CN110396293A - A kind of easily molded three-layer nuclear shell particle toughening polymer composites and preparation method - Google Patents
A kind of easily molded three-layer nuclear shell particle toughening polymer composites and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of easily molded three-layer nuclear 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 three-layer nuclear shell particle；The polymer is thermosetting polymer and thermoplastic polymer；The core-shell particles are made of biology base stone portion, soft hypostracum and hard outer shell three parts；The present invention without plasticizer etc. can composite material plasticizing processing, while toughening polymer, outermost layer crust layer can effectively enhance composite material, high production efficiency, easy processing molding are at low cost, simple process, performance is controllable, suitable for preparing the composite material of various performance requirements.
Description
Technical field
The present invention relates to technical field of polymer materials, further say, are to be related to a kind of easily molded three-layer nuclear shell particle
Toughened composite polymer 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.At present
The core-shell particles of double-layer structure be used for polymeric matrix toughening when, as patent CN201510364028.8 with
Double bond is introduced starch granules by CN201510362426.6, carries out seeding polymerization in this, as seed particles, poly- through soap-free emulsion
Conjunction prepares stone (starch)-soft shell (polyethyl acrylate) particle, uses its plasticizing polylactic acid.Particle is using in above-mentioned patent
In the process since stickiness is unfavorable for dispersing in the base greatly, formability is poor, while toughening effect also has certain limitation.And
And ethyl acrylate etc. derives from petroleum resources, will cause different degrees of pollution in preparation process, not can solve environmental protection
And the problem of sustainable development.Therefore, develop easily molded bio-based polymers core-shell particles to polymer in green package material
Material etc. in fields using most important.
Summary of the invention
To solve the technical problems existing in the prior art, the present invention provides a kind of easily molded three-layer nuclear shell particle toughenings
Polymer composites and preparation method.Core-shell particles of the invention increase again outside the second layer soft shell of two layers of core-shell particles
One layer of hard shell, third layer (outer shell) can not only increase core-shell particles at nuclearity, while enhancing can be played to matrix again
Effect.Toughness and rigidity can be realized by change shell size simultaneously while being improved, toughening polymer has been better solved
Rigidity-toughness balanced problem.A kind of toughened composite polymer material can be prepared after being blended with thermopolymer.
An object of the present invention is to provide a kind of easily molded three-layer nuclear 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 three-layer nuclear shell particle；It is preferred that 20-60 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 core-shell particles are made of biology base stone portion, soft hypostracum and hard outer shell three parts；
Biology base stone portion is modified starch, and the soft hypostracum is copolymerized by soft monomer to be formed, the hard outer shell
It is copolymerized and is formed by hard monomer；
The modified starch is the modified starch containing carbon-carbon double bond, general structure are as follows:Wherein St
For 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 soft 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
Alcohol, undecylenate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, ethylene, lauryl acrylate, acrylic acid -2-
One of ethylhexyl, lauryl methacrylate or combination；
The hard monomer is methyl acrylate, vinylacetate, styrene, vinyl chloride, acrylonitrile, methyl methacrylate
One of ester, acrylamide, divinylbenzene or combination.
The partial size of the easily molded three-layer nuclear shell particle is 120~700nm, preferably 180~600nm.
The core-shell particles are by including that the raw material of following components is prepared:
The initiator includes potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, peroxidating toluoyl, two isobutyl of azo
Base 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 three-layer nuclear shell particle.
The preparation method of the core-shell particles includes:
A. it by dry modified starch, soft 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, 1-3h is reacted, prepares easily molded three-layer nuclear shell particle 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 of easily molded three-layer nuclear shell particle toughening polymer composites
Method.
Include:
When polymer is thermoplastic polymer, the component is by being made the biology base nucleocapsid after the dosage melt blending
Particle toughening polymer composites；
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 biology base Toughened With Core-Shell Particles 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.
Three-layer nuclear shell particle of the invention, including biology base stone portion, soft hypostracum and outer shell three parts form, inner casing
Layer can be prepared with outer shell using bio-based monomer or the copolymerization of petroleum base monomer, while core-shell structure is controllable, and particle is easy
Blending toughening etc. in processing and forming, suitable for various polymer.
