CN110437581A - A kind of multi-layer core-shell particle toughening polymer composites and preparation method - Google Patents
A kind of multi-layer core-shell particle toughening polymer composites and preparation method Download PDFInfo
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- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
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Abstract
This application discloses a kind of multi-layer core-shell particle toughening 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 polymer；1~100 parts by weight of multi-layer core-shell particle；The polymer is thermosetting polymer and thermoplastic polymer；The multi-layer core-shell particle is made of modified starch core, biology base soft formation, polymer hard formation and functional modified layer.Multi-layer core-shell particle of the invention both is from using raw material in biology base, it is from a wealth of sources, and it is environmentally protective sustainable, structure is controllable with performance, enhance suitable for various polymer toughenings, and can realize and mix on traditional simple synthesis device with polymer, industrialized production environmental-friendly, easy to accomplish.
Description
Technical field
The present invention relates to technical field of polymer materials, further say, are that be related to a kind of multi-layer core-shell particle toughening poly-
Compound composite material and preparation method.
Background technique
With gradually reducing for fossil energy reserves, global energy crisis is also increasingly approaching.Energy based on fossil energy
Source structure has apparent unsustainable property.The utilization of fossil energy, and cause the key factor of environmental change and pollution.
Since global fossil resource is reduced increasingly, it is faced with using fossil resource and environment as traditional chemical industry of cost increasingly severeer
Situation, make full use of biomass resource substitute fossil resource, synthesize high molecular material or production needed for raw material, for getting rid of
High molecular material product and raw material have a very big significance dependent on the status of fossil resources.Biomass resource as cleaning, can
Regenerated resource, its utilization are most important for the energy problem for alleviating the whole world.Using biomass as raw material, using physics, change
The transformation technologies such as, biology can be processed into various biobased products.Bio-based polymers material has abundant raw material, cost
It is low, pollution less, low power consumption and other advantages, reduce petrochemicals production and use process in pollution on the environment, lead to
The MOLECULE DESIGN to bio-based polymers material is crossed, make to be partially or completely instead of the polymer of petroleum-based products
The hot spot direction studied at this stage.
Plastics are present in contemporary society as a kind of widely applied material, and thermosetting plastics is based on thermosetting resin
Ingredient is wanted, thermosetting resin after hardening, due to intermolecular cross-linking, forms reticular structure, and heat resistance is high, and compression is unlikely to deform,
But rigidity is big, hardness is high, property is crisp, at high cost since polymer-modified main chain realizes that the technique of toughening is more complex, therefore often passes through
The method of toughener is added to improve the toughness of thermosetting polymer.Thermoplastic is a kind of most widely used plastics, is used
Toughener improves its service performance, extends its application range and is of great significance.
With the further investigation to polymer toughener toughening mechanism, toughener is by simple rubber or elastomer, organic
Or the core-shell particles of inorganic rigid particle gradually till now.It, can be real by changing shell size using hard core-soft core particle
Existing toughness and rigidity improve simultaneously, have better solved the rigidity-toughness balanced problem of toughening polymer.However, being often used petroleum at present
Base monomer prepares polymer core shell particles, has been further exacerbated by the consumption of fossil energy, and cause problem of environmental pollution.Patent
It refers to that MBS resin is made of Methyl Methacrylate-Butadiene-Styrene Copolymer in CN201710849099.6, is a kind of
Excellent macromolecule modifier can improve the macromolecule transparency and impact resistance.Patent CN201710318841.0 is mainly with third
Olefin(e) acid butyl ester is core, is prepared for ACR impact modifier by shell of methyl methacrylate.Use MBS and ACR resin toughening PVC
Or good rigidity-toughness balanced may be implemented in PMMA.But methyl methacrylate, butyl acrylate, styrene and butadiene are equal
It will cause different degrees of pollution in petroleum resources, preparation process, not can solve environmentally friendly and sustainable development ask
Topic.Therefore, develop bio-based polymers core-shell particles to polymer in the fields such as environmentally friendly packing material using most important.
Summary of the invention
To solve the problem in the prior art, the present invention provides a kind of multi-layer core-shell particle toughening polymer is compound
Material and preparation method.Core-shell particles of the invention are prepared using bio-based monomer, environmentally protective, safe and non-toxic, with thermal polymerization
Object can prepare a kind of toughened composite polymer material after being blended.
