CN106589648A - Thermoplastic composite material and preparation method thereof - Google Patents
Thermoplastic composite material and preparation method thereof Download PDFInfo
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- CN106589648A CN106589648A CN201611187163.0A CN201611187163A CN106589648A CN 106589648 A CN106589648 A CN 106589648A CN 201611187163 A CN201611187163 A CN 201611187163A CN 106589648 A CN106589648 A CN 106589648A
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- thermoplastic composite
- maleic anhydride
- styrene
- corn stalk
- auxiliary agent
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention provides a thermoplastic composite material. The thermoplastic composite material comprises, by weight, 100 parts of recovered polystyrene, homo-polypropylene and a styrene-butadiene-styrene block polymer, 1.0-5.0 parts of one or two of maleic anhydride grafted polypropylene and a maleic anhydride grafted styrene-ethyelne-butylene-styrene polymer, 10-43 parts of corn straw fibers and 0.5-2.0 parts of an assistant; and the styrene-butadiene-styrene block polymer accounts for 20-30% of the total weight of the recovered polystyrene and the homo-polypropylene. Addition of the corn straw fibers and the maleic anhydride grafted SEBS in the thermoplastic composite material makes the thermoplastic composite material have environmentally friendly property and good mechanical performances.
Description
Technical field
The present invention relates to technical field of composite materials, more particularly to a kind of thermoplastic composite and preparation method thereof.
Background technology
Corn stalk is more sturdy in grass, and length is 0.8～3m, a diameter of 2～4.5cm, there is significantly section
And internode.Every mu of Semen Maydiss can produce 400～500kg of corn straw.Corn stalk is mainly made up of leaf and stem, wherein stem again by crust and
Marrow is constituted.3 kinds of compositions can be seen on the cross section of corn stem using optical microscope：Epidermal tissue, basic parenchyma
With micro-pipe tissue.
Epidermis is plant stem outermost confluent monolayer cells, is that a kind of long cell is alternately arranged with two short cells, is almost full with
SiO2With another kind of composition of the cell with bolt matter short cell.Due to mineralization and bolt matter, corn stalk epidermis contains more
Corn stalk silicide and waxiness.Typically at 520～1550 μm, two ends taper has aobvious fibre length in corn stalk on cell wall
The section stricture of vagina of work and few pit.
The main component of corn stalk is cellulose, hemicellulose, lignin, crude protein, fat and water.Wherein, cellulose
It is insoluble in the homogeneous polysaccharide of water；It is the straight-chain macromolecular compound being made up of D-Glucose base, in cellulose macromolecule
D-Glucose base between connected in the way of being coupled with cellobiose, the C of cellobiose1Hemiacetal is remain on position
Form, there is reproducibility, and in C4On leave a free hydroxyl, cellulose has individual X ray picture；Hemicellulose is except fibre
Plant cell wall polysaccharide beyond dimension element and pectin, different from cellulose, hemicellulose is two or more monosaccharide composition
Heterogeneity polysaccharide, molecular weight is relatively low, and the degree of polymerization is little, mostly with side chain.Therefore, constituting the principal monosaccharides of cellulose includes wood
Sugar, mannose and glucose；Constituting the principal monosaccharides of hemicellulose is：Galactose, arabinose, xylose glucose, fucose,
Rhamnose, glucuronic acid and galacturonic acid.
Lignin is a kind of natural high molecular polymer, is by ehter bond and carbon-carbon bond by phenylpropane monomer
Be formed by connecting, the aromatic polymer compound with three dimensional structure.The lignin of corn stalk belongs to lignum-vitae base-Syringa oblata Lindl. base
Lignin, basic structural unit is lignum-vitae base and Syringa oblata Lindl. base, and containing a small amount of p-hydroxybenzene, Syringa oblata Lindl. base is created with more
Ratio between wooden base is 0.5～1.0.Mainly contain 7%～12% ester group compound in lignin, phosphorus content up to 60%～
66%.The unstable chemcial property of lignin, makes corn stalk compared with easy cooking.
