CN102276906A - 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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- CN102276906A CN102276906A CN2011101895119A CN201110189511A CN102276906A CN 102276906 A CN102276906 A CN 102276906A CN 2011101895119 A CN2011101895119 A CN 2011101895119A CN 201110189511 A CN201110189511 A CN 201110189511A CN 102276906 A CN102276906 A CN 102276906A
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- vinyl alcohol
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- ethylene
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- 238000005516 engineering process Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 title abstract description 7
- 229920001577 copolymer Polymers 0.000 title abstract 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 43
- 239000011159 matrix material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical class OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims description 11
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000007601 warm air drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 238000005034 decoration Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 229920002261 Corn starch Polymers 0.000 abstract 1
- 235000019759 Maize starch Nutrition 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 abstract 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 17
- 230000004888 barrier function Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 206010020675 Hypermetropia Diseases 0.000 description 1
- -1 SP451B Polymers 0.000 description 1
- CCTYIJIKDVBOTE-UHFFFAOYSA-L calcium;octadecanoic acid;sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O.CCCCCCCCCCCCCCCCCC(O)=O CCTYIJIKDVBOTE-UHFFFAOYSA-L 0.000 description 1
- 235000013574 canned fruits Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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 makes the composite membrane 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 is just used the vacuum packaging of PE/EVOH/PA/RVOH/PE five-layer co-squeezing membrane.Accelerating the research of EVOH composite membrane 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 ethylene-vinyl alcohol copolymer manufacturing cost height is difficult for degraded, makes its application be subjected to certain limitation.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, provides a kind of mechanical property good, low cost of manufacture, easily 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, make 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%, 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%, stearic acid 3wt%.
Described stablizer can be optothermal stabilizer T-68.
Described 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 stearic acid, mixes 12-18 minute (preferred 15 minutes) down at 45-55 ℃ (preferred 50 ℃);
(2) W-Gum being dried to water content 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) will mix 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 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, low cost of manufacture, more easily 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 described in further detail.
Each embodiment raw material weight proportioning sees Table 1.
Each embodiment specifications of raw materials, provider are as follows:
Calcium sulfate, Hebei Xingtai Shuanghua Plaster Products Co., Ltd.;
W-Gum, the farsighted development in science and technology company limited that reaches of Wuhan dragon;
EVOH, SP451B, plastic cement company limited of Dongguan HTC;
Stabilizer T-68, Hangzhou are matched happy chemical industry company limited;
Antioxidant 1010, Nanjing Jia Yin Science and Technology Ltd.;
Stearic acid, the Shanghai card is won industry and trade company limited.
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 stearic acid, mixes 15 minutes down at 50 ℃;
(2) W-Gum being dried to water content is 2%;
(3) ethylene-vinyl alcohol copolymer is placed 100 ℃ warm air drying treatment 3 hours;
(4) will mix 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 results are shown in 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 |
| 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 (5)
1. modified ethylene vinyl alcohol copolymer matrix material, it is characterized in that, make by following raw materials by weight percent: calcium sulfate 10-50wt%, W-Gum 10-40wt%, ethylene-vinyl alcohol copolymer 20-60wt%, stablizer 1-10wt%, oxidation inhibitor 1-10wt%, stearic acid 1-20wt%.
2. modified ethylene vinyl alcohol copolymer matrix material according to claim 1 is characterized in that, is made by following raw materials by weight percent: calcium sulfate 15wt%, W-Gum 20wt%, ethylene-vinyl alcohol copolymer 60wt%, stablizer 1wt%, oxidation inhibitor 1wt%, stearic acid 3wt%.
3. modified ethylene vinyl alcohol copolymer matrix material according to claim 1 and 2 is characterized in that, described stablizer is optothermal stabilizer T-68, and described oxidation inhibitor is antioxidant 1010.
4. the preparation technology of modified ethylene vinyl alcohol copolymer matrix material as claimed in claim 1 or 2 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 stearic acid, mixes 12-18 minute down at 45-55 ℃;
(2) W-Gum being dried to water content 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) will mix 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.
5. the preparation technology of modified ethylene vinyl alcohol copolymer matrix material according to claim 4 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 stearic acid, mixes 15 minutes down at 50 ℃;
(2) W-Gum being dried to water content is below 3%;
(3) ethylene-vinyl alcohol copolymer is placed 100 ℃ warm air drying treatment 3 hours or vacuum-drying 5 hours;
(4) will mix 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101895119A CN102276906B (en) | 2011-07-07 | 2011-07-07 | Modified ethane-vinyl alcohol copolymer composite material and preparation technology thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101895119A CN102276906B (en) | 2011-07-07 | 2011-07-07 | Modified ethane-vinyl alcohol copolymer composite material and preparation technology thereof |
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| Publication Number | Publication Date |
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| CN102276906A true CN102276906A (en) | 2011-12-14 |
| CN102276906B CN102276906B (en) | 2012-11-28 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819809A (en) * | 2014-03-19 | 2014-05-28 | 福建师范大学 | EVOH (Ethylene-Vinyl Alcohol Copolymer) based wood-plastic composite material and preparation method thereof |
| CN103819801A (en) * | 2014-03-13 | 2014-05-28 | 福建师范大学 | Polyolefin wood-plastic composite and preparation method thereof |
| CN103819949A (en) * | 2014-03-13 | 2014-05-28 | 福建师范大学 | Surface modification method for inorganic powder |
| CN103834093A (en) * | 2014-03-19 | 2014-06-04 | 福建师范大学 | Ethylene-vinyl alcohol copolymer-based wood/plastic composite board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2011
- 2011-07-07 CN CN2011101895119A patent/CN102276906B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819801A (en) * | 2014-03-13 | 2014-05-28 | 福建师范大学 | Polyolefin wood-plastic composite and preparation method thereof |
| CN103819949A (en) * | 2014-03-13 | 2014-05-28 | 福建师范大学 | Surface modification method for inorganic powder |
| 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 |
| CN103819809A (en) * | 2014-03-19 | 2014-05-28 | 福建师范大学 | EVOH (Ethylene-Vinyl Alcohol Copolymer) based wood-plastic composite material and preparation method thereof |
| CN103834093A (en) * | 2014-03-19 | 2014-06-04 | 福建师范大学 | Ethylene-vinyl alcohol copolymer-based wood/plastic composite board |
| 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 |
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| CN102276906B (en) | 2012-11-28 |
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