CN102558714A - Polyvinyl chloride/modified nano montmorillonite compound material and preparation method thereof - Google Patents
Polyvinyl chloride/modified nano montmorillonite compound material and preparation method thereof Download PDFInfo
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- CN102558714A CN102558714A CN2011104588517A CN201110458851A CN102558714A CN 102558714 A CN102558714 A CN 102558714A CN 2011104588517 A CN2011104588517 A CN 2011104588517A CN 201110458851 A CN201110458851 A CN 201110458851A CN 102558714 A CN102558714 A CN 102558714A
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Abstract
The invention discloses a polyvinyl chloride/modified nano montmorillonite compound material, which belongs to the technical field of engineering, in particular to a high-filling non-plasticized polyvinyl chloride/modified nano montmorillonite compound material and a preparation method thereof. The polyvinyl chloride/modified nano montmorillonite compound material is prepared from the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 10-200 parts of nano montmorillonite, 1-6 parts of a surface modifier, 0-10 parts of a high molecular modifier, 1-8 parts of a thermal stabilizer and 0.2-5 parts of a lubricating agent. A series of compound materials with different toughness can be obtained by adjusting a formula according to different requirements, and a preparation process is simple and has high economical practicability.
Description
Technical field
The invention belongs to field of engineering technology, be specifically related to a kind of high filling not plasticized polyvinyl chloride/modified Nano smectite matrix material and preparation method thereof.
Background technology
SE (PVC) is that a kind of output is big, the resins for universal use of high comprehensive performance, has plurality of advantages such as good physics, mechanics, chemistry and electric property and flame retardant resistance, the transparency, chemical proofing.Along with the growth of economy, country widelys popularize and uses chemical building material, and the ratio of boardy product improves constantly in the PVC goods, and especially demand growth such as tubing, sheet material, section bar are rapid.Be performances such as the rigidity that improves the PVC goods, thermotolerance; In recent years, the research of relevant SE/organo montmorillonite (OMIT) nano composite material is active day by day, is on March 17th, 2004 as open day; Publication number is the Chinese invention patent of CN1482170A; Disclose a kind of SE/montmorillonite nano-composite material and preparation method thereof, its starting material comprise SE, intercalation resin (vinylchlorid one vinyl acetate copolymer, anti-impact type esters of acrylic acid) and organically modified montmorillonite clay, stablizer (lead salt, organotin, calcium stearate, barium stearate etc.) and processing aid; Adopt the mother material fusion intercalation to prepare; But these SE/organic montmorillonite nano composite materials of having reported belong to intercalation type nano composite material mostly, can not give full play to the nanoscale effect of nano-dispersed phase, and the compactedness of smectite is not high; The consumption of smectite in proportioning is little, and enhancing and mechanical property such as toughness reinforcing are undesirable; Even be scattered in the polymeric matrix after organic montmorillonite peeled off in matrix resin, mechanical property is also undesirable.
Summary of the invention
Above-mentioned defective to the prior art existence; One of the object of the invention is to provide a kind of can fill nano montmorillonite in a large number; Compactedness is higher; Can significantly reduce production costs, and not increase material plasticity, mechanical property SE/modified Nano smectite matrix material preferably such as strengthen and toughness reinforcing.
Another object of the present invention provides the preparation method of a kind of above-mentioned SE/modified Nano smectite matrix material.
Polyvinyl chloride/nano smectite matrix material of the present invention is processed by the following weight parts proportion raw material: 100 parts of SE, 10-200 parts of nano montmorillonites; Surface-modifying agent is I-6 part; 0-10 parts of macromolecule modifiers, 1-8 parts of thermo-stabilizers, 0.2-5 parts of lubricants.
The polymerization degree of SE used in the present invention is 700-4000.
The particle diameter of nano montmorillonite used in the present invention is not more than 6 μ m.