At present, thermoplastic composite adopts pure plastic injection mostly, consumes a large amount of fossil resources, pollution environment, crucial
Mechanical property is nor highly desirable.
The content of the invention
Present invention solves the technical problem that be that a kind of thermoplastic composite is provided, the thermoplastic that the application is provided
Low cost, the feature of environmental protection is good, and excellent in mechanical performance.
In view of this, this application provides a kind of thermoplastic composite, including：
Reclaim polystyrene+HOPP+weight portion of s-B-S block polymer 100；
In the polymer of maleic anhydride inoculated polypropylene and maleic anhydride graft phenylethene-ethylene-butylene, Styrene one
Plant or two kind of 1.0～5.0 weight portion；
The weight portion of corn stalk fiber 10～43；
The weight portion of auxiliary agent 0.5～2.0；
S-B-S block polymer is the recovery polystyrene and the HOPP total amount
20%～30%.
Preferably, the recovery polystyrene and the mass ratio of the HOPP are 10：(3～10).
Preferably, the maleic anhydride inoculated polypropylene and maleic anhydride graft phenylethene-ethylene-butylene, Styrene
One or two content in polymer is 1.0～4.3 weight portions.
Preferably, the content of the corn stalk fiber is 25～43 weight portions.
Preferably, the auxiliary agent is included in colour carbon black, antioxidant, silane coupler, heat stabilizer and light stabilizer
One or more.
Preferably, the auxiliary agent includes the colour carbon black of 0.5～1.5 weight portion, and the content of antioxidant 300 is the pigment
The 20% of white carbon black.
Present invention also provides the preparation method of the thermoplastic composite described in such scheme, comprises the following steps：
Maleic anhydride graft phenylethene-ethylene-butylene, Styrene is added after corn stalk fiber powder is mixed with auxiliary agent
Polymer and maleic anhydride inoculated polypropylene in one or two, reclaim polystyrene, HOPP and styrene-fourth
Styrene block polymer, obtains compound；
By the compound extruding pelletization, thermoplastic composite is obtained.
Preferably, the corn stalk powder also includes before mixing with the auxiliary agent：
The corn stalk powder is carried out into stirring at low speed, then carries out high-speed stirred, be then heated to 100～105 DEG C；
The rotating speed of the stirring at low speed is 700～800r/min, and the time is 5～10min, and the rotating speed of the high-speed stirred is
1200～1500r/min, the time is 25～35min.
Preferably, the temperature of the mixing is 120～127 DEG C.
Preferably, the temperature of the extrusion is 120～200 DEG C.
This application provides a kind of thermoplastic composite, it includes：Recovery polystyrene, HOPP, styrene-
Butadiene-styrene block polymer, maleic anhydride inoculated polypropylene and maleic anhydride graft phenylethene-Ethylene/Butylene-benzene second
In the polymer of alkene one or two, corn stalk fiber and auxiliary agent, wherein, corn stalk fiber is used as thermoplastic composite material
The filler of material, makes thermoplastic composite low cost, the feature of environmental protection good；Maleic anhydride graft phenylethene-ethylene-butylene, Styrene
Polymer as corn stalk fiber and plastics polymer coupler so that there is bonding with plastics and make in corn stalk fiber
With maleic anhydride inoculated polypropylene can also be used as corn stalk fiber and the bulking agent of plastic resin；Styrene-butadiene-
Styrenic block polymers make both Compatibility improvements, so as to increase as the compatilizer for reclaiming polystyrene and HOPP
The strong mechanical property of composite.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limit.
The embodiment of the invention discloses a kind of thermoplastic composite, including：
Reclaim polystyrene+HOPP+weight portion of s-B-S block polymer 100；
In the polymer of maleic anhydride inoculated polypropylene and maleic anhydride graft phenylethene-ethylene-butylene, Styrene one
Plant or two kind of 1.0～5.0 weight portion；
The weight portion of corn straw 10～43；
The weight portion of auxiliary agent 0.5～2.0；
S-B-S block polymer is the recovery polystyrene and the HOPP total amount
20%～30%.