Biology base Toughened With Core-Shell Particles composite material of the present invention, including easily molded three-layer nuclear shell particle polymerize with thermosetting property
Object/thermoplastic polymer two parts can regulate and control polymer performance by core-shell particles, compared to other nucleocapsid grains for toughening
Son, the raw material that three-layer nuclear shell particle of the invention uses are easy to get extensively, and structure is controllable with performance, and outer layer hard shell makes core-shell particles
It is easy molding, toughening can enhance polymeric matrix simultaneously.Core-shell particles of the invention enhance suitable for various polymer toughenings, and
It can realize and mix on traditional simple synthesis device with polymer, simple process, industrialized production easy to accomplish.
Detailed description of the invention
Fig. 1 is the TEM transmission electron microscope picture of particle prepared by embodiment 6.
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, 15 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 1.89.
Embodiment 2
By 100 parts and 150 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 three-decker core-shell particles
Embodiment 3
By 100 parts in embodiment 2Modified starch 2With 50 parts of 2- methylene -1,3- cyclic heptane dioxides50 parts of clothing health
Sour N-butyl mixing is added in 300 parts of deionized waters, is sufficiently stirred 30 minutes under room temperature, 1 part of initiator azo two is then added
Isobutyronitrile is warming up to 60 DEG C, stirs and cause polymerization, reacts 8h, 10 parts of styrene (limited public affairs of Hangzhou Jesse's card chemical industry are added
Department), 3h is reacted, ethanol washing, suction filtration and dry preparation three-decker is addedEasily molded core-shell particles 1, measure particle diameter column
In table 1.
Embodiment 4
By 100 parts in embodiment 2Modified starch 2500 parts of addition is mixed with 50 parts of itaconic acids, 100 parts of positive heptyl esters of itaconic acid
It in deionized water, is sufficiently stirred under room temperature 30 minutes, 2 parts of initiator azodiisobutyronitriles is then added, be warming up to 70 DEG C, stirring
And cause polymerization, 6h is reacted, 10 parts of acrylonitrile, 15 parts of styrene (Hangzhou Jesse blocks Chemical Co., Ltd.) are added, reacts 2h, adds
Enter ethanol washing, filters and drying prepares three-deckerEasily molded core-shell particles 2, measure particle diameter and be listed in table 1.
Embodiment 5
By 100 parts in embodiment 2Modified starch 2With 100 parts of 2- methylene -1,3- cyclic heptane dioxides80 parts of clothing
The positive heptyl ester mixing of health acid is added in 600 parts of deionized waters, is sufficiently stirred 30 minutes under room temperature, 2 parts of initiator over cures are then added
Sour potassium is warming up to 70 DEG C, stirs and cause polymerization, reacts 6h, and 20 parts of acrylamides are added, and reacts 2h, and ethanol washing is added, and takes out
It filters and dries preparation three-deckerEasily molded core-shell particles 3, measure particle diameter and be listed in table 1.
Embodiment 6
By 100 parts in embodiment 1Modified starch 1It mixes and is added in 600 parts of deionized waters with 180 parts of methyl undecylenates,
It is sufficiently stirred under room temperature 30 minutes, 3 parts of initiator potassium persulfates is then added, is warming up to 70 DEG C, stirs and cause polymerization, reacted
40 parts of vinyl chloride are added in 6h, react 2h, and ethanol washing is added, and filter and drying prepares three-deckerEasily molded core-shell particles 4,
It measures particle diameter and is listed in table 1.
Table 1
Three, easily molded three-layer nuclear shell particle toughening thermosetting material
Embodiment 7
It will be in 30 parts of embodiments 3Easily molded core-shell particles 1With epoxy resin (E-44, Guangzhou Zhong Ye Chemical Co., Ltd.
