CN105733211A - Composition containing starch nano particles and preparation method thereof - Google Patents
Composition containing starch nano particles and preparation method thereof 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
- 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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- C—CHEMISTRY; METALLURGY
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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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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a composition containing starch nano particles and a preparation method thereof. The composition comprises the following components in parts by weight: 1-100 parts of polymer, 2-40 parts of modified starch nano particles and 0-15 parts of auxiliary, wherein the structural formula of the modified starch nano particles is St-R0CH(R1)-R2; St represents a starch molecule; R0 is siloxy or ester group with 1-6 carbon atoms; and R1 and R2 are at least one of hydrogen atom, hydrocarbyl with 1-20 carbon atoms and organic group with 2-20 carbon atoms and containing amino, unsaturated double bond or epoxy group. The composition containing starch nano particles disclosed by the invention has the advantages of high tensile strength, good impact toughness, large elongation at break and the like and is suitable for preparing daily high molecular material articles and devices with high requirement on mechanical properties; and with relatively low content of modified starch nano particles, a composition with excellent mechanical properties still can be obtained without adding any plasticizer.
Description
Technical field
The present invention relates to nano composite material technical field, be specifically related to a kind of containing starch nano particle
Composition and preparation method thereof.
Background technology
Nano-starch have wide material sources, renewable, nontoxic, biodegradable, good biocompatibility and
The many merits such as nano particle effect, in fields such as nano composite material, biological medicine, light industry, chemical industry
There is important potential using value, be one of the focus of nanosecond science and technology area research.
Polymer, such as polyester and polyolefin, the hot strength of self and impact strength are relatively low, by adding
Nano filling can improve its mechanical performance, plays bigger using value.Existing nanometer reinforced filling includes
CNT and graphene oxide etc., the preparation process of this two classes reinforcing agent is complex and high cost.Natural shallow lake
Powder is applied as a kind of environment-friendly type filler in boiomacromolecule and green tire
[CN101787148A], is prepared for environmental protection composite.But, native starch particle diameter generally exists
More than tens microns, molecular hydrophylic is strong, intramolecular and intermolecular hydrogen bonding active force strong, and starch with
The intermolecular forces of polymeric matrix (such as Biopolvester) is weak, causes starch to disperse in polymeric matrix tired
Difficulty,.Visible, starch uses mainly as inert filler in polymeric matrix, has had a strong impact on its reinforcement
Effect.How to improve starch dispersion in polymeric matrix, be substantially reduced the size of amylum grain, carry
Interaction (especially chemical bonding) between high amylum grain and polymeric matrix is to improve starch to increase
The key of the strength polymer impact of performance, is also technical problem urgently to be resolved hurrily.
Summary of the invention
In view of this, it is an object of the invention to propose a kind of composition containing starch nano particle and
Preparation method, to improve starch dispersion in polymeric matrix, to reduce the size of amylum grain, raising
Interaction (especially chemical bonding) between amylum grain and polymeric matrix, thus improve starch and mend
The mechanical performance of strength polymer.
Based on above-mentioned purpose, the composition containing starch nano particle that the present invention provides, with weight portion
Meter, including polymer 1～100 parts, modified starch nano particle 2～40 parts and auxiliary agent 0～15 parts；
The structural formula of described modified starch nano particle is: St-R0CH(R1)-R2, wherein,
St represents starch molecule,
R0For the one in siloxy that carbon number is 1～6 or ester group,
R1And R2It is 2～20 and contain for alkyl that hydrogen atom, carbon number are 1～20, carbon number
At least one in the organic group of amino, unsaturated double-bond or epoxy radicals.
In some embodiments of the invention, described polymer is the polyester that weight average molecular weight is not less than 50,000
Or at least one in polyolefin.
In some embodiments of the invention, described polymer is PLA, poly-(succinic acid butanediol
Ester), in tetramethylene adipate and the copolymer of mutual-phenenyl two acid bromide two alcohol ester, fatty poly-ester carbonate
At least one.
In some embodiments of the invention, the particle diameter of described modified starch nano particle is 50～300 to receive
Rice, dynamic light scattering polydispersity index is 0.01～0.5, and substitution value is 0.005～1.5.
