CN109021511A - A method of polylactic acid mechanical property is improved using rigid-flexible core shell nanoparticles - Google Patents
A method of polylactic acid mechanical property is improved using rigid-flexible core shell nanoparticles Download PDFInfo
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- CN109021511A CN109021511A CN201810510956.4A CN201810510956A CN109021511A CN 109021511 A CN109021511 A CN 109021511A CN 201810510956 A CN201810510956 A CN 201810510956A CN 109021511 A CN109021511 A CN 109021511A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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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Abstract
The present invention provides a kind of method for improving polylactic acid mechanical property using rigid-flexible core shell nanoparticles, the following steps are included: step 1: preparing rigid-flexible core shell nanoparticles using chemical copolymerization grafting method, wherein rigid phase is kernel, flexible is mutually shell, it is connected between two-phase by covalent bond, the active function groups with polylactic acid molecule chain reaction are contained in soft shell end；Step 2: the rigid-flexible core shell nanoparticles that mass fraction is 1% are added planetary ball mill with the polylactic acid after drying and mix；Step 3: the material melts after mixing, which are blended, is made modified material；Step 4: the modification material after melt blending uses injection molding or hot-forming.Core shell nanoparticles used include rigid phase and flexible phase simultaneously, and are connected between two-phase by covalent bond, do not occur mutually to separate, can play the synergistic effect of enhancing and toughening.
Description
Technical field
The present invention relates to a kind of methods for improving polylactic acid mechanical property more particularly to a kind of utilization core shell nanoparticles to change
Into the method for polylactic acid mechanical property, belong to technical field of material modification.
Background technique
With economic and science and technology fast development, plastics are extensive because of its excellent performance such as light, high-strength and corrosion-resistant
The every field for producing and living applied to people.However, being formed since conventional petroleum base plastics in nature are difficult to degrade
" white pollution " living environment of the mankind and marine organisms caused seriously threaten.Especially in recent years, with express delivery and fastly
The rapid development of meal cause, the plastics package pollution generated also form huge pressure to ecological environment.In addition, production modeling
The petroleum of material is non-renewable resources, and a large amount of use of conventional plastic also necessarily causes the acceleration of resource and the energy deficient.Thus,
In recent years, biodegradable plastics becomes the emphasis of people's extensive concern and research.Novel biodegradable plastics can be in micro- life
Degradable under the action of object is carbon dioxide and water, be can be realized using easy and low cost landfill or composting technology discarded
The harmless treatment of plastics.In numerous biodegradable polymers, polylactic acid (PLA) good, bio-compatible with its processing performance
Property the advantages such as good and easily biological-degradable and be used to prepare tableware, agricultural film, medical material and sports goods etc., have wide
Application value.Moreover, the raw material for preparing of polylactic acid is mainly derived from the renewable crops such as corn, beet and potato, it is raw
It produces and treatment process is pollution-free, be a kind of ideal renewable environmental protection macromolecule material.But polylactic acid toughness is poor, strong
Degree is not high, thermal stability is lower, and which has limited it widely to apply.
Currently, the main mechanical property for improving polylactic acid by the way of addition rubber or rigid particles.In polylactic acid poly
The toughness of polylactic acid, but its intensity and modulus sharp fall can be obviously improved by closing addition rubber toughening agent in object.Therefore, in order to
The loss for reducing strength and stiffness has research that rigid nano particle is added in polylactic acid, such as nano clay, silica, two
Titanium oxide, calcium carbonate, talcum powder and carbon nanotube etc. improve its mechanical property, but these rigid nano particles are to polylactic acid
Toughness promotion is smaller, or even the case where elongation at break decline occurs.It is added simultaneously in polylactic acid for this purpose, some scholars use
The method of rubber grain and rigid nano particle is to realizing balance that polylactic acid intensity and toughness are promoted, but result of study table
Bright, flexible rubber and rigid nano particle do not play the role of while toughening and enhancing.This may be because added
Because mutually separating and can not generating the synergistic effect of activeness and quietness between flexible toughener and rigidity reinforced agent.Therefore, balance is poly-
The promotion of lactic acid intensity and toughness is the important development direction of polylactic acid mechanical property improving environment, this will also determine that its future exists
A possibility that more areas replace conventional plastic and are widely used.
