obtained PAE and MACMT/MACM12 resin and expanding material, mica powder, colorant etc. are passed through melt blending, be placed in water dissolution filter, wash and after vacuum-drying, utilize ball mill and vibratory screening apparatus classification, obtaining homogeneous cladded type 3D and print nylon composite powder material.Embodiment 4
(1) by m-phthalic acid, dodecanedioic acid, 3,3 '-dimethyl-4,4 '-diamino cyclohexyl-methane (MACM), diethylenetriamine and required auxiliary agent by a certain percentage (see table 1) join in autoclave successively, and wherein the content of diethylenetriamine is the 5mol% of raw material monomer.With nitrogen replacement gas 6 times, then inflated with nitrogen to pressure is 0.2MPa, sealed reactor.Heat temperature raising, controls temperature rise rate, makes temperature rise to 210 DEG C stage by stage, constant temperature and pressure 1 hour, and wherein open 90 DEG C time and stir, stir speed (S.S.) is 60r/min, starts slow venting when pressure is at 1.8MPa; Then continue to be heated to 275 DEG C, control pressure is at 2.2MPa, pressurize isothermal reaction 2 hours, slowly exit afterwards, exitted in 2 hours to normal pressure, then 1 hour is vacuumized, reaction terminates, suppresses, discharging, transparent polyamide MACMI/MACM12 (2) can be obtained PVP and MACMI/MACM12 resin and expanding material, vermiculite power, colorant etc. are passed through melt blending, be placed in water dissolution filter, wash and after vacuum-drying, utilize ball mill and vibratory screening apparatus classification, obtaining homogeneous cladded type 3D and print nylon composite powder material.
The transparent polyamide matrix material that can be used for 3D printing obtained to embodiment 1 ~ 4 all meets the performance index of table 2.
Table 1 embodiment 1 ~ 4 formula table
The transparent polyamide composite property index that table 23D prints
Claims (10)
1. can be used for a preparation method for the high-strength transparence polyamide compoiste material that 3D prints, it is characterized in that, comprise the following steps:
(1) by aromatic dicarboxylic acid mono, binary aliphatic acid mono, cycloalphatic diamine monomer, polyamine monomers and auxiliary agent join in autoclave by a certain percentage successively, after substitution gas under the protection of shielding gas, be warming up to 200 ~ 220 DEG C stage by stage, constant temperature and pressure reaction 0.5 ~ 3 hour, then continue to be heated to 250 ~ 300 DEG C, control pressure is at 1.5 ~ 3MPa, pressurize isothermal reaction 1 ~ 5 hour, slowly exit afterwards, exitted in 1 ~ 3 hour to normal pressure, then 0.5 ~ 3 hour is vacuumized, reaction terminates, suppress, discharging obtains high workability transparent polyamide,
(2) water-soluble polymer and high workability transparent nylon resin and expanding material, nanoparticle, colorant etc. are passed through melt blending, be placed in water dissolution filter, washing and vacuum-drying after, classification, obtain homogeneous cladded type 3D printing nylon composite powder material.
2. a kind of preparation method of high-strength transparence polyamide compoiste material that can be used for 3D and print according to claim 1, is characterized in that, described aromatic dicarboxylic acid mono is one or more in m-phthalic acid, terephthalic acid and naphthalene diacid; Described binary aliphatic acid mono is one or more in pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid, tetradecane diacid, pentadecane diacid, Thapsic acid, pentadecane dicarboxylic acid, octadecane diacid, nonadecen diacid, octadecane dicarboxylic acid, nonadecane dicarboxylic acid; Described aromatic dicarboxylic acid mono and the mol ratio of binary aliphatic acid mono are 1: 9 ~ 9: 1.
3. a kind of preparation method that can be used for the high-strength transparence polyamide compoiste material that 3D prints according to claim 1, it is characterized in that, described cycloalphatic diamine monomer is 4, 4 '-diamino cyclohexyl-methane (PACM), 4, 4 '-diamino cyclohexyl propane (PACP), 3, 3 '-dimethyl-4, 4 '-diamino cyclohexyl propane (MACM), 3, 3 '-diethyl-4, 4 '-diamino cyclohexyl propane (EACM), 3, 3 ', 5, 5 '-tetramethyl--4, one or more in your ketone diamines (IPD) of 4 '-diamino cyclohexyl propane (TMACM) and different fluorine, described polyamine monomers is one or more in triaminotriphenyl methylmethane, polymine, diethylenetriamine, triethylene tetramine, polyamide-amide and polyetheramine T403, the content of described polyamine monomers is the 0.1mol% ~ 15mol% of total monomer of polyamide amount, the add-on of cycloalphatic diamine monomer and polyamine monomers summation are 1.0 ~ 1.1 times of diprotic acid molar weight.
4. a kind of preparation method that can be used for the high-strength transparence polyamide compoiste material that 3D prints according to claim 1, it is characterized in that, described auxiliary agent comprises end-capping reagent, end-capping reagent is phenylformic acid, acetic acid, propionic acid or Tetra hydro Phthalic anhydride, and addition is 0.01 ~ 1wt% of diprotic acid and diamine monomer total mass.
5. a kind of preparation method that can be used for the high-strength transparence polyamide compoiste material that 3D prints according to claim 1, it is characterized in that, described auxiliary agent comprises oxidation inhibitor, and oxidation inhibitor is one or more mixing in stannous octoate, dibutyl tin laurate and tin protochloride; Addition is 0.01 ~ 1wt% of diprotic acid and diamine monomer total mass.
