CN106084696A - A kind of environmental-protection flame-retardant 3D printed material and preparation method thereof - Google Patents

A kind of environmental-protection flame-retardant 3D printed material and preparation method thereof Download PDF

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Publication number
CN106084696A
CN106084696A CN201610574905.9A CN201610574905A CN106084696A CN 106084696 A CN106084696 A CN 106084696A CN 201610574905 A CN201610574905 A CN 201610574905A CN 106084696 A CN106084696 A CN 106084696A
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parts
retardant
environmental
printed material
protection flame
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章云
张贝尼
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Wuhu Kaiaoer Environmental Science and Technology Co Ltd
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Wuhu Kaiaoer Environmental Science and Technology Co Ltd
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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
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A kind of environmental-protection flame-retardant 3D printed material and preparation method thereof, belongs to 3D printed material field, and the material of the present invention is made up of the raw material of following parts by weight: polylactic acid 30 35 parts, straw 30 35 parts, glass fibre 20 25 parts, wood powder 10 20 parts, paper pulp 10 20 parts, coupling agent 24 parts, fire retardant 24 parts, lubricant 12 parts, 12 parts of antioxidant, poly butylene succinate 12 parts, Polyethylene Glycol 12 parts, dispersant 12 parts.3D printed material obtained by the present invention has economic and environment-friendly feature, and by adding straw, wood powder and glass fibre, the product printed has the feature of high-quality, high-impact, high intensity in a short time, again can fast decoupled after certain time；And add fire retardant, there is low cost, good flame resistance, environmental protection, the features such as production technology is simple, it is easy to industrialized production, easy to use.

