CN107760024A - A kind of nylon based composites of 3D printing neck protector and preparation method thereof - Google Patents

A kind of nylon based composites of 3D printing neck protector and preparation method thereof Download PDF

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Publication number
CN107760024A
CN107760024A CN201610680095.5A CN201610680095A CN107760024A CN 107760024 A CN107760024 A CN 107760024A CN 201610680095 A CN201610680095 A CN 201610680095A CN 107760024 A CN107760024 A CN 107760024A
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China
Prior art keywords
based composites
neck protector
printing
nylon
nylon based
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Pending
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CN201610680095.5A
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Chinese (zh)
Inventor
周利波
刘刚
谢众
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Heilongjiang Xinda Enterprise Group Co Ltd
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Heilongjiang Xinda Enterprise Group Co Ltd
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Priority to CN201610680095.5A priority Critical patent/CN107760024A/en
Publication of CN107760024A publication Critical patent/CN107760024A/en
Pending legal-status Critical Current

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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
    • 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
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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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)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)

Abstract

The present invention relates to a kind of suitable for nylon based composites of 3D printing neck protector and preparation method thereof, it is prepared by the raw material of following components and mass percentage content:Nylon resin 40 88.6, reinforcing fiber 10 30, coupling agent 0.2 1, inorganic mineral 5 10, antioxidant 0.2 1.Above-mentioned raw materials extrude wire drawing after high-speed mixer mixes, using double screw extruder.Compared with prior art, the composite that the present invention is prepared has good pliability, impact strength, heat resistance and elongation at break are greatly improved simultaneously, the performance requirement of neck protector can be met, 3D printing neck protector is carried out using the composite, print smooth, finished product has the advantages that any surface finish, appearance looks elegant, well-balanced, dimensionally stable.