In some embodiments of the invention, described auxiliary agent is radical initiator, hydrolysis-resisting agent, helps friendship
At least one in connection agent, antioxidant, nucleator and fire retardant.
In some embodiments of the invention, polymer-modified 1～100 part is also included, described modified poly
Thing is containing in epoxide group, acid anhydrides or the thermoplastic polyester of hydroxy-acid group or TPO on side chain
At least one.
The present invention also provides for a kind of method preparing the above-mentioned composition containing starch nano particle, including with
Lower step:
First polymer, modified starch nano particle, auxiliary agent are passed through high-speed mixer according to weight
Premix uniformly, then by above-mentioned pre-composition more than polymer or polymer-modified fusing point 1～50 DEG C pass through
Screw extruder or banbury melting mixing obtain the described composition containing starch nano particle.
The present invention also provides for a kind of method preparing the above-mentioned composition containing starch nano particle, including with
Lower step:
First polymer, polymer-modified, modified starch nano particle, auxiliary agent are led to according to weight
Cross high-speed mixer premix uniformly, then by above-mentioned pre-composition more than polymer or polymer-modified fusing point
1～50 DEG C obtains the described group containing starch nano particle by screw extruder or banbury melting mixing
Compound.
In some embodiments of the invention, the preparation method of described modified starch nano particle includes following
Step:
By solvent, water, modifying agent, starch mixing, obtain starch mixture；
Starch mixture stirs at 70～90 DEG C reaction 0.5～2 hour, and the starch obtaining clarification is molten
Liquid；
After starch solution cools down, in starch solution, add ethanol solution, obtain suspension；
By suspension after ultrasonic or cell disruptor processes, more by centrifugation, wash, separate, be dried,
Obtain modified starch nano particle；
The general structure of described modifying agent is, R3CH(R4)-R5, wherein:
R3For the one in the silane group of carbon number 1～6, hydroxy-acid group, acid chloride groups；
R4And R5It is 2～20 and contain for alkyl that hydrogen atom, carbon number are 1～20, carbon number
At least one in the organic group of isocyanates, unsaturated double-bond or epoxy radicals.
As can be seen here, the composition containing starch nano particle obtained by the present invention has hot strength
The advantage such as high, impact flexibility is good, elongation at break is big, is suitable for preparation to high daily of mechanical property requirements
Articles for use and device, mainly have benefited from nano effect (nanoscale dispersion) and the modification of starch nano particle
The association of the chemical bonding (interface binding force) between starch nano particle active function groups and polymeric matrix
Same effect, therefore under relatively low modified starch nanoparticle content, even if without any plasticizer, still
So can obtain the composition that mechanical performance is excellent.If adding the polymer-modified of certain content can enter
One step improves the chemical bonding between modified starch nano particle and polymeric matrix, and then is conducive to improving
Mechanical performance.What deserves to be explained is, the composition containing starch nano particle that the present invention obtains also has
The reproducible feature of biodegradable, completely or partially component completely.
Accompanying drawing explanation
Fig. 1 is the red of epoxidation starch nano particle and the native starch nano particle of the embodiment of the present invention 1
External spectrum figure；
Fig. 2 is the red of double bond starch nano particle and the native starch nano particle of the embodiment of the present invention 2
External spectrum figure.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with being embodied as
Example, and combine accompanying drawing, the present invention is described in more detail.
Embodiment 1
The preparation of epoxidation starch nano particle:
By 900mL dimethyl sulfoxide, 100mL water and 10mL γ-glycidyl ether oxygen propyl trimethoxy
Silane mixture, is warming up to 90 DEG C after 500rpm stirring 15min under room temperature, weighs the natural Ma Ling of 10g
Sweet potato starch dispersion wherein obtains starch mixture；Above-mentioned starch mixture is stirred at 90 DEG C 90min
Form the starch solution of clear；After being cooled to room temperature, 5L dilution there are 1.25g Span and 3.75g
The ethanol solution of tween dropwise instills above-mentioned starch solution and is stirred continuously, and obtains epoxidation nano-starch and hangs
Turbid liquid；Above-mentioned suspension is carried out ultrasonically treated 60min, washs 3 to its centrifugation and with ethanol
Secondary, 90 DEG C of dry 48h, obtain epoxidation nano-starch particle.