Production) 100 parts of heating are blended, 50 parts of curing agent methyl tetrahydro phthalic anhydrides are added, mixture is poured into preheating by vacuum degassing bubble
In Teflon mould, curing molding, cooling and demolding obtains the sheet material of 1mm thickness, and is cut into standard batten according to relevant criterion
For 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 2Modified starch 2With 50 parts of 2- methylene -1,3- cyclic heptane dioxides50 parts of clothing health
Sour N-butyl mixing is added in 300 parts of deionized waters, is sufficiently stirred 30 minutes under room temperature, 1 part of initiator azo two is then added
Isobutyronitrile is warming up to 60 DEG C, stirs and cause polymerization, reacts 8h, and ethanol washing is added, and filters and is prepared by dryingCore-shell particles 1。
By 30 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 50 parts of embodiments 4Easily molded core-shell particles 2With polyimide resin (PI, the limited public affairs of the beneficial chemical industry in Qinyang City day
Department's production) 100 parts of heating are blended, 80 parts of curing agent phthalic anhydrides are added, mixture is poured into preheating by vacuum degassing bubble
Teflon mould in, curing molding, cooling and demolding obtains the sheet material of 1mm thickness, and is cut into standard sample according to relevant criterion
Item is used for Mechanics Performance Testing, and 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 2500 parts of addition is mixed with 50 parts of itaconic acids, 100 parts of positive heptyl esters of itaconic acid
It in deionized water, is sufficiently stirred under room temperature 30 minutes, 2 parts of initiator azodiisobutyronitriles is then added, be warming up to 70 DEG C, stirring
And cause polymerization, 6h is reacted, ethanol washing is added, filters and is prepared by dryingCore-shell particles 2。
By 50 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 6It is functionalized core-shell particles 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 6It is functionalized core-shell particles 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 effect, the toughened thermosetting composite material being had excellent performance.In comparative example 2,4
The thermoset ting resin composite of two layers of Toughened With Core-Shell Particles is compared, under same ratio addition, toughened thermosetting of the invention
Material (embodiment 7,8) impact strength and bending strength are higher, and outer layer hard shell makes core-shell particles be easy molding, in the same of toughening
When can enhance polymeric matrix, improve the impact strength of material, have excellent performance.
Four, easily molded three-layer nuclear shell particle toughening thermoplastic material
Embodiment 11
It will be in 20 parts of embodiments 5Easily molded core-shell particles 3With 100 parts of polylactic acid (production of NatureWorks company, the U.S.)
It is in 170 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 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 2Modified starch 2With 100 parts of 2- methylene -1,3- cyclic heptane dioxides80 parts of clothing
The positive heptyl ester mixing of health acid is added in 600 parts of deionized waters, is sufficiently stirred 30 minutes under room temperature, 2 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 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 50 parts of embodiments 6Easily molded core-shell particles 4With polycaprolactone (production of Wuhan seamount Science and Technology Ltd.) 100
Part in 60 DEG C of progresss melt blending 5min, it is hot-forming that intermingling material is passed through into vulcanizing press, obtains the sheet material of 1mm thickness, and
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 1Modified starch 1It mixes and is added in 600 parts of deionized waters with 180 parts of methyl undecylenates,
It is sufficiently stirred under room temperature 30 minutes, 3 parts of initiator potassium persulfates is then added, is warming up to 70 DEG C, stirs and cause polymerization, reacted
Ethanol washing is added in 6h, filters and is prepared by dryingCore-shell particles 4。
By 50 partsCore-shell particles 4It is melted at 60 DEG C for 100 parts with polycaprolactone (production of Wuhan seamount Science and Technology Ltd.)
Melt and 5min is blended, intermingling material is hot-forming by vulcanizing press, the sheet material of 1mm thickness is obtained, and cut out according to relevant criterion
Mechanics Performance Testing is used at standard batten.Every test result is included in table 3.