Raw material based on recovery polystyrene and HOPP in the application, for its application that originates does not have to this
It is special to limit.Preferably, the polystyrene that reclaims described herein is preferably 10 with the mass ratio of polystyrene：(3
～8).
The s-B-S block polymer is abbreviated as SBS, and herein described SBS is thermoplastic elastic
Body, it is used as the compatilizer for reclaiming polystyrene and HOPP so that the bad recovery polystyrene of the script compatibility with
HOPP Compatibility improvement.Lack its poor mechanical property if SBS in thermoplastic compound in the application, show as heat
Plastic composites are especially fragile, are easily broken off；But SBS additions are too many, then stretch moduluses to thermoplastic composite,
Bending moduluses can be reduced a lot, and tensile strength also can be reduced.SBS is poly- for the recovery polystyrene and the homopolymerization in the application
The 20%～30% of propylene total amount；The amount of the SBS more than 30%, then the stretch moduluses of thermoplastic composite, bending moduluses
All substantially reduce, less than 20%, then com-patibilising effect is not obvious, and thermoplastic composite is excessively fragile.The application is to the SBS's
Source has no particular limits, and is commercially available prod or prepares according to preparation method well known to those skilled in the art.
Maleic anhydride graft phenylethene-ethylene-butylene, Styrene (maleic anhydride-g-SBS) polymer is used as thermoplasticity
The polymer coupler of composite, model SEBS 1901P be a kind of Jing anhydride be grafted styrene-ethylene-butadiene-
Styrol copolymer, is a kind of thermoplastic elastomer (TPE) with polarized.Cellulose, hemicellulose in corn straw and wooden
Contain substantial amounts of hydroxyl, carboxyl and aldehyde radical isopolarity group in element, the anhydride group in such maleic anhydride-g-SBS can
To react bonding with above-mentioned polar group, while SEBS very good with the compatibility for reclaiming polystyrene and HOPP, because
This, maleic anhydride-g-SBS serves the cross structure beam action of straw and resin, so as to improve thermoplastic composite
Mechanical property.Maleic anhydride inoculated polypropylene also can be used as corn straw and the bulking agent of resin.The maleic anhydride grafting
SEBS is 1.0～5.0 weight portions with one or two the content in maleic anhydride inoculated polypropylene, and its content is less than 1.0 weights
Amount part, then very little, the not effect with bulking agent more than 5.0 weight portions, then increases the anhydride group quantity reacted with corn straw
Hold effect increase unobvious, and cost is improved.In herein described maleic anhydride-g-SBS and maleic anhydride inoculated polypropylene
One or two content be preferably 1～3.5 weight portion, example, can be 1.5,2.2,2.5,3.0 or 3.5 (weight
Part).The application is not limited the maleic anhydride-g-SBS with the source of maleic anhydride inoculated polypropylene, can be commercially available
Product, it is also possible to prepare according to mode well known to those skilled in the art.
Filler of the application using corn stalk fiber as thermoplastic composite, it also has to thermoplastic composite
Potentiation.The content of the corn stalk fiber is 10～43 weight portions, and the content is to reclaim styrene+styrene+SBS
Sum is that on the basis of 100 weight portions, the content of the corn straw is preferably 15～32 weight portions, more preferably 18～28 weights
Amount part, example, preferably 15,18,20,23,25,28,30 or 35 (weight portion).The granularity of the corn stalk fiber is preferred
For 60～80 mesh.