6. a kind of preparation method that can be used for the high-strength transparence polyamide compoiste material that 3D prints according to claim 1, it is characterized in that, described auxiliary agent comprises catalyzer, catalyzer is sodium phosphate, phosphoric acid, calcium phosphate, sodium phosphite, phosphorous acid magnesium, Arizona bacilli, one or more in zinc phosphite, inferior sodium phosphate, ortho phosphorous acid magnesium, Lime Hypophosphate and ortho phosphorous acid zinc, addition is 0.01 ~ 0.5wt% of diprotic acid and diamine monomer total mass.
7. a kind of preparation method that can be used for the high-strength transparence polyamide compoiste material that 3D prints according to claim 1, is characterized in that, also comprise dispersion agent, whitening agent, thermo-stabilizer, softening agent, releasing agent and fire retardant in described auxiliary agent; The content of described each auxiliary agent is diprotic acid and diamine monomer total mass 0.01 ~ 0.5wt%.
8. a kind of preparation method that can be used for the high-strength transparence polyamide compoiste material that 3D prints according to claim 1, it is characterized in that, described shielding gas is the one in nitrogen, argon gas, helium and carbonic acid gas.
9. a kind of preparation method that can be used for the high-strength transparence polyamide compoiste material that 3D prints according to claim 1, it is characterized in that, described nanoparticle is one or more in lithium algae soil, polynite, Feldspar Powder, talcum powder, mica powder, vermiculite, montmorillonite and hectorite, and addition is the 1wt% ~ 30wt% of polymeric amide total amount; Described water-soluble polymer is one or more in polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyacrylamide (PAM), polyacrylic acid (PAA), polyvinylpyrrolidone (PVP) and polyamideepichlorohydrin (PAE), and addition is 1 ~ 30% of polymeric amide total amount.
10. can be used for the high-strength transparence polyamide compoiste material that 3D prints, it is characterized in that, obtained by transparent polyamide resin, water-soluble polymer, expanding material, nanoparticle and colorant;
Wherein, being synthesized by nanoparticle, aromatic dicarboxylic acid mono, binary aliphatic acid mono, cycloalphatic diamine monomer, polyamine monomers and auxiliary agent of described transparent polyamide resin; Described nanoparticle add-on is 1wt% ~ 30wt%; The mol ratio of aromatic dicarboxylic acid mono and binary aliphatic acid mono is 1: 9 ~ 9: 1; The content of polyamine monomers is the 0.1mol% ~ 15mol% of total monomer of polyamide amount.
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| CN107304271A (en) * | 2016-04-21 | 2017-10-31 | 中国石油化工股份有限公司 | One kind is based on polyacrylic composite and its preparation method and application |
| CN108203509A (en) * | 2016-12-19 | 2018-06-26 | 财团法人纺织产业综合研究所 | Modify polyamide and preparation method thereof and nylon composite fibre |
| CN110240799A (en) * | 2018-03-09 | 2019-09-17 | 中国石油化工股份有限公司 | 3D printing composition and its preparation method and application |
| CN111978479A (en) * | 2020-08-11 | 2020-11-24 | 珠海赛纳三维科技有限公司 | Material for three-dimensional molding, three-dimensional object, and sliced layer thereof |
| CN115087687A (en) * | 2020-02-10 | 2022-09-20 | 阿科玛法国公司 | Polyamide powder and corresponding production method |
| CN115873400A (en) * | 2021-09-30 | 2023-03-31 | 上海金发科技发展有限公司 | PA6 composition and preparation method and application thereof |
| CN115873240A (en) * | 2021-09-29 | 2023-03-31 | 万华化学集团股份有限公司 | Nylon powder for 3D printing with high reuse rate |
| CN116554466A (en) * | 2023-06-12 | 2023-08-08 | 广州硅碳新材料有限公司 | Organosilicon modified polyamide and preparation method and application thereof |
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Cited By (12)
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| CN107304271A (en) * | 2016-04-21 | 2017-10-31 | 中国石油化工股份有限公司 | One kind is based on polyacrylic composite and its preparation method and application |
| CN107304271B (en) * | 2016-04-21 | 2020-05-12 | 中国石油化工股份有限公司 | Polypropylene-based composite material and preparation method and application thereof |
| CN108203509A (en) * | 2016-12-19 | 2018-06-26 | 财团法人纺织产业综合研究所 | Modify polyamide and preparation method thereof and nylon composite fibre |
| CN110240799A (en) * | 2018-03-09 | 2019-09-17 | 中国石油化工股份有限公司 | 3D printing composition and its preparation method and application |
| CN115087687A (en) * | 2020-02-10 | 2022-09-20 | 阿科玛法国公司 | Polyamide powder and corresponding production method |
| CN111978479A (en) * | 2020-08-11 | 2020-11-24 | 珠海赛纳三维科技有限公司 | Material for three-dimensional molding, three-dimensional object, and sliced layer thereof |
| CN111978479B (en) * | 2020-08-11 | 2021-11-12 | 珠海赛纳三维科技有限公司 | Material for three-dimensional molding, three-dimensional object, and sliced layer thereof |
| CN115873240A (en) * | 2021-09-29 | 2023-03-31 | 万华化学集团股份有限公司 | Nylon powder for 3D printing with high reuse rate |
| CN115873400A (en) * | 2021-09-30 | 2023-03-31 | 上海金发科技发展有限公司 | PA6 composition and preparation method and application thereof |
| CN115873400B (en) * | 2021-09-30 | 2024-04-02 | 上海金发科技发展有限公司 | PA6 composition and preparation method and application thereof |
| CN116554466A (en) * | 2023-06-12 | 2023-08-08 | 广州硅碳新材料有限公司 | Organosilicon modified polyamide and preparation method and application thereof |
| CN116554466B (en) * | 2023-06-12 | 2023-11-21 | 广州硅碳新材料有限公司 | Organosilicon modified polyamide and preparation method and application thereof |
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