CN104945837B - A kind of ABS/PLA alloy resin compositions for 3D printing and preparation method thereof - Google Patents
A kind of ABS/PLA alloy resin compositions for 3D printing and preparation method thereof Download PDFInfo
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- CN104945837B CN104945837B CN201510412955.2A CN201510412955A CN104945837B CN 104945837 B CN104945837 B CN 104945837B CN 201510412955 A CN201510412955 A CN 201510412955A CN 104945837 B CN104945837 B CN 104945837B
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Abstract
The present invention relates to a kind of ABS/PLA alloy resin compositions for 3D printing and preparation method thereof, the raw material components of following parts by weight are included：30 70 parts of ABS resin, 30 70 parts of PLA resin, 0.1 1.0 parts of crosslinking agent, 0.5 1.5 parts of processing aid；Its preparation method comprises the following steps：Above-mentioned raw material are premixed 3 10 minutes in high-speed mixer, then premix obtains ABS/PLA alloy resin compositions through double screw extruder extruding pelletization.The invention has the advantages that：The method being blended using reactive extrursion, make macromolecular reaction occurs between ABS resin and PLA resin during extruding pelletization, improve compatibility therebetween, so as to prepare the ABS/PLA alloy resins with high intensity, high tenacity, high-dimensional stability and low-carbon environment-friendly, the alloy resin composition is highly suitable as the consumptive material of 3D printing.
Description
【Technical field】
The present invention relates to processing of high molecular material technical field, is that a kind of ABS/PLA for 3D printing is closed specifically
Golden resin combination and preparation method thereof.
【Background technology】
3D printing be one kind based on mathematical model file, with powdery metal or plastics etc. can jointing material, lead to
Carry out the technology of constructed object after the mode successively printed.3D printing technique is gradual in fields such as automobile, medical treatment, toy models
Grow up.At present, mainly there are ABS, PA, PLA and PVA etc., wherein ABS and PLA using more plastics 3D printing consumptive material
It is most commonly seen.PLA is presently the most the biodegradable polymer of successful Non oil-based route synthesis, and it comes from nature and returned
It is attributed to naturally, with higher mechanical strength, solvent resistance is good, high glaze, the excellent advantage such as transparent and environment-friendly, but
Resistance to heat differential, toughness extreme difference.ABS resin is the terpolymer of acrylonitrile, butadiene and styrene, has outstanding impact tough
Property, easy processing mouldability and heat resistance, it is but relatively large as the shrinkage factor of each dimension after 3D printing consumptive material its cooling.Cause
This, all there is the defects of obvious in PLA or the single resins of ABS, as 3D printing consumptive material if improving compatibility by PLA and ABS trees
Fat alloy can then combine the advantage of the two as 3D printing consumptive material, can be prepared high intensity, high glaze, high-dimensional stability,
The alloy resin of high tenacity and low-carbon environment-friendly, the alloy resin are more suitable for 3D printing consumptive material.
Patent CN201010555337.0 discloses a kind of PLA/Polycarbonate alloy material and preparation method, can answer
For 3D printing rapid shaping field.
Patent CN201210104877.6 discloses a kind of ABS/PMMA/PLA ternarys biological plastics alloy material, passes through
Three component PMMA introducing improves ABS and PLA compatibility.
Patent CN201010611328.9 discloses a kind of PLA/ABS resin composite and preparation method thereof, the hair
Bright is to be used as compatilizer using at least one of SEBS grafted maleic anhydrides, POE grafted maleic anhydrides, ABS grafted maleic anhydrides
Improve the compatibility of PLA and ABS resin product.
Patent CN201080049252.3 discloses a kind of heat resistance PLA/ABS resin combinations, and the invention is by making PLA
Reacted with epoxy functionalized oligomeric cahin extension agent and ABS, so as to which the PLA/ABS resin combinations for improving PLA heat resistances be prepared.
However, these above-mentioned technical schemes often exist as impact property is insufficient, the low, raw material sources of rigidity are limited and
The defects of cost is higher, these defects greatly limit extensive use of the PLA/ABS alloy resins in 3D printing field.But
On a kind of technical process is simple, physical and mechanical properties is excellent, the ABS/ for being suitable for 3D printing of dimensionally stable, low-carbon environment-friendly
PLA alloy resin compositions and preparation method thereof, it yet there are no report.
【The content of the invention】
The purpose of the present invention is to be directed to deficiency of the prior art, there is provided a kind of ABS/PLA alloy trees for 3D printing
Oil/fat composition.
