CN108059806A - A kind of 3D printing PLA/TPU composite materials - Google Patents
A kind of 3D printing PLA/TPU composite materials Download PDFInfo
- Publication number
- CN108059806A CN108059806A CN201610971583.1A CN201610971583A CN108059806A CN 108059806 A CN108059806 A CN 108059806A CN 201610971583 A CN201610971583 A CN 201610971583A CN 108059806 A CN108059806 A CN 108059806A
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- Prior art keywords
- pla
- parts
- tpu
- composite materials
- tpu composite
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Classifications
-
- 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08L2205/03—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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of biodegradable 3D printing PLA/TPU materials, include the component of following parts by weight：40 60 parts of PLA, polyurethane（TPU）15 30 parts, thermoplastic starch 5~20%, 15 parts of crosslinking agent, 2 10 parts of inorganic filler, 0.5 1 parts of stabilizer；The present invention targetedly selects TPU to be modified processing to PLA so that PLA modified materials show excellent toughness.The material is while 3D printing material category has been widened so that degradable class 3D printing material shows more preferably mechanical property.
Description
Technical field
The present invention relates to 3D printing fields, and PLA material is modified more particularly to a kind of biodegradable 3D printing.
Background technology
The development of 3D printing technique proposes 3D printing material new requirement, by taking melting extrusion forming technique as an example, needs
Consider plastics fuse dimension and processability is designed nozzle temperature, to the large-scale hollow product of printing, then must
It must consider how to separate the packing material at center with skin-material, it is necessary to consider that the two has good bonding before separation
Property, skin-material is avoided to collapse.
Polylactic acid（PLA）The advantages of be to have nontoxic, without pungent smell, melting temperature is relatively low, degradable pollution-free, cold
But shrinking percentage is small, and transparent easy dyeing etc., these characteristics meet requirement of the 3D printing technique to polymer material；But polylactic acid
There is also crystallinity is smaller, ester bond bond energy is small in strand, the factor being easily broken off causes that the heat distortion temperature of polylactic acid is low, punching
The defects of hit intensity is low, toughness is bad, this causes the products application printed by polylactic acid scope to be very restricted.
TPU is a kind of special elastic synthesis material between ordinary rubber and plastics, by polyisocyanates, low
Molecular polylol is prepared.It had not only had the high resiliency of rubber, but also the thermoplastic processing with thermoplastic, while also had
There are high-modulus, high intensity, high elongation rate, high resiliency and the performances such as excellent wear-resisting, oil resistant, low temperature resistant, ageing-resistant extensive
Toughening modifying applied to plastics.Thermoplastic polyurethane elastomer collection toughness, durability, flexibility, biocompatibility and biology
The advantages that stability, in one, can be widely used as the medical materials such as drug controlled release, therefore use polyurethane toughened polylactic acid
It is to improve the brittle good method of polylactic acid.
The content of the invention
It is an object of the invention to provide it is a kind of can 3D printing PLA/TPU composite materials and preparation method thereof.Utilize PLA
Melt blending is carried out by different ratio with TPU, small molecule crosslinking agent, stabilizer and other components, to realize crosslinking, toughening and increasing
Strong wait is modified, and finally obtains the PLA/TPU composite material materials available for 3D printing.
In order to realize the purpose of foregoing invention, the present invention provides following technical scheme：
（1）It is a kind of can 3D printing PLA/TPU composite materials, be made of following components in parts by weight：40-60 parts of PLA gathers
Urethane（TPU）15-30 parts, thermoplastic starch 5~20%, 1-5 parts of crosslinking agent, 2-10 parts of inorganic filler, 0.5-1 parts of stabilizer.
（2）The one kind of the crosslinking agent in benzoyl peroxide, tetraalkyl butyl acrylate；The inorganic filler is
Nano silicon dioxide, nano-calcium carbonate, carbon nanotubes, graphite, graphene are one or more；The heat stabilizer is phosphite ester
One or more of class, calcium zinc stabilizer.
The advantage of the invention is that：
（1）The PLA/TPU composite materials of the present invention have good toughness, the product size printed by 3D printing technique
Stablize.
（2）The special elastic property of PLA/TPU material use polyurethane, to improve the shortcomings that polylactic acid elasticity is poor；Drop
The glass transition temperature of lact-acid oligomer improves its mechanical performance.
Specific embodiment
It is set forth in the present invention be it is a kind of can 3D printing PLA/TPU composite materials, below by way of specific embodiment into
One step illustrates, but the present invention is not limited only to following embodiment.
Embodiment one
(1) a kind of 3D printing PLA/TPU composite materials include the component of following parts by weight：20 parts of 60 parts of PLA, TPU, thermoplastic
10 parts of starch of property, 5 parts of crosslinking agent, 5 parts of inorganic filler, 1.0 parts of stabilizer.
