CN110343353A - A kind of degradable Toughened With Core-Shell Particles polymer composites and preparation method - Google Patents
A kind of degradable Toughened With Core-Shell Particles polymer composites and preparation method Download PDFInfo
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
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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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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 invention discloses a kind of degradable Toughened With Core-Shell Particles polymer composites and preparation methods.The composite material is to be blended by the raw material including following components and obtained: 100 parts by weight of degradable polymer；1~100 parts by weight of core-shell particles；The degradable polymer is at least one of polylactic acid, polycaprolactone, polyhydroxyalkanoate, poly-β-hydroxybutyric acid, poly- hydroxy-glutaric acid ester, two hydroxypropyl acrylate of poly- fumaric acid, polyglycolic acid, poly butylene succinate, polyadipate/butylene terephthalate, starch, cellulose, chitosan, lignin.The present invention truly ensure that the mechanical property of degradable polymer and the balanced of degradation property and regulation, can realize mixing, industrialized production environmental-friendly, easy to accomplish on traditional simple synthesis device.
Description
Technical field
The present invention relates to technical field of polymer materials, and it is multiple to be specifically related to a kind of degradable Toughened With Core-Shell Particles polymer
Condensation material and preparation method.
Background technique
The a large amount of of conventional plastic use and discard caused white pollution, especially ocean plastic garbage, it has also become complete
The problem of social concerns, how to solve white pollution problems is the key subjects for being worth research.Greatly develop biodegrade
It is to solve one of the effective way of white pollution that plastics, which gradually substitute conventional plastic,.Degradable polymer toughening is always macromolecule
One of Material Field important subject.Toughener is gradually sent out by simple rubber or elastomer, organic or inorganic rigid particles
The core-shell particles of exhibition till now, but its safety is gradually taken seriously, such as using PCL toughening PLA, due to currently used for synthesis
The catalyst of PCL is mostly strong acid or highly basic or metal-based catalysts, and remaining has adverse effect to the application of polymerizate.Therefore
Exploitation novel toughening substance is extremely important.Polymer core shell particles include the soft core of hard shell-and hard core-soft core two
Kind, integrate soft or hard two-phase, particle size does not change because of processing conditions, and the chemical structure by changing shell obtains
With the preferable compatibility of matrix, it is widely used in polymer modification as one kind more preferably toughener.
Using hard core-soft core particle, toughness and rigidity can be realized by change shell size while being improved, better solved
The rigidity-toughness balanced problem of toughening polymer.Hard core-soft core particle realizes that rigidity-toughness balanced is more attractive to toughening polymer.So
And polymer core shell particles used at present cannot all degrade, its biological degradability is affected after being blended with degradable polymer
Energy.Double bond is introduced starch granules by patent ZL 201510364028.8 and ZL 201510362426.6, through emulsifier-free emulsion polymerization
Stone (starch)-soft shell (polyethyl acrylate) particle is prepared, realizes good rigidity-toughness balanced using its plasticizing polylactic acid, so
And the starch kernel in core-shell particles can degrade, but polyethyl acrylate shell cannot still degrade, and therefore, still fail thoroughly
Solve the problems, such as polymer core shell particles degradable.Therefore, develop degradable polymer Toughened With Core-Shell Particles degradable polymer
It is most important in the fields such as packaging material.
Summary of the invention
To solve the problem in the prior art, it is multiple that the present invention provides a kind of degradable Toughened With Core-Shell Particles polymer
Condensation material and preparation method.Core-shell particles of the invention are prepared using bio-based monomer, and Wholly-degradable, core-shell structure is controllable,
A kind of toughened composite polymer material that can be degradable can be prepared after being blended with degradable polymer.
An object of the present invention is to provide a kind of degradable Toughened With Core-Shell Particles polymer composites.
The composite material is to be blended by the raw material including following components and obtained:
Each component according to parts by weight,
100 parts by weight of degradable polymer；
1~100 parts by weight of core-shell particles；It is preferred that 5~80 parts by weight.