Second object of the present invention is to provide a kind of preparation of the ABS/PLA alloy resin compositions for 3D printing
Method.
To achieve the above object, the present invention adopts the technical scheme that：A kind of ABS/PLA alloy resins for 3D printing
Composition, described ABS/PLA alloy resin compositions include the raw material components of following parts by weight：
Preferably, the average weight-molecular mass of described ABS resin is 80,000-150,000g/mol, described ABS
Rubber content is 11%-60% in resin, and the number average bead diameter of rubber is 0.6-3.0um.
Preferably, described PLA resin is PLLA (PLLA), dextrorotation PLA (PDLA) or PDLLA
(PDLLA), its average weight-molecular mass is 80,000-300,000g/mol.
Preferably, described crosslinking agent be benzoyl peroxide, cumyl peroxide, peroxy dicarbonate, two-
(t-butylperoxyisopropyl) benzene or 2,5- dimethyl -2,5- bis(t-butylperoxy) hexanes.
Preferably, described processing aid includes antioxidant, lubricant and releasing agent.
Preferably, described antioxidant is Hinered phenols antioxidant or phosphite ester kind antioxidant, and described lubricant is
Pentaerythritol stearate or ethylene bis stearic acid amide, described releasing agent are silicone releasing agent.
To realize above-mentioned second purpose, the present invention adopts the technical scheme that：A kind of ABS/PLA for 3D printing is closed
The preparation method of golden resin combination, comprises the following steps：
(1) stocked up by following components and content：ABS resin 30-70 parts by weight, PLA resin 30-70 parts by weight, crosslinking agent
0.1-1.0 parts by weight, processing aid 0.5-1.5 parts by weight；
(2) material got ready in step (1) is premixed in super mixer；
(3) by the premix obtained in step (2) by double screw extruder, in 180-200 DEG C of extrusion temperature and 200-
Melting extrusion is carried out under the conditions of 500 revs/min of screw speed, cooling granulation, obtains the ABS/PLA alloy trees for 3D printing
Oil/fat composition.
The invention has the advantages that：
1st, compared with prior art, the present invention uses the technological means of reactive blending, triggers in peroxide crosslinking agent
Under make between ABS resin and PLA resin macromolecular radical reaction to occur during extruding pelletization, the ABS and PLA of generation are total to
Polymers effectively improves the compatibility of the two, so as to prepare the high intensity with Good All-around Property, high tenacity, high size
The ABS/PLA alloy resin compositions of stability and low-carbon environment-friendly；
2nd, preparation method technical process of the invention is simple, cost is low and gained alloy resin is environment-friendly, in 3D fields
With very optimistic market prospects.
【Embodiment】
Embodiment provided by the invention is elaborated with reference to embodiment.
The present invention provides a kind of ABS/PLA alloy resin compositions for 3D printing, and it includes following components and content：
The average weight-molecular mass of described ABS resin is 80,000-150,000g/mol, in described ABS resin
Rubber content is 11%-60%, and the number average bead diameter of rubber is 0.6-3.0um.
Described PLA resin is PLLA (PLLA), dextrorotation PLA (PDLA) or PDLLA (PDLLA),
Its average weight-molecular mass 80,000-300,000g/mol.
Described crosslinking agent is benzoyl peroxide, cumyl peroxide, peroxy dicarbonate, two-(tert-butyl group mistake
Aoxidize isopropyl) benzene or 2,5- dimethyl -2,5- bis(t-butylperoxy) hexanes.
Described processing aid includes antioxidant, lubricant and releasing agent.
Described antioxidant is Hinered phenols antioxidant or phosphite ester kind antioxidant, and described lubricant is pentaerythrite
Stearate or ethylene bis stearic acid amide, described releasing agent are silicone releasing agent.
Its preparation method comprises the following steps：
(1) stocked up by described component and content；
(2) material got ready in step (1) is premixed in super mixer；
(3) by the premix obtained in step (2) by double screw extruder, in 180-200 DEG C of extrusion temperature and 200-
Melting extrusion is carried out under the conditions of 500 revs/min of screw speed, cooling granulation, obtains the ABS/PLA alloy trees for 3D printing
Oil/fat composition.
The raw material of embodiment 1 forms
The raw material of embodiment 2 forms
The raw material of embodiment 3 forms
The raw material of embodiment 4 forms
The raw material of embodiment 5 forms
The raw material of embodiment 6 forms
The raw material of embodiment 7 forms
The raw material of embodiment 8 forms
The raw material of embodiment 9 forms
The raw material of embodiment 10 forms
The raw material of embodiment 11 forms
Comparative example 1
50 parts of ABS resin,
50 parts of PLA resin,
1.5 parts of processing aid (antioxidant, lubricant and releasing agent).