Description

A kind of nylon based composites of 3D printing neck protector and preparation method thereof
Technical field
The invention belongs to polymeric material field, suitable for the material of 3D printing, is beaten more particularly, to one kind suitable for 3D Print nylon based composites of neck protector and preparation method thereof.
Background technology
One kind of 3D printing technique, i.e. rapid shaping technique, it is a kind of based on mathematical model file, with metal Or plastics etc. can jointing material, by section, the mode successively printed carrys out the technology of constructed object.In mold design, industry Machine components manufacture, automobile, aviation, and the field such as medicine obtains broad development.3D printing technique is mainly consolidated including cubic light Change, laser sintered method, melting layer area method etc., wherein fusion stacking formula printing technique（FDM）It is particularly important one kind, it is applied Scope is also extremely wide.
Fusion sediment formula printing technique（FDM）Cardinal principle be by right under the melting temperature of slightly above printed material Heating thermoplastic material makes its melting be extruded from nozzle, is controlled by computer, is piled into finished product from level to level.Fusion stacking formula at present Printing technique（FDM）The printed material used is mainly ABS, nylon, PLA（PLA）Deng.
Nylon (PA) is earliest, the most widely used thermoplastic engineering plastic of development, has high-strength, high temperature resistant, wear-resisting, resistance to The excellent performance such as impact, corrosion-resistant, endurance, oil resistant, self-lubricating, is widely used in automobile component, electronic apparatus, oil The fields such as work, Aero-Space, it is the high polymer material that yield is maximum, purposes is most wide, kind is most in five large-engineering plastics.
Pure PA mechanical property is preferable, but pure PA tensile strength (injection) up to 60MPa or so simultaneously, passes through 3D The tensile strength being molded reluctantly after printing only has 20MPa or so, and hydrogen bond is easily formed between the phthalidyl and hydrone of nylon, With stronger water imbibition, cause poor product size stability, dry state and the defects such as low temperature impact strength is low, it is impossible to meet that 3D is beaten Print neck protector is actually needed.Therefore, nylon based composites want extensively be sent out in 3D printing neck protector field Using research and development are particularly significant suitable for the nylon based composites of 3D printing neck protector and preparation method thereof.
The content of the invention
The defects of purpose of the present invention is exactly to overcome prior art to exist and provide it is a kind of there is good pliability, The nylon base suitable for 3D printing neck protector that impact strength, heat resistance and elongation at break are greatly improved simultaneously Composite and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of nylon based composites suitable for 3D printing neck protector, it is characterised in that the material is by following components and matter The raw material of amount degree is prepared:Nylon resin 40-88.6, reinforcing fiber 10-30, coupling agent 0.2-1, inorganic mineral 5-10, antioxidant 0.2-1.
The melt index of the composite is 5-10g/10min
Described nylon resin is PA6, PA66, the one or more in PA11 and PA12.
Described reinforcing fiber is short glass fiber, grows and cut glass fibre, chopped carbon fiber, grow one cut in carbon fiber Kind is several.
Described coupling agent is Silane coupling agent KH550, KH560, the one or more in KH570 and KH792.
Described inorganic mineral is the one or more in wollastonite, vermiculite, talcum powder, calcium carbonate.
Described antioxidant be antioxidant 1098, irgasfos 168, antioxidant 1010, copper halide, KI, 2 '-it is bis- One or more in (4-methyl-6-tert-butyl group-phenol) methane.
Suitable for the preparation method of the nylon based composites of 3D printing neck protector, using following steps:
（1）According to following components and weight/mass percentage composition dispensing:Nylon resin 40-88.6, reinforcing fiber 10-30, coupling agent 0.2-1, inorganic mineral 5-10, antioxidant 0.2-1;
（2）Said components are placed at mixing 1-10 minutes in high-speed mixer, pre-composition is obtained, pre-composition is placed in baking oven In, dried 3 hours at a temperature of 40-60 DEG C;
（3）Dried pre-composition is placed in double screw extruder and carries out extrusion wire drawing, that is, obtains being applied to 3D printing neck The nylon based composites of protector.
The setting temperature of described high-speed mixer is 35-45 DEG C, rotating speed 2000-4500r/min.
8 sections of temperature of described double screw extruder are set as successively:160-240 DEG C, 170-250 DEG C, 180-260 DEG C, 190-270 DEG C, 190-270 DEG C, 200-270 DEG C, 210-280 DEG C, 220-280 DEG C, 230-280 DEG C of die head temperature, screw rod rotation Speed is 150-180r/min, rate of feeding 10-15r/min.
Compared with prior art, the present invention has advantages below:
1st, the one or more that the present invention is added in coupling agent KH550, KH560, KH570 and KH792.Coupling agent is a kind of both sexes The material of structure, a part of group in its molecule can be with the hydroxyl reaction on filler surface；Another part organic group can be with Nylon macromolecular chain forms physical entanglement, therefore coupling agent asks the effect of similar " bridge " of serving in filler and nylon, makes The two closely coheres, and reduces interfacial effect, makes gained nylon based composites performance more stable.
2nd, nylon based composites of the invention have super good pliability and elongation at break, while impact strength, suction Water rate and heat resistance have obtained good improvement.
3rd, nylon based composites of the invention can be used for 3D printing neck protector, and whole printing process is smoothly smooth, beats It is bright and clean to print off finished surface, outward appearance is beautiful, well-balanced, and size is surely peaceful, meets the use demand of neck protector.
4th, production process of the present invention is simple, easy to operate, is easy to industrialized production.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention Scope be only limitted to following instance.In the case where not departing from above method thought of the present invention, known according to ordinary skill Know the various replacements or change made with customary means, should be included in the scope of the present invention.
Embodiment 1
Suitable for the preparation method of the modification of nylon based composites of 3D printing, using following steps:
（1）51.5 parts（Weight ratio, similarly hereinafter）PA66 resins, 24 parts of short glass fibers, 12 parts of chopped carbon fibers, 10 parts of silicon ashes Stone, 2 parts of coupling agent KH550,0.5 part of antioxidant 1010,.
（2）Press（1）Middle proportioning weighs each material, is mixed 5 minutes in high-speed mixer, and high-speed mixer temperature setting is 40 DEG C, rotating speed be arranged to 2500r/min and obtain pre-composition, pre-composition is placed in baking oven, dried at a temperature of 50 DEG C 3 small When.
（3）Will（2）The dried pre-composition of gained, which is placed in double screw extruder, carries out extrusion wire drawing, double screw extruder Temperature is set as successively:180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 225 DEG C, 230 DEG C, 235 DEG C, die head temperature 240 DEG C, screw rod rotary speed is 150-180r/min, rate of feeding 10-15r/min.
（4）Will（3）Gained nylon based composites silk material carries out 3D printing and makes neck protector, and print procedure is smooth, beats Printing product surface is smooth well-balanced, specious, dimensionally stable, can be used as conventional injecting products.
Embodiment 2
Suitable for the preparation method of the modification of nylon based composites of 3D printing, using following steps:
（1）77.7 parts（Weight ratio, similarly hereinafter）PA6 resins, 15 parts long to cut glass fibre, 5 parts of talcum powder, 1 part of KH560,1.3 parts Irgasfos 168.
（2）Press（1）Middle proportioning weighs each material, is mixed 3 minutes in high-speed mixer, and high-speed mixer temperature setting is 50 DEG C, rotating speed be arranged to 3000r/min and obtain pre-composition, pre-composition is placed in baking oven, dried at a temperature of 50 DEG C 3 small When.
（3）Will（2）The dried pre-composition of gained, which is placed in double screw extruder, carries out extrusion wire drawing, double screw extruder Temperature is set as successively:185 DEG C, 195 DEG C, 210 DEG C, 220 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, die head temperature 250 DEG C, screw rod rotary speed is 150-180r/min, rate of feeding 10-15r/min.
（4）Will（3）Gained nylon based composites silk material carries out 3D printing and makes neck protector, and print procedure is smooth, beats Printing product surface is smooth well-balanced, specious, dimensionally stable, can be used as conventional injecting products.

