CN102775671A - Modified polyethylene for supercritical CO2 foaming and preparation method thereof - Google Patents
Modified polyethylene for supercritical CO2 foaming and preparation method thereof Download PDFInfo
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- CN102775671A CN102775671A CN2012103021424A CN201210302142A CN102775671A CN 102775671 A CN102775671 A CN 102775671A CN 2012103021424 A CN2012103021424 A CN 2012103021424A CN 201210302142 A CN201210302142 A CN 201210302142A CN 102775671 A CN102775671 A CN 102775671A
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Abstract
The invention discloses a modified polyethylene for supercritical CO2 foaming, which comprises the following components in parts of by weight: 100 parts of base resin, 0.1-5 parts of surfactant, 1-25 parts of solubilizer and 0.1-10 parts of nucleating agent. After organically combining the components, the obtained modified polyethylene can be directly used for supercritical CO2 foaming to lower the manufacturing cost of equipment and simplify the foaming equipment structure and foaming technique; and thus, the foaming equipment structure and foaming technique are easy to control.
Description
Technical field
The present invention relates to a kind of modified poly ethylene, belong to polymeric material field.
Background technology
EPE (Expandable Polyethylene) is the expandability Vilaterm, claims EPE again, is to be the high foamed polyethylene goods of main raw material extruding formation with new LDPE (film grade) (LDPE).Polyethylene foams has that unicellular structure characteristics, thermal conductivity are low, moisture absorption and perviousness is little, anticorrosive, good impact resistance and excellent electric insulation performance etc.; The application of polyethylene foams penetrates into social every field; Be widely used in building heat preservation, refrigerator lagging material, sports buildings facility etc., and packing such as the vibrationproof of electronic machine and precision instrument etc.
The suitability for industrialized production of polyethylene foams mainly adopts the physical blowing method of extruding, and in a very long time, domestic highly foaming polyethylene is produced most of freonll-11 (F-12) physical blowing technology that adopts in the past.Because freonll-11 is to the destruction of atmospheric ozone layer, from environmental protection requirement, freonll-11 physical blowing technology gradually by low molecular weight hydrocarbons such as butane physical blowing technology replacement.The pollution problem that butane physical blowing production technique had both solved F-12 also makes quality product increase, and production cost descends to some extent, is most representative in the world at present highly foaming polyethylene production technique.
But this type of butane low molecular weight hydrocarbons whipping agent is inflammable and explosive, the safe precaution measure of each link such as foaming machine and whole production, storage and transportation is had relatively high expectations, and have potential safety hazard all the time; This type of butane low molecular weight hydrocarbons whipping agent direct sources petroleum resources are a kind of non-renewable industrial chemicals simultaneously.Along with the sustainable growth of global population and world economy, crisis of resource and ecological environment problem more and more receive people's attention.The twentieth century end utilizes rare gas elementes such as nitrogen, carbonic acid gas to become the focus that people study as pneumatogen, and this type rare gas element source is abundant, and cost is low, the resource that need not to consume petroleum, and can avoid destruction to ozonosphere.In addition, burning and blast do not take place in these gases generally speaking, and processing safety is high, is the main direction of studying in the physical blowing technological development.
At the beginning of the 80's of 20th century, (MIT proposes the notion of cellular plastic: the abscess of smaller szie can the passivation crack tip when material damage, bring out crazing produces in Massachusetts Institute Technology.And supercritical CO
2Be to use the most general pneumatogen in the micro-foaming material preparation, except supercritical CO
2Outside the performance of the material excellence of foaming technique preparation itself, with supercritical CO
2For the foam process of whipping agent has the characteristic of environmental protection, so supercritical CO
2Foaming technique has received academia and industry member is paid attention to widely.
At home, the technology of butane polyethylene foamed is quite ripe, and general general LDPE need not any modification, as long as the suitable processing parameter of control, promptly available butane foams.But, because CO
2Solubleness in LDPE is less, if directly carry out supercritical CO with LDPE
2Foaming then is difficult to obtain satisfactory froth product, therefore, must carry out modification to LDPE, makes it satisfy supercritical CO
2The requirement of foaming.If on foaming machine to LDPE directly carry out modification, and and then foam, then can significantly improve the cost of equipment, and device structure also can be very complicated, processing condition are difficult to regulation and control.Therefore, be necessary to develop a kind of supercritical CO that is used for
2The modified poly ethylene PP Pipe Compound of foaming.
Summary of the invention
For the modification of directly carrying out that overcomes in the prior art on foaming machine LDPE causes foaming machine complex structure, equipment manufacturing cost is high, foam process is difficult to regulate and control technological deficiency, the present invention provides a kind of can directly be used for supercritical CO
2Polyethylene foamed;
Another object of the present invention provides a kind of above-mentioned supercritical CO that is used for
2The preparation method of polyethylene foamed.