Surface-modifying agent used in the present invention is selected from one or more mixtures in titanate coupling agent, zirconium aluminate, aluminic acid ester, SULPHOSUCCINIC ACID ESTER, silane coupling agent, higher fatty acid and salt thereof, non-ionics, two (2 one hydroxyethyl) methyl tallow based quaternary ammonium salt, octadecyl tribromide ammonium, its chlorinated polypropylene wax and OPE, the polyoxyethylene glycol.
Macromolecule modifier used in the present invention is selected from one or more mixtures of chlorinatedpolyethylene (CPE), polyacrylic ester (ACR), all acrylic ester class (AIM), ethene one acetate ethylene copolymer (EVA), methyl acrylate-butadiene-styrene ternary graft copolymers (MBS), acrylonitrile-butadiene-styrene copolymer (ABS) type anti-impact macromolecule modifier.
Thermo-stabilizer used in the present invention is organotin stabilizer or lead salt stabilizer, is selected from one or more mixtures in dibutyl tin laurate, two LAURIC ACID 99 MIN dioctyl tins, dialkyl group toxilic acid dibutyl tin, two (Thiovanic acid isooctyl acrylate) dibutyl tin, LAURIC ACID 99 MIN toxilic acid dibutyl tin, tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead phthalate, two alkali formula lead phosphates, the lead stearate.
Lubricant used in the present invention comprises one or more mixtures in paraffin, Triple Pressed Stearic Acid, barium stearate, calcium stearate, Zinic stearas, the OPE.
SE according to the invention/modified Nano smectite matrix material preferred manufacturing procedure is made up of following steps successively:
(1) with nano montmorillonite ll0-130 ℃ preheating and drying 2-4 hour;
(2) the surface-treated dilution agent is made into the solution of 5-15wt% with 60-90 ℃ of sherwood oils;
(3) in high-speed mixer, will, step (2) join in the nano montmorillonite by the surface-treated agent solution after handling, and high-speed stirring was handled 10-40 minutes, made the modified Nano smectite;
(4) by above-mentioned weight part ratio SE, macromolecule modifier, thermo-stabilizer, lubricant and modified Nano smectite are mixed in the high speed kneader; Discharging after being 80-90 ℃ to temperature, then in two roller mills in 170-180 ℃ of following melt blending 20-40min.
The invention has the beneficial effects as follows through adopting surface-modifying agent that the surface and the edge of nano montmorillonite are carried out the coupling modification, make organic group be covered in the smectite surface, change its surface property; Thereby make smectite change into the organic montmorillonite of oleophilic drainage, and have good affinity, through after the surface-treated with most of organic solvents and polymer by hydrophilic oleophobic; The interlamellar spacing of smectite increases to 2nm or bigger about by 1nm; And rely on the interaction of smectite and polymkeric substance, make the silicate lamella progressively be dissociated into thickness less than 50nm, grow * wide be the basic nano unit of 100nm * 100nm; And evenly spread in the matrix; The final nano montmorillonite that particle diameter is not more than 6 μ m of realizing is dispersed in the PVC RESINS, has given full play to the nanoscale effect of nano-dispersed phase, has improved the compactedness of nano montmorillonite in PVC RESINS; Reduce the production cost of material effectively, and can not increase the plasticity of material; In addition owing to after having added macromolecule modifier and stablizer, improved the shock resistance and the stability of material, enhancing and toughness reinforcing mechanics effect are more satisfactory.Compare with existing organic cation intercal type remodeling technology, technology of the present invention is simpler, and production cost is lower, and mechanical properties such as the shock resistance of material are better.
The present invention is according to demands of different; Can be through the adjustment prescription; Like ratio of the content of nano montmorillonite, nano montmorillonite surface-treated kind and consumption, nano montmorillonite and macromolecule modifier etc. and obtain a series of different flexible matrix materials that have; And preparation technology is simple, and economic and practical is strong.
Embodiment
Following embodiment can make those skilled in the art more comprehensively understand the present invention, but does not limit the present invention in any way.
