CN105367867A - Enhancing type polyolefin/clay nanocomposite and preparing method thereof - Google Patents
Enhancing type polyolefin/clay nanocomposite and preparing method thereof Download PDFInfo
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- CN105367867A CN105367867A CN201510744267.6A CN201510744267A CN105367867A CN 105367867 A CN105367867 A CN 105367867A CN 201510744267 A CN201510744267 A CN 201510744267A CN 105367867 A CN105367867 A CN 105367867A
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- clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to an enhancing type polyolefin/clay nanocomposite which is prepared from polyolefin and modified clay in a melt blending and aggregation mode. The modified clay is prepared through reaction and pretreatment through a coupling agent containing double bonds; the clay comprises SiO2 and Al2O3, and the clay is aluminosilicate mineral dust with the granularity smaller than 200 meshes and a layered or fibroid structure. According to the enhancing type polyolefin/clay nanocomposite, a reaction with quaternary ammonium salt is not needed, the clay is dispersed in a solvent first and then reacts with the coupling agent containing double bonds, and the modified clay is obtained. The double bonds of the coupling agent are opened in the melt blending process through a reaction blending method and react with polyolefin and derivatives of polyolefin, and strong interaction of chemical bonds between the clay and polyolefin and between the clay and the derivatives of the polyolefin is established. The clay is evenly dispersed in the polymer through the shearing force of a screw, and the thus the mechanical property and the performance on other aspects of the materials are greatly improved.
Description
Technical field
The present invention relates to nano composite material technical field, especially relate to a kind of enhancement type Polyolefin/Clay Nanocomposites and preparation method thereof.
Background technology
In recent years, in order to improve the performances such as polyolefinic mechanics, barrier properties for gases, a lot of scientific research institution and company attempt preparing Polyolefin/Clay Nanocomposites.Clay layer itself has high modulus and the excellent specific property such as intensity, very large specific surface area.It is added with suitable process the use properties that significantly can improve products obtained therefrom in polymkeric substance, expand its use field.
Generally speaking, prepare composite nano polymer/clay material and have following three kinds of modes: solution method, situ aggregation method and melt-blending process.Solution method needs polymkeric substance and filler clay to dissolve simultaneously or stable is scattered in certain suitable solvent, and except desolventizing after the two Homogeneous phase mixing, drying and moulding, obtains matrix material.This method restricted application.First, polymkeric substance must have good solvent, and extremely insoluble polyolefine such as such as high density polyethylene(HDPE), polypropylene etc. can not use this method.Secondly, solution method needs to use a large amount of solvent, and organic solvent poisonous often, extremely unfavorable and increase production cost to environmental protection.Therefore solution method generally uses in the scientific research of laboratory, few suitability for industrialized production.Situ aggregation method principle is then that polymerizing catalyst is carried on clay layer, then mixes with polymer monomer and trigger polyreaction, while polymerization, prepare matrix material.Situ aggregation method is applicable to that fusing point is higher, processing degradation comparatively significantly polymkeric substance.But, because needs carry out redesigning and synthesize to polymerisation catalysts, whole conversion unit parameter is adjusted, adds into product difficulty and cost, be unfavorable for popularization.
Melt-blending process is current the most widely used Nano-composite materials method.When this method utilizes blended, clay layer is scattered among polymer melt by the shearing force of screw rod uniformly, and multiple method prepares the finished product can to use injection moulding, extrude etc., and the scope of application is the most extensive, early investment and production cost lower.But the lamella polarity of clay is very high, bad with the polyolefin backbone consistency of low polarity; And clay layer and interlayer ion have very strong interaction, be therefore difficult to make it enter polymeric matrix with the dispersion of the state of monolithic layer, thus make the modified effect of clay can not get fully playing.In order to solve an above difficult problem, way general at present uses quaternary ammonium salt to carry out modification by the method for ion-exchange to clay.Quaternary ammonium salt can reduce surface of clay polarity, and the interlamellar spacing expanding clay is with the interaction between lower layer, thus improves clay dispersion in the polymer.