An object of the present invention is to provide a kind of multi-layer core-shell particle toughening 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 polymer；
1~100 parts by weight of multi-layer core-shell particle；It is preferred that 5-60 parts by weight；
The polymer is thermosetting polymer and thermoplastic polymer；
The thermosetting polymer is unsaturated polyester (UP), epoxy resin, phenolic resin, alkyd resin, amino resins, span
At least one of bismaleimide resin, polyimide resin, furane resins and organic siliconresin；
The thermoplastic polymer includes polylactic acid, polyhydroxyalkanoate, polyformaldehyde, polyvinyl chloride, polymethyl
Sour methyl esters, polyethylene terephthalate, polystyrene, polycarbonate, polyamide, polyester, polyphenylene oxide, polysulfones, polyurethane,
Polypropylene, polycaprolactone, poly-β-hydroxybutyric acid, poly- hydroxy-glutaric acid ester, two hydroxypropyl acrylate of poly- fumaric acid, polyglycolic acid, polybutadiene
At least one of sour butanediol ester, polyadipate/butylene terephthalate；
The multi-layer core-shell particle is made of modified starch core, biology base soft formation, polymer hard formation and functional modified layer；
The modified starch core 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 modified starch is 0.1~2.5；Preferably 1.5~2.5.
The biology base soft formation is that biology base monomer polymerization forms；The polymer hard formation is polymerized for hard monomer；Institute
Functional modified layer is stated to be polymerized for functionalized monomer；
The bio-based monomer is(annulenones acetal, n=0,1 or 2), itaconic acid, oleic acid, fumaric acid, sub- oil
Acid, linolenic acid, ricinoleic acid, itaconic acid fatty ester, oleic acid fatty ester, fumaric acid fatty ester, linoleic acid fatty ester, linolenic acid fat
Ester, undecenoic acid, undecylene aldehyde, citronellal, citronellol, citronellyl acetate, muconic acid, muconic acid esters, laurene, lemon
One of aldehyde, nerol, undecylenate or combination；
The hard monomer is methyl acrylate, methyl methacrylate, styrene, vinyl chloride, one in divinylbenzene
Kind or combination；
The functionalized monomer is glycidyl methacrylate, linoleic acid ethylene oxidic ester, flax acid glycidyl
Ester, oleic acid ethylene oxidic ester, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl three are different
Npropoxysilane, γ-methacryloxymethyl dimethoxysilane, vinyltriethoxysilane, vinyl trimethoxy
Base silane, vinyl three (2- methoxyethoxy) silane, vinyl silane triisopropoxide, in vinyltriacetoxy silane
One kind or combination.
The partial size of the multiple modification biology base core-shell particles is 150~500nm；Preferably 200~450nm.
The core-shell particles are by including that the raw material of following components is prepared:
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.
It is copolymerized to be formed with annulenones acetal free radical open loop hydridization by carbon-carbon double bond free radical addition polymerization or carbon-carbon double bond
The multiple modification biology base core-shell particles.
The core-shell particles are prepared by method comprising the following steps:
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；
C. hard monomer is added, after reacting 1-3h, functionalized monomer is added, reacts 1-2h, prepares multiple modification biology base
Core-shell particles lotion；
D. it is demulsified, obtains core-shell particles powder.
Some conven-tional adjuvants can also be added in the composite material of the application according to the actual situation, such as: antioxidant 1010,168,
1076；Light stabilizer 770,622,944,783；Lead sulfate tribasic, zinc stearate, calcium stearate etc., dosage are also conventional
Dosage, technical staff can be determines according to actual conditions.
The second object of the present invention is to provide a kind of preparation method of multi-layer core-shell particle toughening polymer composites.
Include:
When polymer is thermoplastic polymer, the component is by being made the multilayer core capsomere after the dosage melt blending
Sub- toughened composite polymer material；
When polymer is thermosetting polymer, the component heats blending by the dosage in a solvent, or in a solvent
Removal solvent is blended in heating, and the multi-layer core-shell particle toughening polymer composites are made in vacuum degassing bubble after solidification.