Use infrared spectrum, dynamic light scattering, substitution value formula respectively to epoxidation starch nano particle
Form characterizes with chemical constitution, and result is as follows: particle diameter 125 ± 10nm, polydispersity index
0.14, substitution value 0.30, infrared spectrum is shown in accompanying drawing 1.Wherein starch substitution value is calculated by below equation
Arrive:
Ds=(162*w%)/(M-(M-1) * w%)
In formula, 162 represent glucose residue molecular weight, and M represents substituent molecular weight, and w% represents replacement
The mass fraction of base.Owing to a starch structure unit only having 3 hydroxyls, therefore starch substitution value
Maximum theoretical is 3.
The structural formula of this epoxidation starch nano particle is:
From figure 1 it appears that 2800cm-1Place is on γ-glycidyl ether oxygen propyl trimethoxy silicane
The stretching vibration peak of methylene (-CH2-), 1080cm-1Place and 800cm-1Place is γ-glycidol ether
The stretching vibration peak of silicon oxygen bond (-Si-O-), 910cm on oxygen propyl trimethoxy silicane-1Place is epoxy radicals
The characteristic peak of group, it was demonstrated that γ-glycidyl ether oxygen propyl trimethoxy silicane is successfully coated on starch nano grain
Sub-surface, i.e. epoxidation starch nano particle are successfully prepared.
Embodiment 2
The preparation of double bond starch nano particle
By 800mL dimethyl sulfoxide, 100mL water and 10mL γ-(methacryloxypropyl) propyl group front three
TMOS mixes, and is warming up to 85 DEG C, weighs 10g cassava under room temperature after 500rpm stirring 15min
Starch dispersion wherein obtains starch mixture；Above-mentioned starch mixture is stirred at 85 DEG C 60min shape
Become the starch solution of clear；It is cooled to room temperature and that 5L ethanol solution is dropwise instilled above-mentioned starch is molten
Liquid, is stirred continuously, and obtains the nano-starch suspension of double bond；Above-mentioned suspension is utilized cell pulverization
Machine processes 30min, washs 3 times to its centrifugation and with ethanol, 90 DEG C of dry 48h, obtains double bond
Change nano-starch particle.Infrared spectrum, dynamic light scattering, substitution value formula is used respectively double bondization to be formed sediment
The form of powder nano particle characterizes with chemical constitution, and result is as follows: particle diameter 140 ± 10nm, many points
Divergence index 0.23, substitution value 0.28, infrared spectrum is shown in accompanying drawing 1.The wherein calculating side of starch substitution value
Method is with embodiment 1.
The structural formula of this double bond starch nano particle is:
From figure 2 it can be seen that 1720cm-1And 1670cm-1The most corresponding γ-(methacryl in place
Oxygen) carbonyl (C=O) characteristic peak and double bond (-C=C-) characteristic peak, explanation on propyl trimethoxy silicane
Double bond starch nano particle is successfully prepared.
Embodiment 3
The preparation of amination starch nano particle
First by 900mL dimethyl sulfoxide (DMSO), 100mL water and 10mL N-β-(aminoethyl)-γ-aminopropyl
Methyl dimethoxysilane mixes, and is warming up to 90 DEG C, weighs under room temperature after 500rpm stirring 15min
10g Native tapioca starch disperses wherein, and 800rpm stirs, and heating water bath 60min forms clear
Starch solution, be cooled to room temperature；The ethanol that 5L mass concentration is 99.7% is added dropwise over above-mentioned shallow lake
In powder solution, it is stirred continuously, stir speed (S.S.) 750rpm, obtains amidized nano-starch suspension；
Described suspension is carried out ultrasonically treated 60min, to its centrifugation and with ethanol wash 3 times, 90 DEG C
It is dried 48h, obtains amination nano-starch particle.Use dynamic light scattering, substitution value formula the most right
The form of amination starch nano particle characterizes with chemical constitution, and result is as follows: particle diameter 130 ± 10
Nm, polydispersity coefficient 0.18, substitution value 0.36.