Description

A kind of environmental-protection flame-retardant 3D printed material and preparation method thereof
Technical field
The present invention relates to 3D printed material field, be specifically related to a kind of environmental-protection flame-retardant 3D printed material and preparation side thereof Method.
Background technology
Along with 3D prints the increase day by day of demand, available material category gradually increases, and expands from initial resin, plastics To metal, pottery etc..At present, 3D printed material mainly include engineering plastics, photosensitive resin, rubber type of material, metal material and Ceramic material etc..Although 3D printing consumables kind is a lot, but great majority are all with high molecular polymer as primary raw material, as ABS, PE, PC etc., these materials broadly fall into nondegradable material, discarded 3D printed material and 3D printing goods and cause environment Certain impact, and it is high to have cost of manufacture, and energy consumption is high, processing conditions requires fracture complicated, easy, do not have flame retardant effect etc. Shortcoming.At present, developing a kind of environmental protection, degradable, cost of manufacture is cheap, has woodiness touch, and is produced Goods to have the 3D printed material of preferable physical and mechanical properties and fire resistance particularly important.
Summary of the invention
A kind of environmental-protection flame-retardant 3D printed material and preparation side thereof is provided for the problems of the prior art present invention Method, obtained material is economic and environment-friendly, and intensity is high in a short time, after certain time again can fast decoupled, low cost, fire-retardant, Environmental protection, easy to use.
In order to solve the problems referred to above, the present invention by the following technical solutions:
A kind of environmental-protection flame-retardant 3D printed material, is made up of the raw material of following parts by weight: polylactic acid 30-35 part, straw 30-35 part, glass fibre 20-25 part, wood powder 10-20 part, paper pulp 10-20 part, coupling agent 2-4 part, fire retardant 2-4 part, lubrication Agent 1-2 part, antioxidant 1-2 part, poly butylene succinate 1-2 part, Polyethylene Glycol 1-2 part, dispersant 1-2 part.
Described straw is one or more in rice straw, wheat stalk, corn straw.
Described wood powder is Poplar Powder or pine powder.
One or more in silane coupler, aluminate coupling agent, titanate coupling agent selected by described coupling agent.
Described fire retardant is APP.
Two or more in Tissuemat E, zinc stearate, calcium stearate, erucyl amide selected by described lubricant The mixture of meaning ratio.
Described antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, 1,3,5-tri- (3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid, three [2.4-di-tert-butyl-phenyl] phosphite ester, double (tertiary fourth of 2,4-bis- Base phenol) mixture of one or more arbitrary proportions in pentaerythritol diphosphites.
Described dispersant is any one in organic silicone, OPE, stearic acid.
The preparation method of a kind of environmental-protection flame-retardant 3D printed material, comprises the following steps:
Step one: weigh straw and grinding machine for grinding put into by glass fibre, then sieve, obtain 70 mesh～120 mesh Mixed-powder；
Step 2: weigh polylactic acid, wood powder, paper pulp, coupling agent, fire retardant, lubricant, antioxidant, poly-succinic fourth two Alcohol ester, Polyethylene Glycol and dispersant, join in blender together with the mixed-powder in step one, and low whipping speed is 25r/ Under conditions of min～50r/min, stirring mixing 5min～10min, obtains raw mixture；
Step 3: raw mixture is joined and carries out pelletize in double screw extruder, the firstth district of described extruder Section heating-up temperature is 120 DEG C～140 DEG C, and second section heating-up temperature is 150 DEG C～170 DEG C, the 3rd section heating-up temperature It it is 180 DEG C～190 DEG C.
The beneficial effects of the present invention is: the 3D printed material obtained by the present invention has economic and environment-friendly feature, passes through Adding straw, wood powder and glass fibre, the product printed has the feature of high-quality, high-impact, high intensity in a short time, Again can fast decoupled after certain time；And add fire retardant, and there is low cost, good flame resistance, environmental protection, production technology is simple, It is prone to industrialized production, the feature such as easy to use.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
A kind of environmental-protection flame-retardant 3D printed material, is made up of the raw material of following parts by weight: polylactic acid 30 parts, straw 30 Part, glass fibre 20 parts, Poplar Powder 10 parts, paper pulp 10 parts, silane coupler 2 parts, APP 2 parts, lubricant 1 part, four [β- (3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester 1 part, poly butylene succinate 1 part, Polyethylene Glycol 1 part, Organic silicone 1 part.
