CN100400582C - Elastic cover material for container and production method thereof - Google Patents
Elastic cover material for container and production method thereof Download PDFInfo
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- CN100400582C CN100400582C CNB2005100224836A CN200510022483A CN100400582C CN 100400582 C CN100400582 C CN 100400582C CN B2005100224836 A CNB2005100224836 A CN B2005100224836A CN 200510022483 A CN200510022483 A CN 200510022483A CN 100400582 C CN100400582 C CN 100400582C
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- propylene
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Abstract
The present invention provides an elastic cover material for a container, which has small odor and is suitable for being used as a food container. The components comprise polypropylene 5 to 84 phr, poly (a-olefin-ethylene (or propylene)) 10 to 89 phr, ternary ethylene propylene rubber latex 5 to 84 phr and vulcanized crosslinking agent 0.8 to 10 phr according to per hectogram. The manufacturing process of the present invention has the following steps 1. Materials are mixed after weighed; 2. The mixed materials are fed into a twin screw extruder, and the vulcanized crosslinking auxiliary agent is added in the mixed materials; 3. Extruded rubber strips which are mixed and dynamically vulcanized are dried after the treatment of underwater granulation. Because poly (a-olefin-ethylene) or poly (a-olefin-propylene) is used, the present invention can contact oil and fat food and alcohol food. The degradation of polypropylene can be decreased in the process of dynamic vulcanization. Phenolic resin and sulfur are not used as cross-linking agents, and the odor of dynamic vulcanized rubber can be decreased.
Description
Technical field
The present invention relates to a kind of elastic cover material for container and manufacture method thereof.
Background technology
Airtight, liquid is close or the not only airtight but also sealing cover container that liquid is close is the goods that deflection is repeatedly used, advantage such as must have that the compressive set rate is low, anti-fatigue performance is good and wear-resisting.In addition, preferably has soft hand feeling, fine environment adaptability: for example use, use or in microwave oven, use as kitchen tackle at the extremely frigid zones below-30 ℃.
The elastomeric cap of Shi Yonging at low temperatures, general thermoplastic elastomer (TPE) just can meet the demands.Modal TPE has thermoplastic polyolefin elastomer, as: ethylene-propylene diene copolymer (EPDM), metallocene polyolefin elastomers (mPOE), Polyurethane Thermoplastic Elastomer (TPU) and copolyester elastomer etc.But elastomeric tensile elasticity of this class and poor heat resistance must be by solving the crosslinked of TPE, the dynamic crosslinking sulfuration thermoplastic elastomer (TPV) in Here it is the cross-linked elastomer.
The production method of TPV is: with thermoplastic material such as polypropylene (PP) and compatible easily rubber polymer such as EPDM melting mixing under the high temperature high-shear, in polymkeric substance, add vulcanization system simultaneously, as: sulphur or resol.Because EPDM viscosity is higher than PP, therefore, the former disperses in the latter, and along with shear agitation intensity increases, size of particles diminishes gradually.In this case, vulcanization system is rapid and the realization of EPDM chain is crosslinked, forms the cross-linked rubber particulate in PP.
The shortcoming of above-mentioned TPV is: 1, with vulcanization crosslinking systems such as sulphur, resol, product odour is big, is not suitable as food product containers and uses; 2, because EPDM need could feed in the dual-screw-stem machine complex manufacturing after the pelletizing; 3, cost an arm and a leg.
Summary of the invention
Technical problem to be solved by this invention provides a kind of elastic cover material for container and manufacture method thereof, and this elastic cover material smell is little, is suitable as food product containers usefulness, and its manufacturing approach craft is simple.
The technical scheme that technical solution problem of the present invention is adopted is: elastic cover material for container, its composition comprising by every hectogram umber (phr): polypropylene 5-84phr, poly-(alpha-olefin-ethene or propylene) 10-89phr, ethylene-propylene diene copolymer 5-84phr and vulcanization crosslinking agent 0.8-10phr.
The manufacture method of elastic cover material for container may further comprise the steps: mix the back of 1) weighing; 2) with in the material feeding twin screw extruder that mixes, add the vulcanization crosslinking auxiliary agent; 3) adhesive tape of extruding behind mixing dynamic vulcanization, the granulation after drying gets final product under water.