Performance evaluation mode and its implementation standard
The each component that is used in embodiment 1-11 and comparative example 1 in the ABS/PLA alloy resin compositions of 3D printing and its
Content is stocked up according to the component and content of each embodiment and comparative example respectively.First the material got ready is entered in high-speed mixer
Row is sufficiently stirred premix, then by premix by double screw extruder, in 180-200 DEG C of extrusion temperature and 200-500 revs/min
Melting extrusion is carried out under the conditions of screw speed, cooling granulation, obtains ABS/PLA alloy resin compositions.
Wherein, in above-described embodiment and comparative example：
ABS resin, trade mark HR-181, South Korea's brocade lake petrochemical iy produced；
PLA resin, trade mark 3051D, the production of Natureworks companies of the U.S.；
Two-(t-butylperoxyisopropyl) benzene, it is commercially available；
2,5- dimethyl -2,5- bis(t-butylperoxy) hexanes, it is commercially available；
Benzoyl peroxide, it is commercially available；
Cumyl peroxide, it is commercially available；
Peroxy dicarbonate, it is commercially available；
Processing aid, including phosphite ester kind antioxidant IRGAFOS168, hindered phenol IRGANOX245, lubricant stearic acid
Ester (PETS) and silicone releasing agent MB-50, its weight ratio are 3:2:3:2.
Measuring mechanical property：
Measuring mechanical property is carried out to the ABS/PLA alloy resins obtained by embodiment 1-11 and comparative example 1, as a result such as table
Shown in 1：
IZOD notch impact strengths：Tested according to ASTM D256 standards, batten thickness is 6.4mm；
Heat distortion temperature：Tested according to ASTM D648 standards, test condition 0.45MPa；
Bending modulus：Tested according to ASTM D790 standards, test speed 3mm/min；
Melt index：Tested according to ASTM D1238 standards, test condition is 200 DEG C of * 5Kg.
The measuring mechanical property result of table 1
The measuring mechanical property result (Continued) of table 1
According to data in table 1, under the conditions of existing for crosslinking agent, ABS and PLA resin realize reaction in extrusion
Blending, the ABS/PLA alloy resin compositions of excellent combination property can be prepared, this is due to the crosslinking in extrusion
Agent is heated to produce living radical, and living radical captures the active hydrogen on ABS and PLA resin strand so as to produce macromolecular
Chain active site, ABS and PLA resin molecule interchain living radical are combined the copolymer for producing ABS and PLA, so as to improve
Compatibility between the two.The mechanical properties results of embodiment 1,3,5,7,9,10,11 and embodiment 2,4,6,8 are contrasted,
The effect of crosslinking agent 2,5- dimethyl -2,5- bis(t-butylperoxy) hexanes is better than crosslinking agent benzoyl peroxide, peroxide
Change two carbonic esters, cumyl peroxide, two-(t-butylperoxyisopropyl) benzene, because crosslinking agent 2,5- dimethyl-
2,5- bis(t-butylperoxy) hexanes have the double peroxy-radical in remaining four kinds of crosslinking agent, and it can produce more activity
Free radical, so as to trigger more branching reactions.In theory, improving the dosage of crosslinking agent also can occur more macromolecular chains
Branching reaction, but excessive addition can cause moieties chain break to be degraded to be unfavorable for the combination property of product on the contrary on the contrary,
This is confirmed in the mechanical properties results of embodiment 7 and 8.In general, when both ABS and PLA are with 1:1 ratio is total to
It is mixed, while add the crosslinking agent 2 of 0.2 parts by weight, 5- dimethyl -2,5- bis(t-butylperoxy) hexanes, make the ABS/ of acquisition
PLA alloy resins are embodiment 4, and its intensity, toughness, processability, heat-resisting level of aggregation are optimal, in addition environment-friendly, very suitable
Cooperate as 3D printing consumptive material.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, on the premise of the inventive method is not departed from, can also make some improvement and supplement, and these are improved and supplement also should be regarded as
Protection scope of the present invention.