Described straw be rice straw, wheat stalk, corn straw weight ratio be the mixture of 1:1:1.
Described lubricant selects zinc stearate and the mixture that weight ratio is 1:1 of calcium stearate.
The preparation method of a kind of environmental-protection flame-retardant 3D printed material, comprises the following steps:
Step one: weigh straw and grinding machine for grinding put into by glass fibre, then sieve, obtains 70 mesh purpose mixing Powder；
Step 2: weigh polylactic acid, Poplar Powder, paper pulp, silane coupler, APP, lubricant, four [β-(3,5-bis- Tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, poly butylene succinate, Polyethylene Glycol and organic silicone, with step Mixed-powder in one joins in blender together, and low whipping speed is stirring mixing 5min under conditions of 25r/min, obtains former Material mixture；
Step 3: raw mixture is joined and carries out pelletize in double screw extruder, the firstth district of described extruder Section heating-up temperature is 120 DEG C, and second section heating-up temperature is 150 DEG C, and the 3rd section heating-up temperature is 180 DEG C.
Embodiment 2
A kind of environmental-protection flame-retardant 3D printed material, is made up of the raw material of following parts by weight: polylactic acid 32 parts, rice straw 32 parts, glass fibre 23 parts, pine powder 16 parts, paper pulp 15 parts, silane coupler 3 parts, APP 3 parts, lubricant 2 parts, three [2.4-di-tert-butyl-phenyl] phosphite ester 1 part, poly butylene succinate 1 part, Polyethylene Glycol 2 parts, organic silicone 2 parts.
Described lubricant selects zinc stearate, calcium stearate, erucyl amide weight ratio to be the mixture of 1:1:1.
The preparation method of a kind of environmental-protection flame-retardant 3D printed material, comprises the following steps:
Step one: weigh rice straw and grinding machine for grinding put into by glass fibre, then sieve, obtain 100 purposes Mixed-powder；
Step 2: weigh polylactic acid, pine powder, paper pulp, silane coupler, APP, lubricant, three [2.4-bis-uncles Butyl phenyl] phosphite ester, poly butylene succinate, mixed-powder one in Polyethylene Glycol and organic silicone, with step one Rising joins in blender, and low whipping speed is stirring mixing 8min under conditions of 40r/min, obtains raw mixture；
Step 3: raw mixture is joined and carries out pelletize in double screw extruder, the firstth district of described extruder Section heating-up temperature is 130 DEG C, and second section heating-up temperature is 160 DEG C, and the 3rd section heating-up temperature is 190 DEG C.
Embodiment 3
A kind of environmental-protection flame-retardant 3D printed material, is made up of the raw material of following parts by weight: polylactic acid 35 parts, straw 35 Part, glass fibre 25 parts, Poplar Powder 20 parts, paper pulp 20 parts, titanate coupling agent 4 parts, APP 4 parts, lubricant 2 parts, three [2.4-di-tert-butyl-phenyl] phosphite ester 2 parts, poly butylene succinate 2 parts, Polyethylene Glycol 2 parts, OPE 2 Part.
Described straw be rice straw, wheat stalk, corn straw weight ratio be the mixture of 1:1:1.
Described lubricant selects zinc stearate, calcium stearate, erucyl amide weight ratio to be the mixture of 1:1:1.
The preparation method of a kind of environmental-protection flame-retardant 3D printed material, comprises the following steps:
Step one: weigh straw and grinding machine for grinding put into by glass fibre, then sieve, obtain the mixing of 120 mesh Powder；
Step 2: weigh polylactic acid, Poplar Powder, paper pulp, titanate coupling agent, APP, lubricant, three [2.4-bis- Tert-butyl-phenyl] phosphite ester, poly butylene succinate, the mixing in Polyethylene Glycol and OPE, with step one Powder joins in blender together, and low whipping speed is stirring mixing 10min under conditions of 50r/min, obtains raw mixture；
Step 3: raw mixture is joined and carries out pelletize in double screw extruder, the firstth district of described extruder Section heating-up temperature is 140 DEG C, and second section heating-up temperature is 170 DEG C, and the 3rd section heating-up temperature is 190 DEG C.
The main performance of environmental-protection flame-retardant 3D printed material prepared by embodiment 1-3 is as shown in table 1.
Table 1
It should be appreciated that these are only the preferred embodiments of the present invention, it is impossible to therefore limit the scope of the claims of the present invention, Every equivalent structure utilizing description of the invention content to be made or equivalence flow process conversion, or directly or indirectly it is used in other phases The technical field closed, is the most in like manner included in the scope of patent protection of the present invention.

