CN105218939B - A kind of foamable 3D printing material and preparation method thereof - Google Patents

A kind of foamable 3D printing material and preparation method thereof Download PDF

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Publication number
CN105218939B
CN105218939B CN201510744091.4A CN201510744091A CN105218939B CN 105218939 B CN105218939 B CN 105218939B CN 201510744091 A CN201510744091 A CN 201510744091A CN 105218939 B CN105218939 B CN 105218939B
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Prior art keywords
wax
preparation
printing
toughener
foaming agent
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CN201510744091.4A
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CN105218939A (en
Inventor
吴立新
王剑磊
郑幼丹
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Molding Of Porous Articles (AREA)

Abstract

The present invention relates to a kind of foamable 3D printing material and preparation method thereof.The printed material mainly includes：Toughener, wax, tackifying resin, stearic acid, antioxidant, pigment and foaming agent.The material has flexible characteristic, 3D printing can be carried out on garment material, the third dimension of pattern can be strengthened after foaming, and blowing temperature and foamed time can be adjusted to reach desired foaming effect, and the problem of shrinkage factor influences end article performance greatly is not present, while print procedure and the environment-protecting and non-poisonous evil of foaming process, odorlessness.

Description

A kind of foamable 3D printing material and preparation method thereof
Technical field
The present invention relates to a kind of foamable 3D printing material and preparation method thereof, belong to the Material Field of rapid shaping.
Background technology
3D printing, i.e. rapid shaping (Rapid Prototype, RP) technology, is to develop rapidly 1990s A kind of advanced manufacturing technology, be a kind of key technology for serving manufacturing industry new product development.It to promote enterprise product Innovation, shortening new-product development cycle, raising product competitiveness etc. play positive impetus.The technology since the advent of the world, Gradually it is widely used in the manufacturing industry of countries in the world, and thus expedites the emergence of out an emerging technical field.At present Rapid shaping technique mainly includes fused glass pellet (Fused Deposition Modeling, FDM), selective laser and burnt Form type (Selective Laser Sintering, SLS), Stereolithography (stereo lithography Apparatus, SLA), laminated solid body shaping (Laminated Object Manufacturing, LOM) etc. technology, wherein FDM It is with fastest developing speed, using most.
FDM refers to that thread thermoplastic is sent into shower nozzle by wire feeder, and molten state is heated in the showerhead, is squeezed through nozzle Go out.The filamentary material of molten state is extruded out, and the path controlled according to the individual-layer data of three-dimensional software is extruded and specified Position coagulation forming, layer by layer deposition solidification, eventually forms whole three-dimensional objects.FDM operating environment is clean, safety, technique letter It is single, easily operated, and rubbish is not produced, therefore operation occasion has been widened significantly.Its raw materials is carried in the form of spool silk For, it is easy to carry and quick-replaceable.
Expanded material refers to that foaming agent gasifies or expanded so as to produce the material of loose structure in material internal, can be less Density of material and consumption are reduced on the premise of loss material mechanical property, while the light-high-strength and feature that meet material will Ask.Expanded material fatigue life is long, with preferable toughness, heat endurance, energy absorption and insulating properties, automobile, household electrical appliances, Electronics, building, consumer goods industries and military field have broad application prospects.