Claims (4)
- A kind of 1. ABS/PLA alloy resin compositions for 3D printing, it is characterised in that described ABS/PLA alloy resins Composition includes the raw material components of following parts by weight：ABS resin 30-70,PLA resin 30-70,Crosslinking agent 0.1-0.5,Processing aid 0.5-1.5；Described processing aid includes antioxidant, lubricant and releasing agent；Described antioxidant is Hinered phenols antioxidant or Asia Phosphoric acid ester antioxidant, described lubricant are pentaerythritol stearate or ethylene bis stearic acid amide, described releasing agent For silicone releasing agent；Described crosslinking agent is 2,5- dimethyl -2,5- double（T-butylperoxy）Hexane.
- 2. ABS/PLA alloy resin compositions according to claim 1, it is characterised in that the weight of described ABS resin is equal Relative molecular mass is 80,000-150,000g/mol, and rubber content is 11%-60% in described ABS resin, and the number of rubber is equal Particle diameter is 0.6-3.0 μm.
- 3. ABS/PLA alloy resin compositions according to claim 1, it is characterised in that described PLA resin is left-handed PLA PLLA, dextrorotation PLA PDLA or PDLLA PDLLA, its average weight-molecular mass are 80,000-300, 000g/mol。
- 4. the preparation method of a kind of ABS/PLA alloy resin compositions for 3D printing, it is characterised in that including following step Suddenly：（1）Stocked up by following components and content：ABS resin 30-70 parts by weight, PLA resin 30-70 parts by weight, crosslinking agent 0.1- 0.5 parts by weight, processing aid 0.5-1.5 parts by weight；Described processing aid includes antioxidant, lubricant and releasing agent；It is described Antioxidant be Hinered phenols antioxidant or phosphite ester kind antioxidant, described lubricant is pentaerythritol stearate or second The double stearic amides of support, described releasing agent is silicone releasing agent；Described crosslinking agent is 2,5- dimethyl -2,5- double（Uncle Butyl peroxy）Hexane；（2）By step（1）In the material got ready premixed in super mixer；（3）By step（2）In obtained premix by double screw extruder, in 180-200 DEG C of extrusion temperature and 200-500 Rev/min screw speed under the conditions of carry out melting extrusion, cooling granulation, obtain the ABS/PLA alloy resins for 3D printing Composition.
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| CN106893280A (en) * | 2015-12-18 | 2017-06-27 | 四川鑫达企业集团有限公司 | A kind of biodegradable 3D printing alloy material and preparation method |
| CN108129811B (en) * | 2015-12-30 | 2020-09-29 | 浦江县汕淋贸易有限公司 | Quantum dot luminescent composite for 3D printing |
| CN105504656A (en) * | 2016-01-04 | 2016-04-20 | 王文广 | Biomass plastic alloy material |
| CN105936678A (en) * | 2016-06-01 | 2016-09-14 | 广西医科大学 | Reinforcing flexibilizer used for 3D printing of ABS, ABS composite material, production method of ABS composite material |
| CN106009569B (en) * | 2016-07-08 | 2018-06-15 | 中北大学 | A kind of polydactyl acid 3D printing material based on ABS reclaiming material |
| CN106189048A (en) * | 2016-07-29 | 2016-12-07 | 苏州秉创科技有限公司 | A kind of bio-based 3D printing consumables |
| CN106947210A (en) * | 2017-04-20 | 2017-07-14 | 合肥智慧殿投资管理有限公司 | A kind of 3D printing material |
| CN110204852A (en) * | 2019-05-30 | 2019-09-06 | 安徽三绿实业有限公司 | A kind of bloom 3D printing material and preparation method thereof |
| CN112708249A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | PLA/ASA plastic composition, preparation method and application |
| CN112063099A (en) * | 2020-09-18 | 2020-12-11 | 深圳市百奥降解材料科技有限公司 | Degradable ABS plastic and preparation method thereof |
| CN113354933A (en) * | 2021-06-18 | 2021-09-07 | 东莞市百富塑料科技有限公司 | Preparation process of degradable ABS plastic |
| CN114106532B (en) * | 2021-11-17 | 2023-09-26 | 金发科技股份有限公司 | Flame-retardant high-toughness PLA alloy material, and preparation method and application thereof |
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| CN102558637B (en) * | 2011-12-28 | 2014-06-18 | 广州鹿山新材料股份有限公司 | Organic peroxide master batches and preparation method thereof |
| WO2013186883A1 (en) * | 2012-06-13 | 2013-12-19 | パナソニック株式会社 | Poly(lactic acid) resin composition, method for producing molded article, molded article, and holder for electronic device |
| CN104031304B (en) * | 2014-04-30 | 2016-02-24 | 中国科学院化学研究所 | A kind of ultraviolet light cross-linking polymer materials for 3D printing and its preparation method and application |
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