CN109096711A - A kind of rice meal modified polylactic acid composite material and preparation method - Google Patents
A kind of rice meal modified polylactic acid composite material and preparation method Download PDFInfo
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- CN109096711A CN109096711A CN201810723820.1A CN201810723820A CN109096711A CN 109096711 A CN109096711 A CN 109096711A CN 201810723820 A CN201810723820 A CN 201810723820A CN 109096711 A CN109096711 A CN 109096711A
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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
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- 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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- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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Abstract
The invention discloses a kind of rice meal modified polylactic acid composite material and preparation methods, rice meal modified polylactic acid composite material prepared by the present invention is compared with traditional poly-lactic acid material (PLA), it is advantageous that composite material cost is further decreased, composite material cost reduces by 1000 yuan/ton than traditional polylactic acid.Meanwhile the toughness of composite material is significantly increased compared to polylactic acid and does not influence its natural self-degradation characteristic.There is far reaching significance for the application in fields such as disposable tablewares.Not only single cost reduces, but also comprehensive mechanical property is improved.
Description
Technical field
The present invention relates to polymeric material fields, are specifically related to a kind of rice meal modified polylactic acid composite material and preparation side
Method.
Background technique
In recent years, national economic rapid development, energy-saving and emission-reduction and low-carbon economy become the hot topic of economic development.It is raw
Object degradative plastics and relevant modified composite material are of increasing concern.Because biodegradable plastic refers to one kind by nature
Such as effect of bacterium, mould (fungi) and algae of existing microorganism and cause degradation plastics.In packing film, agricultural thin
The fields such as film, disposable plastic bag and disposable plastic tableware have a extensive future.However, the raw materials for production of current plastics are still
Mainly petrochemical industry is refined, in addition being not easily accomplished the main original that natural self-degradation results in plastics as environmental pollution
Cause.Polylactic acid (PLA) is a kind of using non-petroleum base as the new material of raw material.Polylactic acid (PLA) is poly- by primary raw material of lactic acid
Obtained polymer is closed, raw material sources are abundant and can regenerate.The production process of polylactic acid (PLA) is pollution-free, and product
Natural self-degradation may be implemented.However, polylactic acid (PLA) is because playing that production technology is complicated, with high costs, toughness of material is poor etc. no
Foot largely limits its industrial applicability and using scale.Polylactic acid (PLA) these deficiencies force the mankind to poly- cream
Sour (PLA) is modified research, reduces material cost, improves polylactic acid comprehensive performance and carries out further further investigation.
Rice meal is made with the rice grinds of Rice Cropping.Rice meal is extensive with abundance, and yield is high, valence
The cheap feature of lattice.The research of rice meal modified polylactic acid material is rarely reported.
Summary of the invention
It is above-mentioned to solve the purpose of the present invention is to provide a kind of rice meal modified polylactic acid composite material and preparation method
The problem of being proposed in background technique.
To achieve the above object, the invention provides the following technical scheme:
A kind of rice meal modified polylactic acid composite material, is grouped as by the group of following mass ratio: polylactic acid (PLA) 100 increases
Tough dose of 10-25, inorganic filler 2-10, auxiliary agent 1-3.5, rice meal 5-15, plasticizer 5-10, coupling agent 0.1-2, initiator 0.2-
1.5。
Preferably, the toughener can be selected from polyolefin elastomer (POE), n-butyl acrylate-ethylene oxidic ester
(PTW), at least one of haloflex (CPE), s-B-S (SBS) etc..
Preferably, the inorganic filler can be selected from CaCO3Nano particle and SiO2Nano particle, talcum particles, BaSO4
One or more of nano particle.