But the preparation method of expanded material concentrates on conventionally manufactured field substantially at present, such as supercritical fluid prepares poly- Compound foaming technique, two times opening mold, required die sinking are costly, and the construction cycle is long.It is a kind of expandable that this just promotes us to develop 3D printing material, its preparation method is combined with rapid shaping technique, thus significantly lifted product development rate, greatly Supporting dynamics of the big increase to individuation product.In addition, this 3D printing material is flexible material, it can be carried out on garment material 3D printing, can strengthen the third dimension of pattern after foaming, and it is desired to reach to adjust blowing temperature and foamed time Foaming effect.
The content of the invention
For the market vacancy in current 3D printing consumptive material field, it is an object of the invention to provide a kind of foamable 3D printing Material and preparation method thereof, the material has a flexible characteristic, and in the absence of shrinkage factor it is big and the problem of influence end article performance, While print procedure and the environment-protecting and non-poisonous evil of foaming process, odorlessness.
Material prescription uses toughener 5%-80%, wax 5%-90%, tackifying resin 1%-60%, stearic acid in the present invention 0%-20%, antioxidant 0%-5%, pigment 0%-5%, foaming agent 0.1%-50%.
The toughener is haloflex, styrene butadiene thermoplasticelastomer, ethylene-vinyl acetate copolymerization Thing, ethylene propylene diene rubber and ethylene-octene block copolymer, or combinations thereof.
The wax is Tissuemat E, ethylene-vinyl acetate copolymer wax, microwax, chlorinated paraffin, model casting wax, poly- Propylene wax, or combinations thereof.
The tackifying resin is C5 Petropols, C9 Petropols, hydrogenated aromatic Petropols, terpene resin, rosin Resin, or combinations thereof.
The foaming agent is bicarbonate, carbonate, polycarboxylate, polycarboxylate, sulfohydrazide, azodicarbonamide, ammonia Base urea, expended microsphere, or combinations thereof.
The preparation process of material of the present invention is：
1) by stearic acid, antioxidant, pigment, foaming agent and toughener, wax, 0.1-2000 points of tackifying resin mixed at high speed Clock, is mixed by double screw extruder and plastifies and granulate, make high concentration master batch, stearic acid, antioxidant, pigment, foaming agent are total Weight accounts for the 0.5%-80% of master batch weight；
2) by master batch and toughener, wax, tackifying resin mixed at high speed 0.1-2000 minutes, master batch accounts for gross weight 0.5%-50%；
3) mixed and plastified by double screw extruder, and granulated by pelleter；
4) by single screw extrusion machine wire drawing, the silk of pull-out can be directly used for 3D printing；
5) baking oven that the product of 3D printing is put to 100-220 DEG C is foamed for 0.1-60 minutes, forms end article.
Brief description of the drawings
The 3D printing pattern on fabric of accompanying drawing 1.
The final foaming effect of accompanying drawing 2.
Embodiment
To allow the features described above and advantage of the present invention to become apparent, hereafter elaborated for embodiment.
First, by following component proportion (weight/mass percentage composition)：
2nd, preparation method
Prepared by this material the step of is (being calculated by material gross mass 100g)：
1) the peaceful stearic acid 1801 of 4g sections, 1g BASF irgasfos 168s, 2g Koster KR312,5g expandable microspheres are weighed 951DU120 and 14g Dow POE 8411,25g BASF Luwax EVA3, are put into high mixer high-speed stirred 10min
TS1/℃ TS2/℃ TS3/℃ TS4/℃ TS5/℃ TS6/℃ FR/% n/r/min
70 75 85 100 100 80 10 50
2) plasticizing in HAAKE double screw extruders is put into extrude and granulate using pelleter, process conditions：
3) master batch is put into 15g BASF Luwax EVA3,14g Dow POE 8411 and 20g Hengfeng C9 Petropols High mixer high-speed stirred 5min.
TS1/℃ TS2/℃ TS3/℃ TS4/℃ TS5/℃ TS6/℃ FR/% n/r/min
75 78 85 95 95 85 15 80
4) plasticizing in HAAKE double screw extruders is put into extrude and granulate using pelleter, process conditions：
5) grain made is put into single screw extrusion machine wire drawing and wound, the silk of pull-out can be directly used for 3D printing, technique Condition：
One area/DEG C 2nd area/DEG C Die orifice/DEG C Rotating speed n/r/min
85 95 80 700
6) 160 DEG C of baking oven 8 minutes the product that completes will be printed is put into, carry out foaming operation, form end article.

Claims (4)