Summary of the invention
A kind of utilization rigidity-is provided the purpose of the invention is to promote the mechanical properties such as the intensity of polylactic acid and toughness
The method that flexible core shell nanoparticles improve polylactic acid mechanical property.
The object of the present invention is achieved like this:
A method of polylactic acid mechanical property is improved using rigid-flexible core shell nanoparticles, comprising the following steps:
Step 1: rigid-flexible core shell nanoparticles are prepared using chemical copolymerization grafting method, wherein rigid phase is interior
Core, flexible is mutually shell, is connected between two-phase by covalent bond, the work with polylactic acid molecule chain reaction is contained in soft shell end
Property functional group；
Step 2: the rigid-flexible core shell nanoparticles that mass fraction is 1% and the polylactic acid after drying are added planetary
Ball mill mixes；
Step 3: the material melts after mixing, which are blended, is made modified material；
Step 4: the modification material after melt blending uses injection molding or hot-forming.
The invention also includes structure features some in this way:
1. the rigid phase is silica, carbon nanotube, graphene or silsesquioxane, the flexible phase is elongation
For 2000% polybutylacrylate rubber；
2. time >=30min that the planetary ball mill mixes；
3. material melts, which are blended, uses closed mixing machine or double screw extruder；The temperature of closed mixing be 160~
190 DEG C, revolving speed is 30~100r/min, and mixing time is 3~10min；The temperature of double screw extruder is 150~190 DEG C, into
Material screw speed is 10~30rpm, and driving screw running speed is 100~180rpm；
4. when hot-forming, hot pressing temperature is 160~190 DEG C, and hot pressing time is 3~10min, hot pressing pressure is 0.5~
10MPa, when injection molding, injection molding machine temperature is 170~190 DEG C.
Compared with prior art, the beneficial effects of the present invention are:
(1) core shell nanoparticles used in include rigid phase and flexible phase simultaneously, and are connected between two-phase by covalent bond, no
Generation mutually separates, and can play the synergistic effect of enhancing and toughening；
(2) active function groups that can be reacted with matrix are contained in core-shell modifiers end, not only increase modifying agent and matrix
Between interfacial adhesion effect, reduce unsticking phenomenon occur, moreover it is possible to promote the dispersion of modifying agent in the base；
(3) only adding a small amount of (such as 1wt.%) core shell nanoparticles can be realized the promotion of polylactic acid mechanical property, no
Only save manufacturing cost, moreover it is possible to guarantee that the thermal property of polylactic acid and processing performance are unaffected；
(4) first matrix and modifying agent are mixed using ball mill, heating incorporation time can be reduced, to reduce poly-
The intensity decline that lactic acid is generated by thermal degradation.
Detailed description of the invention
Fig. 1 is the preparation flow figure of rigid-flexible core shell nanoparticles.；
Fig. 2 is the preparation method of modified poly- newborn lactic acid.
Specific embodiment
Present invention is further described in detail with specific embodiment by 1-2 with reference to the accompanying drawing.
The invention proposes a kind of methods for promoting polylactic acid biodegradable polymers intensity and toughness, including following step
It is rapid:
The first step, it is total using the chemistry of electronics transfer regenerated catalyst-atom transfer radical polymerization (ARGET ATRP)
Poly- grafting method prepares rigid-flexible core shell nanoparticles.Rigid phase selection rigidity inside nucleocapsid particles is higher and surface is living
Property hydroxyl group nano silica (SiO abundant2) particle, the flexible mutually selection elongation of outer layer is up to poly- the third of 2000%
Olefin(e) acid butyl ester (PBA) rubber.By chemical method in SiO2Surface grafting PBA is connected between two-phase by covalent bond, is not easy to send out
It is raw mutually to separate, good synergistic effect can be played.It is living plus end by chemical reaction in the casing ends of core shell nanoparticles
Property functional group, be coupled it with substrate molecule, form the effect of preferable interfacial adhesion；Second step, by dry polylactic acid and system
The core-shell nano modifying agent that the mass fraction got ready is 1% is added planetary ball mill and carries out uniformly mixing to shorten its heat fusing
Incorporation time under state, to minimize the thermal degradation loss of polylactic acid；Third step, the mixed poly- cream of ball mill
The mixing in banburying machine of acid and modifying agent is blended, and makes polylactic acid and modifying agent material melts so as to subsequent forming；4th step,
Material after melting mixing is formed by the way of injection molding or hot pressing.