Preferably, the auxiliary agent includes ultraviolet absorbing agent, lubricant, dispersing agent, according to mass ratio, ultraviolet radiation absorption
Agent, lubricant, dispersing agent are (0.1-0.5): (0.2-0.6): (0.4-0.9)；The ultraviolet absorbing agent be 2- hydroxyl -4- just
Octyloxybenzophenone (UV-531) etc.；The lubricant can be selected from White Mineral Oil, amido silicon oil, polyethylene wax, zinc stearate
At least one of Deng；The dispersing agent can be selected from dehydrated alcohol, butyl ester containing carboxylated polypropylene (PBACOOH) oligomer etc..
Preferably, the plasticizer is epoxidized soybean oil.
Preferably, the coupling agent is aluminate coupling agent.
Preferably, the initiator is low molecular poly (PEG).
A kind of preparation method of rice meal modified polylactic acid composite material, comprising the following steps:
S1, inorganic filler processing: the inorganic filler of 2-10 mass parts is dried 0.5-1 hours, takes out and leaves unused in air
0.5-2 hours；The drying temperature is 60-80 degree；
The pretreatment of S2, rice meal: by the coupling agent of 0.1-2 mass parts, 0.2-1.5 mass parts initiator and 5-15 mass
The rice meal of part is sufficiently stirred 1-10 minutes inside high-speed stirred bucket, then handles step S1 well inorganic filler and 0.2-1.5
The initiator of mass parts, which is added in agitator, continues stirring 1-5 minutes, takes out idle 0.5-2 hours in air, is made big
Rice flour pretreated material；
The pretreatment of S3, polylactic acid (PLA) particle: the particles of polylactic acid of 100 mass parts is being had into agitating and heating function
It is dried 0.5-2 hours in mixing tank, the drying temperature is 40-80 degree, and 5-10 mass parts plasticizer is then added and stirs 2-10
Minute；
S4, semifinished material: rice meal pretreated material is made in step S2 and is added in the PLA particle of step S3, together
When 10-25 mass parts toughener, 1-3.5 mass parts auxiliary agent is added, stir, take out stand-by, semifinished material is made；
This process is without heating；
S5, semifinished material obtained by step S4 is granulated by being granulated machining, gained plastic grain is modified for rice meal
Lactic acid composite material.
Preferably, pelletizer used in the step S5 is double-screw extruding pelletizing machine.
Compared with prior art, the beneficial effects of the present invention are: rice meal polydactyl acid composite wood prepared by the present invention
Material is compared with traditional poly-lactic acid material (PLA), it is advantageous that composite material cost is further decreased, composite material cost
1000 yuan/ton are reduced than traditional polylactic acid.Meanwhile the toughness of composite material is significantly increased compared to polylactic acid and does not influence its day
Right self-degradation characteristic.There is far reaching significance for the application in fields such as disposable tablewares.Not only single cost reduces, but also comprehensive
Closing mechanical property is improved.
1, it initiates and utilizes abundance, cheap rice meal and inorganic filler replace PLA particle, reduce cost；
2, the heat resisting temperature of PLA is improved, 40-45 DEG C of heat resisting temperature of PLA pure raw material, composite material heat resisting temperature can be improved
To 48-50 DEG C.
3, compound comprehensive performance is improved.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
In the embodiment of the present invention, a kind of rice meal modified polylactic acid composite material is grouped as by the group of following mass ratio: poly-
Lactic acid (PLA) 100, toughener 10-25, inorganic filler 2-10, auxiliary agent 1-3.5, rice meal 5-15, plasticizer 5-10, coupling agent
0.1-2, initiator 0.2-1.5.
Preferably, the toughener can be selected from polyolefin elastomer (POE), n-butyl acrylate-ethylene oxidic ester
(PTW), at least one of haloflex (CPE), s-B-S (SBS) etc..
Preferably, the inorganic filler can be selected from CaCO3Nano particle and SiO2Nano particle, talcum particles, BaSO4
One or more of nano particle.