Curing agent is conventional solidified dose of this field, such as: ethylenediamine, diethylenetriamine, diaminodiphenylmethane, methyl four
Hydrogen phthalic anhydride, phthalic anhydride, diallyl bisphenol, methyl ethyl ketone peroxide etc., dosage is conventional amount used, with thermosetting property tree
100 parts of rouge meters, curing agent are 10-100 parts, are preferably 20-80 parts by weight in the present invention；
Solvent is conventional organic solvent, such as acetone, diphenyl-methane, dimethylformamide, N-Methyl pyrrolidone, with heat
100 parts of thermosetting resin meters, solvent adding amount are generally 20-50 parts.
Multi-layer core-shell particle toughening composite material of the present invention, including multi-layer core-shell particle and thermosetting polymer/thermoplasticity
Polymer two parts, compared to other core-shell particles for toughening, biology base core-shell particles of the invention are all made of biology base
Monomer preparation, not only can be with toughened composite polymer material, but also overcame petroleum base monomer shortage of resources, and environmental pollution is big to ask
Topic.
Beneficial effects of the present invention: the preparation method provided according to the present invention multi-layer core-shell particle toughening polymerization obtained
Object composite material, the problem of can solve polymer composites rigidity-toughness balanced, and also preparation method provided by the invention is obtained
The core-shell particles obtained both are from using raw material in biology base, from a wealth of sources and environmentally protective sustainable, and structure and performance can
Control, being suitable for various polymer toughenings enhances, and can realize and mix on traditional simple synthesis device with polymer, environment
Industrialized production friendly, easy to accomplish.
Detailed description of the invention
Fig. 1 is the TEM transmission electron microscope picture of core-shell particles prepared by embodiment 5.
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 300 parts of ethyl acetate mixing of cornstarch (Changchun great achievement corn development corporation, Ltd.), cooling is abundant
After stirring, 15 parts of pyridine, after heating is sufficiently stirred gradually are added dropwise, 10 parts of acrylic acid is added dropwise and continues to stir, be added after reaction anhydrous
Ethanol washing filters and dryModified starch 1, measurement degree of substitution is 1.50.
Embodiment 2
By 100 parts and 180 parts of ethyl acetate mixing of soybean starch (Tian Quan Food Co., Ltd), after cooling is sufficiently stirred,
10 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, anhydrous second is added after reaction
Alcohol washing, filters and dryModified starch 2, measurement degree of substitution is 2.30.Two, the preparation of core-shell particles
Embodiment 3
By 100 parts in embodiment 1Modified starch 1It mixes and is added in 200 parts of deionized waters with 100 parts of itaconic acid N-butyls,
It is sufficiently stirred under room temperature 20 minutes, 1 part of initiator potassium persulfate is then added, is warming up to 80 DEG C, stirs and cause polymerization, reacted
4h adds 10 parts of methyl methacrylates, reacts 3h, is eventually adding 5 parts of γ-methacryloxypropyl trimethoxy silicon
Alkane (Hangzhou Jesse blocks Chemical Co., Ltd.), reacts 2h, and ethanol washing, suction filtration and dry preparation is addedMulti-layer core-shell particle 1, survey
It obtains particle diameter and is listed in table 1.
Embodiment 4
By 100 parts in embodiment 2Modified starch 2It mixes and is added in 400 parts of deionized waters with 150 parts of methyl undecylenates,
It is sufficiently stirred under room temperature 60 minutes, 2 parts of initiator azodiisobutyronitriles is then added, is warming up to 60 DEG C, stirs and cause polymerization,
8h is reacted, 20 parts of methyl acrylates are added, reacts 3h, is eventually adding 20 parts of vinyltriethoxysilane (Hangzhou Jesse card
Chemical Co., Ltd.), 1h is reacted, ethanol washing is added, filters and is prepared by dryingMulti-layer core-shell particle 2, measure particle diameter column
In table 1.
Embodiment 5
By 100 parts in embodiment 1Modified starch 1It mixes and adds with 100 parts of itaconic acid N-butyls, 100 parts of positive heptyl esters of itaconic acid
Enter in 700 parts of deionized waters, is sufficiently stirred under room temperature 30 minutes, 3 parts of initiator azodiisobutyronitriles are then added, are warming up to 70
DEG C, polymerization is stirred and caused, 6h is reacted, adds 10 parts of methyl acrylates, 20 parts of methyl methacrylates, reacts 2h, finally
40 parts of glycidyl methacrylate are added, react 1h, ethanol washing is added, filters and is prepared by dryingMulti-layer core-shell particle 3,
It measures particle diameter and is listed in table 1.