The object of the invention comes concrete the realization through following technical scheme:
A kind of supercritical CO that is used for
2The modified poly ethylene of foaming, its each component comprises by weight: 100 parts of matrix resins, 0.1-5 parts in tensio-active agent, 1-25 parts of solubilizing agent, 0.1-10 parts of nucleators, wherein,
Said matrix resin is that (be called for short: LDPE), among the LDPE of the commercially available various trades mark, number average can be used for the matrix resin of this modified poly ethylene to the new LDPE (film grade) that under high pressure obtains through radical polymerization mostly;
Said surperficial method agent is anion surfactant or cationic surfactant or zwitterionic surfactant or non-ionic surface active agent;
Said solubilizing agent be contain polar functional group vinyl monomer and vinyl monomer random copolymers or on the molecular chain of said new LDPE (film grade), introduce the grafted polyethylene that polar group obtains through graft reaction;
Said nucleator is an inorganic filler particle.
The above-mentioned supercritical CO that is used for
2The modified poly ethylene of foaming, its each component is preferably by weight: 100 parts of matrix resins, 0.3-2 parts in tensio-active agent, 1.5-10 parts of solubilizing agent, 0.5-2 parts of nucleators.
The above-mentioned supercritical CO that is used for
2The modified poly ethylene of foaming, each component further is:
The density of said new LDPE (film grade) is 0.85-0.95g/cm
3, melting index is 1.5-3.0 g/10min;
Said tensio-active agent is selected from one or more in OP-10, sorbester p17, the polysorbate60;
Said solubilizing agent is selected from Injecatable EVA Copolymer (to be called for short: EVA), ethylene-acrylic acid copolymer (is called for short: EAA), ethylene-methyl acrylate copolymer (is called for short: EMA), ethylene-ethyl acrylate copolymer (is called for short: the mixture of one or more EEA); Solubilizing agent can also be selected from polar monomer grafted Vilaterm; Wherein, The polar monomer of said grafted polyethylene is selected from a kind of in maleic anhydride, vinylformic acid, methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, methylacrylic acid, TEB 3K, Jia Jibingxisuanyizhi, NSC 20956, vinylformic acid glycidyl ether, the methyl propenoic acid glycidyl ether, and the mass concentration of the polar monomer of said grafted polyethylene in Vilaterm is 0.1%-10.0%;
Said nucleator is selected from a kind of in aluminum oxide, silicon-dioxide, lime carbonate, calcium sulfate, polynite, kaolin, mica, talcum powder, the calcium sulfate, and its particle diameter is the 200-2000 order.Preferably talc powder or lime carbonate, particle diameter are the 500-1800 order, and optimum grain-diameter is the 700-1300 order.
Further; A kind of in the preferred vinylformic acid of the monomer of said grafted polyethylene, methylacrylic acid and the methyl propenoic acid glycidyl ether; The monomeric mass concentration in Vilaterm of said grafted polyethylene is 0.5%-5.0%, and optimum is a methyl propenoic acid glycidyl ether.
Further, said solubilizing agent is Injecatable EVA Copolymer or ethylene-acrylic acid copolymer, optimal ethylene-acetate ethylene copolymer.
Further, said tensio-active agent is OP-10.
The above-mentioned supercritical CO that is used for
2The preparation method of the modified poly ethylene of foaming:
Each component is mixed in the high speed kneader, use twin screw extruder extruding pelletization between 160-180 ℃ then, obtain being used for supercritical CO
2The modified poly ethylene of foaming.
The above-mentioned supercritical CO that is used for
2The application method of modified poly ethylene in the preparation of porous plastics of foaming:
With the supercritical CO that is used for for preparing
2The modified poly ethylene of foaming directly carries out supercritical CO on foaming machine
2Foaming gets foam article.
Beneficial effect of the present invention:
Adopt LDPE as matrix resin among the present invention, constitute the skeleton of foam materials; Tensio-active agent is mainly used in stable bubble hole and control action kou is played in the growth of abscess; Solubilizing agent is mainly used in increases the solubleness of supercritical co in matrix resin; Nucleator is mainly used in the crystallization nucleation of Vilaterm at the abscess growth phase, thereby improves poly crystallization rate, increases the intensity of bubble wall, avoids and bubble and abscess break.Through blend, these several kinds of components are organically combined, thereby make this modified poly ethylene can directly be used for supercritical CO
2Foam, reduced the cost of equipment, foaming machine structure and foam process are oversimplified, thereby be easy to regulation and control, and the resulting product foaming effect is good.