1. a kind of preparation method for the 3D printing product that foams, it is characterised in that：Methods described comprises the following steps：
1) by stearic acid, antioxidant, pigment, foaming agent and toughener, wax, tackifying resin mixed at high speed 0.1-2000 minutes, lead to Cross double screw extruder mixing to plastify and granulate, make high concentration master batch, stearic acid, antioxidant, pigment, foaming agent gross weight are accounted for The 0.5%-80% of master batch weight；
2) by master batch and toughener, wax, tackifying resin mixed at high speed 0.1-2000 minutes, master batch accounts for the 0.5%- of gross weight 50%；
3) mixed and plastified by double screw extruder, and granulated by pelleter；
4) by single screw extrusion machine wire drawing, the silk of pull-out can be directly used for 3D printing；
5) baking oven that the product of 3D printing is put to 100-220 DEG C is foamed for 0.1-60 minutes, forms end article；
Wherein, the foaming agent is expended microsphere, and the percentage by weight of the raw material is：Toughener 5%-80%, wax 5%- 90%, tackifying resin 1%-60%, stearic acid 0%-20%, antioxidant 0%-5%, pigment 0%-5%, foaming agent 0.1%- 50%.
2. preparation method as claimed in claim 1, it is characterised in that：The toughener is haloflex, styrene-fourth two Thermoplastic olefinic elastomer, ethylene-vinyl acetate copolymer, ethylene propylene diene rubber and ethylene-octene block copolymer, or they Combination.
3. preparation method as claimed in claim 1, it is characterised in that：The wax is Tissuemat E, ethene-vinyl acetate copolymerization Thing wax, chlorinated paraffin, polypropylene wax, or combinations thereof.
4. preparation method as claimed in claim 1, it is characterised in that：The tackifying resin is C5 Petropols, C9 oil trees Fat, hydrogenated aromatic Petropols, terpene resin, rosin resin, or combinations thereof.
CN201510744091.4A 2015-11-05 2015-11-05 A kind of foamable 3D printing material and preparation method thereof Active CN105218939B (en)

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CN105670312A (en) * 2016-02-24 2016-06-15 江苏道勤新材料科技有限公司 3D (three-dimensional) printing foaming bouncing ball material
CN105802254A (en) * 2016-05-10 2016-07-27 江苏道勤新材料科技有限公司 TPE (thermoplastic elastomer) based 3D printing material
CN105802271A (en) * 2016-05-10 2016-07-27 江苏道勤新材料科技有限公司 3D printing material with high elasticity
CN106317913B (en) * 2016-08-29 2019-06-04 福建省二轻工业研究所 A kind of industry casting wax 3D printing wire rod and its manufacture craft
CN106313481A (en) * 2016-08-30 2017-01-11 成都思维智造科技有限公司 Manufacturing technique of wax wire special for 3D printer
CN107160673A (en) * 2017-04-12 2017-09-15 福建科盛工贸有限公司 A kind of method that enhancing FDM3D prints product mechanical property
CN107254151A (en) * 2017-06-06 2017-10-17 贵州当科技有限公司 Microporous foam 3D printing polymer consumptive material and preparation method thereof and process units
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CN107915898B (en) * 2017-10-30 2019-12-03 惠州市优恒科三维材料有限公司 Cross-linking, print speed is fastly, printing fineness is high, can be used to cast simultaneously and the 3D printing of model forms wax and preparation method thereof
CN107936459B (en) * 2017-12-07 2019-08-20 中国科学院福建物质结构研究所 It is a kind of for the composition of fused glass pellet 3D printer, preparation and its application
CN108129728A (en) * 2017-12-18 2018-06-08 定远县宝隆机械制造有限公司 A kind of investment casting wax formula
CN109456565A (en) * 2018-09-13 2019-03-12 苏州巴夏科技发展有限公司 A kind of intelligent macromolecule material, preparation method and its utilize method
CN109608892A (en) * 2018-11-22 2019-04-12 浙江闪铸三维科技有限公司 A kind of 3D printing wax material composition
CN109569529A (en) * 2019-01-08 2019-04-05 福建师范大学 A kind of preparation method of biology base 3D printing adsorbent material
CA3157206A1 (en) 2019-05-21 2020-11-26 Bauer Hockey Ltd. Helmets comprising additively-manufactured components
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TWI821428B (en) * 2019-10-04 2023-11-11 豐泰企業股份有限公司 Three-dimensional printing thermal expansion structure manufacturing method
CN110862673B (en) * 2019-12-03 2022-04-01 诺思贝瑞新材料科技（苏州）有限公司 Foaming thermoplastic elastomer material for 3D printing and preparation method thereof
CN113943408B (en) * 2020-07-16 2022-09-06 福建泉州海滨防护装备有限公司 Polymer-based composite material foaming part and preparation method thereof
CN113183455A (en) * 2021-04-29 2021-07-30 苏州聚复高分子材料有限公司 Foaming wire rod and preparation method thereof, FDM printing method, printing equipment and storage medium
CN113563627B (en) * 2021-05-06 2023-01-20 深圳光华伟业股份有限公司 Controllable lightweight foam material for FDM printing and preparation method and application thereof

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