Claims (10)

  1. A kind of 1. nylon based composites suitable for 3D printing neck protector, it is characterised in that the material by following components and The raw material of mass percentage content is prepared:Nylon resin 40-88.6, reinforcing fiber 10-30, coupling agent 0.2-1, inorganic ore deposit Thing 5-10, antioxidant 0.2-1.
  2. A kind of 2. nylon based composites suitable for 3D printing neck protector according to claim 1, it is characterised in that The melt index of the composite is 5-10g/10min.
  3. A kind of 3. nylon based composites suitable for 3D printing neck protector according to claim 1, it is characterised in that Described nylon resin is PA6, PA66, the one or more in PA11 and PA12.
  4. A kind of 4. nylon based composites suitable for 3D printing neck protector according to claim 1, it is characterised in that Described reinforcing fiber is short glass fiber, length cuts glass fibre, chopped carbon fiber, long one kind or several cut in carbon fiber Kind.
  5. A kind of 5. nylon based composites suitable for 3D printing neck protector according to claim 1, it is characterised in that Described coupling agent is Silane coupling agent KH550, KH560, the one or more in KH570 and KH792.
  6. A kind of 6. nylon based composites suitable for 3D printing neck protector according to claim 1, it is characterised in that Described inorganic mineral is the one or more in wollastonite, vermiculite, talcum powder, calcium carbonate.
  7. A kind of 7. nylon based composites suitable for 3D printing neck protector according to claim 1, it is characterised in that Described antioxidant is antioxidant 1098, irgasfos 168, antioxidant 1010, copper halide, KI, 2 ' a pair ofs (4 monomethyls 1 The phenol of one tert-butyl group one) one or more in methane.
  8. A kind of 8. system of nylon based composites suitable for 3D printing neck protector as any one of claim 1-7 Preparation Method, it is characterised in that this method uses following steps:
    （1）According to following components and weight/mass percentage composition dispensing:Nylon resin 40-88.6, reinforcing fiber 10-30, coupling agent 0.2-1, inorganic mineral 5-10, antioxidant 0.2-1;
    （2）Said components are placed at mixing 1-10 minutes in high-speed mixer, pre-composition is obtained, pre-composition is placed in baking oven In, dried 3 hours at a temperature of 40-60 DEG C;
    （3）Dried pre-composition is placed in double screw extruder and carries out extrusion wire drawing, that is, obtains being applied to 3D printing neck The nylon based composites of protector.
  9. 9. a kind of preparation method of nylon based composites suitable for 3D printing neck protector according to claim 5, Characterized in that, the setting temperature of described high-speed mixer is 35-45 DEG C, rotating speed 2000-4500r/min.
  10. 10. prepare a kind of preparation of the nylon based composites for 3D printing neck protector according to described in claim 5 Method, it is characterised in that 8 sections of temperature of described double screw extruder are set as successively:160-240 DEG C, 170-250 DEG C, 180-260 DEG C, 190-270 DEG C, 190-270 DEG C, 200-270 DEG C, 210-280 DEG C, 220-280 DEG C, die head temperature 230-280 DEG C, screw rod rotary speed is 150-180r/min, rate of feeding 10-15r/min.
CN201610680095.5A 2016-08-18 2016-08-18 A kind of nylon based composites of 3D printing neck protector and preparation method thereof Pending CN107760024A (en)