Embodiment 6
By 100 parts in embodiment 2Modified starch 2With 100 parts of 2- methylene -1,3- cyclic heptane dioxides100 parts of clothing
The mixing of health acid N-butyl is added in 700 parts of deionized waters, is sufficiently stirred 30 minutes under room temperature, 4 parts of initiator over cures are then added
Sour potassium is warming up to 70 DEG C, stirs and cause polymerization, reacts 6h, adds 30 parts of methyl methacrylates, reacts 2h, finally plus
Enter 25 parts of γ-methacryloxypropyl trimethoxy silanes (Hangzhou Jesse blocks Chemical Co., Ltd.), 25 parts of metering systems
Acid glycidyl ester reacts 1h, and ethanol washing is added, and filters and is prepared by dryingMulti-layer core-shell particle 4, measure particle diameter and be listed in
Table 1.
Table 1
| Partial size (nm) | |
| Embodiment 3 | 210 |
| Embodiment 4 | 390 |
| Embodiment 5 | 380 |
| Embodiment 6 | 450 |
Three, multi-layer core-shell particle toughening same with thermosetting compound material
Embodiment 7
It will be in 40 parts of embodiments 3Multi-layer core-shell particle 1(E-44, Guangzhou Zhong Ye Chemical Co., Ltd. are raw with epoxy resin
Producing) 100 parts of heating are blended, 50 parts of curing agent methyl tetrahydro phthalic anhydrides are added, mixture is poured into the poly- of preheating by vacuum degassing bubble
In Teflon mold, curing molding, cooling and demolding obtains the sheet material of 1mm thickness, and is cut into standard batten according to relevant criterion and uses
In Mechanics Performance Testing, every test result is included in table 2.
Comparative example 1
By 100 parts of Commercial epoxy resins (E-44, the production of Guangzhou Zhong Ye Chemical Co., Ltd.), 50 parts of solidification methyl are added
Tetrahydrophthalic anhydride, vacuum degassing bubble, is poured into the Teflon mould of preheating, curing molding, cooling and demolding, obtains 1 millimeter
Thick sheet, and standard batten is cut into for Mechanics Performance Testing according to relevant criterion, every test result is included in table 2.
Comparative example 2
By 100 parts in embodiment 1Modified starch 1It mixes and is added in 200 parts of deionized waters with 100 parts of itaconic acid N-butyls,
It is sufficiently stirred under room temperature 20 minutes, 1 part of initiator potassium persulfate is then added, is warming up to 80 DEG C, stirs and cause polymerization, reacted
Ethanol washing is added in 4h, filters and is prepared by dryingCore-shell particles 1。
By 40 partsCore-shell particles 1Altogether with 100 parts of heating of epoxy resin (E-44, the production of Guangzhou Zhong Ye Chemical Co., Ltd.)
It is mixed, 50 parts of solidification methyl tetrahydro phthalic anhydrides are added, mixture is poured into the Teflon mould of preheating by vacuum degassing bubble,
Curing molding, cooling and demolding obtain the sheet material of 1mm thickness, and are cut into standard batten according to relevant criterion and are used for Mechanics Performance Testing,
Every test result is included in table 2.
Embodiment 8
It will be in 5 parts of embodiments 4Multi-layer core-shell particle 2(PI, Qinyang Tianyi Chemical Co., Ltd. are raw with polyimide resin
Producing) 100 parts of heating are blended, 80 parts of curing agent phthalic anhydrides are added, mixture is poured into the poly- of preheating by vacuum degassing bubble
In Teflon mold, curing molding, cooling and demolding obtains the sheet material of 1mm thickness, and is cut into standard batten according to relevant criterion and uses
In Mechanics Performance Testing, every test result is included in table 2.
Comparative example 3
By 100 parts of polyimide resins (PI, Qinyang Tianyi Chemical Co., Ltd.'s production), 80 parts of curing agent neighbour's benzene are added
Dicarboxylic acid anhydride, vacuum degassing bubble, mixture is poured into the Teflon mould of preheating, curing molding, cooling and demolding obtains
Standard batten is cut into for Mechanics Performance Testing to the sheet material of 1mm thickness, and according to relevant criterion, and every test result is included in table 2
In.