The invention has the beneficial effects as follows: 1. do not use oil fill to regulate soft durometer, and use metallocene poly-(alpha-olefin-ethene) or poly-(alpha-olefin-propylene), can with lipid food, alcohol type Food Contact.2. do not use the bigger superoxide of the resol, sulphur and the smell that have smell as linking agent, can reduce the smell of dynamic vulcanization glue.3. adopt poly-(alpha-olefin-ethene) or poly-(alpha-olefin-propylene), can reduce polyacrylic degraded in the dynamic vulcanization process.4. adopt the carrier of nano silicon, improve shock strength when improving modulus as the dynamic vulcanization agent.
Embodiment α
The composition of elastic cover material for container comprises by every hectogram umber: polypropylene 5-84phr, poly-(alpha-olefin-ethene or propylene) 10-89phr, ethylene-propylene diene copolymer 5-84phr, vulcanization crosslinking agent 0.8-10phr.Wherein the vulcanization crosslinking agent is made up of superoxide 0.3-2phr and nano silicon 0.5-8phr; Or be that 0.3-2phr and nano silicon 0.5-8phr form by superoxide and TAC sum; Or be that 0.3-2phr and 0.5-8phr nano silicon are formed by superoxide and EGDMA sum.Described polypropylene is homo-polypropylene, block copolymerization polypropylene, atactic copolymerized polypropene or metallocene polypropylene.
Its manufacture method may further comprise the steps:
1, weighs back the mixing;
2, with in the material feeding twin screw extruder that mixes, add the vulcanization crosslinking agent;
3, the adhesive tape of extruding behind mixing dynamic vulcanization, the granulation after drying gets final product under water.
4, produced elastic cover material for container directly injection moulding form the container elastomeric cap, also can with injection moulding formation container elastomeric cap again after PP, EPDM or poly-(alpha-olefin-ethene or propylene) mix.
In above-mentioned the 4th step,, in the 4th step, just PP must be added,, in the 4th step, PP can also be added again if in the first step, added PP if in the first step, do not add PP.EPDM and poly-(alpha-olefin-ethene or propylene) are in like manner.
Poly-(alpha-olefin-ethene or propylene) is the polymkeric substance of metallocene catalyst polymerisation, is the alpha-olefin of 4-8 carbon atom and the copolymerization product of ethene or propylene, and the content of alpha-olefin is 3-30% in the multipolymer.Metallocene is the transition metal formed Organometallic complexes that links to each other with cyclopentadiene.Metallocene-polyolefin is to be that catalyzer carries out the prepared polymkeric substance of olefinic polyreaction with metallocene coordination compound (metallocene).Metallocene catalysis polymeric advantage is: 1) active high: ethene, propylene all can, non-selectivity; 2) catalysis in a homogeneous system is remarkable; 3) product ten minutes homogeneous; 4) alpha-olefin height stereoregular; 5), adjust catalyst concn or change the catalyzer ligand, but regulate polymer molecular weight freely designs micmstructure of polymer by changing polymerization temperature; 6) most of interpolymers and vinyl polymerization can be made, and the polar monomer catalyzed polymerization can be made; 7) a metallocene product isotactic or a rule; 8) the metallocene catalyst life-span is long, stable in the air.
In the dynamic vulcanization that with toughness reinforcing is the PP of purpose and EPDM,, adopt superoxide to make linking agent for preventing the mobile variation of materials processing behind the dynamic vulcanization.Because this class linking agent also has the tendency of initiation to saturated bond, therefore, its consumption not only directly determines the crosslinking degree of EPDM, and relevant with the palliating degradation degree of PP, and both are determining the toughness reinforcing of material and other performance jointly.In addition, superoxide also can make the PP degraded, and stretching and crooked intensity and modulus descend with the dosage of crosslinking agent increase.When linking agent is an amount of, can guarantee under PP degraded situation seldom, to make EPDM full cross-linked and be uniformly distributed in PP external phase.Excessive linking agent but makes PP degraded aggravation, and makes EPDM form bigger discrete particles, and its result had both made and stretched and bending property decline, and impelling strength is descended.Therefore, linking agent and consumption thereof are the keys that dynamic vulcanization PP/EPDM obtains good over-all properties.