Priority Applications (1)

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CN201610680095.5A CN107760024A (en) 2016-08-18 2016-08-18 A kind of nylon based composites of 3D printing neck protector and preparation method thereof

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Application Number Priority Date Filing Date Title
CN201610680095.5A CN107760024A (en) 2016-08-18 2016-08-18 A kind of nylon based composites of 3D printing neck protector and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108485251A (en) * 2018-03-14 2018-09-04 广东省肇庆市质量计量监督检测所 A kind of printer enhancing nylon composite materials and preparation method thereof
CN109575584A (en) * 2018-11-20 2019-04-05 贵州航天天马机电科技有限公司 A kind of 3D printing nylon wire rod and preparation method thereof
CN110105754A (en) * 2019-03-27 2019-08-09 王小健 A kind of 3D printing anti-bacteria nylon material and preparation method thereof
CN111423721A (en) * 2020-04-09 2020-07-17 大连理工大学 Talcum powder reinforced nylon composite material suitable for desktop processing environment and preparation method and application thereof
CN111423720A (en) * 2020-04-09 2020-07-17 大连理工大学 3D printing-oriented modified carbon fiber reinforced polyamide 6 composite material and preparation method and application thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108485251A (en) * 2018-03-14 2018-09-04 广东省肇庆市质量计量监督检测所 A kind of printer enhancing nylon composite materials and preparation method thereof
CN109575584A (en) * 2018-11-20 2019-04-05 贵州航天天马机电科技有限公司 A kind of 3D printing nylon wire rod and preparation method thereof
CN109575584B (en) * 2018-11-20 2021-02-12 贵州航天天马机电科技有限公司 Nylon wire for 3D printing and preparation method thereof
CN110105754A (en) * 2019-03-27 2019-08-09 王小健 A kind of 3D printing anti-bacteria nylon material and preparation method thereof
CN111423721A (en) * 2020-04-09 2020-07-17 大连理工大学 Talcum powder reinforced nylon composite material suitable for desktop processing environment and preparation method and application thereof
CN111423720A (en) * 2020-04-09 2020-07-17 大连理工大学 3D printing-oriented modified carbon fiber reinforced polyamide 6 composite material and preparation method and application thereof

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Application publication date: 20180306