Preferably, the auxiliary agent includes ultraviolet absorbing agent, lubricant, dispersing agent, according to mass ratio, ultraviolet radiation absorption
Agent, lubricant, dispersing agent are (0.1-0.5): (0.2-0.6): (0.4-0.9)；The ultraviolet absorbing agent be 2- hydroxyl -4- just
Octyloxybenzophenone (UV-531) etc.；The lubricant can be selected from White Mineral Oil, amido silicon oil, polyethylene wax, zinc stearate
At least one of Deng；The dispersing agent can be selected from dehydrated alcohol, butyl ester containing carboxylated polypropylene (PBACOOH) oligomer etc..
Preferably, the plasticizer is epoxidized soybean oil.
Preferably, the coupling agent is aluminate coupling agent.
Preferably, the initiator is low molecular poly (PEG).
A kind of preparation method of rice meal modified polylactic acid composite material, comprising the following steps:
S1, inorganic filler processing: the inorganic filler of 2-10 mass parts is dried 0.5-1 hours, takes out and leaves unused in air
0.5-2 hours；The drying temperature is 60-80 degree；
The pretreatment of S2, rice meal: by the coupling agent of 0.1-2 mass parts, 0.2-1.5 mass parts initiator and 5-15 mass
The rice meal of part is sufficiently stirred 1-10 minutes inside high-speed stirred bucket, then handles step S1 well inorganic filler and 0.2-1.5
The initiator of mass parts, which is added in agitator, continues stirring 1-5 minutes, takes out idle 0.5-2 hours in air, is made big
Rice flour pretreated material；
The pretreatment of S3, polylactic acid (PLA) particle: the particles of polylactic acid of 100 mass parts is being had into agitating and heating function
It is dried 0.5-2 hours in mixing tank, the drying temperature is 40-80 degree, and 5-10 mass parts plasticizer is then added and stirs 2-10
Minute；
S4, semifinished material: rice meal pretreated material is made in step S2 and is added in the PLA particle of step S3, together
When 10-25 mass parts toughener, 1-3.5 mass parts auxiliary agent is added, stir, take out stand-by, semifinished material is made；
This process is without heating；
S5, semifinished material obtained by step S4 is granulated by being granulated machining, gained plastic grain is modified for rice meal
Lactic acid composite material.
Preferably, pelletizer used in the step S5 is double-screw extruding pelletizing machine.
Embodiment one
By CaCO35 parts of nano particle takes out stand-by material A after drying 1 hour in 80 degree；By 10 parts of rice meal, aluminic acid
0.4 part and 0.5 part PEG-200 of ester coupling agent is sufficiently stirred after 1.5 minutes inside high-speed stirred bucket puts into height for material A together
It is stand-by to obtain material B within fast mixing tank stirring 1.5 minutes；By 100 parts of particles of polylactic acid in agitating and heating function mixing tank
Drying 0.5 hour, drying temperature are 40 degree, and 5 parts of epoxidized soybean oils are added after drying and continue stirring 2 minutes, material B is then added
Material C is stirred to obtain with 10 parts of polyolefin elastomers, 0.5 part of UV-531,0.5 part of zinc stearate；Then by material
Material C extruding pelletization is obtained composite material D by dual-screw pelletizer by C；Composite material D is finally passed through into injection molding performance test
Batten.
The performance test batten of injection formed is subjected to the performances such as tensile strength, elongation at break, notch impact strength, density
It is detected, the results are shown in Table 1 and table 2.
Embodiment two
By 2 parts of CaCO33 parts of talcum particles of nano particle take out stand-by material A after drying 1 hour in 80 degree；It will be big
0.4 part and 0.5 part 10 parts of rice flour, aluminate coupling agent PEG-200 be sufficiently stirred inside high-speed stirred bucket 1.5 minutes after by object
Material A put into together high speed mixing tank stir 1.5 minutes material B it is stand-by；100 parts of particles of polylactic acid is being had into agitating and heating
It is dried 0.5 hour in function mixing tank, drying temperature is 40 degree, 5 parts of epoxidized soybean oils is added after drying and continue stirring 2 minutes,
Then material B is added and 5 parts of polyolefin elastomers, 5 parts of PTW, 0.5 part of UV-531,0.5 part of zinc stearate is sufficiently stirred
It is uniform to obtain material C；Then material C extruding pelletization is obtained into composite material D by dual-screw pelletizer by material C；It will finally answer
Condensation material D passes through injection molding performance test batten.