Although aforesaid method improves the dispersiveness of clay, ignore the interaction between clay and polymkeric substance.The naturally occurring functional group of surface of clay is less, and cause the interface performance of clay and polymeric matrix poor, the external force suffered by material cannot be delivered to the filler of rigidity, thus the enhancement of filler is significantly weakened.Filler even can be transformed into additional impurity in extreme circumstances, the too early inefficacy of induced material, fracture.Meanwhile, quaternary ammonium salt thermally-stabilised lower, seriously limits its application in some high-melting-point polymer.Introduce active group by methods such as coupling agent and clay layer section hydroxyl direct reaction to be then subject to surface of clay and for the hydroxyl value quantitative limitation of reacting, the interfacial characteristics significantly improving clay can be difficult to.Meanwhile, due to the polarity difference of clay and polymkeric substance, often need to add compatilizer in the process preparing matrix material, as maleic anhydride grafted polymer etc., add production cost.
Summary of the invention
In order to overcome the deficiency in background technology, the invention discloses a kind of enhancement type Polyolefin/Clay Nanocomposites, and this enhancement type Polyolefin/Clay Nanocomposites preparation method.Clay consistency in the polymer can not only be improved with dispersed, more can introduce functional group in the mode of unusual simple and effective at surface of clay, thus between polymkeric substance and clay filler, build stronger interaction, the performance of gained matrix material is significantly promoted when not using any additive.
In order to realize described goal of the invention, the present invention adopts following technical scheme: a kind of enhancement type Polyolefin/Clay Nanocomposites, is polymerized by polyolefine and modified clay melt blending; Described modified clay reacts pre-treatment by the coupling agent containing double bond and forms; Described clay component comprises SiO
2and Al
2o
3, described clay is that granularity is less than 200 orders, structure is stratiform or fibrous aluminosilicate mineral powder.
Clay of the present invention is one or more in kaolin, mica, polynite, polygorskite, sepiolite, vermiculite.
One or more in the preferred kaolin of clay of the present invention, mica, polynite, polygorskite.
Polynite of the present invention is one or more mixtures in sodium-based montmorillonite or calcium-base montmorillonite.
The polymkeric substance of polyene hydrocarbons and their derivates of the present invention to be main chain be carbochain.
Polyene hydrocarbons and their derivates of the present invention is PE, PP, PS, PMMA, PVDF, PVC.
A preparation method for enhancement type Polyolefin/Clay Nanocomposites, comprises the following steps:
1) by undressed clay dispersion in solvent, preparation concentration be the suspension that 0.1-25wt% is stable.
2) under the condition of room temperature to 80 DEG C, pH value 3 ~ 11, add the coupling agent containing carbon-carbon double bond, itself and clay are reacted, the mass ratio of described coupling agent and clay is coupling agent: clay=10:1 ~ 1:100.
3) by step 2) in gained modified clay and polyene hydrocarbons and their derivates, radical initiator press and mix, prepare composite nano polymer/clay material by the method for melt blending.
The preparation method of enhancement type Polyolefin/Clay Nanocomposites of the present invention, in used solvent comprise water, alcohols, Benzene and Homologues, acetone, one or more in tetrahydrofuran (THF) or DMF.
Coupling agent of the present invention is titanate coupling agent, silane coupling agent or aluminic acid coupling agent containing carbon-carbon double bond.
Radical initiator of the present invention is thermal initiation radical initiator, comprises BPO, AIBN, DCP; In described composite nano polymer/clay material, clay content is 0.1-20wt%, and initiator content is 0.001-5wt%.