(2) in the present invention, the crosslinking agent refers to that those can be in intermolecular bridging action of line style, so that multiple
Linear molecule is mutually bonded the substance for being cross-linked into net structure, and specifically those promote or adjust polymer molecule interchain to be total to
The substance that valence link or ionic bond are formed.Optional crosslinking agent of the invention includes but not limited to：Benzoyl peroxide and tetraalkyl third
One kind in olefin(e) acid butyl ester.
(3) thermoplastic starch of the present invention is to mix potato starch with plasticizer, and plasticizer is citric acid three
Butyl ester, triethyl citrate, tributyl 2-acetylcitrate, triacetyl glycerine, dibutyl sebacate, epoxidized soybean oil, oneself two
Acid propylene glycol polyester or di-2-ethylhexyl maleate.
(4) inorganic filler of the present invention is nano silicon dioxide, in addition, inorganic filler may also function as nucleating agent
Effect.
(5) heat stabilizer of the present invention is one or more of phosphorous acid esters, calcium zinc stabilizer.
(6) above-mentioned uniformly mixed experiment material by 3D printing consumptive material production line is squeezed out, obtains beating suitable for 3D
The PLA/TPU consumptive materials of print, wherein the 10 of extruder section temperature be followed successively by 155 DEG C, 160 DEG C, 170 DEG C, 170 DEG C, 170 DEG C, 170
℃、170℃、170℃、175℃、180℃.Screw speed is 110r/min, and rate of feeding is 4.6 r/min.
Embodiment two
(1) a kind of 3D printing PLA/TPU composite materials include the component of following parts by weight：30 parts of 50 parts of PLA, TPU, thermoplastic
15 parts of starch of property, 2 parts of crosslinking agent, 3 parts of inorganic filler, 0.5 part of stabilizer.
(2) in the present invention, the crosslinking agent refers to that those can be in intermolecular bridging action of line style, so that multiple
Linear molecule is mutually bonded the substance for being cross-linked into net structure, and specifically those promote or adjust polymer molecule interchain to be total to
The substance that valence link or ionic bond are formed.Optional crosslinking agent of the invention includes but not limited to：Benzoyl peroxide and tetraalkyl third
One kind in olefin(e) acid butyl ester.
(3) thermoplastic starch of the present invention is to mix potato starch with plasticizer, and plasticizer is citric acid three
Butyl ester, triethyl citrate, tributyl 2-acetylcitrate, triacetyl glycerine, dibutyl sebacate, epoxidized soybean oil, oneself two
Acid propylene glycol polyester or di-2-ethylhexyl maleate.
(4) inorganic filler of the present invention is nano silicon dioxide, in addition, inorganic filler may also function as nucleating agent
Effect.
(5) heat stabilizer of the present invention is one or more of phosphorous acid esters, calcium zinc stabilizer.
(6) above-mentioned uniformly mixed experiment material by 3D printing consumptive material production line is squeezed out, obtains beating suitable for 3D
The PLA/TPU consumptive materials of print, wherein the 10 of extruder section temperature be followed successively by 150 DEG C, 160 DEG C, 173 DEG C, 173 DEG C, 173 DEG C, 173
℃、173℃、173℃、180℃、180℃.Screw speed is 115r/min, and rate of feeding is 4.6 r/min.
Claims (8)
1. a kind of PLA/TPU composite materials for being suitable for 3D printing, are made of following components in parts by weight：40-60 parts of PLA gathers
Urethane（TPU）15-30 parts, thermoplastic starch 5~20%, 1-5 parts of crosslinking agent, 2-10 parts of inorganic filler, 0.5-1 parts of stabilizer.
2. PLA/ TPU composite materials according to claim 1, it is characterised in that the PLA be 2002D, 2003D,
One or more of 4032D.
3. PLA/TPU composite materials according to claim 1, it is characterised in that the TPU is capa6500, in 600C
It is one or more of.
4. PLA/TPU composite materials according to claim 1, it is characterised in that the thermoplastic starch is that potato is formed sediment
Powder is mixed with plasticizer, and plasticizer is tributyl citrate, triethyl citrate, tributyl 2-acetylcitrate, three triacetins
Ester, dibutyl sebacate, epoxidized soybean oil, adipic acid propanediol polyester or di-2-ethylhexyl maleate.
5. PLA/TPU composite materials according to claim 1, it is characterised in that the crosslinking agent is selected from benzoyl peroxide first
One kind in acyl, tetraalkyl butyl acrylate.
6. PLA/TPU composite materials according to claim 1, it is characterised in that the inorganic filler is nanometer titanium dioxide
Silicon, nano-calcium carbonate, carbon nanotubes, graphite, graphene are one or more.
7. PLA/TPU composite materials according to claim 1, the heat stabilizer is phosphorous acid esters, calcium zinc stabilizer
One or more of.