Embodiment 4
The preparation of starch nano particle
By 900mL dimethyl sulfoxide, the mixing of 100mL water, rise after 500rpm stirring 15min under room temperature
Temperature, to 90 DEG C, weighs the dispersion of 10g tapioca and wherein obtains starch mixture；Above-mentioned starch is mixed
Thing stirs 70min at 90 DEG C and forms the starch solution of clear；After being cooled to room temperature 5L is dilute
The ethanol solution releasing 4g tween dropwise instills above-mentioned starch solution and is stirred continuously, and obtains nano-starch
Suspension；Above-mentioned suspension is carried out ultrasonically treated 60min, washs 3 to its centrifugation and with ethanol
Secondary, 90 DEG C of dry 48h, obtain nano-starch particle.Use dynamic light scattering to starch nano particle
Morphological Characterization, its particle diameter is 110 ± 10nm, and polydispersity index is 0.2.
Embodiment 5
The preparation of the composition containing starch nano particle
By poly butylene succinate 100 grams, 10 grams of double bond starch nano particle, 1 gram of antioxidant,
Radical initiator 0.5 gram mixes in super mixer, then by above-mentioned pre-composition at 130 DEG C
Obtained containing starch nano grain by banbury melting mixing 5 minutes (rotor speed is 50 revs/min)
The composition of son, resulting composition is hot-forming by vulcanizing press, obtain 1mm and 3mm
Thick flaky material, is cut into standard batten according to relevant criterion and arranges for Mechanics Performance Testing, test result
Enter in table 1.
Embodiment 6
The preparation of the composition containing starch nano particle
Copolymer 20 by PLA 80 grams, tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester
Gram, 8 grams of epoxidation starch nano particle, 1 gram of antioxidant, hydrolysis-resisting agent 1 gram be in super mixer
Mixing, then by above-mentioned pre-composition, at 175 DEG C, by banbury melting mixing, within 5 minutes, (rotor turns
Speed is 50 revs/min) obtain the composition containing starch nano particle, resulting composition is passed through flat board
Vulcanizer is hot-forming, obtains the thick flaky material of 1mm and 3mm, is cut into mark according to relevant criterion
Quasi-batten is used for Mechanics Performance Testing, and test result is listed in table 1.
Embodiment 7
The preparation of the composition containing starch nano particle
By PLA 90 grams, fatty poly-ester carbonate 10 grams, 5 grams of double bond starch nano particle, resist
Oxygen agent 1 gram, radical initiator 0.2 gram, hydrolysis-resisting agent 1 gram mix in super mixer,
Then by above-mentioned pre-composition 170 DEG C by banbury melting mixing 5 minutes (rotor speed is 50 turns/
Minute) obtain the composition containing starch nano particle, by resulting composition by vulcanizing press hot pressing
Shaping, obtains the thick flaky material of 1mm and 3mm, according to relevant criterion be cut into standard batten for
Mechanics Performance Testing, test result is listed in table 1.
Embodiment 8
The preparation of the composition containing starch nano particle
By PLA 5000 grams, 300 grams of epoxidation starch nano particle, 50 grams of antioxidant, resistant to hydrolysis
Agent 25 grams mixes in high-speed mixer, is then blended by double screw extruder by above-mentioned pre-composition
Extrusion (screw speed is 150 revs/min, temperature 180-200 DEG C) obtains containing starch nano particle
Composition, resulting composition is hot-forming by vulcanizing press, obtain 1mm and 3mm thickness
Flaky material, is cut into standard batten according to relevant criterion and lists table in for Mechanics Performance Testing, test result
In 1.
Embodiment 9
The preparation of the composition containing starch nano particle
By PLA 5000 grams, 250 grams of double bond starch nano particle, dicumyl peroxide 5 grams, help
Crosslinking agent 10 grams, 50 grams of antioxidant mix in high-speed mixer, are then led to by above-mentioned pre-composition
Cross double screw extruder blending extrusion (screw speed is 200 revs/min, temperature 180-200 DEG C) to obtain
Containing the composition of starch nano particle, resulting composition is hot-forming by vulcanizing press, obtain
The flaky material that 1mm and 3mm is thick, is cut into standard batten according to relevant criterion and surveys for mechanical property
Examination, test result is listed in table 1.
