CN102276906B - Modified ethane-vinyl alcohol copolymer composite material and preparation technology thereof - Google Patents
Modified ethane-vinyl alcohol copolymer composite material and preparation technology thereof Download PDFInfo
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- CN102276906B CN102276906B CN2011101895119A CN201110189511A CN102276906B CN 102276906 B CN102276906 B CN 102276906B CN 2011101895119 A CN2011101895119 A CN 2011101895119A CN 201110189511 A CN201110189511 A CN 201110189511A CN 102276906 B CN102276906 B CN 102276906B
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Abstract
A modified ethane-vinyl alcohol copolymer composite material and a preparation technology thereof. The modified ethane-vinyl alcohol copolymer composite material comprises: by weight, 10 to 50% of calcium sulfate, 10 to 40% of maize starch, 20 to 60%of an ethane-vinyl alcohol copolymer, 1 to 10% of a stabilizing agent, 1 to 10% of an anti-oxidant and 1 to 20% of an eleaostearic acid. The invention also comprises the preparation technology of the modified ethane-vinyl alcohol copolymer composite material. The modified ethane-vinyl alcohol copolymer composite material has good mechanical properties, a low manufacturing cost and a good biodegradability, can replace natural for utilization in the fields of indoor and outdoor decoration, building industries and the like, and opens a new approach for reduction of waste and old plastic products and improvement of a calcium sulfate comprehensive utilization ratio.
Description
Technical field
The present invention relates to a kind of ethylene-vinyl alcohol copolymer matrix material and preparation technology thereof, especially relate to a kind of modified ethylene vinyl alcohol copolymer matrix material and preparation technology thereof.
Background technology
Ethylene-vinyl alcohol copolymer (EVOH) is to use maximum high barrier material always.The film of this material also has two-way stretch type, aluminium-vapour deposition type, tamanori application type etc. except non-stretching type, the two-way stretch type also comprises heat resistant type, is mainly used in the sterile packed goods.
The barrier property of EVOH depends on the content of ethene, and in general when ethylene content increased, barrier properties for gases descended, but is easy to processing.
The EVOH distinguishing feature is that gas is had fabulous barrier and fabulous processibility, and in addition, the transparency, glossiness, physical strength, retractility, wear resistance, winter hardiness and surface strength are all very excellent.
At packaging field, EVOH processes the composite package intermediate barrier layer, is applied in all rigid and flexible packagings; In grocery trade, be used for sterile packed, heat jar and pressure pad, packing milk preparation, meat, canned fruit and seasonings; Aspect non-food product, be used for packing solvent, pharmaceutical chemicals, air conditioner structure spare, gasoline can liner, electronic component etc.Aspect food product pack, the plastic containers of EVOH fully can instead of glass and metal vessel, and domestic how tame aquatic products company outlet seafood just uses PE/EVOH/PA/RVOH/PE five-layer co-squeezing membrane vacuum-packed.Accelerating the research of EVOH composite package simultaneously, abroad also at research EVOH stretch orientation, new E VOH film is 3 times of existing high performance non-stretching EVOH film to the barrier property of gas.EVOH also can be used as barrier material and is coated on other synthetic resin packaging materials in addition, plays to strengthen the barrier property effect.
The EVOH product not only can be used for the production of film aspect, can also apply to aspects such as makeup soft packaging, ground heating pipes, jelly cup and pesticide bottle in a large number.
But the ethylene-vinyl alcohol copolymer manufacturing cost is high, is difficult for degraded, makes its application receive certain limitation.
Summary of the invention
The technical problem that the present invention will solve is, overcomes the deficiency of prior art, provides a kind of mechanical property good, and low cost of manufacture is prone to the modified ethylene vinyl alcohol copolymer matrix material and the preparation technology thereof of degraded.
The present invention solve the technical problem the technical scheme that is adopted:
The present invention's modified ethylene vinyl alcohol copolymer matrix material; Process by following raw materials by weight percent: calcium sulfate 10-50wt%; W-Gum 10-40wt%, ethylene-vinyl alcohol copolymer (EVOH) 20-60wt%, stablizer 1-10wt%; Oxidation inhibitor 1-10wt%, Triple Pressed Stearic Acid 1-20wt%.
Preferred weight percent is: calcium sulfate 15wt%, W-Gum 20wt%, ethylene-vinyl alcohol copolymer (EVOH) 60wt%, stablizer 1wt%, oxidation inhibitor 1wt%, Triple Pressed Stearic Acid 3wt%.
Said stablizer can be optothermal stabilizer T-68.