Comparative example 4
By 100 parts in embodiment 2Modified starch 2It mixes and is added in 400 parts of deionized waters with 150 parts of methyl undecylenates,
It is sufficiently stirred under room temperature 60 minutes, 2 parts of initiator azodiisobutyronitriles is then added, is warming up to 60 DEG C, stirs and cause polymerization,
8h is reacted, ethanol washing is added, filters and is prepared by dryingCore-shell particles 2。
By 5 partsCore-shell particles 2With 100 parts of heating of polyimide resin (PI, Qinyang Tianyi Chemical Co., Ltd.'s production)
It is blended, 80 parts of curing agent phthalic anhydrides is added, mixture is poured into the Teflon mould of preheating by vacuum degassing bubble
In, curing molding, cooling and demolding obtains the sheet material of 1mm thickness, and is cut into standard batten according to relevant criterion and surveys for mechanical property
Examination, every test result are included in table 2.
Embodiment 9
It will be in 60 parts of embodiments 6Multi-layer core-shell particle 4(BMI, the photochemical factory in Hubei peak are raw with bimaleimide resin
Produce) 100 parts heat and be blended in 30 parts of solvent diphenyl-methanes, 20 parts of curing agent diallyl bisphenols are added, are uniformly mixed back spin
Solvent is steamed, mixture is poured into the Teflon mould of preheating, curing molding, cooling and demolding obtains by vacuum degassing bubble
Standard batten is cut into for Mechanics Performance Testing to the sheet material of 1mm thickness, and according to relevant criterion, and every test result is included in table 2
In.
Comparative example 5
By 100 parts of commercially available bimaleimide resins (BMI, the photochemical plant produced in Hubei peak), in 30 parts of solvent hexichol first
It heats and is blended in alkane, 20 parts of curing agent diallyl bisphenols are added, rotate out solvent, vacuum degassing bubble, casting after mixing
Into the Teflon mould of preheating, vacuum degassing bubble, curing molding, cooling and demolding obtains the sheet of 1 millimeters thick, and root
Standard batten is cut into for Mechanics Performance Testing according to relevant criterion, and every test result is included in table 2.
Embodiment 10
It will be in 20 parts of embodiments 6Multi-layer core-shell particle 4With phenolic resin (PF, the production of Beijing Tai Er Chemical Co., Ltd.)
100 parts of heating are blended, and 20 parts of curing agent hexamethylenetetramines are added, and mixture is poured into poly- the four of preheating by vacuum degassing bubble
In vinyl fluoride mold, curing molding, cooling and demolding obtains the sheet material of 1mm thickness, and is cut into standard batten according to relevant criterion and is used for
Mechanics Performance Testing, every test result are included in table 2.
Comparative example 6
By 100 parts of commercial phenolic resin (PF, the production of Beijing Tai Er Chemical Co., Ltd.), 20 parts of curing agent, six first are added
Urotropine, vacuum degassing bubble, mixture is poured into the Teflon mould of preheating, curing molding, cooling and demolding obtains
The sheet material of 1mm thickness, and standard batten is cut into for Mechanics Performance Testing according to relevant criterion, every test result is included in table 2.
Table 2
With the pure thermosetting resin comparison of comparative example 1,3,5,6 as can be seen that embodiment 7~10 is for variety classes from table
Thermosetting resin has apparent toughening reinforcing effect, the toughened thermosetting composite material being had excellent performance.With comparative example
2, the thermoset ting resin composite of two layers of Toughened With Core-Shell Particles is compared in 4, under same ratio addition, toughening heat of the invention
Thermoset material (embodiment 7,8) impact strength and bending strength are higher, and functionalized layer improves compatibility to increase toughness, outer layer
Hard shell makes core-shell particles be easy molding, can enhance polymeric matrix while toughening, improve the impact strength of material, performance
It is excellent.
Four, multi-layer core-shell particle toughening thermoplastic composite
Embodiment 11
It will be in 20 parts of embodiments 5Multi-layer core-shell particle 3Exist with 100 parts of polylactic acid (production of NatureWorks company, the U.S.)
170 DEG C of progress melt blending 5min, intermingling material is hot-forming by vulcanizing press, obtain the sheet material of 1mm thickness, and according to
Relevant criterion is cut into standard batten for Mechanics Performance Testing, and every test result is included in table 3.
Comparative example 7
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, every test result are included in table 3.
