CN1164666C - Polyethylene/nylon blend separation material - Google Patents
Polyethylene/nylon blend separation material Download PDFInfo
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- CN1164666C CN1164666C CNB011066970A CN01106697A CN1164666C CN 1164666 C CN1164666 C CN 1164666C CN B011066970 A CNB011066970 A CN B011066970A CN 01106697 A CN01106697 A CN 01106697A CN 1164666 C CN1164666 C CN 1164666C
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- nylon
- vinyl alcohol
- alcohol copolymer
- polyethylene
- barrier material
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Abstract
The present invention relates to a macromolecule alloy material, namely, lyethylene /nylon blend barrier material having good barrier performance for an organic solvent. The material is formed by blending polyethylene, nylon and a nylon grafted ethene-vinyl alcohol copolymer. The material form a hollow container product, and thin layered nylon discontinuous phases which are mutually parallel and are mutually overlapped can be formed in the container wall of the product. The present invention has an excellent barrier effect on the organic solvent and can be widely applied to the fields of automobile fuel tanks, pesticide packaging, paint packaging, cosmetic packaging, etc.
Description
The present invention relates to a kind ofly has the high molecule alloy material of excellent barrier properties, a kind of specifically polyethylene/nylon blend separation material and goods thereof to organic solvent.
Organic solvent or the storage, packing etc. that relate to the product (as agricultural chemicals, paint etc.) of organic solvent to aspect, a lot of producers adopt metal or Glass Containers, but owing to reasons such as metal cost height, easy-to-rust, Glass breadks easilies, increasing manufacturer tends to use polyolefine material to replace metal and glass applications in the storage and the packing of the product that relates to organic solvent, yet polyolefine is relatively poor to the barriering effect of organic solvent (particularly varsol), cause the organic solvent seepage, cause environmental pollution.The present invention relates to a kind of polyethylene alloy material that organic solvent is had the good barrier effect, this material is used for organic solvent or relates to the storage and the packing of the product of organic solvent, can effectively intercept the seepage of organic solvent, can be applicable to fields such as fuel tank of vehicle, pesticides packaging, paint packing and cosmetic package.
Polyolefine material is carried out modification, and numerous with the patent that improves its barrier property, the method that is provided mainly contains three classes:
First kind method is that in type vessel prepd internal surface is carried out special processing, as fluoridize or the sulfonation processing, improve its barrier property, all these class methods are had illustrated as patents such as CN 2 299 025, US 4 467 075, US 4,394 333, JP 55-80439 to organic solvent.But this surface-treated method, complicated operation may cause new environmental pollution, and can not implement for this method of container in irregular shape.
Second class methods are to adopt multi-layer co-extruded technology, make wall of container form multilayered structure, to improve its barrier property, all provide multi-layer co-extruded technology to produce container as JP 59-103727, US 5 695 839, US 5 679 425 etc.This method complex process, production unit needs particular design, and production cost is higher.
Owing to above reason, adopt the 3rd class methods at present in the world mostly, promptly so-called " lamination (Laminar) bottle blowing method ", this method is utilized blend such as polyolefine, separating polymer, expanding material, cooperate suitable moulding process again, through slush molding is vessel prepd, can form in wall of container that multilayer is parallel to each other, discontinuous obstruct phase, can improve its barrier property to organic solvent greatly.
In patent CN 1 166 399, the method that people such as Xu's happy have introduced a kind of irradiation increase-volume prepares the high barrier high-density polyethylene material.This method mainly is under the x ray irradiation x situation, introduce polar group on the sub polyethylene subchain, increased the consistency between high density polyethylene(HDPE) and the nylon, make the existing mechanical strength preferably of material of preparation, can form the microfacies laminate structure again, organic solvent is had stronger iris action, but this method is not suitable on a large scale, the suitability for industrialized production of serialization.In the patent CN 1 035908 and US 5 602 200 of E.I.Du Pont Company's application, introduced a kind of method of producing polyolefine/blend of nylon.This method prepares barrier material by the polyolefin blend that polyethylene and ethylene-vinyl alcohol copolymer, nylon, alkyl carboxylic acid replace, and comes article of manufacture by laminated or injection molding technique simultaneously.But the nylon component concentration is higher in this material, causes product cost to rise, and needs to buy forming machine supporting with it, that E.I.Du Pont Company designs voluntarily, can not produce on common forming machine.Also provide a kind of method of producing the polyolefins blend separation material among the patent US 5 641833 of Korea S Yukong Ltd. application.This method is utilized polyolefine that polyolefine, separating polymer, alkyl carboxylic acid replace and small molecules insatiable hunger to close polar compound blend in the presence of superoxide and is formed.Owing to use small molecules polar compound and organo-peroxide, the technology that this method provides is difficult controls, reacts complicated, and may cause the physical strength of intermingling material to descend.In patent US 5 712043, a kind of method for preparing polyolefine/nylon blend separation material has been proposed, the polyolefin blend that uses poly-(ether-ester-acid amides) or itself and alkyl carboxylic acid to replace is expanding material, this method has been avoided the limitation of above-mentioned patent report method, but because poly-(ether-ester-acid amides) needs independent polymerization preparation, and this polymerization technique complexity, the production cost height, poly-(ether-ester-acid amides) is relatively poor with polyolefinic consistency simultaneously.