According to the present invention, the auxiliary agent is auxiliary agent well known to those skilled in the art, to this application without special limit
System.Preferably, herein described auxiliary agent is stable including colour carbon black, antioxidant, silane coupler, heat stabilizer and light
One or more in agent；The pigment is preferably colour carbon black, and the silane coupler is preferably KH-550 silane couplers,
Specially aminopropyl triethoxysilane, the antioxidant is preferably antioxidant 300 (4,4'- thiobiss (the 6- tert-butyl group -3- first
Base phenol) or 4,4'- thiobiss (6- tert-butyl-m-cresols)).Which kind of material specifically added in the auxiliary agent, according to actual needs
It is added.Example, the content of the colour carbon black is 0.5～1.5 weight portion, and the content of antioxidant 300 is the white carbon black
20%.
The application reclaims polystyrene, HOPP, SBS, maleic anhydride by the addition in thermoplastic composite
Maleated SEBS, maleic anhydride inoculated polypropylene, corn stalk fiber and auxiliary agent, make the mechanical property of thermoplastic composite compared with
It is good.
Present invention also provides a kind of preparation method of thermoplastic composite, comprises the following steps：
The poly- of maleic anhydride graft phenylethene-ethylene-butylene, Styrene is added after stalk fibre powder is mixed with auxiliary agent
In compound and HOPP one or two, reclaim polystyrene, HOPP and s-B-S
Block polymer, obtains compound；
By the compound extruding pelletization, thermoplastic composite is obtained.
During thermoplastic composite is prepared, preferably, it is mixed with auxiliary agent in corn stalk fiber
Before, need for corn stalk fiber to carry out heating eliminating water, in the process, it is preferred to use high-speed mixer (high mixer) conduct adds
Equipment for Heating Processing.The temperature of heating instrument is set as 110～130 DEG C, high mixer by the high mixer as heat treatment apparatus
Cylinder carries chuck, and conduction oil is marked with chuck, and Electrothermal ring is cased with outside chuck.The process of corn stalk fiber powder heating is concrete
For：
Corn stalk fiber powder is poured in high mixer, is covered in closing, start stirring at low speed, the stirring paddle of stirring at low speed turns
Number is 700～800r/min, and after 5～10min of stirring high-speed stirred is opened, and revolution is 1200～1500r/min, the time is 25～
35min。
Auxiliary agent is added when corn stalk powder temperature is 100～105 DEG C, temperature is to open blow-off valve after 120～127 DEG C.
Heretofore described corn stalk fiber powder is after corn straw is harvested in autumn, to go after natural wind sun dehydration
Fall root, leaf, dust, then after skin flesh is separated, flesh is discarded, the powder that straw skin is ground using pulverizer, its
Fineness is 60～80 mesh.
According to the present invention, by the corn stalk powder after heat treated and surface treatment and maleic anhydride graft phenylethene-second
In the polymer and HOPP of alkene-butylene-styrene one or two, reclaim polystyrene, HOPP, benzene second
The high temperature mixing again of alkene-butadiene-styrene block polymer, mixes 5～10min under room temperature, obtain compound.
The application obtains thermoplastic composite then by the compound extruding pelletization.Specifically, compound is poured into
In wood moulding special twin screw extruder hopper, extruder main frame and feeding machine are started, extrusion temperature is 120～200 DEG C.
For a further understanding of the present invention, with reference to the thermoplastic composite that embodiment is provided the present invention, this
Bright protection domain is not limited by the following examples.
Embodiment 1
Corn stalk fiber powder is poured in high mixer, is covered in closing, start stirring at low speed, the stirring paddle of stirring at low speed turns
Number is 750r/min, and high-speed stirred is started after stirring at low speed 5min, and revolution is 1500r/min, and the time is 25min；
When stalk fibre powder temperature reaches 100～105 DEG C, the row of unlatching after adding auxiliary agent, temperature to reach 120～127 DEG C
Material valve, discharges stalk fibre powder；
By the stalk fibre powder after heat treated and surface treatment and plastic substrate and elastomer mixed at high speed again, room temperature
Lower mixing 5min, obtains compound；
The compound for obtaining is poured in double screw extruder hopper, then starts extruder main frame and feeding machine, extrusion temperature
Spend for 120～200 DEG C, obtain thermoplastic composite.