Description of drawings
According to accompanying drawing and embodiment the present invention is done further explain below:
Fig. 1 is the profile scanning Electronic Speculum structure iron of the embodiment of the invention 1 gained foam article;
Fig. 2 is the profile scanning Electronic Speculum structure iron of the embodiment of the invention 2 gained foam articles;
Fig. 3 is the profile scanning Electronic Speculum structure iron of the embodiment of the invention 3 gained foam articles..
Embodiment
Embodiment 1:
The LDPE of 100kg, the OP-10 of 0.3kg, the EVA of 1.5kg, the talcum powder (1000 order) of 1kg are mixed in the high speed kneader, use twin screw extruder extruding pelletization between 160-180 ℃ then, gained is used for supercritical CO
2The modified poly ethylene of foaming carries out supercritical CO on EPE production unit (this equipment is produced in Chongqing prompt one-tenth plastic cement Ltd)
2Foaming obtains foam article, and its thickness is that 2-15mm, width are 800-1000mm, and its structure is with reference to profile scanning Electronic Speculum structure iron (accompanying drawing 1).
Embodiment 2:
Maleic anhydride and the 100g Di Cumyl Peroxide 99 of 1.5kg are dissolved in the small amount of acetone; In the high speed kneader, mix then with 100 kilograms LDPE; After treating that acetone volatilizees fully; Between 130-160 ℃, carry out extruding pelletization through single screw extrusion machine, can obtain the LDPE of maleic anhydride graft.
Again the LDPE of the maleic anhydride graft of the LDPE of 100kg, 0.3kgOP-10,1.5kg, the talcum powder (1300 order) of 1kg are mixed in the high speed kneader; Use twin screw extruder extruding pelletization between 160-180 ℃ then, the gained pellet is used for supercritical CO
2The modified poly ethylene of foaming carries out supercritical CO on EPE production unit (this equipment is produced in Chongqing prompt one-tenth plastic cement Ltd)
2Foaming obtains foam article, and its thickness is that 2-15mm, width are 800-1000mm, and its structure is with reference to profile scanning Electronic Speculum structure iron (accompanying drawing 2).
Embodiment 3:
The 100g Di Cumyl Peroxide 99 is dissolved in the methyl propenoic acid glycidyl ether (GMA) of 1.5 kg; In the high speed kneader, mix then with the LDPE of 100kg; Between 130-160 ℃, carry out extruding pelletization with single screw extrusion machine afterwards, can obtain GMA grafted LDPE.
Talcum powder (1000 order) with the LDPE of 100kg, 0.3kgOP-10,1.5kgGMA grafted LDPE, 1kg mixes in the high speed kneader again, uses twin screw extruder extruding pelletization between 160-180 ℃ then, and gained is used for supercritical CO
2The modified poly ethylene of foaming carries out supercritical CO on the EPE production unit
2Foaming obtains foam article, and its thickness is that 2-15mm, width are 800-1000mm, and its structure is with reference to profile scanning Electronic Speculum structure iron (accompanying drawing 3).
Embodiment 4:
The LDPE of 100kg, the OP-10 of 0.1kg, the EAA of 1kg, the talcum powder (2000 order) of 0.1kg are mixed in the high speed kneader, use twin screw extruder extruding pelletization between 160-180 ℃ then, gained is used for supercritical CO
2The modified poly ethylene of foaming carries out supercritical CO on the EPE production unit
2Foaming obtains foam article, and its thickness is that 2-15mm, width are 800-1000mm.
Embodiment 5:
The LDPE of 100kg, the sorbester p17 of 5kg, the EMA of 25kg, the Paris white (200 order) of 10kg are mixed in the high speed kneader, use twin screw extruder extruding pelletization between 160-180 ℃ then, gained is used for supercritical CO
2The modified poly ethylene of foaming carries out supercritical CO on the EPE production unit
2Foaming obtains foam article, and its thickness is that 2-15mm, width are 800-1000mm.
Embodiment 6:
The LDPE of 100kg, the OP-10 of 0.3kg, the EEA of 1.5kg, the Paris white (1800 order) of 0.5kg are mixed in the high speed kneader, use twin screw extruder extruding pelletization between 160-180 ℃ then, gained is used for supercritical CO
2The modified poly ethylene of foaming carries out supercritical CO on the EPE production unit
2Foaming obtains foam article, and its thickness is that 2-15mm, width are 800-1000mm.