Owing to have employed technique scheme, the present invention has following beneficial effect: in the present invention, and without the need to reacting with quaternary ammonium salt, first clay is scattered in solvent, then reacts with the coupling agent containing double bond, obtains modified clay.In melt blending process, make the double bond in coupling agent open by the method for reactive blending, with polyolefine and derivatives reaction thereof, between clay and polyene hydrocarbons and their derivates, build the strong interaction of chemical bond.Utilize the shearing force of screw rod that clay is uniformly dispersed in the polymer, thus significantly improve the various aspects of performance such as material mechanical performance.
Accompanying drawing explanation
Fig. 1 be inventive samples E FESEM photo.
Fig. 2 be inventive samples J FESEM photo.
Embodiment
By explanation the present invention that the following examples can be detailed, disclose object of the present invention and be intended to protect all technological improvements in the scope of the invention.
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Use Instron5567 mechanical property tester, 50KN sensor, draw speed 50mm/min, probe temperature is 25 DEG C, and specimen shape meets ASTMD638V standard.
The modification of clay:
Embodiment 1
1 gram of polynite (MMT) is scattered in 50 grams of water, adds coupling agent Vinyltrichlorosilane0.5 gram, regulates pH to 4, and 50 DEG C are reacted 4 hours.Product centrifuge washing 3 times, 80 DEG C of vacuum dryings, to constant weight, obtain product A.
Embodiment 2
3 grams of micas are scattered in (water/ethanol=9/1, w/w) in 100 grams of water mixed alkoxide solutions, add coupling agent Vinyltris (β-methoxyethoxy) silane0.03 gram, regulate pH to 4.8, room temperature reaction 1 hour.Product centrifuge washing 3 times, 80 DEG C of vacuum dryings, to constant weight, obtain product B.
Embodiment 3
5 grams of kaolinites are scattered in 15 grams of water, add coupling agent Vinyltriethoxysilane50 gram, regulate pH to 3, and 80 DEG C are reacted 0.5 hour.Product centrifuge washing 3 times, 80 DEG C of vacuum dryings, to constant weight, obtain product C.
Embodiment 4
10 grams of polygorskites are scattered in 500 grams of water, add coupling agent Vinyltrimethoxysilane8 gram, regulate pH to 5, room temperature reaction 6 hours.Product centrifuge washing 3 times, 80 DEG C of vacuum dryings, to constant weight, obtain product D.
The preparation of matrix material:
Embodiment 5
1 gram of product A, 49 grams of PE and 0.5 gram DCP add twin screw extruder (L/D=40, screw speed 100rpm), and melt blending at 200 DEG C, obtains product E.
Embodiment 6
3 grams of product B, 47 grams of PP and 2.5 gram DCP add twin screw extruder (L/D=40, screw speed 80rpm), and melt blending at 220 DEG C, obtains product F.
Embodiment 7
0.05 gram of product C, 49.95 grams of PS and 0.5 milligram BPO add twin screw extruder (L/D=40, screw speed 50rpm), and melt blending at 225 DEG C, obtains product G.
Embodiment 8
10 grams of product D, 40 grams of PMMA and 0.75 gram AIBN add twin screw extruder (L/D=40, screw speed 50rpm), and melt blending at 220 DEG C, obtains product H.
Comparative example
Use traditional quaternary ammonium salt-modified clay.10g polynite and 1.2mol CETRIMIDE POWDER are at 90 DEG C of deionized water for stirring 4h, and cross and filter excess of solvent, product centrifuge washing 3 times, 80 DEG C of vacuum dryings, to constant weight, obtain product I.1 gram of product I, 49 grams of PE and 0.5 gram DCP add twin screw extruder (L/D=40, screw speed 100rpm), and melt blending at 200 DEG C, obtains product J.