The object of the present invention is to provide the high barrier property polyethylene/nylon blend barrier rib material that a kind of preparation technology is simple, can implement on common forming machine.
The objective of the invention is to realize with following proposal:
1. one kind has the polyethylene/nylon blend separation material of excellent barrier properties to organic solvent, is cooperated by following several components to form:
(a) weight content is 70～95% polyethylene (PE)
(b) weight content is 3～25% nylon (PA)
(c) weight content is nylon grafted ethene-vinyl alcohol copolymer (EVOH-g-PA) of 2～10%
Wherein polyethylene is high density polyethylene(HDPE) (HDPE).
Wherein nylon is nylon-6 or nylon-66.
Wherein nylon grafted ethene-vinyl alcohol copolymer (EVOH-g-PA) is an expanding material, and its structure is bound up on the side group of ethylene-vinyl alcohol copolymer (EVOH) for the nylon side chain.Can add simultaneously polyethylene that the part alkyl carboxylic acid replaces such as ethylene-acrylic acid copolymer (EAA), maleic anhydride grafted polyethylene etc. as compatilizer, to increase the consistency of high density polyethylene(HDPE) and nylon.
Wherein the content of ethylene component is 80～95% (molar content) among the EVOH.The nylon components contents is 5～15% (weight contents) among the EVOH-g-PA.EVOH-g-PA is that product and diprotic acid, diamine or the caprolactam of EVOH or ethylene-vinyl acetate copolymer (EVA) hydrolysis or alcoholysis prepares at 190～230 ℃ of melt blending graft reactions.
The preparation process of vessel prepd of the present invention is:
The mixture of high density polyethylene(HDPE), nylon, nylon grafted ethylene-vinyl alcohol copolymer or itself and ethylene-acrylic acid copolymer extruded under 190～230 ℃, lower screw speed be tubular parison, using pressurized air inflation, slush molding down at 180～200 ℃ then is container.
Embodiment:
Each Example formulations is as shown in table 1, and made hollow bottle performance is as shown in table 2.
Table 1 embodiment of the invention prescription (parts by weight)
Fill a prescription 12345678
HDPE 100 90 85 85 90 90 93 93
PA - 10 10 10 7 7 5 5
EVOH-g-PA - - 5 3 3 2 2 1
MPE - - - 2 - 1 - 1
Annotate: MPE is the maleic anhydride graft high density polyethylene(HDPE).Used nylon is among the embodiment 1,3,4,5,6 and 8
PA-6; 2, used nylon is PA-66 in 7.
Prescription the 1, the 2nd is filled a prescription as a comparison, and the enforcement of prescription 3～8 is as follows:
The mixture of high density polyethylene(HDPE), nylon, nylon grafted ethylene-vinyl alcohol copolymer or itself and ethylene-acrylic acid copolymer extruded under 190～230 ℃, lower screw speed be tubular parison, using pressurized air inflation, slush molding down at 180～200 ℃ then is container.
Table 2 embodiment of the invention product properties
Formula number solvent infiltration capacity (g/d) impact property
1 5.32 NB(a)
2 1.57 B(b)
3 0.42 NB
4 0.23 NB
5 0.16 NB
6 0.11 NB
7 0.31 NB
8 0.19 NB
Annotate: (a) Not Breaking (b) Breaking
The hollow bottle barrier property of the present invention's preparation and the used container bottle of impact property test, its volume is 250ml, container wall thickness is 1mm.During the test solvent barrier property, dress 200ml xylene solvent is tightened bottle cap in the container bottle, uses rubber belt sealing, in 40 ℃ of placements 30 days, measures its weight loss.The impact property of measuring vessel bottle with dress 200ml water in the bottle, is tightened bottle cap, highly freely falls in 1.5 meters.