8. PLA/TPU composite materials according to claim 1, include the following steps：
1) mixed after in proportion fully drying PLA, TPU, thermoplastic starch, crosslinking agent, stabilizer, inorganic filler with high mixer
Uniformly；
2) mixture for obtaining step 1) is added in double screw extruder and squeezes out, and extrudate utilizes receipts after air cooling
Volume machine is wound；
Method as claimed in claim 8, the double screw extruder of step 2 have 10 temperature controlled zones, and temperature is followed successively by 150-170
℃、160-180℃、170-185℃、170-185℃、170-185℃、170-190℃、170-190℃、170-190℃、175-
190℃、180-190℃；Screw speed is 100 ~ 120r/min, and rate of feeding is 4.5 ~ 6.5 r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610971583.1A CN108059806A (en) | 2016-11-07 | 2016-11-07 | A kind of 3D printing PLA/TPU composite materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610971583.1A CN108059806A (en) | 2016-11-07 | 2016-11-07 | A kind of 3D printing PLA/TPU composite materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108059806A true CN108059806A (en) | 2018-05-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610971583.1A Pending CN108059806A (en) | 2016-11-07 | 2016-11-07 | A kind of 3D printing PLA/TPU composite materials |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181251A (en) * | 2018-07-13 | 2019-01-11 | 刘辉 | A kind of modified polylactic acid material product |
| CN110396286A (en) * | 2019-07-23 | 2019-11-01 | 南宁师范大学 | Excellent 3D printing consumptive material and preparation method thereof at a low price |
| CN111378262A (en) * | 2020-04-16 | 2020-07-07 | 孝感市易生新材料有限公司 | Polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, preparation method thereof and application thereof in 3D printing consumables |
| CN113372658A (en) * | 2021-06-08 | 2021-09-10 | 明丹医疗科技有限公司 | 3D printing TPX composite material suitable for medical treatment and aviation and preparation method thereof |
| CN113881207A (en) * | 2021-11-02 | 2022-01-04 | 清华大学 | Degradable shape memory flexible substrate material, preparation method thereof and thickness regulation and control method |
| CN114292501A (en) * | 2021-12-03 | 2022-04-08 | 东莞职业技术学院 | Biodegradable material and preparation method and application thereof |
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| CN101519527A (en) * | 2009-03-24 | 2009-09-02 | 山东威高集团医用高分子制品股份有限公司 | Medical degradable composite material |
| US20140148534A1 (en) * | 2011-06-30 | 2014-05-29 | Shanghai Zaihe Industrial Investment Co., Ltd. | Thermolastic starch, biodegradable polyester/starch composite material and preparation method thereof |
| CN104448738A (en) * | 2014-11-21 | 2015-03-25 | 甘肃圣大方舟马铃薯变性淀粉有限公司 | Bio-based 3D printing material and preparation method thereof |
| CN104530668A (en) * | 2014-12-17 | 2015-04-22 | 广州飞胜高分子材料有限公司 | 3D printing material having self-cleaning antibacterial function as well as preparation method and application of 3D printing material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101519527A (en) * | 2009-03-24 | 2009-09-02 | 山东威高集团医用高分子制品股份有限公司 | Medical degradable composite material |
| US20140148534A1 (en) * | 2011-06-30 | 2014-05-29 | Shanghai Zaihe Industrial Investment Co., Ltd. | Thermolastic starch, biodegradable polyester/starch composite material and preparation method thereof |
| CN104448738A (en) * | 2014-11-21 | 2015-03-25 | 甘肃圣大方舟马铃薯变性淀粉有限公司 | Bio-based 3D printing material and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181251A (en) * | 2018-07-13 | 2019-01-11 | 刘辉 | A kind of modified polylactic acid material product |
| CN110396286A (en) * | 2019-07-23 | 2019-11-01 | 南宁师范大学 | Excellent 3D printing consumptive material and preparation method thereof at a low price |
| CN110396286B (en) * | 2019-07-23 | 2021-05-25 | 南宁师范大学 | Low-price excellent 3D printing consumable and preparation method thereof |
| CN111378262A (en) * | 2020-04-16 | 2020-07-07 | 孝感市易生新材料有限公司 | Polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, preparation method thereof and application thereof in 3D printing consumables |
| CN111378262B (en) * | 2020-04-16 | 2023-03-21 | 孝感市易生新材料有限公司 | Polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, preparation method thereof and application thereof in 3D printing consumables |
| CN113372658A (en) * | 2021-06-08 | 2021-09-10 | 明丹医疗科技有限公司 | 3D printing TPX composite material suitable for medical treatment and aviation and preparation method thereof |
| CN113881207A (en) * | 2021-11-02 | 2022-01-04 | 清华大学 | Degradable shape memory flexible substrate material, preparation method thereof and thickness regulation and control method |
| CN114292501A (en) * | 2021-12-03 | 2022-04-08 | 东莞职业技术学院 | Biodegradable material and preparation method and application thereof |
| CN114292501B (en) * | 2021-12-03 | 2023-10-20 | 东莞职业技术学院 | Biodegradable material and preparation method and application thereof |
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Application publication date: 20180522 |
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