The degradable polymer is polylactic acid, polycaprolactone, polyhydroxyalkanoate, poly-β-hydroxybutyric acid, poly- hydroxyl penta
Two acid esters, two hydroxypropyl acrylate of poly- fumaric acid, polyglycolic acid, poly butylene succinate, polyadipate/terephthalic acid (TPA) fourth two
At least one of ester, starch, cellulose, chitosan, lignin；
The core-shell particles include: stone portion and soft shell layer；
The stone portion is modified starch, and soft shell layer is copolymerized by bio-based monomer to be formed；
The modified starch is the modified starch containing carbon-carbon double bond,
General structure are as follows:
Wherein St is starch molecule, R1Group is one kind of carbonyl, silicon oxygen bond, ammonia ester bond, ehter bond, ester bond, R2Group is hydrogen
Atom or alkyl；
The degree of substitution of the modified starch is 0.01~2.5；Preferably 0.5~2.5.
The bio-based monomer is(annulenones acetal, n=0,1 or 2), itaconic acid, oleic acid, fumaric acid, sub- oil
Acid, linolenic acid, itaconic acid fatty ester, oleic acid fatty ester, fumaric acid fatty ester, linoleic acid fatty ester, in linolenic acid fatty ester
A kind of or combination.
The biology base core-shell particles partial size is 20~1300nm, preferably 150~800nm.
The core-shell particles are obtained by including the polymerizable raw material of following components:
The initiator is potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, peroxidating toluoyl, azo diisobutyl
Amidine hydrochloride, two isobutyl imidazoline hydrochloride of azo, azo dicyano valeric acid, at least one in azo dicyclohexyl formonitrile HCN
Kind.
The core-shell particles are to be opened by carbon-carbon double bond free radical addition polymerization or carbon-carbon double bond with annulenones acetal free radical
Ring hydridization is copolymerized to be formed.
The preparation of the core-shell particles includes:
A. it by dry modified starch, bio-based monomer and removes water mixing and emulsifying, stirs 20-60min；
B. initiator is added, is warming up to 60-80 DEG C, reacts 4-8h, prepares biology base core-shell particles lotion；
C. it is demulsified, obtains core-shell particles powder.
The second object of the present invention is to provide a kind of preparation method of degradable Toughened With Core-Shell Particles polymer composites.
Include:
The component is by being made the degradable Toughened With Core-Shell Particles polymer composites after the dosage melt blending.
The biodegradable toughening composition of the present invention, including fully biodegradable core-shell particles and degradable polymer
Two parts, can by core-shell particles regulate and control polymer performance, compared to other core-shell particles for toughening, this method it is basic
Thinking is the pattern for regulating and controlling core-shell particles by using bio-based monomer, totally biodegradable, size, structure composition, simultaneously
It is blended with degradable polymer, solving after common toughening particle is blended with degradable polymer influences its biodegradability
Problem.
Beneficial effects of the present invention: the preparation method provided according to the present invention fully biodegradable nucleocapsid grain obtained
Sub- toughening degradable polymer composite material, biodegradability is excellent, and structure is controllable with performance, can be in traditional simple conjunction
Mixing, industrialized production environmental-friendly, easy to accomplish are realized on forming apparatus.
Detailed description of the invention
Fig. 1 is the TEM transmission electron microscope picture of core-shell particles 2 of the invention.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
Unless otherwise specified, other reagents are purchased in Sinopharm Chemical Reagent Co., Ltd..