Said oxidation inhibitor can be 1010.
The preparation technology of the present invention's modified ethylene vinyl alcohol copolymer matrix material may further comprise the steps:
(1) calcium sulfate is pulverized, crossed 100 mesh sieves, place the dry 23-25 of baking oven hour (preferred 24 hours) of 75-85 ℃ (preferred 80 ℃); Dry back adds in the high-speed mixer, adds oxidation inhibitor and Triple Pressed Stearic Acid, mixes 12-18 minute (preferred 15 minutes) down at 45-55 ℃ (preferred 50 ℃);
(2) W-Gum being dried to water cut is below 3%;
(3) ethylene-vinyl alcohol copolymer is placed warm air drying treatment 2-4 hour (preferred 3 hours) or vacuum-drying 4-6 hour (preferred 5 hours) of 95-105 ℃ (preferred 100 ℃);
(4) with mixing 15-25 minute (preferred 20 minutes) in the dried ethylene-vinyl alcohol copolymer adding of stablizer, step (1) gained mixture, the dried W-Gum of step (2) and step (3) high-speed mixer;
(5) place forcing machine to extrude in step (4) gained mixture, granulation.
The present invention adds Triple Pressed Stearic Acid calcium sulfate is carried out the surface active modification, improves the consistency of calcium sulfate and W-Gum, can improve the flowability of melt and the surface flatness of matrix material as lubricant simultaneously.
The present invention is with modification calcium sulfate, W-Gum, EVOH three's uniform mixing; Improved the flowability of material; Reduce the stress concentration at interface between calcium sulfate, W-Gum, the EVOH, increased interfacial layer thickness, improved the mechanical property of matrix material on the whole.
The present invention's modified ethylene vinyl alcohol copolymer matrix material; Mechanical property is good, and low cost of manufacture is prone to degraded; Can replace natural timber to be used for fields such as indoor and outdoor decoration, construction industry, for the harm that reduces waste or used plastics and the comprehensive utilization ratio that improves calcium sulfate are also opened up a new way.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explain.
Each embodiment raw material weight proportioning is seen table 1.
Each embodiment specifications of raw materials, provider are following:
Calcium sulfate, Hebei Xingtai Shuanghua Plaster Products Co., Ltd.;
W-Gum, the farsighted development in science and technology ltd that reaches of Wuhan dragon;
EVOH, SP451B, plastic cement ltd of Dongguan HTC;
Stabilizer T-68, Hangzhou are matched happy chemical industry ltd;
Antioxidant 1010, Nanjing Jia Yin Science and Technology Ltd.;
Triple Pressed Stearic Acid, the Shanghai card is won industry and trade ltd.
The preparation method:
(1) calcium sulfate is pulverized, crossed 100 mesh sieves, place 80 ℃ dry 24 hours of baking oven; Dry back adds in the high-speed mixer, adds antioxidant 1010 and Triple Pressed Stearic Acid, mixes 15 minutes down at 50 ℃;
(2) W-Gum being dried to water cut is 2%;
(3) ethylene-vinyl alcohol copolymer is placed 100 ℃ warm air drying treatment 3 hours;
(4) with mixing 20 minutes in the dried ethylene-vinyl alcohol copolymer adding of stablizer, step (1) gained mixture, the dried W-Gum of step (2) and step (3) high-speed mixer;
(5) place forcing machine to extrude in step (4) gained mixture, granulation.The surface is glossy during extruding pelletization, flows steadily.
Each embodiment product performance detects; Tensile strength is pressed the test of GB/T 1040-92 prescriptive procedure; Flexural strength is pressed the test of GB/T 1936. 1-1991 prescriptive procedures, and shock strength is pressed the test of GB/T 1043-93 prescriptive procedure, and degradation rate is pressed the test of GB/T 19276.2 prescriptive procedures.The result sees table 2.
Table 1 embodiment 1-3 raw material weight proportioning
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Calcium sulfate (kg) | 15 | 15 | 20 |
| W-Gum (kg) | 20 | 25 | 20 |
| EVOH（kg） | 60 | 55 | 50 |
| Stabilizer T-68 (kg) | 1 | 1 | 1 |
| Antioxidant 1010 (kg) | 1 | 1 | 1 |
| Triple Pressed Stearic Acid (kg) | 3 | 3 | 8 |
Table 2 embodiment 1-3 product performance detected result relatively
| ? | Tensile strength (MPa) | Flexural strength (MPa) | Shock strength (KJ/m 2） | Degradation rate (%) |
| Embodiment 1 | 35．4 | 10．4 | 68．7 | 55.6 |
| Embodiment 2 | 34．8 | 9．7 | 65．4 | 52．3 |
| Embodiment 3 | 34．1 | 9．1 | 62．3 | 50.7 |
Claims (6)
1. a modified ethylene vinyl alcohol copolymer matrix material is characterized in that, is processed by following raw materials by weight percent: calcium sulfate 15wt%; W-Gum 20wt%, ethylene-vinyl alcohol copolymer 60wt%, stablizer 1wt%; Oxidation inhibitor 1wt%, Triple Pressed Stearic Acid 3wt%.