In embodiment 5 ~ 10, the performance index of sample are as shown in Table 1:
The performance index of table one sample E ~ H
| Sample | Tensile modulus | Tensile strength | Elongation at break |
| E | +52％ | +28％ | -7％ |
| J | +19％ | +8％ | -37％ |
| F | +77％ | +39％ | -23％ |
| G | +26％ | +15％ | -7％ |
| H | +85％ | +33％ | -31％ |
Table two is unloaded straight polymer properties:
The unloaded straight polymer properties of table two
| Sample | Tensile modulus (GPa) | Tensile strength (MPa) | Elongation at break (%) |
| PE | 1.0 | 24 | 700 |
| PP | 1.1 | 30 | 230 |
| PS | 2.3 | 35 | 45 |
| PMMA | 2.7 | 65 | 3 |
As can be seen from the mechanical property of nano composite material shown in table one and table two and straight polymer obviously, use the modified clay prepared by the present invention, the mechanical property of gained nano composite material is increased dramatically, and elongation at break loss less (sample E, F, G and H).For PE, only the adding of 2wt% clay, tensile modulus and intensity improve 52% and 28% respectively; For polymkeric substance such as PP, PMMA and PS, have also been obtained the lifting of significantly mechanical property when lower clay addition.And for the said products, the reduction of elongation at break is but relatively slight, there is not the situation that general matrix material significantly reduces along with strength enhancing toughness.As a comparison, use the clay of traditional method modification, mechanical property promotes not obvious, and elongation at break loss comparatively large (product J), this also show the great function of clay alteration mode used in the present invention.
FESEM photo (Fig. 1) then indicates different clay treatment mode to the impact of its dispersiveness.Image right is the PE matrix material (sample E) using method therefor of the present invention to prepare, and clay layer presents peels off state distribution; And left side uses quaternary ammonium salt-modified sample (sample J), clay layer thickness reaches 200-600nm, obvious aggregate structure.Different clay dispersibility shows: use the clay prepared of traditional way, very weak with interpolymer interaction, be difficult to dispersed in the polymer by modes such as melt blendings and with raising material property; And use clay prepared by surface treatment mode of the present invention, with polymer compatibility, interact better, thus better can represent the enhancement of clay layer.
Part not in the detailed description of the invention is prior art.
Claims (10)
1. an enhancement type Polyolefin/Clay Nanocomposites, is characterized in that: be polymerized by polyene hydrocarbons and their derivates and modified clay melt blending; Described modified clay reacts pre-treatment by the coupling agent containing double bond and forms; Described clay component comprises SiO
2and Al
2o
3, described clay is that granularity is less than 200 orders, structure is stratiform or fibrous aluminosilicate mineral powder.
2. enhancement type Polyolefin/Clay Nanocomposites as claimed in claim 1, is characterized in that: described clay is one or more in kaolin, mica, polynite, polygorskite, sepiolite, vermiculite.
3. enhancement type Polyolefin/Clay Nanocomposites as claimed in claim 2, is characterized in that: one or more in the preferred kaolin of described clay, mica, polynite, polygorskite.
4. as claimed in claim 2 or claim 3 enhancement type Polyolefin/Clay Nanocomposites, is characterized in that: described polynite is one or more mixtures in sodium-based montmorillonite or calcium-base montmorillonite.
5. enhancement type Polyolefin/Clay Nanocomposites as claimed in claim 1, is characterized in that: the polymkeric substance of described polyene hydrocarbons and their derivates to be main chain be carbochain.
6. enhancement type Polyolefin/Clay Nanocomposites as claimed in claim 5, is characterized in that: described polyene hydrocarbons and their derivates is PE, PP, PS, PMMA, PVDF, PVC.
7. a preparation method for enhancement type Polyolefin/Clay Nanocomposites as claimed in claim 1, is characterized in that: comprise the following steps:
1) by undressed clay dispersion in solvent, preparation concentration be the suspension that 0.1-25wt% is stable;
2) under the condition of room temperature to 80 DEG C, pH value 3 ~ 11, add the coupling agent containing carbon-carbon double bond, itself and clay are reacted, the mass ratio of described coupling agent and clay is coupling agent: clay=10:1 ~ 1:100;
3) by step 2) in gained modified clay mix with polyene hydrocarbons and their derivates, radical initiator, prepare composite nano polymer/clay material by the method for melt blending.