One, the preparation of modified starch
Embodiment 1
By 100 parts and 100 parts of ethyl acetate mixing of cornstarch (production of Changchun great achievement corn development corporation, Ltd.), cooling
After being sufficiently stirred, 10 parts of pyridine, after heating is sufficiently stirred gradually are added dropwise, 5 parts of acrylic acid is added dropwise and continues to stir, nothing is added after reaction
Water-ethanol washing, filters and dryModified starch 1。
Embodiment 2
By 100 parts and 85 parts of butyl acetate mixing of tapioca (production of Shanghai Food Co., Ltd's today), cooling is abundant
After stirring, 16 parts of ethylenediamine, after heating is sufficiently stirred gradually are added dropwise, 10 parts of silane coupling agent KH570 is added dropwise and continues to stir, instead
Should after dehydrated alcohol washing is added, filter and dryModified starch 2。
Embodiment 3
By 100 parts and 70 parts of methyl acetate mixing of potato starch (production of Beijing Geese Habitat Yi Lin Food Co., Ltd), drop
After temperature is sufficiently stirred, 14 parts of pyrroles, after heating is sufficiently stirred gradually are added dropwise, 15 parts of isocyanatoethyl continuation are added dropwise
Stirring is added dehydrated alcohol washing, filters and dry after reactionModified starch 3。
Embodiment 4
By 100 parts and 60 parts of ethyl acetate mixing of soybean starch (production of Tian Quan Food Co., Ltd), cooling is sufficiently stirred
Afterwards, 18 parts of triethylamine, after heating is sufficiently stirred gradually are added dropwise, 15 parts of glycidyl methacrylate reaction is added dropwise and continues to stir
It mixes, dehydrated alcohol washing is added after reaction, filters and dryModified starch 4。
Embodiment 5
By 100 parts and 50 parts of ethyl acetate mixing of soybean starch (production of Tian Quan Food Co., Ltd), cooling is sufficiently stirred
Afterwards, 20 parts of pyridine, after heating is sufficiently stirred gradually are added dropwise, 20 parts of acryloyl chloride reaction is added dropwise and continues to stir, nothing is added after reaction
Water-ethanol washing, filters and dryModified starch 5。
Two, the preparation of the core-shell particles of fully biodegradable
Embodiment 6
By 100 parts in embodiment 1Modified starch 1It mixes and is added in 100 parts of deionized waters with 10 parts of itaconic acid N-butyls, often
It is sufficiently stirred under temperature 30 minutes, 0.05 part of initiator potassium persulfate is then added, polymerization is stirred and caused in heating, and reaction is certain
Ethanol washing is added in time, filters and is prepared by dryingCore-shell particles 1。
Embodiment 7
By 100 parts in embodiment 1Modified starch 1With 10 parts of itaconic acid N-butyls, 10 parts of 2- methylene -1,3- dioxy rings penta
AlkaneMixing is added in 200 parts of deionized waters, is sufficiently stirred 30 minutes under room temperature, 0.1 part of initiator over cure is then added
Polymerization is stirred and is caused in sour ammonium, heating, reacts certain time, and ethanol washing, suction filtration and dry preparation is addedCore-shell particles 2。
Embodiment 8
By 100 parts in embodiment 1Modified starch 1With 20 parts of itaconic acid N-butyls, the positive heptyl ester of 20 parts of itaconic acids, 20 parts of Asias 2-
Methyl-1,3-dioxy hexamethyleneMixing is added in 400 parts of deionized waters, is sufficiently stirred 30 minutes under room temperature, then plus
Enter 0.5 part of initiator azodiisobutyronitrile, heat up, stir and cause polymerization, react certain time, ethanol washing is added, filters
And dry preparationCore-shell particles 3。
Embodiment 9
By 100 parts in embodiment 2Modified starch 2500 parts of addition is mixed with 60 parts of itaconic acid N-butyls, 60 parts of itaconic acids to go
It in ionized water, being sufficiently stirred under room temperature 30 minutes, 1 part of initiator potassium persulfate is then added, polymerization is stirred and is caused in heating,
Certain time is reacted, ethanol washing is added, filters and is prepared by dryingCore-shell particles 4。
Embodiment 10
By 100 parts in embodiment 3Modified starch 3It mixes and is added in 600 parts of deionized waters with 200 parts of positive heptyl esters of fumaric acid,
It is sufficiently stirred under room temperature 30 minutes, 2 parts of initiator peroxidating toluoyls is then added, polymerization, reaction one are stirred and caused in heating
It fixes time, ethanol washing is added, filter and is prepared by dryingCore-shell particles 5。
Embodiment 11