The performance test batten of injection formed is subjected to the performances such as tensile strength, elongation at break, notch impact strength, density
It is detected, the results are shown in Table 1 and table 2.
Embodiment three
By CaCO35 parts of particle takes out stand-by material A after drying 1 hour in 80 degree；10 parts of rice meal, Aluminate is even
It is mixed that material A is put into high speed after being sufficiently stirred inside high-speed stirred bucket 1.5 minutes by connection 0.4 part and 0.5 part PEG-200 of agent together
It is stand-by that charging basket stirring obtains material B in 1.5 minutes；100 parts of particles of polylactic acid is dried in having agitating and heating function mixing tank
0.5 hour, drying temperature was 40 degree, and 5 parts of epoxidized soybean oils are added after drying and continue stirring 2 minutes, material B and 5 is then added
Part polyolefin elastomer, 5 parts of PTW, 0.5 part of UV-531,0.5 part of zinc stearate stir to obtain material C；Then
Material C extruding pelletization is obtained into composite material D by dual-screw pelletizer by material C；Composite material D is finally passed through into injection molding property
It can test bars.
The performance test batten of injection formed is subjected to the performances such as tensile strength, elongation at break, notch impact strength, density
It is detected, the results are shown in Table 1 and table 2.
Example IV
Stand-by material A is taken out after 5 parts of talcum particles are dried 1 hour in 80 degree；10 parts of rice meal, Aluminate is even
It is mixed that material A is put into high speed after being sufficiently stirred inside high-speed stirred bucket 1.5 minutes by connection 0.4 part and 0.5 part PEG-200 of agent together
It is stand-by that charging basket stirring obtains material B in 1.5 minutes；100 parts of particles of polylactic acid is dried in having agitating and heating function mixing tank
0.5 hour, drying temperature was 40 degree, and 5 parts of epoxidized soybean oils are added after drying and continue stirring 2 minutes, material B and 10 is then added
The PTW, 0.5 part of UV-531,0.5 part of zinc stearate of part stir to obtain material C；Then material C is made by twin-screw
Material C extruding pelletization is obtained composite material D by grain machine；Composite material D is finally passed through into injection molding performance test batten.
The performance test batten of injection formed is subjected to tensile strength, elongation at break, notch impact strength, density, heat-resisting
The performances such as temperature, elasticity modulus, hardness are detected, and the results are shown in Table 1 and table 2.
Table 1
| Embodiment | Tensile strength (MPa) | Elongation at break (%) | Notch impact strength (Kj/m2) | Density (g/cm3) |
| 1 | 66.1 | 22 | 5.5 | 1.30 |
| 2 | 66.3 | 21 | 5.6 | 1.31 |
| 3 | 66.0 | 22 | 5.8 | 1.31 |
| 4 | 65.9 | 24 | 6 | 1.30 |
Table 2
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art,
It is still possible to modify the technical solutions described in the foregoing embodiments, or part of technical characteristic is carried out etc.
With replacement, all within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this
Within the protection scope of invention.
Claims (9)
1. a kind of rice meal modified polylactic acid composite material, which is characterized in that be grouped as by the group of following mass ratio: polylactic acid
(PLA) 100, toughener 10-25, inorganic filler 2-10, auxiliary agent 1-3.5, rice meal 5-15, plasticizer 5-10, coupling agent 0.1-
2, initiator 0.2-1.5.
2. a kind of rice meal modified polylactic acid composite material according to claim 1, which is characterized in that the toughener can
Selected from polyolefin elastomer (POE), n-butyl acrylate-ethylene oxidic ester (PTW), haloflex (CPE), styrene-fourth
At least one of styrene (SBS) etc..