Embodiment 10
The preparation of the composition containing starch nano particle
By poly butylene succinate 100 grams, maleic anhydride graft polybutylene succinate (PBS) 20 grams, ring
Oxidized starch nano particle 15 grams, 1.2 grams of antioxidant mix, then by upper in super mixer
State pre-composition to be obtained by banbury melting mixing 5 minutes (rotor speed is 50 revs/min) at 130 DEG C
To the composition containing starch nano particle, resulting composition is hot-forming by vulcanizing press,
To the flaky material that 1mm and 3mm is thick, it is cut into standard batten for mechanical property according to relevant criterion
Test, test result is listed in table 1.
Embodiment 11
The preparation of the composition containing starch nano particle
By PLA 90 grams, epoxidized fat adoption carbonic ester 10 grams, amination starch nano particle 5
Gram, 1 gram of antioxidant, hydrolysis-resisting agent 1 gram mix, then by above-mentioned premix in super mixer
Thing is contained by banbury melting mixing 5 minutes (rotor speed is 50 revs/min) at 170 DEG C
The composition of starch nano particle, resulting composition is hot-forming by vulcanizing press, obtain 1mm
The flaky material thick with 3mm, is cut into standard batten for Mechanics Performance Testing, survey according to relevant criterion
Test result is listed in table 1.
Embodiment 12
The preparation of the composition containing starch nano particle
By the copolymer 80 grams of tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester, maleic anhydride grafting
The copolymer of tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester 20 grams, epoxidation starch nano particle
10 grams, 1 gram of antioxidant, hydrolysis-resisting agent 1 gram mix, then by above-mentioned pre-in super mixer
Mixed thing is contained by banbury melting mixing 5 minutes (rotor speed is 50 revs/min) at 130 DEG C
There is the composition of starch nano particle, resulting composition is hot-forming by vulcanizing press, obtain 1
The flaky material that mm and 3mm is thick, is cut into standard batten according to relevant criterion and surveys for mechanical property
Examination, test result is listed in table 1.
Comparative example 1
PLA 5000 grams, particle diameter are 300 grams of the normal wood sweet potato starch particle of 10～20 microns, resist
Oxygen agent 50 grams, hydrolysis-resisting agent 25 grams mix in high-speed mixer, are then led to by above-mentioned pre-composition
Cross double screw extruder blending extrusion (screw speed is 150 revs/min, temperature 180～200 DEG C) to obtain
To the composition containing amylum grain, resulting composition is hot-forming by vulcanizing press, obtain 1
The flaky material that mm and 3mm is thick, is cut into standard batten according to relevant criterion and surveys for mechanical property
Examination, test result is listed in table 1.
Comparative example 2
By PLA 5000 grams, 250 grams of starch nano particle, dicumyl peroxide 5 grams, assistant crosslinking agent
10 grams, 50 grams of antioxidant mixes, then by above-mentioned pre-composition by double spiral shells in high-speed mixer
Bar extruder blending extrusion (screw speed is 200 revs/min, temperature 180～200 DEG C) is contained
The composition of starch nano particle, resulting composition is hot-forming by vulcanizing press, obtain 1mm
The flaky material thick with 3mm, is cut into standard batten for Mechanics Performance Testing, survey according to relevant criterion
Test result is listed in table 1.