EXAMPLE l
Get the nano montmorillonite and the surface-modifying agent of predetermined weight part by table l prescription, earlier with nano montmorillonite l30 ℃ of preheating and drying 2 hours, the surface-treated dilution agent is made into the solution of 5wt% with 90 ℃ of sherwood oils; The back joins the surface-modifying agent diluent in the nano montmorillonite in high-speed mixer, and high-speed stirring was handled 10 minutes, made the modified Nano smectite; Mix in the high speed kneader by the various materials and the modified Nano smectite of table l prescription predetermined weight part, be 80 ℃ to temperature after discharging.Behind 180 ℃ of following melt blending 20min, descending sheet in two roller mills, require sample preparation, test result to see table 2 then according to GB.
Embodiment 2
Get the nano montmorillonite and the surface-modifying agent of predetermined weight part by table l prescription, earlier with nano montmorillonite 110 ℃ of preheating and dryings 4 hours, the surface-treated dilution agent is made into the solution of 10wt% with 60 ℃ of sherwood oils; The back joins the surface-modifying agent diluent in the nano montmorillonite in high-speed mixer, and high-speed stirring was handled 20 minutes, made the modified Nano smectite; Mix in the high speed kneader by the various materials and the modified Nano smectite of table l prescription predetermined weight part, be 80 ℃ to temperature after discharging.Behind 175 ℃ of following melt blending 30min, descending sheet in two roller mills, require sample preparation, test result to see table 2 according to GB then, all the other are with embodiment 1.
Embodiment 3
Get the nano montmorillonite and the surface-modifying agent of predetermined weight part by table l prescription, earlier with nano montmorillonite 120 ℃ of preheating and dryings 3 hours, the surface-treated dilution agent is made into the solution of 10wt% with 80 ℃ of sherwood oils; The back joins the surface-modifying agent diluent in the nano montmorillonite in high-speed mixer, and high-speed stirring was handled 30 minutes, made the modified Nano smectite; Mix in the high speed kneader by the various materials and the modified Nano smectite of table l prescription predetermined weight part, be 90 ℃ to temperature after discharging.Behind 170 ℃ of following melt blending 40min, descending sheet in two roller mills, require sample preparation, test result to see table 2 according to GB then, all the other are with embodiment 1.
Embodiment 4
Get the nano montmorillonite and the surface-modifying agent of predetermined weight part by table l prescription, earlier with nano montmorillonite 120 ℃ of preheating and dryings 4 hours, the surface-treated dilution agent is made into the solution of 15wt% with 90 ℃ of sherwood oils; The back joins the surface-modifying agent diluent in the nano montmorillonite in high-speed mixer, and high-speed stirring was handled 40 minutes, made the modified Nano smectite; By table l prescription various materials of predetermined weight part and modified Nano smectite are mixed in the high speed kneader, be 90 ℃ to temperature after discharging.Behind 175 ℃ of following melt blending 30min, descending sheet in two roller mills, require sample preparation, test result to see table 2 according to GB then, all the other are with embodiment 1.
The weight part prescription of table 1 SE (PVC) smectite matrix material
The test result of table 2 SE (PVC) smectite matrix material
Claims (9)
1. SE/modified Nano smectite matrix material; It is characterized in that it is to be processed by the following weight parts proportion raw material: 100 parts of SE; 10-200 parts of nano montmorillonites, surface-modifying agent are I-6 part, 0-10 parts of macromolecule modifiers; 1-8 parts of thermo-stabilizers, 0.2-5 parts of lubricants.
2. a kind of SE according to claim 1/modified Nano smectite matrix material, the polymerization degree that it is characterized in that described SE is 700-4000.
3. a kind of SE according to claim 1/modified Nano smectite matrix material is characterized in that the particle diameter of described nano montmorillonite is not more than 6 μ m.
4. a kind of SE according to claim 1/modified Nano smectite matrix material is characterized in that described surface-modifying agent is selected from one or more mixtures in titanate coupling agent, zirconium aluminate, aluminic acid ester, SULPHOSUCCINIC ACID ESTER, silane coupling agent, higher fatty acid and salt thereof, non-ionics, two (2 one hydroxyethyl) methyl tallow based quaternary ammonium salt, octadecyl tribromide ammonium, its chlorinated polypropylene wax and OPE, the polyoxyethylene glycol.