3. a kind of rice meal modified polylactic acid composite material according to claim 1, which is characterized in that the inorganic filler
It can be selected from CaCO3Nano particle and SiO2Nano particle, talcum particles, BaSO4One or more of nano particle.
4. a kind of rice meal modified polylactic acid composite material according to claim 1, which is characterized in that the auxiliary agent includes
Ultraviolet absorbing agent, lubricant, dispersing agent, according to mass ratio, ultraviolet absorbing agent, lubricant, dispersing agent are (0.1-0.5):
(0.2-0.6): (0.4-0.9)；The ultraviolet absorbing agent is 2-hydroxy-4-n-octoxybenzophenone (UV-531) etc.；Institute
Stating lubricant can be selected from least one of White Mineral Oil, amido silicon oil, polyethylene wax, zinc stearate etc.；The dispersing agent can be with
Selected from dehydrated alcohol, butyl ester containing carboxylated polypropylene (PBACOOH) oligomer etc..
5. a kind of rice meal modified polylactic acid composite material according to claim 1, which is characterized in that the plasticizer is
Epoxidized soybean oil.
6. a kind of rice meal modified polylactic acid composite material according to claim 1, which is characterized in that the coupling agent is
Aluminate coupling agent.
7. a kind of rice meal modified polylactic acid composite material according to claim 1, which is characterized in that the initiator is
Low molecular poly (PEG).
8. a kind of preparation method of rice meal modified polylactic acid composite material, which comprises the following steps:
S1, inorganic filler processing: the inorganic filler of 2-10 mass parts is dried 0.5-1 hours, takes out idle 0.5-2 in air
Hour；The drying temperature is 60-80 degree；
The pretreatment of S2, rice meal: by the coupling agent of 0.1-2 mass parts, 0.2-1.5 mass parts initiator and 5-15 mass parts
Rice meal is sufficiently stirred 1-10 minutes inside high-speed stirred bucket, then handles step S1 well inorganic filler and 0.2-1.5 mass
The initiator of part, which is added in agitator, continues stirring 1-5 minutes, takes out idle 0.5-2 hours in air, rice meal is made
Pretreated material；
The pretreatment of S3, polylactic acid (PLA) particle: the particles of polylactic acid of 100 mass parts is being had into agitating and heating function mixing
It is dried 0.5-2 hours in bucket, the drying temperature is 40-80 degree, and 5-10 mass parts plasticizer is then added and stirs 2-10 minutes；
S4, semifinished material: rice meal pretreated material is made in step S2 and is added in the PLA particle of step S3, is added simultaneously
Enter 10-25 mass parts toughener, 1-3.5 mass parts auxiliary agent, stir, takes out stand-by, obtained semifinished material；This mistake
Cheng Wuxu heating；
S5, semifinished material obtained by step S4 is granulated by being granulated machining, gained plastic grain is the modified poly- cream of rice meal
Sour composite material.
9. a kind of preparation method of rice meal modified polylactic acid composite material according to claim 8, which is characterized in that institute
Stating pelletizer used in step S5 is double-screw extruding pelletizing machine.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810482A (en) * | 2019-02-18 | 2019-05-28 | 巩义市欧洁源环保技术服务有限公司 | A kind of prepared slices of Chinese crude drugs inner wrapping polylactic acid membrane material and preparation method thereof |
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| US20110098419A1 (en) * | 2005-10-03 | 2011-04-28 | Masahiro Satoh | Functional filler and resin composition containing same |
| CN102558795A (en) * | 2010-12-17 | 2012-07-11 | 上海杰事杰新材料(集团)股份有限公司 | Polylactic acid-starch blended material and preparation method thereof |
| US20120245292A1 (en) * | 2011-03-25 | 2012-09-27 | Hyundai Motor Company | Manufacturing method of polylactic acid composite composition |
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