The additive amount of core-shell nano modifying agent of the present invention can change according to the actual application；The third step preparation
Screw Extrusion replacement can be used in banburying in method；The end active functional group of the nucleocapsid particles shell is can be with poly- cream
The group that acid molecule chain is chemically bonded, such as amino group；The core shell nanoparticles use the chemistry side of surface grafting
Method synthesis, such as atom transfer radical polymerization and ring-opening polymerisation.
Embodiment 1
The first step prepares rigid-flexible core shell nanoparticles, preparation process such as Fig. 1 using the method that chemical graft is copolymerized
It is shown, it is broadly divided into the following steps:
1. Silanization reaction: weighing 1.0g SiO with electronic balance2, it is put into the three-necked flask of 100mL, then at three mouthfuls
20mL toluene is added in bottle, ultrasound is mixed uniformly, and after leading to nitrogen 30min, the 3- aminopropyl-triethoxy of 2mL is added dropwise
Silane (APTES), reacts 16h after mixed liquor is warming up to 95 DEG C.After being cooled to room temperature, centrifugation obtains solid, with toluene, acetone
The washing of (or ethyl alcohol) ultrasonic disperse, then be collected by centrifugation and purified, this process repeats 3-4 times, and clean sample is placed in 60 DEG C
Lower vacuum drying, by dried white solid powder (SiO2-NH2) clayed into power with mortar, it is fitted into spare in sample cell.
2. being bonded initiator: weighing 1.0g SiO with electronic balance2-NH2It is put into the there-necked flask of 100mL, 15mL first is added
Benzene, then 2mL triethylamine is added with pipette, above-mentioned there-necked flask is placed in ice-water bath, magnetic agitation is opened, (logical N230min),
Then the mixed liquor of the 2- bromine isobutyl acylbromide (BiB) of the 2mL mixed in advance and the toluene of 5mL is added dropwise, is reacted at 0 DEG C
Then 3h is warmed to room temperature lower reaction 12h and product is collected by centrifugation after reaction, with acetone and washes of absolute alcohol (2-3 times),
Dispersion is collected by centrifugation again, and place the product in be dried in vacuo for 24 hours at 60 DEG C.Faint yellow solid grind into powder after drying is packed into
Sample cell is spare.
3. graft copolymerization: using ARGET ATRP method in Nano-meter SiO_22Surface grafting hydrophobic monomer butyl acrylate
(BA), the method is as follows: BA (10mL), FeCl3·6H2O (29mg, 0.1mmol), PPh3(212mg, 0.8mmol), EBiB (45 μ
L, 0.3mmol), DMF (14mL, 182mmol) and SiO2- Br (250mg) is sequentially added in there-necked flask, ultrasonic 5min, Jiang Sankou
Bottle is fixed on iron stand, opens magnetic agitation, leads to N230min, the VC (528mg, 3mmol) being dissolved in DMF slowly add
Enter and (can be added with syringe) there-necked flask, then seal there-necked flask, is finally slowly adjusted to temperature to react at 90 DEG C.React 8h
Later, there-necked flask is opened, eccentric cleaning is carried out with tetrahydrofuran after reaction solution is cooling, is ensured with this all unreacted
PBA is cleaned up completely, is finally placed in kept dry in vacuum, and the sample finally obtained is exactly SiO2-PBA。
4. sulphur-bromine " click " reacts: by the SiO of preparation2- PBA nucleocapsid particles, triethylamine and mercapto (base) ethylamine exists
In THF.Reaction a whole night is stirred at room temperature in mixed liquor, then by vacuum distillation concentration, the product acetone (second after concentration
Alcohol) it cleans, it is dried for standby under vacuum.