By 100 parts in embodiment 4Modified starch 4It mixes and adds with the positive heptyl ester of 150 parts of fumaric acid, 150 parts of linolenic acid N-butyls
Enter in 700 parts of deionized waters, be sufficiently stirred under room temperature 30 minutes, 3 parts of initiator azo diisobutyl amidine hydrochlorides are then added,
Polymerization is stirred and is caused in heating, reacts certain time, and ethanol washing, suction filtration and dry preparation is addedCore-shell particles 6。
Embodiment 12
By 100 parts in embodiment 5Modified starch 5With the positive heptyl ester of 100 parts of fumaric acid, the positive heptyl ester of 100 parts of itaconic acids, 100 parts
2- methylene -1,3- cyclic heptane dioxideMixing is added in 800 parts of deionized waters, is sufficiently stirred 30 minutes under room temperature, so
4 parts of initiator potassium persulfates are added afterwards, polymerization is stirred and caused in heating, reacts certain time, and ethanol washing is added, and filters simultaneously
Dry preparationCore-shell particles 7。
Three, the preparation of biodegradable composite
Embodiment 13
It will be in 100 parts of embodiments 6Core-shell particles 1With 100 parts of polylactic acid (production of NatureWorks company, the U.S.) 170
DEG C carry out melt blending 5min, by intermingling material by vulcanizing press it is hot-forming, obtain the sheet material of 1mm thickness, and according to phase
Pass standard is cut into standard batten for Mechanics Performance Testing, carries out controlled composting biodegrade examination according to (GB/T19277-2011)
The biodegradability of research core-shell particles is tested, every test result is included in table 1.
Embodiment 14
It will be in 50 parts of embodiments 7Core-shell particles 2With 100 parts of polylactic acid (production of NatureWorks company, the U.S.) at 170 DEG C
Melt blending 5min is carried out, intermingling material is hot-forming by vulcanizing press, the sheet material of 1mm thickness is obtained, and according to correlation
Standard is cut into standard batten for Mechanics Performance Testing, carries out controlled composting biodegradation test according to (GB/T19277-2011)
The biodegradability of core-shell particles is studied, every test result is included in table 1.
Embodiment 15
It will be in 100 parts of embodiments 12Core-shell particles 7With 100 parts of polylactic acid (production of NatureWorks company, the U.S.) 170
DEG C carry out melt blending 5min, by intermingling material by vulcanizing press it is hot-forming, obtain the sheet material of 1mm thickness, and according to phase
Pass standard is cut into standard batten for Mechanics Performance Testing, carries out controlled composting biodegrade examination according to (GB/T19277-2011)
The biodegradability of research core-shell particles is tested, every test result is included in table 1.
Embodiment 16
It will be in 80 parts of embodiments 8Core-shell particles 3With 100 parts of polycaprolactone (production of Wuhan seamount Science and Technology Ltd.) 60
DEG C carry out melt blending 5min, by intermingling material by vulcanizing press it is hot-forming, obtain the sheet material of 1mm thickness, and according to phase
Pass standard is cut into standard batten for Mechanics Performance Testing, carries out controlled composting biodegrade examination according to (GB/T19277-2011)
The biodegradability of research core-shell particles is tested, every test result is included in table 1.
Embodiment 17
It will be in 40 parts of embodiments 9Core-shell particles 4(Hubei is real raw along Biotechnology Co., Ltd with polyhydroxyalkanoate
Produce) 100 parts in 160 DEG C of progresss melt blending 5min, intermingling material is hot-forming by vulcanizing press, obtain 1mm thickness
Sheet material, and standard batten is cut into for Mechanics Performance Testing according to relevant criterion, it is carried out according to (GB/T19277-2011) controlled
The biodegradability of Compost Biodegradation experimental study core-shell particles, every test result are included in table 1.
Embodiment 18
It will be in 20 parts of embodiments 10Core-shell particles 5(Jin Jin happy Industrial Co., Ltd. in Shanghai is raw with poly butylene succinate
Produce) 100 parts in 120 DEG C of progresss melt blending 5min, intermingling material is hot-forming by vulcanizing press, obtain 1mm thickness
Sheet material, and standard batten is cut into for Mechanics Performance Testing according to relevant criterion, it is carried out according to (GB/T19277-2011) controlled
The biodegradability of Compost Biodegradation experimental study core-shell particles, every test result are included in table 1.