Comparative example 8
By 100 parts in embodiment 1Modified starch 1It mixes and adds with 100 parts of itaconic acid N-butyls, 100 parts of positive heptyl esters of itaconic acid
Enter in 700 parts of deionized waters, is sufficiently stirred under room temperature 30 minutes, 3 parts of initiator azodiisobutyronitriles are then added, are warming up to 70
DEG C, polymerization is stirred and caused, 6h is reacted, ethanol washing is added, filters and is prepared by dryingCore-shell particles 3。
By 20 partsCore-shell particles 3It is melted at 170 DEG C for 100 parts with polylactic acid (production of NatureWorks company, the U.S.)
5min is blended, intermingling material is hot-forming by vulcanizing press, the sheet material of 1mm thickness is obtained, and be cut into according to relevant criterion
Standard batten is used for Mechanics Performance Testing, and every test result is included in table 3.
Embodiment 12
It will be in 5 parts of embodiments 6Multi-layer core-shell particle 4With 100 parts of polycaprolactone (production of Wuhan seamount Science and Technology Ltd.)
It is in 60 DEG C of progress melt blending 5min, intermingling material is hot-forming by vulcanizing press, obtain the sheet material of 1mm thickness, and root
Standard batten is cut into for Mechanics Performance Testing according to relevant criterion, and every test result is included in table 3.
Comparative example 9
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, every test result are included in table 3.
Comparative example 10
By 100 parts in embodiment 2Modified starch 2With 100 parts of 2- methylene -1,3- cyclic heptane dioxides100 parts of clothing
The mixing of health acid N-butyl is added in 700 parts of deionized waters, is sufficiently stirred 30 minutes under room temperature, 4 parts of initiator over cures are then added
Sour potassium is warming up to 70 DEG C, stirs and cause polymerization, reacts 6h, and ethanol washing is added, and filters and is prepared by dryingCore-shell particles 4。
By 5 partsCore-shell particles 4It is melted at 60 DEG C for 100 parts with polycaprolactone (production of Wuhan seamount Science and Technology Ltd.)
5min is blended, intermingling material is hot-forming by vulcanizing press, the sheet material of 1mm thickness is obtained, and be cut into according to relevant criterion
Standard batten is used for Mechanics Performance Testing.Every test result is included in table 3.
Embodiment 13
It will be in 40 parts of embodiments 4Multi-layer core-shell particle 2(PC, the rich U.S. plastic engineering of Dongguan City are limited public raw with polycarbonate
Produce) 100 parts in 240 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, every test result is included in table 3.
Comparative example 11
By 100 parts of polycarbonate (PC, the rich U.S. limited public production of plastic engineering of Dongguan City) in 240 DEG C of progress melt blendings
5min, intermingling material is hot-forming by vulcanizing press, the sheet material of 1mm thickness is obtained, and standard is cut into according to relevant criterion
Batten is used for Mechanics Performance Testing, and every test result is included in table 3.
Embodiment 14
It will be in 60 parts of embodiments 6Multi-layer core-shell particle 4With 100 parts of polyformaldehyde (POM, Mitsubishi, FG2015) at 190 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, and every test result is included in table 3.
Comparative example 12
By 100 parts of polyformaldehyde (POM, Mitsubishi, FG2015) in 190 DEG C of progress melt blending 5min, by intermingling material
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, every test result are included in table 3.
Table 3
As can be seen from the table, embodiment 11,12 has apparent toughening enhancing effect for variety classes thermoplastic material
Fruit, the toughened thermoplastic composite material being had excellent performance.Pure PLA material tensile strength 64.2MPa in comparative example 7, fracture
Elongation 6.7% in comparative example 8, adds the PLA composite material tensile strength 59.6MPa of two layers of core-shell particles, elongation at break
120.5%, and in embodiment 11, add the PLA composite material tensile strength 69.8MPa of multi-layer core-shell particle, elongation at break
200.6%, illustrate that multi-layer core-shell particle can be realized polymer toughening, while outermost layer hard monomer polymer layer can be mentioned effectively
The tensile strength of high material, same result appear in PCL, PC, POM material.
The present invention provides a kind of multi-layer core-shell particle toughening polymer composites and preparation methods, without plasticizer etc.
Can composite material plasticizing processing, the functionalized layer of outer layer can effectively increase the compatibility between polymer and particle, improve
Toughening effect, while crust layer can effectively enhance composite material, high production efficiency, easy processing molding is at low cost, technique letter
Single, performance is controllable, suitable for preparing the composite material of various performance requirements.