Embodiment 7:
The 100g Di Cumyl Peroxide 99 is dissolved in the methyl propenoic acid glycidyl ether (GMA) of 0.1 kg; In the high speed kneader, mix then with the LDPE of 100kg; Between 130-160 ℃, carry out extruding pelletization with single screw extrusion machine afterwards, can obtain GMA grafted LDPE.
Talcum powder (500 order) with the LDPE of 100kg, 2kg polysorbate60,10kgGMA grafted LDPE, 2kg mixes in the high speed kneader again, uses twin screw extruder extruding pelletization between 160-180 ℃ then, and gained is used for supercritical CO
2The modified poly ethylene of foaming carries out supercritical CO on the EPE production unit
2Foaming obtains foam article, and its thickness is that 2-15mm, width are 800-1000mm.
Embodiment 8:
The 100g Di Cumyl Peroxide 99 is dissolved in the vinylformic acid of 10 kg, in the high speed kneader, mixes then, between 130-160 ℃, carry out extruding pelletization with single screw extrusion machine afterwards, can obtain acrylic acid-grafted LDPE with the LDPE of 100kg.
Again the LDPE of 100kg, 0.3kg polysorbate60, the acrylic acid-grafted LDPE of 1.5kg, the Paris white (600 order) of 1kg are mixed in the high speed kneader; Use twin screw extruder extruding pelletization between 160-180 ℃ then, the gained pellet is used for supercritical CO
2The modified poly ethylene of foaming carries out supercritical CO on the EPE production unit
2Foaming obtains foam article, and its thickness is that 2-15mm, width are 800-1000mm.
Embodiment 9:
The 100g Di Cumyl Peroxide 99 is dissolved in the methylacrylic acid of 0.5kg, in the high speed kneader, mixes then, between 130-160 ℃, carry out extruding pelletization with single screw extrusion machine afterwards, can obtain methylacrylic acid grafted LDPE with the LDPE of 100kg.
Again the LDPE of 100kg, 0.3kg polysorbate60, the methylacrylic acid grafted LDPE of 1.5kg, the silicon-dioxide (1200 order) of 1kg are mixed in the high speed kneader; Use twin screw extruder extruding pelletization between 160-180 ℃ then, the gained pellet is used for supercritical CO
2The modified poly ethylene of foaming carries out supercritical CO on the EPE production unit
2Foaming obtains foam article, and its thickness is that 2-15mm, width are 800-1000mm.
Embodiment 10:
The 100g Di Cumyl Peroxide 99 is dissolved in the methyl propenoic acid glycidyl ether (GMA) of 5kg; In the high speed kneader, mix then with the LDPE of 100kg; Between 130-160 ℃, carry out extruding pelletization with single screw extrusion machine afterwards, can obtain GMA grafted LDPE.
Again the LDPE of 100kg, 0.3kg sorbester p17, the methylacrylic acid grafted LDPE of 1.5kg, the polynite (800 order) of 1kg are mixed in the high speed kneader; Use twin screw extruder extruding pelletization between 160-180 ℃ then, the gained pellet is used for supercritical CO
2The modified poly ethylene of foaming carries out supercritical CO on the EPE production unit
2Foaming obtains foam article, and its thickness is that 2-15mm, width are 800-1000mm.
The density of the LDPE that is adopted in the foregoing description is 0.85-0.95g/cm
3, melting index is 1.5-3.0g/10min.
The above is merely the preferred embodiments of the present invention; Be not limited to the present invention; Although the present invention has been carried out detailed explanation with reference to previous embodiment; For a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. one kind is used for supercritical CO
2The modified poly ethylene of foaming, it is characterized in that: its each component comprises by weight: 100 parts of matrix resins, 0.1-5 parts in tensio-active agent, 1-25 parts of solubilizing agent, 0.1-10 parts of nucleators, wherein,
The new LDPE (film grade) of said matrix resin under high pressure obtaining through radical polymerization;
Said surperficial method agent is anion surfactant or cationic surfactant or zwitterionic surfactant or non-ionic surface active agent;
Said solubilizing agent be contain polar functional group vinyl monomer and vinyl monomer random copolymers or on the molecular chain of said new LDPE (film grade), introduce the grafted polyethylene that polar group obtains through graft reaction;
Said nucleator is an inorganic filler particle.
2. the supercritical CO that is used for according to claim 1
2The modified poly ethylene of foaming, it is characterized in that: its each component comprises by weight: 100 parts of matrix resins, 0.3-2 parts in tensio-active agent, 1.5-10 parts of solubilizing agent, 0.5-2 parts of nucleators.