Embodiment 19
It will be in 5 parts of embodiments 11Core-shell particles 6(the prosperous rich science and technology in Hangzhou is limited with polyadipate/butylene terephthalate
Company's production) 100 parts in 130 DEG C of progresss melt blending 5min, it is hot-forming that intermingling material is passed through into vulcanizing press, is obtained
The sheet material of 1mm thickness, and standard batten is cut into for Mechanics Performance Testing according to relevant criterion, according to (GB/T19277-2011) into
Row controlled composting biodegradation test studies the biodegradability of core-shell particles, and every test result is included in table 1.
Comparative example 1
By 100 parts of cornstarch (production of Changchun great achievement corn development corporation, Ltd.) and polylactic acid (U.S. NatureWorks
Company's production) 100 parts in 170 DEG C of progresss melt blending 5min, it is hot-forming that intermingling material is passed through into vulcanizing press, is obtained
The sheet material of 1mm thickness, and standard batten is cut into for Mechanics Performance Testing according to relevant criterion, according to (GB/T19277-2011) into
Row controlled composting biodegradation test studies the biodegradability of core-shell particles, and every test result is included in table 1.
Comparative example 2
By 50 portions of tapiocas (production of Shanghai Food Co., Ltd's today) and polylactic acid (NatureWorks company, the U.S.
Production) 100 parts in 170 DEG C of progresss melt blending 5min, intermingling material is hot-forming by vulcanizing press, it is thick to obtain 1mm
Sheet material, and standard batten is cut into for Mechanics Performance Testing according to relevant criterion, according to (GB/T19277-2011) carry out by
The biodegradability of Compost Biodegradation experimental study core-shell particles is controlled, every test result is included in table 1.
Comparative example 3
100 parts of polylactic acid (production of NatureWorks company, the U.S.) are weighed in 170 DEG C of progress melt-processed 5min, is led to afterwards
It crosses that vulcanizing press is hot-forming, obtains the sheet material of 1mm thickness, and standard batten is cut into according to relevant criterion and is surveyed for mechanical property
Examination carries out the biodegradability of controlled composting biodegradation test research core-shell particles according to (GB/T19277-2011), respectively
Item test result is included in table 1.
Comparative example 4
By 100 parts in embodiment 1Modified starch 1It mixes and is added in 100 parts of deionized waters with 10 parts of ethyl acrylates, room temperature
Under be sufficiently stirred 30 minutes, 0.05 part of initiator ammonium persulfate is then added, polymerization is stirred and caused in heating, and reaction one is periodically
Between, ethanol washing is added, filters and drying prepares core-shell particles 8.
It will be in 100 parts of comparative examples 3Core-shell particles 8With 100 parts of polylactic acid (production of NatureWorks company, the U.S.) 170
DEG C carry out melt blending 5min, by intermingling material by vulcanizing press it is hot-forming, obtain the sheet material of 1mm thickness, and according to phase
Pass standard is cut into standard batten for Mechanics Performance Testing, carries out controlled composting biodegrade examination according to (GB/T19277-2011)
The biodegradability of research core-shell particles is tested, every test result is included in table 1.
Comparative example 5
100 parts of polycaprolactone (production of Wuhan seamount Science and Technology Ltd.) is weighed in 60 DEG C of progress melt-processed 5min, after
It is hot-forming by vulcanizing press, the sheet material of 1mm thickness is obtained, and standard batten is cut into for mechanical property according to relevant criterion
Test carries out the biodegradability of controlled composting biodegradation test research core-shell particles according to (GB/T19277-2011),
Every test result is included in table 1.
Comparative example 6
100 parts of polyhydroxyalkanoate (Hubei is real to be produced along Biotechnology Co., Ltd) is weighed to be melted at 160 DEG C
5min is processed, it is hot-forming by vulcanizing press afterwards, the sheet material of 1mm thickness is obtained, and standard batten is cut into according to relevant criterion
For Mechanics Performance Testing, the life of controlled composting biodegradation test research core-shell particles is carried out according to (GB/T19277-2011)
Object degradation property, every test result are included in table 1.