5. a kind of SE according to claim 1/modified Nano smectite matrix material is characterized in that described macromolecule modifier is selected from one or more mixtures in chlorinatedpolyethylene (CPE), polyacrylic ester (ACR), all acrylic ester class (AIM), ethene one acetate ethylene copolymer (EVA), methyl acrylate-butadiene-styrene ternary graft copolymers (MBS), acrylonitrile-butadiene-styrene copolymer (ABS) type anti-impact macromolecule modifier.
6. a kind of SE according to claim 1/modified Nano smectite matrix material is characterized in that described thermo-stabilizer is organotin stabilizer or lead salt stabilizer.
7. a kind of SE according to claim 6/modified Nano smectite matrix material is characterized in that described thermo-stabilizer is selected from one or more mixtures in dibutyl tin laurate, two LAURIC ACID 99 MIN dioctyl tins, dialkyl group toxilic acid dibutyl tin, two (Thiovanic acid isooctyl acrylate) dibutyl tin, LAURIC ACID 99 MIN toxilic acid dibutyl tin, tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead phthalate, two alkali formula lead phosphates, the lead stearate.
8. a kind of SE according to claim 1/modified Nano smectite matrix material is characterized in that described lubricant is selected from one or more mixtures in paraffin, Triple Pressed Stearic Acid, barium stearate, calcium stearate, Zinic stearas, the OPE.
9. method for preparing the described a kind of SE of claim 1/modified Nano smectite matrix material is characterized in that this method may further comprise the steps composition:
(1) with nano montmorillonite ll0-130 ℃ preheating and drying 2-4 hour;
(2) the surface-treated dilution agent is made into the solution of 5-15wt% with 60-90 ℃ of sherwood oils;
(3) in high-speed mixer, will, step (2) join in the nano montmorillonite by the surface-treated agent solution after handling, and high-speed stirring was handled 10-40 minutes, made the modified Nano smectite;
(4) by above-mentioned weight part ratio SE, macromolecule modifier, thermo-stabilizer, lubricant and modified Nano smectite are mixed in the high speed kneader; Discharging after being 80-90 ℃ to temperature, then in two roller mills in 170-180 ℃ of following melt blending 20-40min.
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Cited By (5)
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| CN104479239A (en) * | 2014-11-07 | 2015-04-01 | 安徽省三乐门窗幕墙工程有限公司 | Antioxidation door-window plastic-steel section material and preparation method thereof |
| CN105860335A (en) * | 2016-04-25 | 2016-08-17 | 广西隆安瑞丰工贸有限公司 | Preparation method of novel PVC (polyvinyl chloride) heat stabilizer |
| CN106633533A (en) * | 2016-12-31 | 2017-05-10 | 永高股份有限公司 | Composite material for high-impact polyvinyl chloride reinforced pipe |
| CN110644917A (en) * | 2019-07-22 | 2020-01-03 | 国网浙江省电力有限公司湖州供电公司 | 500kV insulating horizontal ladder cross bidirectional rotary support |
| CN112300511A (en) * | 2019-07-26 | 2021-02-02 | 北京梦之墨科技有限公司 | Metal-phobic high-molecular material, metal-phobic part and liquid metal-based equipment |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104479239A (en) * | 2014-11-07 | 2015-04-01 | 安徽省三乐门窗幕墙工程有限公司 | Antioxidation door-window plastic-steel section material and preparation method thereof |
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| CN106633533A (en) * | 2016-12-31 | 2017-05-10 | 永高股份有限公司 | Composite material for high-impact polyvinyl chloride reinforced pipe |
| CN110644917A (en) * | 2019-07-22 | 2020-01-03 | 国网浙江省电力有限公司湖州供电公司 | 500kV insulating horizontal ladder cross bidirectional rotary support |
| CN112300511A (en) * | 2019-07-26 | 2021-02-02 | 北京梦之墨科技有限公司 | Metal-phobic high-molecular material, metal-phobic part and liquid metal-based equipment |
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