Claims (10)
1. a kind of multi-layer core-shell particle toughening polymer composites, it is characterised in that the composite material is by including with the following group
The raw material divided is blended and obtains:
Each component according to parts by weight,
100 parts by weight of polymer；
1~100 parts by weight of multi-layer core-shell particle；It is preferred that 5-60 parts by weight；
The polymer is thermosetting polymer and thermoplastic polymer；
The thermosetting polymer is that unsaturated polyester (UP), epoxy resin, phenolic resin, alkyd resin, amino resins, span carry out acyl
At least one of imide resin, polyimide resin, furane resins and organic siliconresin；
The thermoplastic polymer includes polylactic acid, polyhydroxyalkanoate, polyformaldehyde, polyvinyl chloride, poly-methyl methacrylate
Ester, polyethylene terephthalate, polystyrene, polycarbonate, polyamide, polyester, polyphenylene oxide, polysulfones, polyurethane, poly- third
Alkene, polycaprolactone, poly-β-hydroxybutyric acid, poly- hydroxy-glutaric acid ester, two hydroxypropyl acrylate of poly- fumaric acid, polyglycolic acid, poly-succinic fourth
At least one of diol ester, polyadipate/butylene terephthalate；
The multi-layer core-shell particle is made of modified starch core, biology base soft formation, polymer hard formation and functional modified layer；
The modified starch core 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；It is modified
The degree of substitution of starch is 0.1~2.5；
The biology base soft formation is that biology base monomer polymerization forms；The polymer hard formation is polymerized for hard monomer；The official
Energy modified layer is polymerized for functionalized monomer；
The bio-based monomer is(annulenones acetal, n=0,1 or 2), itaconic acid, oleic acid, fumaric acid, linoleic acid, Asia
Numb acid, ricinoleic acid, itaconic acid fatty ester, oleic acid fatty ester, fumaric acid fatty ester, linoleic acid fatty ester, linolenic acid fatty ester, ten
Monoenoic acid, undecylene aldehyde, citronellal, citronellol, citronellyl acetate, muconic acid, muconic acid esters, laurene, citral, flores aurantii
One of alcohol, undecylenate or combination；
The hard monomer be one of methyl acrylate, methyl methacrylate, styrene, vinyl chloride, divinylbenzene or
Combination；
The functionalized monomer is glycidyl methacrylate, linoleic acid ethylene oxidic ester, flax acid glycidyl ester, oil
Acid glycidyl ester, γ-methacryloxypropyl trimethoxy silane, three isopropyl oxygen of γ-methacryloxypropyl
Base silane, γ-methacryloxymethyl dimethoxysilane, vinyltriethoxysilane, vinyl trimethoxy silicon
Alkane, vinyl three (2- methoxyethoxy) silane, vinyl silane triisopropoxide, one in vinyltriacetoxy silane
Kind or combination.
2. composite material as described in claim 1, it is characterised in that:
The degree of substitution of the modified starch is 1.5~2.5.
3. composite material as described in claim 1, it is characterised in that:
The partial size of the multiple modification biology base core-shell particles is 150~500nm.
4. composite material as claimed in claim 3, it is characterised in that:
The partial size of the multiple modification biology base core-shell particles is 200~450nm.
5. composite material as described in claim 1, it is characterised in that:
The core-shell particles are by including that the raw material of following components is prepared:
6. composite material as claimed in claim 5, it is characterised in that:
7. composite material 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. composite material 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
Multiple modification biology base core-shell particles.
9. composite material as claimed in claim 5, it is characterised in that:
The core-shell particles are prepared by method comprising the following steps:
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；
C. hard monomer is added, after reacting 1-3h, functionalized monomer is added, reacts 1-2h, prepares multiple modification biology base nucleocapsid
Particle lotion；
D. it is demulsified, obtains core-shell particles powder.
10. a kind of preparation method of the multi-layer core-shell particle toughening polymer composites as described in one of claim 1~9,
It is characterized in that the described method includes:
When polymer is thermoplastic polymer, the component increases by the multi-layer core-shell particle is made after the dosage melt blending
Tough polymer composites；
When polymer is thermosetting polymer, the component heats blending by the dosage in a solvent, or heats in a solvent
Removal solvent is blended, the multi-layer core-shell particle toughening polymer composites are made in vacuum degassing bubble after solidification.
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