Comparative example 7
By 100 parts in embodiment 3Modified starch 4It mixes and is added in 600 parts of deionized waters with 200 parts of methyl acrylates, often
It being sufficiently stirred under temperature 30 minutes, 3 parts of initiator azo diisobutyl amidine hydrochlorides is then added, polymerization is stirred and is caused in heating,
Certain time is reacted, ethanol washing is added, filters and is prepared by dryingCore-shell particles 9。
It will be in 20 parts of comparative examples 4Core-shell particles 9(Jin Jin happy Industrial Co., Ltd. in Shanghai is raw with poly butylene succinate
Produce) 100 parts in 120 DEG C of progresss melt blending 5min, intermingling material is hot-forming by vulcanizing press, obtain 1mm thickness
Sheet material, and standard batten is cut into for Mechanics Performance Testing according to relevant criterion, it is carried out according to (GB/T19277-2011) controlled
The biodegradability of Compost Biodegradation experimental study core-shell particles, every test result are included in table 1.
Comparative example 8
By 100 parts in embodiment 4Modified starch 5Addition 700 is mixed with 150 parts of methyl acrylates, 150 parts of ethyl acrylates
It in part deionized water, is sufficiently stirred under room temperature 30 minutes, 4 parts of initiator potassium persulfates is then added, heating is stirred and caused poly-
It closes, reacts certain time, ethanol washing, suction filtration and dry preparation is addedCore-shell particles 10。
It will be in 5 parts of comparative examples 5Core-shell particles 10(the prosperous rich science and technology in Hangzhou is limited with polyadipate/butylene terephthalate
Company's production) 100 parts in 130 DEG C of progresss melt blending 5min, it is hot-forming that intermingling material is passed through into vulcanizing press, is obtained
The sheet material of 1mm thickness, and standard batten is cut into for Mechanics Performance Testing according to relevant criterion, according to (GB/T19277-2011) into
Row controlled composting biodegradation test studies the biodegradability of core-shell particles, and every test result is included in table 1.
Table 1
aComparative example 1, comparative example 2 can not homogeneous blends；
bAfter GB/T19277-2011:45d the biological decomposition percentage of reference material whether > 70%.
As can be seen from the table, native starch can not be hot pressed into profile with poly-lactic acid material homogeneous blend in comparative example 1,2
Material does not have performance；By the comparison of comparative example 3~4 and embodiment 13~15 it can be found that pure poly-lactic acid material in comparative example 3
Degradable but tension fracture elongation rate is extremely low, although increasing the toughness of polylactic acid in comparative example 4, be blended core-shell particles without
Method is degradable, and composite material is caused to lose degradation property, and the core of fully biodegradable is added in embodiment 13~15
Shell particles had not only been realized to poly-lactic acid material toughening under the premise of hardly changing tensile strength, but also guaranteed finally compound
Material reaches degradation and requires；It is same it can be concluded that similar conclusion by other comparative examples and embodiment, so, the present invention mentions
A kind of fully biodegradable Toughened With Core-Shell Particles degradable polymer composite material and preparation method thereof is supplied, truly
It ensure that the mechanical property of degradable polymer and the balanced of degradation property and regulation, it can be on traditional simple synthesis device
Realize mixing, industrialized production environmental-friendly, easy to accomplish.