Embodiment 13
It will be in 40 parts of embodiments 4It is functionalized core-shell particles 2With polycarbonate (PC, the limited public affairs of the rich U.S. plastic engineering of Dongguan City
Production) 100 parts in 240 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, 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 6It is functionalized core-shell particles 4With 100 parts of polyformaldehyde (POM, Mitsubishi, FG2015) 190
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, 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 effect for variety classes thermoplastic material, obtains
To the toughened thermoplastic composite material haveing excellent performance.Pure PLA material tensile strength 64.2MPa, elongation at break in comparative example 7
6.7%, in comparative example 8, add the PLA composite material tensile strength 58.8MPa of two layers of core-shell particles, elongation at break
107.8%, and in embodiment 11, the PLA composite material tensile strength 69.8MPa of easily molded three-layer nuclear shell particle is added, is broken
Elongation 110.6% illustrates that easily molded three-layer nuclear shell particle can be realized polymer toughening, while outermost layer hard monomer polymer layer
The tensile strength of material can be effectively improved, same result appears in PCL, PC, POM material.
The present invention provides a kind of easily molded three-layer nuclear shell particle toughening polymer composites and preparation methods, without increasing
Mould agent etc. can composite material plasticizing processing, while toughening polymer, outermost layer crust layer can effectively enhance composite wood
Material, high production efficiency, easy processing molding, at low cost, simple process, performance is controllable, suitable for preparing answering for various performance requirements
Condensation material.
Claims (10)
1. a kind of easily molded three-layer nuclear shell particle toughening polymer composites, it is characterised in that: the composite material is by wrapping
The raw material for including following components is blended and obtains:
Each component according to parts by weight,
100 parts by weight of polymer；
1~100 parts by weight of three-layer nuclear shell particle；It is preferred that 20-60 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 core-shell particles are made of biology base stone portion, soft hypostracum and hard outer shell three parts；
Biology base stone portion is modified starch, and the soft hypostracum is copolymerized by soft monomer to be formed, and the hard outer shell is by hard
Monomer is copolymerized to be formed；
The modified starch is the modified starch containing carbon-carbon double bond, general structure are as follows:Wherein St is to form sediment
Powder 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 soft monomer is(annulenones acetal, n=0,1 or 2), itaconic acid, oleic acid, fumaric acid, linoleic acid, flax
Acid, ricinoleic acid, itaconic acid fatty ester, oleic acid fatty ester, fumaric acid fatty ester, linoleic acid fatty ester, linolenic acid fatty ester, 11
Olefin(e) acid, undecylene aldehyde, citronellal, citronellol, citronellyl acetate, muconic acid, muconic acid esters, laurene, citral, flores aurantii
Alcohol, undecylenate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, ethylene, lauryl acrylate, acrylic acid -2-
One of ethylhexyl, lauryl methacrylate or combination；
The hard monomer is methyl acrylate, vinylacetate, styrene, vinyl chloride, acrylonitrile, methyl methacrylate, third
One of acrylamide, divinylbenzene or combination.
2. 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. Toughened With Core-Shell Particles polymer composites as described in claim 1, it is characterised in that:
The partial size of the easily molded three-layer nuclear shell particle is 120~700nm.
4. Toughened With Core-Shell Particles polymer composites as claimed in claim 3, it is characterised in that:
The partial size of the easily molded three-layer nuclear shell particle is 180~600nm.
5. Toughened With Core-Shell Particles polymer composites 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. Toughened With Core-Shell Particles polymer composites as claimed in claim 5, it is characterised in that:
7. Toughened With Core-Shell Particles polymer composites as claimed in claim 5, it is characterised in that:
The initiator includes potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, peroxidating toluoyl, azo diisobutyl amidine
At least one of hydrochloride, two isobutyl imidazoline hydrochloride of azo, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN.
8. 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
Three-layer nuclear shell particle.
9. Toughened With Core-Shell Particles polymer composites as claimed in claim 5, it is characterised in that:
The preparation method of the core-shell particles includes:
A. it by dry modified starch, soft 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, 1-3h is reacted, prepares easily molded three-layer nuclear shell particle lotion；
D. it is demulsified, obtains core-shell particles powder.
10. a kind of preparation of the easily molded three-layer nuclear shell particle toughening polymer composites as described in one of claim 1~9
Method, it is characterised in that the described method includes:
When polymer is thermoplastic polymer, the component is by being made the biology base core-shell particles after the dosage melt blending
Toughened composite polymer material；
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 biology base Toughened With Core-Shell Particles polymer composites are made in vacuum degassing bubble after solidification.
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