2. a modified ethylene vinyl alcohol copolymer matrix material is characterized in that, is processed by following raw materials by weight percent: calcium sulfate 15wt%; W-Gum 25wt%, ethylene-vinyl alcohol copolymer 55wt%, stablizer 1wt%; Oxidation inhibitor 1wt%, Triple Pressed Stearic Acid 3wt%.
3. a modified ethylene vinyl alcohol copolymer matrix material is characterized in that, is processed by following raw materials by weight percent: calcium sulfate 20wt%; W-Gum 20wt%, ethylene-vinyl alcohol copolymer 50wt%, stablizer 1wt%; Oxidation inhibitor 1wt%, Triple Pressed Stearic Acid 8wt%.
4. according to claim 1 or 2 or 3 described modified ethylene vinyl alcohol copolymer matrix materials, it is characterized in that said stablizer is optothermal stabilizer T-68, said oxidation inhibitor is antioxidant 1010.
5. the preparation technology like the said modified ethylene vinyl alcohol copolymer matrix material of one of claim 1-4 is characterized in that, may further comprise the steps:
(1) calcium sulfate is pulverized, crossed 100 mesh sieves, place 75-85 ℃ the dry 23-25 of baking oven hour; Dry back adds in the high-speed mixer, adds oxidation inhibitor and Triple Pressed Stearic Acid, mixes 12-18 minute down at 45-55 ℃;
(2) W-Gum being dried to water cut is below 3%;
(3) ethylene-vinyl alcohol copolymer is placed 95-105 ℃ warm air drying treatment 2-4 hour or vacuum-drying 4-6 hour;
(4) with mixing 15-25 minute in the dried ethylene-vinyl alcohol copolymer adding of stablizer, step (1) gained mixture, the dried W-Gum of step (2) and step (3) high-speed mixer;
(5) place forcing machine to extrude in step (4) gained mixture, granulation.
6. the preparation technology of modified ethylene vinyl alcohol copolymer matrix material according to claim 5 is characterized in that, may further comprise the steps:
(1) calcium sulfate is pulverized, crossed 100 mesh sieves, place 80 ℃ dry 24 hours of baking oven; Dry back adds in the high-speed mixer, adds oxidation inhibitor and Triple Pressed Stearic Acid, mixes 15 minutes down at 50 ℃;
(2) W-Gum being dried to water cut is below 3%;
(3) ethylene-vinyl alcohol copolymer is placed 100 ℃ warm air drying treatment 3 hours or vacuum-drying 5 hours;
(4) with mixing 20 minutes in the dried ethylene-vinyl alcohol copolymer adding of stablizer, step (1) gained mixture, the dried W-Gum of step (2) and step (3) high-speed mixer;
(5) place forcing machine to extrude in step (4) gained mixture, granulation.
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| CN103819801B (en) * | 2014-03-13 | 2016-03-30 | 福建师范大学 | A kind of polyolefin-based wood plastic composite and preparation method thereof |
| CN103819949B (en) * | 2014-03-13 | 2015-04-29 | 福建师范大学 | Surface modification method for inorganic powder |
| CN103819809B (en) * | 2014-03-19 | 2016-05-04 | 福建师范大学 | A kind of ethylene-vinyl alcohol copolymer base wood-plastic composite material |
| CN103834093B (en) * | 2014-03-19 | 2016-08-17 | 福建师范大学 | A kind of ethylene-vinyl alcohol copolymer sill plastic composite board |
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| CN1597751A (en) * | 2004-08-03 | 2005-03-23 | 王茜 | Raw material of fully bios degradation plastic and preparation process thereof |
| CN101649072A (en) * | 2009-09-22 | 2010-02-17 | 任伟 | Full-degradable biological material and film product thereof |
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| CN1597751A (en) * | 2004-08-03 | 2005-03-23 | 王茜 | Raw material of fully bios degradation plastic and preparation process thereof |
| CN101649072A (en) * | 2009-09-22 | 2010-02-17 | 任伟 | Full-degradable biological material and film product thereof |
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