Table 1: contain the mechanical performance parameter of starch nano particle composition in embodiment and comparative example
In embodiment, poly butylene succinate used is Hangzhou Xin Fu medicine company limited company product, oneself
Succinate adipate and mutual-phenenyl two acid bromide two alcohol ester's copolymer are BASF product, fatty poly-ester carbonate
(PPC) being Henan Tianguan Enterprise Group Co's product, PLA is Natureworks PLA
2003D, radical initiator is cumyl peroxide, and all antioxidant are antioxidant 1010, water resistant
Solution agent is carbodiimides.Polymer-modified is at laboratory self-control product based on above-mentioned polymer
Product, wherein maleic anhydride graft polybutylene succinate (PBS) be by maleic anhydride, micro-benzene vinyl monomer,
Poly butylene succinate and benzoyl peroxide (BPO) pass through double screw extruder at 130 DEG C
Melt extruding acquisition, percent grafting is 2.0wt%；Maleic anhydride grafting tetramethylene adipate and terephthaldehyde
The copolymer of acid butanediol ester is by maleic anhydride, poly butylene succinate and benzoyl peroxide
(BPO) melt extruding acquisition at 130 DEG C by double screw extruder, percent grafting is 1.8wt%；
Epoxidized fat adoption carbonic ester be by methyl glycidyl ether (GMA), fatty poly-ester carbonate and
Benzoyl peroxide (BPO) melt extrudes acquisition, percent grafting by double screw extruder at 130 DEG C
For 2.2wt%.Chemical reagent used is commercially available prod (purity > 97%).
In embodiment, tensile property (hot strength and elongation at break) is marked according to GB/T 1040.1-2006
Quasi-test, rate of extension is 10mm/min；Impact strength is according to ASTM D256 standard testing.Institute
Measuring mechanical property is had to record after all placing 24 hours in 23 DEG C of environment.
From data in table 1, compared with the comparative example 1 using common micro amylum grain, real
Execute the hot strength of example (such as embodiment 8), impact strength, elongation at break are respectively increased 36%,
170% and more than 230%；Compared with the comparative example 2 using unmodified starch nano particle, real
Execute the hot strength of example (such as embodiment 9), impact strength, elongation at break are respectively increased 8.5%,
114% and more than 60%.
As can be seen here, the composition containing starch nano particle obtained by the present invention has hot strength
The advantage such as high, impact flexibility is good, elongation at break is big, is suitable for preparation to high daily of mechanical property requirements
Articles for use and device, mainly have benefited from nano effect (nanoscale dispersion) and the modification of starch nano particle
The association of the chemical bonding (interface binding force) between starch nano particle active function groups and polymeric matrix
Same effect, therefore under relatively low modified starch nanoparticle content, even if without any plasticizer, still
So can obtain the composition that mechanical performance is excellent.If adding the polymer-modified of certain content can enter
One step improves the chemical bonding between modified starch nano particle and polymeric matrix, and then is conducive to improving
Mechanical performance.What deserves to be explained is, the composition containing starch nano particle that the present invention obtains also has
The reproducible feature of biodegradable, completely or partially component completely.
Those of ordinary skill in the field are it is understood that the discussion of any of the above embodiment is merely illustrative
, it is not intended that hint the scope of the present disclosure (including claim) is limited to these examples；At this
Under bright thinking, between the technical characteristic in above example or different embodiment, group can also be carried out
Close, and there is other change of many of the different aspect of the present invention as above, in order to concisely they do not have
Have and provide in details.Therefore, all within the spirit and principles in the present invention, any omission of being done,
Amendment, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (9)
1. the composition containing starch nano particle, it is characterised in that in parts by weight, including gathering
Compound 1～100 parts, modified starch nano particle 2～40 parts and auxiliary agent 0～15 parts；
The structural formula of described modified starch nano particle is: St-R0CH(R1)-R2, wherein,
St represents starch molecule,
R0For the one in siloxy that carbon number is 1～6 or ester group,
R1And R2It is 2～20 and contain for alkyl that hydrogen atom, carbon number are 1～20, carbon number
At least one in the organic group of amino, unsaturated double-bond or epoxy radicals.
Composition containing starch nano particle the most according to claim 1, it is characterised in that institute
State polymer be weight average molecular weight be not less than 50,000 polyester or polyolefin at least one.
Composition containing starch nano particle the most according to claim 1, it is characterised in that institute
Stating polymer is PLA, poly-(succinic acid-butanediol ester), tetramethylene adipate and terephthalic acid (TPA) fourth
At least one in the copolymer of diol ester, fatty poly-ester carbonate.