Second step prepares nucleocapsid particles polydactyl acid nanocomposite, 1. preparation flow is as shown in Fig. 2, be wherein
Core-shell modifiers mix with polylactic acid, be 2. planetary ball mill dispersion, are 3. airtight heating is kneaded, is 4. hot pressing or is molded into
Polylactic acid powder is dried 8h, by the core of polylactic acid and above-mentioned preparation after drying by type under 60 DEG C of vacuum environment before mixing
The core-shell nanoparticles example of 99:1 in mass ratio is blended in beaker, then pours the mixture into the grinding pot of planetary ball mill
It is interior.It is rolled at a high speed in grinding pot using abrasive material and sample, strong shear, impact is generated to material, achieve the purpose that dispersion.It is poly-
Lactic acid and nano modifier disperse 30min in the ball mill, and the material after being dispersed is spare.
Third step, in the material after ball mill disperses, core shell nanoparticles in polylactic acid to a certain extent
Dispersion.Mixed material after dispersion is added in banburying machine and is kneaded.Kneading machine operating temperature may be provided at 160~190
DEG C, 3~10min is run under the revolving speed of 30~100r/min, obtains the modified by nano particles polylactic acid material of melting mixing.If
Convenient for obtaining preliminary molding material, double screw extruder can be used to the material extruding pelletization after above-mentioned dispersion.Twin-screw squeezes
The extruding pelletization condition of machine out are as follows: temperature is 150~190 DEG C, and feed screw speed is 10~30rpm, driving screw running speed
For 100~180rpm.
4th step, the mixed material that above-mentioned banburying or Screw Extrusion obtain are launched to hot pressing between the steel plate of hot press
Molding.Hot rolled sheet preheats 3~10min at 170 DEG C, and after preheating, above-mentioned modified material is added in the mold between two steel plates,
Release agent is coated in mold.Material hot pressing condition are as follows: hot pressing temperature is 160~190 DEG C, and hot pressing time is 3~10min, hot pressing
Pressure is 0.5~10MPa.In hot pressing, when initial hot pressing, pressure, or 0.5~1MPa of pressurization, subsequent hot pressing can not be applied
When, pressure can be 1~10MPa.It can depressurize in hot pressing in fixed interval to exclude air.Above-mentioned banburying or
The mixed material that Screw Extrusion obtains can also pass through injection molding.The material for being kneaded or squeezing out is added in injection molding machine, is molded
Machine temperature is 170~190 DEG C.
Using Nano-meter SiO_22The PBA nucleocapsid particles polydactyl acid polymer of grafting:
Wherein: (1) Nano-meter SiO_2 used in2From the hydrophilic nano of the A380 model of German goldschmidt chemical corporation production
SiO2, particle surface hydroxyl group rich in, initial particle 7nm；
(2) using chemical copolymerization grafting method in Nano-meter SiO_22Surface grafting rubber layer butyl polyacrylate PBA is obtained just
Property-flexibility core shell nanoparticles, grain diameter is about 20nm.
(3) PLA for the 3051D model that polylactic acid used in is produced from NatureWorks company of the U.S., before use, PLA
It is sufficiently dry in vacuum oven；
(3) polylactic acid after 1 part of nano core-shell particle and 99 parts of dryings is mixed using planetary ball mill, disperses 30min
Modified mixed material is obtained afterwards；
(4) resulting mixed material is melted at 170 DEG C, continuous mechanical stirring is poured into after material is completely dissolved
In the mold for having preheated 10min on hot press.Polydactyl acid sample is made after hot pressing 3min at 170 DEG C；
The purer polylactic acid of tensile strength for the polydactyl acid nanocomposite that this example obtains improves 36.9%, draws
It stretches toughness and elongation at break improves 80.4% and 29.5% respectively.The glass transition temperature and melting temperature of polydactyl acid
Degree is almost without changing.
To sum up: the present invention provides a kind of sides that polylactic acid mechanical property is promoted using rigid-flexible core shell nanoparticles
Method.Flexible rubber outer layer is grafted on rigid nano inner core by the method for chemical copolymerization, and rigid inner core and soft shell pass through
Covalent bond is connected, and two-phase laminated flow does not occur, plays the synergistic effect of activeness and quietness.Rubbery outer cover end is contained can be with polylactic acid base
The active amine groups of precursor reactant, the cementation between modified particles and basal body interface is stronger, and particle is not susceptible to unsticking, energy
Play good humidification.Core shell nanoparticles and polylactic acid polymer obtained mix under the action of planetary ball mill
It is even, it can not only effectively realize the dispersion of nano particle, moreover it is possible to shorten the time of subsequent melt mixing, reduce polylactic acid because of heat
Mechanical property reduces caused by decomposition.Compared to traditional granule modified dose, minute quantity is added (such as in polylactic acid matrix
Such core shell nanoparticles 1wt.%) can effectively promote the mechanical property of polylactic acid, to not influence its hot property and add
Work performance is conducive to the application range for expanding polylactic acid.