Superoxide can be used aliphatics dicumyl peroxide, t-amyl peroxy thing, 1,3-1,4 two (tert-butyl hydroperoxide different third) benzene, 2,5 dimethyl 2,5 two (tert-butyl hydroperoxide) hexane, 1,1 '-two (tert-butyl peroxyization)-3,3,5-trimethyl-cyclohexane, 1,3-1,4 two (tert-butyl hydroperoxide different third) benzene, 1,3-1,4 two (tert-butyl hydroperoxide different third) benzene, 2,5 dimethyl, 2,5 two (tert-butyl hydroperoxide) hexanes or 1,1 '-two (tert-butyl peroxyization)-3,3, the 5-trimethyl-cyclohexane.Also can adopt above-mentioned superoxide and TAC (Triallylcyanurate, triallyl cyanurate) or EGDMA (Ethylene glycol dimethacrylate, ethylene glycol dimethacrylate) to share.
Embodiment 1:
The composition of elastic cover material for container comprises by every hectogram umber: block copolymerization propylene 15phr, poly-(alpha-olefin-ethene) 35phr, EPDM 45phr, aliphatics dicumyl peroxide 0.5phr and nano silicon 4.5phr.
According to manufacture method of the present invention dynamic vulcanization granulation in twin screw extruder.
The material that obtains is fit to do-30～+ 60 ℃ of container elastomeric cap of using down.
Embodiment 2:
The composition of elastic cover material for container comprises by every hectogram umber: random copolymerization propylene 31phr, EPDM60phr, t-amyl peroxy thing 1.0phr and nano silicon 8phr.
According to manufacture method of the present invention dynamic vulcanization granulation in twin screw extruder.
The pellet 65phr that obtains is with after poly-(alpha-olefin-ethene) 35phr mixes in mixing machine, and injection moulding is fit to do-30～+ 60 ℃ of container elastomeric cap of using down.
Embodiment 3:
The composition of elastic cover material for container comprises by every hectogram umber: homo-polypropylene 76.7phr, poly-(alpha-olefin-propylene) 10phr, EPDM 5.0phr, 1,3-1,4 two (tert-butyl hydroperoxide different third) benzene 0.3phr and nano silicon 8.0phr.
According to manufacture method of the present invention dynamic vulcanization granulation in twin screw extruder.
The material that obtains is fit to do 0～+ 130 ℃ of container (as microwave oven container) that uses down and uses elastomeric cap.
Embodiment 4:
The composition of elastic cover material for container comprises by every hectogram umber: random copolymerization propylene 5phr, poly-(alpha-olefin-ethene) 89.0phr, EPDM 3.0phr, 2,5 dimethyl 2,5 two (tert-butyl hydroperoxide) hexane 0.6phr and nano silicon 2.4phr.
According to manufacture method of the present invention dynamic vulcanization granulation in twin screw extruder.
The material that obtains is fit to do-30～+ 60 ℃ of containers (as the freeze preservation container) that use down and uses elastomeric cap.
Embodiment 5:
The composition of elastic cover material for container comprises by every hectogram umber: homo-polypropylene 5.0phr, poly-(alpha-olefin-ethene) 10.0phr, EPDM 75.0phr, 1,1 '-two (tert-butyl peroxyizatioies)-3,3,5-trimethyl-cyclohexane 2.0phr and nano silicon 6.0phr.
According to manufacture method of the present invention dynamic vulcanization granulation in twin screw extruder.
The material that obtains is fit to do-30～+ 100 ℃ of container elastomeric cap of using down.
Embodiment 6:
The composition of elastic cover material for container comprises by every hectogram umber: poly-(alpha-olefin-ethene) 49.0phr, EPDM 45.0phr, 1,3-1, mixture 0.8phr and the nano silicon 5.2phr of 4 two (tert-butyl hydroperoxide different third) benzene and TAC.