Claims (10)

1. an environmental-protection flame-retardant 3D printed material, it is characterised in that be made up of the raw material of following parts by weight: polylactic acid 30- 35 parts, straw 30-35 part, glass fibre 20-25 part, wood powder 10-20 part, paper pulp 10-20 part, coupling agent 2-4 part, fire retardant 2- 4 parts, lubricant 1-2 part, antioxidant 1-2 part, poly butylene succinate 1-2 part, Polyethylene Glycol 1-2 part, dispersant 1-2 part.
A kind of environmental-protection flame-retardant 3D printed material the most according to claim 1, it is characterised in that by following parts by weight Raw material forms: polylactic acid 30 parts, straw 30 parts, glass fibre 20 parts, wood powder 10 parts, paper pulp 10 parts, coupling agent 2 parts, fire retardant 2 Part, lubricant 1 part, 1 part of antioxidant, poly butylene succinate 1 part, Polyethylene Glycol 1 part, dispersant 1 part.
A kind of environmental-protection flame-retardant 3D printed material the most according to claim 1, it is characterised in that by following parts by weight Raw material forms: polylactic acid 35 parts, straw 35 parts, glass fibre 25 parts, wood powder 20 parts, paper pulp 20 parts, coupling agent 4 parts, fire retardant 4 Part, lubricant 2 parts, 2 parts of antioxidant, poly butylene succinate 2 parts, Polyethylene Glycol 2 parts, dispersant 2 parts.
A kind of environmental-protection flame-retardant 3D printed material the most according to claim 1, it is characterised in that: described straw is Oryza sativa L. straw One or more in stalk, wheat stalk, corn straw.
A kind of environmental-protection flame-retardant 3D printed material the most according to claim 1, it is characterised in that: described coupling agent is selected One or more in silane coupler, aluminate coupling agent, titanate coupling agent.
A kind of environmental-protection flame-retardant 3D printed material the most according to claim 1, it is characterised in that: described fire retardant is poly- Ammonium phosphate.
A kind of environmental-protection flame-retardant 3D printed material the most according to claim 1, it is characterised in that: described lubricant is selected poly- The mixture of two or more arbitrary proportion in ethylene waxes, zinc stearate, calcium stearate, erucyl amide.
A kind of environmental-protection flame-retardant 3D printed material the most according to claim 1, it is characterised in that: described antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) Isocyanuric acid, three [2.4-di-tert-butyl-phenyl] phosphite ester, double (2,4-DI-tert-butylphenol compounds) pentaerythritol diphosphites In the mixture of one or more arbitrary proportions.
A kind of environmental-protection flame-retardant 3D printed material the most according to claim 1, it is characterised in that: described dispersant is organic Any one in silicone, OPE, stearic acid.
10. the preparation method of the environmental-protection flame-retardant 3D printed material described in an any one of claim 1-9, it is characterised in that Comprise the following steps:
Step one: weigh straw and grinding machine for grinding put into by glass fibre, then sieve, obtains 70 mesh～120 purposes are mixed Close powder；
Step 2: weigh polylactic acid, wood powder, paper pulp, coupling agent, fire retardant, lubricant, antioxidant, poly butylene succinate, Polyethylene Glycol and dispersant, join in blender together with the mixed-powder in step one, low whipping speed be 25r/min～ Under conditions of 50r/min, stirring mixing 5min～10min, obtains raw mixture；
Step 3: joined by raw mixture and carry out pelletize in double screw extruder, the first section of described extruder adds Hot temperature is 120 DEG C～140 DEG C, and second section heating-up temperature is 150 DEG C～170 DEG C, and the 3rd section heating-up temperature is 180 DEG C～190 DEG C.
CN201610574905.9A 2016-07-21 2016-07-21 A kind of environmental-protection flame-retardant 3D printed material and preparation method thereof Pending CN106084696A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107805398A (en) * 2017-10-24 2018-03-16 芜湖蓝天工程塑胶有限公司 Stalk fibrous composite and preparation method thereof
GB2591121A (en) * 2020-01-16 2021-07-21 Floreon Transf Packaging Limited Polylactic acid flame resistant blend

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101020780A (en) * 2007-03-15 2007-08-22 上海交通大学 Prepn process of polylactic acid-base thermoplastic wood-plastic composite material
CN102838859A (en) * 2012-09-28 2012-12-26 江苏嘉铂新材料有限公司 Nanometer bentonite composite flame-retardant polylactic acid bioplastics and preparation method thereof
CN104312119A (en) * 2014-11-06 2015-01-28 芜湖瀚博电子科技有限公司 Straw 3D printing consumable and preparation method thereof
CN104356618A (en) * 2014-10-29 2015-02-18 衢州学院 Biomass wood-plastic composite material for 3D (three-dimensional) printing and preparation method for biomass wood-plastic composite material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101020780A (en) * 2007-03-15 2007-08-22 上海交通大学 Prepn process of polylactic acid-base thermoplastic wood-plastic composite material
CN102838859A (en) * 2012-09-28 2012-12-26 江苏嘉铂新材料有限公司 Nanometer bentonite composite flame-retardant polylactic acid bioplastics and preparation method thereof
CN104356618A (en) * 2014-10-29 2015-02-18 衢州学院 Biomass wood-plastic composite material for 3D (three-dimensional) printing and preparation method for biomass wood-plastic composite material
CN104312119A (en) * 2014-11-06 2015-01-28 芜湖瀚博电子科技有限公司 Straw 3D printing consumable and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107805398A (en) * 2017-10-24 2018-03-16 芜湖蓝天工程塑胶有限公司 Stalk fibrous composite and preparation method thereof
GB2591121A (en) * 2020-01-16 2021-07-21 Floreon Transf Packaging Limited Polylactic acid flame resistant blend

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Application publication date: 20161109