Claims (9)
1. a kind of method for improving polylactic acid mechanical property using rigid-flexible core shell nanoparticles, characterized in that including following
Step:
Step 1: preparing rigid-flexible core shell nanoparticles using chemical copolymerization grafting method, and wherein rigid phase is kernel, soft
Property be mutually shell, between two-phase by covalent bond be connected, the active official with polylactic acid molecule chain reaction is contained in soft shell end
It can group；
Step 2: planetary type ball-milling is added with the polylactic acid after drying in the rigid-flexible core shell nanoparticles that mass fraction is 1%
Machine mixes；
Step 3: the material melts after mixing, which are blended, is made modified material；
Step 4: the modification material after melt blending uses injection molding or hot-forming.
2. a kind of side for improving polylactic acid mechanical property using rigid-flexible core shell nanoparticles according to claim 1
Method, characterized in that the rigid phase is silica, carbon nanotube, graphene or silsesquioxane, and the flexible phase is elongation
The polybutylacrylate rubber that rate is 2000%.
3. according to claim 1 or 2 a kind of polylactic acid mechanical property is improved using rigid-flexible core shell nanoparticles
Method, characterized in that time >=30min that the planetary ball mill mixes.
4. according to claim 1 or 2 a kind of polylactic acid mechanical property is improved using rigid-flexible core shell nanoparticles
Method, characterized in that material melts, which are blended, uses closed mixing machine or double screw extruder；The temperature of closed mixing is
160~190 DEG C, revolving speed is 30~100r/min, and mixing time is 3~10min；The temperature of double screw extruder is 150~190
DEG C, feed screw speed is 10~30rpm, and driving screw running speed is 100~180rpm.
5. a kind of side for improving polylactic acid mechanical property using rigid-flexible core shell nanoparticles according to claim 3
Method, characterized in that material melts, which are blended, uses closed mixing machine or double screw extruder；The temperature of closed mixing is 160
~190 DEG C, revolving speed is 30~100r/min, and mixing time is 3~10min；The temperature of double screw extruder is 150~190 DEG C,
Feed screw speed is 10~30rpm, and driving screw running speed is 100~180rpm.
6. according to claim 1 or 2 a kind of polylactic acid mechanical property is improved using rigid-flexible core shell nanoparticles
Method, characterized in that when hot-forming, hot pressing temperature is 160~190 DEG C, and hot pressing time is 3~10min, and hot pressing pressure is
0.5~10MPa, when injection molding, injection molding machine temperature is 170~190 DEG C.
7. a kind of side for improving polylactic acid mechanical property using rigid-flexible core shell nanoparticles according to claim 3
Method, characterized in that when hot-forming, hot pressing temperature is 160~190 DEG C, and hot pressing time is 3~10min, hot pressing pressure 0.5
~10MPa, when injection molding, injection molding machine temperature is 170~190 DEG C.
8. a kind of side for improving polylactic acid mechanical property using rigid-flexible core shell nanoparticles according to claim 4
Method, characterized in that when hot-forming, hot pressing temperature is 160~190 DEG C, and hot pressing time is 3~10min, hot pressing pressure 0.5
~10MPa, when injection molding, injection molding machine temperature is 170~190 DEG C.
9. a kind of side for improving polylactic acid mechanical property using rigid-flexible core shell nanoparticles according to claim 5
Method, characterized in that when hot-forming, hot pressing temperature is 160~190 DEG C, and hot pressing time is 3~10min, hot pressing pressure 0.5
~10MPa, when injection molding, injection molding machine temperature is 170~190 DEG C.
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| CN112745819A (en) * | 2021-02-05 | 2021-05-04 | 西南石油大学 | Degradable temporary plugging agent and preparation method thereof |
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