According to manufacture method of the present invention dynamic vulcanization granulation in twin screw extruder.
The pellet 70.0phr that obtains is with after homo-polypropylene 30.0phr mixes in mixing machine, and the injection moulding elastomeric cap is fit to do-30～60 ℃ of container elastomeric cap of using down.
Embodiment 7:
The composition of elastic cover material for container comprises by every hectogram umber: polypropylene 20.0phr, poly-(alpha-olefin-ethene) 35.0phr, EPDM 45.0phr, 1,3-1, mixture 0.5phr, the nanometer titanium dioxide thing 0.5phr of 4 two (tert-butyl hydroperoxide different third) benzene and EGDMA.
According to manufacture method of the present invention dynamic vulcanization granulation in twin screw extruder.
The material that obtains is fit to do the container elastomeric cap of use under the low temperature.
Embodiment 8:
The composition of elastic cover material for container comprises by every hectogram umber: mixture 0.9phr and the nano silicon 6.1phr of polypropylene 33.0phr, EPDM 60.0phr, 2,5 dimethyl, 2,5 two (tert-butyl hydroperoxide) hexanes and TAC.
According to manufacture method of the present invention dynamic vulcanization granulation in twin screw extruder.
With the pellet that obtains with after poly-(alpha-olefin-propylene) mixes, injection moulding elastomeric cap, the container elastomeric cap that suitable work does not use in microwave oven.
Embodiment 9:
The composition of elastic cover material for container comprises by every hectogram umber: polypropylene 60.0phr, poly-(alpha-olefin-ethene) 5.0phr, EPDM 28.0phr, 1,1 '-two (tert-butyl peroxyizatioies)-3,3,5-trimethyl-cyclohexane 0.5phr and nano silicon 6.5phr.
According to manufacture method of the present invention dynamic vulcanization granulation in twin screw extruder.
The material that obtains is fit to the container elastomeric cap doing to use in the microwave oven.
The present invention has the following advantages:
1, adopt metallocene poly-(alpha-olefin-ethene or propylene), under peroxidation, EPDM On two keys produce crosslinked; In addition, produce free radical after the peroxide breakdown, can cause poly-(α-Alkene-ethene or propylene) tertiary carbon atom lose hydrogen, form free radical, produce crosslinked. Because luxuriant gold Poly-(alpha-olefin-ethene or propylene) the structural regularity that belongs to polymer is also poorer than EPDM, belongs to Fully unformed, melt viscosity is relatively low, is conducive to improve dynamic vulcanization type PP/EPDM blend Toughening effect.
2, crosslinked to EPDM in the dynamic vulcanization, sulfuration method that need not be traditional is because sulfur-containing aroma too Greatly, be not suitable for packaging for foodstuff, and adopt peroxide to do the vulcanization crosslinking agent.
3. as carrier, nano silicon itself inside rises and increases peroxide with nano silicon Pretend usefulness, can improve heat resistance and be the modulus under the high temperature, can improve impact resistance again, thereby ability Low temperature at high temperature also has good elasticity.
Claims (6)
1. elastic cover material for container, its composition comprises by every hectogram umber: polypropylene 5-84phr, poly-(alpha-olefin-ethene or propylene) 10-89phr, ethylene-propylene diene copolymer 5-84phr and vulcanization crosslinking agent 0.8-10phr, described vulcanization crosslinking agent is made up of superoxide 0.3-2phr and nano silicon 0.5-8phr, or be that 0.3-2phr and nano silicon 0.5-8phr form, or be that 0.3-2phr and 0.5-8phr nano silicon are formed by superoxide and EGDMA sum by superoxide and TAC sum.
2. elastic cover material for container as claimed in claim 1, it is characterized in that: described superoxide is: the aliphatics dicumyl peroxide, the t-amyl peroxy thing, 1,3-1,4 two (tert-butyl hydroperoxide different third) benzene, 2,5 dimethyl 2,5 two (tert-butyl hydroperoxide) hexanes, 1,1 '-two (tert-butyl peroxyizatioies)-3,3, the 5-trimethyl-cyclohexane, 1,3-1,4 two (tert-butyl hydroperoxide different third) benzene, 1,3-1,4 two (tert-butyl hydroperoxide different third) benzene, 2,5 dimethyl 2,5 two (tert-butyl hydroperoxide) hexanes or 1,1 '-two (tert-butyl peroxyizatioies)-3,3, the 5-trimethyl-cyclohexane.