Claims (10)
1. a kind of degradable Toughened With Core-Shell Particles polymer composites, it is characterised in that the composite material is by including following
The raw material of component is blended and obtains:
Each component according to parts by weight,
100 parts by weight of degradable polymer；
1~100 parts by weight of core-shell particles；Preferably 5~80 parts by weight；
The degradable polymer is polylactic acid, polycaprolactone, polyhydroxyalkanoate, poly-β-hydroxybutyric acid, poly- hydroxyl glutaric acid
Ester, two hydroxypropyl acrylate of poly- fumaric acid, polyglycolic acid, poly butylene succinate, polyadipate/butylene terephthalate, shallow lake
At least one of powder, cellulose, chitosan, lignin；
The core-shell particles include:
Stone portion and soft shell layer；
The stone portion is modified starch, and soft shell layer is copolymerized by bio-based monomer to be formed；
The modified starch is the modified starch containing carbon-carbon double bond,
General structure are as follows:
Wherein St is starch molecule, R1Group is one kind of carbonyl, silicon oxygen bond, ammonia ester bond, ehter bond, ester bond, R2Group is hydrogen atom
Or alkyl；
The degree of substitution of the modified starch is 0.01~2.5；
The bio-based monomer is(annulenones acetal, n=0,1 or 2), itaconic acid, oleic acid, fumaric acid, linoleic acid, Asia
One of numb acid, itaconic acid fatty ester, oleic acid fatty ester, fumaric acid fatty ester, linoleic acid fatty ester, linolenic acid fatty ester or
Combination.
2. degradable Toughened With Core-Shell Particles polymer composites as described in claim 1, it is characterised in that:
The degree of substitution of the modified starch is 0.5~2.5.
3. degradable Toughened With Core-Shell Particles polymer composites as described in claim 1, it is characterised in that:
The biology base core-shell particles partial size is 20~1300nm.
4. degradable Toughened With Core-Shell Particles polymer composites as claimed in claim 3, it is characterised in that:
The biology base core-shell particles partial size is 150~800nm.
5. degradable Toughened With Core-Shell Particles polymer composites as described in claim 1, it is characterised in that:
The core-shell particles are obtained by including the polymerizable raw material of following components:
6. degradable Toughened With Core-Shell Particles polymer composites as claimed in claim 5, it is characterised in that:
7. degradable Toughened With Core-Shell Particles polymer composites as claimed in claim 5, it is characterised in that:
The initiator is potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, peroxidating toluoyl, azo diisobutyl amidine salt
At least one of hydrochlorate, two isobutyl imidazoline hydrochloride of azo, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN.
8. degradable Toughened With Core-Shell Particles polymer composites as described in claim 1, it is characterised in that:
It is copolymerized by carbon-carbon double bond free radical addition polymerization or carbon-carbon double bond and annulenones acetal free radical open loop hydridization described in being formed
Core-shell particles.
9. degradable Toughened With Core-Shell Particles polymer composites as claimed in claim 8, it is characterised in that:
The preparation of the core-shell particles includes:
A. it by dry modified starch, bio-based monomer and removes water mixing and emulsifying, stirs 20-60min；
B. initiator is added, is warming up to 60-80 DEG C, reacts 4-8h, prepares biology base core-shell particles lotion；
C. it is demulsified, obtains core-shell particles powder.
10. a kind of preparation side of the degradable Toughened With Core-Shell Particles polymer composites as described in one of claim 1~9
Method, it is characterised in that the described method includes:
The component is by being made the degradable Toughened With Core-Shell Particles polymer composites after the dosage melt blending.
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| CN111849205A (en) * | 2020-08-03 | 2020-10-30 | 包头稀土研究院 | Compound, polylactic acid composite material, preparation method and application |
| CN113831711A (en) * | 2021-10-12 | 2021-12-24 | 江南大学 | High-toughness polylactic acid composition and preparation method thereof |
| CN114058168A (en) * | 2021-12-27 | 2022-02-18 | 江苏尚艾新材料科技有限公司 | High-barrier toughened polylactic acid composite material and preparation method thereof |
| CN114957634A (en) * | 2022-07-04 | 2022-08-30 | 华润化学材料科技股份有限公司 | Degradable polyester rubber and preparation method and application thereof |
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| CN114957634A (en) * | 2022-07-04 | 2022-08-30 | 华润化学材料科技股份有限公司 | Degradable polyester rubber and preparation method and application thereof |
| CN114957634B (en) * | 2022-07-04 | 2023-12-22 | 华润化学材料科技股份有限公司 | Degradable polyester rubber and preparation method and application thereof |
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