3. the supercritical CO that is used for according to claim 1 and 2
2The modified poly ethylene of foaming is characterized in that:
The density of said new LDPE (film grade) is 0.85-0.95g/cm
3, melting index is 1.5-3.0g/10min; Said tensio-active agent is selected from one or more in OP-10, sorbester p17, the polysorbate60;
Said solubilizing agent is selected from one or more the mixture in Injecatable EVA Copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, the ethylene-ethyl acrylate copolymer; Solubilizing agent can also be selected from polar monomer grafted Vilaterm; Wherein, The polar monomer of said grafted polyethylene is selected from a kind of in maleic anhydride, vinylformic acid, methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, methylacrylic acid, TEB 3K, Jia Jibingxisuanyizhi, NSC 20956, vinylformic acid glycidyl ether, the methyl propenoic acid glycidyl ether, and the mass concentration of the polar monomer of said grafted polyethylene in Vilaterm is 0.1%-10.0%;
Said nucleator is selected from a kind of in aluminum oxide, silicon-dioxide, lime carbonate, calcium sulfate, polynite, kaolin, mica, talcum powder, the calcium sulfate, and its particle diameter is the 200-2000 order.
4. the supercritical CO that is used for according to claim 3
2The modified poly ethylene of foaming is characterized in that: the monomer of said grafted polyethylene is a kind of in vinylformic acid, methylacrylic acid and the methyl propenoic acid glycidyl ether, and the mass concentration of the polar monomer of said grafted polyethylene in Vilaterm is 0.5%-5.0%.
5. the supercritical CO that is used for according to claim 4
2The modified poly ethylene of foaming, it is characterized in that: the monomer of said grafted polyethylene is a methyl propenoic acid glycidyl ether.
6. the supercritical CO that is used for according to claim 3
2The modified poly ethylene of foaming, it is characterized in that: said solubilizing agent is Injecatable EVA Copolymer or ethylene-acrylic acid copolymer.
7. the supercritical CO that is used for according to claim 3
2The modified poly ethylene of foaming, it is characterized in that: said tensio-active agent is OP-10.
8. the supercritical CO that is used for according to claim 3
2The modified poly ethylene of foaming, it is characterized in that: said nucleator is talcum powder or lime carbonate, particle diameter is the 500-1800 order.
9. the supercritical CO that is used for according to claim 3
2The modified poly ethylene of foaming, it is characterized in that: said nucleator is talcum powder or lime carbonate, particle diameter is the 700-1300 order.
10. one kind is used for supercritical CO
2The preparation method of the modified poly ethylene of foaming, it is characterized in that: each component is mixed in the high speed kneader, and extruding pelletization between 160-180 ℃ obtains being used for supercritical CO then
2The modified poly ethylene of foaming.
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| CN105801988A (en) * | 2016-05-13 | 2016-07-27 | 马鞍山纽盟知识产权管理服务有限公司 | Special pearl wool bag for precise instrument packaging |
| CN107096061A (en) * | 2017-07-03 | 2017-08-29 | 四川马可视觉网络科技有限公司 | Anti- tarnishing smell show and colour |
| CN108948478A (en) * | 2018-04-27 | 2018-12-07 | 厦门谱睿科技有限公司 | A kind of Pearl wool material of supercritical carbon dioxide foaming |
| CN110256750A (en) * | 2019-06-18 | 2019-09-20 | 东莞市和永包装有限公司 | A kind of low density polyethylene (LDPE) foaming Yoga mat and preparation method thereof |
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| CN115926260A (en) * | 2022-12-28 | 2023-04-07 | 湖北格霖威新材料科技有限公司 | Preparation method of degradable high-strength closed-cell polylactic acid foam material |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103524821A (en) * | 2013-06-19 | 2014-01-22 | 南京迪默森节能科技有限公司 | Polyethylene foam plastic and preparation method thereof |
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| CN110256750A (en) * | 2019-06-18 | 2019-09-20 | 东莞市和永包装有限公司 | A kind of low density polyethylene (LDPE) foaming Yoga mat and preparation method thereof |
| CN110563994A (en) * | 2019-10-08 | 2019-12-13 | 浙江杰上杰新材料有限公司 | Supercritical foaming nucleating agent and preparation method thereof |
| CN110563994B (en) * | 2019-10-08 | 2022-05-24 | 浙江杰上杰新材料有限公司 | Supercritical foaming nucleating agent and preparation method thereof |
| CN115926260A (en) * | 2022-12-28 | 2023-04-07 | 湖北格霖威新材料科技有限公司 | Preparation method of degradable high-strength closed-cell polylactic acid foam material |
| CN115926260B (en) * | 2022-12-28 | 2024-01-26 | 湖北格霖威新材料科技有限公司 | Preparation method of degradable high-strength closed-cell polylactic acid foaming material |
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Application publication date: 20121114 |