Embodiment 2～4
Identical with the preparation method of embodiment 1, difference is：The component of thermoplastic composite and content are different, specifically
As shown in table 1.
The performance of the thermoplastic composite of detection embodiment 2～4, testing result is as shown in table 2.
The tables of data of the thermoplastic composite each component of table 1
Remarks：PS is polystyrene english abbreviation, and the HOPP of embodiment 2 is purchased from Taiwan Li Changrong chemical companies
The model Globalene 6331-11, SBS of the HOPP of Globalene 6231-20, embodiment 3 and embodiment 4
YH-792 is purchased from Ba Ling petrochemical industry, is s-B-S block polymer english abbreviation；Maleic acid in embodiment 3
Acid anhydride graft polypropylene is purchased from EXXELOR PO 1020 (ExxonMobil products, the maleic anhydride inoculated polypropylene in embodiment 4
Purchased from EXXELOR VA 1801.
The performance data table of thermoplastic composite prepared by the embodiment of table 2
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen in the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope for causing.
Claims (10)
1. a kind of thermoplastic composite, including：
Reclaim polystyrene+HOPP+weight portion of s-B-S block polymer 100；
One kind in the polymer of maleic anhydride inoculated polypropylene and maleic anhydride graft phenylethene-ethylene-butylene, Styrene or
Two kind of 1.0～5.0 weight portion；
The weight portion of corn stalk fiber 10～43；
The weight portion of auxiliary agent 0.5～2.0；
S-B-S block polymer is the recovery polystyrene and the HOPP total amount
20%～30%.
2. thermoplastic composite according to claim 1, it is characterised in that the recovery polystyrene and the homopolymerization
Polyacrylic mass ratio is 10：(3～10).
3. thermoplastic composite according to claim 1, it is characterised in that the maleic anhydride inoculated polypropylene and horse
One or two content in the polymer of maleic anhydride grafted styrene-ethylene-butylene-styrene is 1.0～4.3 weight
Part.
4. thermoplastic composite according to claim 1, it is characterised in that the content of the corn stalk fiber is 25
～43 weight portions.
5. thermoplastic composite according to claim 1, it is characterised in that the auxiliary agent includes colour carbon black, antioxygen
One or more in agent, silane coupler, heat stabilizer and light stabilizer.
6. thermoplastic composite according to claim 5, it is characterised in that the auxiliary agent includes 0.5～1.5 weight portion
Colour carbon black, the content of antioxidant 300 is the 20% of the colour carbon black.
7. the preparation method of the thermoplastic composite described in claim 1, comprises the following steps：
The poly- of maleic anhydride graft phenylethene-ethylene-butylene, Styrene is added after corn stalk fiber powder is mixed with auxiliary agent
In compound and maleic anhydride inoculated polypropylene one or two, reclaim polystyrene, HOPP and styrene-fourth two
Alkene-styrenic block polymers, obtains compound；
By the compound extruding pelletization, thermoplastic composite is obtained.
8. preparation method according to claim 7, it is characterised in that before the corn stalk powder mixes with the auxiliary agent
Also include：
The corn stalk powder is carried out into stirring at low speed, then carries out high-speed stirred, be then heated to 100～105 DEG C；
The rotating speed of the stirring at low speed is 700～800r/min, and the time is 5～10min, and the rotating speed of the high-speed stirred is 1200
～1500r/min, the time is 25～35min.
9. the preparation method according to claim 7 or 8, it is characterised in that the temperature of the mixing is 120～127 DEG C.
10. preparation method according to claim 7, it is characterised in that the temperature of the extrusion is 120～200 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114599725A (en) * | 2019-11-06 | 2022-06-07 | 博里利斯股份公司 | Modified recycled polyolefins |
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|---|---|---|---|---|
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| CN114599725B (en) * | 2019-11-06 | 2023-09-08 | 博里利斯股份公司 | Modified recycled polyolefin |
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