3. elastic cover material for container as claimed in claim 1 is characterized in that: described polypropylene is homo-polypropylene, block copolymerization polypropylene, atactic copolymerized polypropene or metallocene polypropylene.
4. elastic cover material for container as claimed in claim 1 is characterized in that: described poly-(alpha-olefin-ethene or propylene) is the alpha-olefin of 4-8 carbon atom and the copolymerization product of ethene or propylene, and the content of alpha-olefin is 3-30% in the multipolymer.
5. make the method for the described elastic cover material for container of claim 1, may further comprise the steps: mix the back of 1) weighing; 2) with in the material feeding twin screw extruder that mixes, add the vulcanization crosslinking auxiliary agent; 3) adhesive tape of extruding behind mixing dynamic vulcanization, the granulation after drying gets final product under water.
6. the manufacture method of elastic cover material for container as claimed in claim 5 is characterized in that: also have after the described step 3) step 4) with pellet with polypropylene, ethylene-propylene diene copolymer or gather (alpha-olefin-ethene or propylene) and mix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100224836A CN100400582C (en) | 2005-12-30 | 2005-12-30 | Elastic cover material for container and production method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100224836A CN100400582C (en) | 2005-12-30 | 2005-12-30 | Elastic cover material for container and production method thereof |
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| CN1803904A CN1803904A (en) | 2006-07-19 |
| CN100400582C true CN100400582C (en) | 2008-07-09 |
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| CNB2005100224836A Active CN100400582C (en) | 2005-12-30 | 2005-12-30 | Elastic cover material for container and production method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666298A (en) * | 2009-11-20 | 2012-09-12 | 阿克泰加Ds有限公司 | Polymer compound for seals for use with fat-containing filling materials |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108912505A (en) * | 2018-06-04 | 2018-11-30 | 广州市美村橡胶科技有限公司 | Rubber mixed mixing material of a kind of food-grade with wear-resistance and oil-resistance acid-alkali-corrosive-resisting and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0995577A (en) * | 1995-09-29 | 1997-04-08 | Nippon Petrochem Co Ltd | Thermoplastic olefin elastomer composition excellent in oil resistance |
| US6344525B1 (en) * | 1999-12-31 | 2002-02-05 | Hyundai Motor Company | Thermoplastic resin composition |
| US6498213B2 (en) * | 2000-05-26 | 2002-12-24 | Hyundai Motor Company | Thermoplastic resin composition |
| CN1569947A (en) * | 2004-04-29 | 2005-01-26 | 武汉固德威科技发展有限公司 | Dynamic wholly vulcanized thermoplastic rubber one-step production process and apparatus |
-
2005
- 2005-12-30 CN CNB2005100224836A patent/CN100400582C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0995577A (en) * | 1995-09-29 | 1997-04-08 | Nippon Petrochem Co Ltd | Thermoplastic olefin elastomer composition excellent in oil resistance |
| US6344525B1 (en) * | 1999-12-31 | 2002-02-05 | Hyundai Motor Company | Thermoplastic resin composition |
| US6498213B2 (en) * | 2000-05-26 | 2002-12-24 | Hyundai Motor Company | Thermoplastic resin composition |
| CN1569947A (en) * | 2004-04-29 | 2005-01-26 | 武汉固德威科技发展有限公司 | Dynamic wholly vulcanized thermoplastic rubber one-step production process and apparatus |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666298A (en) * | 2009-11-20 | 2012-09-12 | 阿克泰加Ds有限公司 | Polymer compound for seals for use with fat-containing filling materials |
| CN102666298B (en) * | 2009-11-20 | 2016-06-08 | 阿克泰加Ds有限公司 | For manufacturing the application compressing method and the polymer complex turning on lid and vessel closure |
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| CN1803904A (en) | 2006-07-19 |
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