Composition containing starch nano particle the most according to claim 1, it is characterised in that institute
The particle diameter stating modified starch nano particle is 50～300 nanometers, and dynamic light scattering polydispersity index is
0.01～0.5, substitution value is 0.005～1.5.
Composition containing starch nano particle the most according to claim 1, it is characterised in that institute
Stating auxiliary agent is in radical initiator, hydrolysis-resisting agent, assistant crosslinking agent, antioxidant, nucleator and fire retardant
At least one.
Composition containing starch nano particle the most according to claim 1, it is characterised in that also
Including polymer-modified 1～100 part, described polymer-modified on side chain containing epoxide group, acid anhydrides or
At least one in the thermoplastic polyester of hydroxy-acid group or TPO.
7. the combination containing starch nano particle prepared in Claims 1 to 5 described in any one
The method of thing, it is characterised in that comprise the following steps:
First polymer, modified starch nano particle, auxiliary agent are passed through high-speed mixer according to weight
Premix uniformly, then by above-mentioned pre-composition more than polymer or polymer-modified fusing point 1～50 DEG C pass through
Screw extruder or banbury melting mixing obtain the described composition containing starch nano particle.
8. the method preparing the composition containing starch nano particle described in claim 6, it is special
Levy and be, comprise the following steps:
First polymer, polymer-modified, modified starch nano particle, auxiliary agent are led to according to weight
Cross high-speed mixer premix uniformly, then by above-mentioned pre-composition more than polymer or polymer-modified fusing point
1～50 DEG C obtains the described group containing starch nano particle by screw extruder or banbury melting mixing
Compound.
9. according to the preparation method of the composition containing starch nano particle described in claim 7 or 8,
It is characterized in that, the preparation method of described modified starch nano particle comprises the following steps:
By solvent, water, modifying agent, starch mixing, obtain starch mixture；
Starch mixture stirs at 70～90 DEG C reaction 0.5～2 hour, and the starch obtaining clarification is molten
Liquid；
After starch solution cools down, in starch solution, add ethanol solution, obtain suspension；
By suspension after ultrasonic or cell disruptor processes, more by centrifugation, wash, separate, be dried,
Obtain modified starch nano particle；
The general structure of described modifying agent is, R3CH(R4)-R5, wherein:
R3For the one in the silane group of carbon number 1～6, hydroxy-acid group, acid chloride groups；
R4And R5It is 2～20 and contain for alkyl that hydrogen atom, carbon number are 1～20, carbon number
At least one in the organic group of isocyanates, unsaturated double-bond or epoxy radicals.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565992A (en) * | 2017-01-03 | 2017-04-19 | 湖北光合生物科技有限公司 | Starch loaded polylactic acid crystallization nucleating agent and preparation method thereof |
| CN108963210A (en) * | 2018-06-26 | 2018-12-07 | 桑顿新能源科技有限公司 | A kind of preparation method of carbon coating monocrystalline tertiary cathode material |
| CN111234484A (en) * | 2020-01-17 | 2020-06-05 | 中国科学院宁波材料技术与工程研究所 | Full-bio-based degradable polylactic acid/starch composite material and preparation method thereof |
| CN114410084A (en) * | 2021-12-29 | 2022-04-29 | 江苏尚艾新材料科技有限公司 | Toughened polylactic acid composite material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565992A (en) * | 2017-01-03 | 2017-04-19 | 湖北光合生物科技有限公司 | Starch loaded polylactic acid crystallization nucleating agent and preparation method thereof |
| CN108963210A (en) * | 2018-06-26 | 2018-12-07 | 桑顿新能源科技有限公司 | A kind of preparation method of carbon coating monocrystalline tertiary cathode material |
| CN111234484A (en) * | 2020-01-17 | 2020-06-05 | 中国科学院宁波材料技术与工程研究所 | Full-bio-based degradable polylactic acid/starch composite material and preparation method thereof |
| CN114410084A (en) * | 2021-12-29 | 2022-04-29 | 江苏尚艾新材料科技有限公司 | Toughened polylactic acid composite material and preparation method thereof |
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| CN105733211B (en) | 2019-06-21 |
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