8. the preparation method of enhancement type Polyolefin/Clay Nanocomposites as claimed in claim 7, is characterized in that: solvent used in step 1) comprises water, alcohols, Benzene and Homologues, acetone, one or more in tetrahydrofuran (THF) or DMF.
9. the preparation method of enhancement type Polyolefin/Clay Nanocomposites as claimed in claim 7, is characterized in that: described coupling agent is titanate coupling agent, silane coupling agent or aluminic acid coupling agent containing carbon-carbon double bond.
10. the preparation method of enhancement type Polyolefin/Clay Nanocomposites as claimed in claim 7, is characterized in that: described radical initiator is thermal initiation radical initiator, comprises BPO, AIBN, DCP; In described composite nano polymer/clay material, clay content is 0.1-20wt%, and initiator content is 0.001-5wt%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009206A (en) * | 2016-08-12 | 2016-10-12 | 安徽中杰信息科技有限公司 | Method for producing environmentally digestible plastic by using silane coupling agent |
| CN106750894A (en) * | 2016-11-18 | 2017-05-31 | 无锡明盛纺织机械有限公司 | A kind of nano composite material and its preparation method and application |
| CN107189281A (en) * | 2017-07-20 | 2017-09-22 | 安徽盛华管业有限公司 | It is a kind of to add wear-resisting toughening PVC tubing and the preparation method that rare-earth coupling agent activation vermiculite is modified |
| CN107868341A (en) * | 2017-12-12 | 2018-04-03 | 安徽申科塑业有限公司 | A kind of environmentally friendly nursery polybag and preparation method thereof |
| CN109111672A (en) * | 2018-06-27 | 2019-01-01 | 武汉工程大学 | A kind of acrylic ester grafted modified zeolite high temperature resistant composite and preparation method thereof |
| CN114479246A (en) * | 2022-02-23 | 2022-05-13 | 平安电气股份有限公司 | Method for preparing polyolefin composite material by using carbonaceous mudstone |
| CN117264433A (en) * | 2023-11-22 | 2023-12-22 | 潍坊云鼎新材料有限公司 | Plant fiber/polyethylene composite material and preparation method thereof |
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| CN1425710A (en) * | 2003-01-09 | 2003-06-25 | 上海交通大学 | Semitransparent triple ethylene-propylene rubber/montmorillonoid inserting nano composition material and its preparing method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009206A (en) * | 2016-08-12 | 2016-10-12 | 安徽中杰信息科技有限公司 | Method for producing environmentally digestible plastic by using silane coupling agent |
| CN106750894A (en) * | 2016-11-18 | 2017-05-31 | 无锡明盛纺织机械有限公司 | A kind of nano composite material and its preparation method and application |
| CN107189281A (en) * | 2017-07-20 | 2017-09-22 | 安徽盛华管业有限公司 | It is a kind of to add wear-resisting toughening PVC tubing and the preparation method that rare-earth coupling agent activation vermiculite is modified |
| CN107868341A (en) * | 2017-12-12 | 2018-04-03 | 安徽申科塑业有限公司 | A kind of environmentally friendly nursery polybag and preparation method thereof |
| CN109111672A (en) * | 2018-06-27 | 2019-01-01 | 武汉工程大学 | A kind of acrylic ester grafted modified zeolite high temperature resistant composite and preparation method thereof |
| CN114479246A (en) * | 2022-02-23 | 2022-05-13 | 平安电气股份有限公司 | Method for preparing polyolefin composite material by using carbonaceous mudstone |
| CN117264433A (en) * | 2023-11-22 | 2023-12-22 | 潍坊云鼎新材料有限公司 | Plant fiber/polyethylene composite material and preparation method thereof |
| CN117264433B (en) * | 2023-11-22 | 2024-03-26 | 潍坊云鼎新材料有限公司 | Plant fiber/polyethylene composite material and preparation method thereof |
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