As can be seen from Table 2, use the hollow container bottle of the high molecule alloy material moulding of the present invention's preparation, high more a lot of to the barrier property of organic solvent dimethylbenzene than the barrier property of pure polyethylene bottle, also have good impact resistance simultaneously.
Claims (7)
1. one kind has the polyethylene/nylon blend separation material of excellent barrier properties to organic solvent, it is characterized in that described barrier material is cooperated by the raw material of following several weight % to form:
Polyethylene 70-95%
Nylon 3-25%
Nylon grafted ethene-vinyl alcohol copolymer 2-10%.
2. barrier material as claimed in claim 1 is characterized in that described polyethylene is a high density polyethylene(HDPE).
3. barrier material as claimed in claim 1 is characterized in that described nylon is nylon-6 or nylon-66.
4. barrier material as claimed in claim 1 is characterized in that described nylon grafted ethene-vinyl alcohol copolymer is an expanding material, and its structure is bound up on the side group of ETHYLENE-VINYL ALCOHOL COPOLYMER thing for the nylon side chain.
5. barrier material as claimed in claim 4, the molar content that it is characterized in that ethylene component in the described ETHYLENE-VINYL ALCOHOL COPOLYMER thing is 80～95%.
6. barrier material as claimed in claim 4, the weight content that it is characterized in that nylon component in described nylon grafted ethene-vinyl alcohol copolymer is 5～15%.
7. barrier material as claimed in claim 4 is characterized in that described nylon grafted ethene-vinyl alcohol copolymer is that product and diprotic acid, diamine or the hexanolactam melting graft reaction of ETHYLENE-VINYL ALCOHOL COPOLYMER thing or ethene-vinyl acetate copolymer hydrolysis or alcoholysis prepares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011066970A CN1164666C (en) | 2001-05-11 | 2001-05-11 | Polyethylene/nylon blend separation material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011066970A CN1164666C (en) | 2001-05-11 | 2001-05-11 | Polyethylene/nylon blend separation material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1321702A CN1321702A (en) | 2001-11-14 |
| CN1164666C true CN1164666C (en) | 2004-09-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011066970A Expired - Fee Related CN1164666C (en) | 2001-05-11 | 2001-05-11 | Polyethylene/nylon blend separation material |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418093B (en) * | 2007-10-26 | 2011-08-17 | 张发饶 | Polyethylene/nylon plastic alloy and production method thereof and compatible binder thereof |
| CN102585333A (en) * | 2012-02-29 | 2012-07-18 | 杨谢 | Formula of PE (Poly Ethylene) or PA (Polyamide) barrier film material and preparation method of PE or PA barrier film material |
| CN103319765B (en) * | 2012-03-22 | 2015-12-16 | 金发科技股份有限公司 | A kind of conduction, barrier polyethylene composition and its preparation method and application |
| CN104804423A (en) * | 2015-04-22 | 2015-07-29 | 合肥康龄养生科技有限公司 | Heat-resistant good-processing-fluidity modified nylon composite material and preparation method thereof |
| CN104804420A (en) * | 2015-04-22 | 2015-07-29 | 合肥康龄养生科技有限公司 | Calcium sulfate reinforced nylon composite and preparation method thereof |
| CN106046772A (en) * | 2016-07-22 | 2016-10-26 | 江阴市龙山合成材料有限公司 | Low-temperature-resistant and ultraviolet-resistant PA6/HDPE (polyamide 6/high-density polyethylene) alloy material |
| CN107266766A (en) * | 2017-06-26 | 2017-10-20 | 台山市世亨包装材料有限公司 | A kind of high-intensity packing material and preparation method thereof |
| CN108314823A (en) * | 2018-02-13 | 2018-07-24 | 南京精工新材料有限公司 | A kind of injection molding oil tank material and preparation method thereof that resists cold |
| CN108342007A (en) * | 2018-02-13 | 2018-07-31 | 南京精工新材料有限公司 | A kind of blowing oil tank material and preparation method thereof |
| CN108467536B (en) * | 2018-03-14 | 2021-02-09 | 河南科技大学 | Method for improving flame retardance and mechanical property of polyethylene/nylon 6 blend |
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2001
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