CN1389515A - Prepn. of composite nylon material capable of being blow moulded - Google Patents
Prepn. of composite nylon material capable of being blow moulded Download PDFInfo
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- CN1389515A CN1389515A CN 02136095 CN02136095A CN1389515A CN 1389515 A CN1389515 A CN 1389515A CN 02136095 CN02136095 CN 02136095 CN 02136095 A CN02136095 A CN 02136095A CN 1389515 A CN1389515 A CN 1389515A
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Abstract
There is a method of preparing the inflatable nylon complex material, and the method is as follows; add the mixture of nylon 6, chain-expanding agent or functionalized polymer and rare-earth oxie which is evenly mixed in the high-speed stirrer into the common double-screw extruding machine, then make the things in the mixture reactively commix under a certain temperature and rotate speed then extrude the commixture and make the particles, and then obtained the inflatable nylon 6 material. The invention's method is simple, the made material retains the capability of original nylon 6 and at the same time improves the impactive tenacity, the strength of its melted body is high, and it can not only be injected to shape, but also be blowed into all kinds of hollow products with complicated shape, which make its applied range greatly enlarged.
Description
Technical field:
The present invention relates to a kind of preparation of composite nylon material capable of being blow moulded, with twin screw extruder the polymkeric substance that polycaprolactam is commonly called as nylon 6 and a small amount of chainextender or functionalization is carried out reactively blending, the body intensity of melting of nylon is increased substantially, thereby but make the nylon blow molding.The invention belongs to technical field of polymer processing.
Background technology:
As everyone knows, polyamide-based is the nylon-type polymkeric substance, low temperature and high temperature use properties excellence, mechanical property is good, tensile strength is high, have excellent abrasive, good self lubricity, impelling strength and high barrier preferably, chemical-resistant resistance and oil-proofness are outstanding, so developed rapidly since coming out.Wherein polycaprolactam is a nylon 6, P.Schlach invention by German I.G.Farbon company in 1938, initial nylon 6 is mainly used in synthon, have only tens percent to be used for engineering plastics, make it have specific function to the nineties by modification, thereby nylon is developed to engineering plastics and functional plastics by general-purpose plastics, and nylon 6 output occupy first of the engineering plastics at present.The number-average molecular weight of common widely used nylon 6 very low (＜30,000), low like this molecular weight make that melt strength and viscosity are too low and be not suitable for blow molding, generally can only injection molding, and this is restricted its range of application.Because nylon 6 good combination properties, fabulous oil resistance and barrier properties for gases are arranged again, can be used to make fuel tank and food container, but require blow molding when making hollow piece such as container, be convenient to scale operation like this, can reduce cost simultaneously.Blow molded polymeric will have suitable melt strength and viscosity, yet that common nylon 6 melts body intensity is low, is difficult to blow molding.The U.S., Japan and other countries are all relevant for the patent of nylon blow molding, and Lavengood etc. (U.S.Pat.No.5,043,384) have adopted nylon 6 and ABS blend to obtain blow moldable nylon, and the over-all properties of this material is near nylon 6, but not as nylon 6; Subramanian etc. have used the Polyolefin and ionic polymer of functionalization to obtain the compound material of blow moldable hemihedral crystal nylon, but wherein ionic polymer is difficult to obtain and cost height (U.S.Pat.No.5,122,570), the research of domestic blow molding about nylon 6 relates to less.
Summary of the invention:
The objective of the invention is at the deficiencies in the prior art, a kind of preparation of composite nylon material capable of being blow moulded is provided, thereby make nylon melt that body intensity improves can be by blow molding, and the material that is added is simple and easy to, improve performance of composites, enlarge its range of application.
For realizing such purpose; in technical scheme of the present invention; a kind of method of polymkeric substance and a small amount of rare earth oxide of nylon and a small amount of chainextender or functionalization being carried out reactively blending with twin screw extruder is proposed; adopt common twin screw extruder; at weight percent is in the nylon 6 of 60-99.8%; the polymkeric substance that adds 0.1-39.9% chainextender or functionalization; the rare earth oxide that adds 0.01-5%; on homogenizer, mix earlier; the rotating speed of homogenizer is 500-8000 rev/min; in common twin screw extruder, make pellet then; extruder temperature is 160-320 ℃; rotating speed is 100-800 rev/min; the residence time of material in screw rod is 1-10 minute, after the material of extruding cools off through the water-cooled cooling tank, through the dicing machine pelletizing; obtain pellet, in baking oven 80-180 ℃ dry 10-30 hour.
Nylon 6 of the present invention is polycaprolactam.
Chainextender of the present invention, be thereby that a class can be reacted the molecular weight that makes nylon with the end group of nylon 6 and increased and to melt body intensity and increase, the material that can make nylon 6 carry out blowing, can get vulcabond (TDI), p-Hydroxybenzoate, 4,4 '-isopropylidene double-basis phenol salicylate, salicylic acid phenyl ester, ethylene glycol, phenol, phenyloxalate (DPO).
The polymkeric substance of functionalization of the present invention, it is the polymkeric substance that the end group of a class and nylon 6 can react, the body intensity of melting of nylon 6 is improved and the energy blow molding, be styrene-maleic anhydride copolymer (SMA), ethylene-vinyl acetate copolymer (EVA), maleic anhydride grafted polyethylene multipolymer (PE-g-MAH), maleic anhydride inoculated polypropylene multipolymer (PP-g-MAH), polyethylene acrylic acid grafts (PE-g-AA), the polypropylene grafted thing of vinylformic acid (PP-g-AA), glycidyl methacrylate-polyethylene graft copolymer (GMA-g-PE), glycidyl methacrylate-polypropylene graft copolymer (GMA-g-PP), maleic anhydride graft styrene-butadiene-styrene multipolymer (MAH-g-SBS), maleic anhydride graft acrylonitrile-butadiene-styrene copolymer (MAH-g-ABS).
Rare earth oxide of the present invention is cerium oxide, lanthanum trioxide, Samarium trioxide, Praseodymium trioxide, Yangization Nd, europium sesquioxide.
The method that the present invention adopts in twin screw extruder polymkeric substance and a small amount of rare earth oxide with nylon 6 and a small amount of chainextender or functionalization to carry out reactively blending, making nylon 6 melt body intensity improves, thereby can carry out blow molding processing, and material has obviously improved impelling strength when having kept original nylon 6 performances.The inventive method is simple, overcome the weakness that is difficult to blow molding, nylon 6 melts body intensity height, except that can injection moulding, can be blow molded into the hollow piece of various complicated shapes again, its range of application is increased greatly, and material can prepare fuel tank of vehicle and high barrier container, and wide application and industrial prospect are arranged.
Embodiment:
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1:
With weight percent 85% nylon 6; 0.3%TDI; 14.5%MAH-g-PP; 0.2% lanthanum trioxide; thorough mixing is even under homogenizer; the homogenizer rotating speed is 1200 rev/mins, mixed material is put into twin screw extruder process, and screw speed is 300 rev/mins; the screw rod charging zone; plasticizing zone; the membrana oralis temperature is respectively 210 ℃; 220 ℃, 235 ℃, 235 ℃; 235 ℃; 235 ℃, 230 ℃ and 225 ℃, material is about 1.5 minutes in the residence time of forcing machine; the material of extruding cools off in cooling tank; through the dicing machine pelletizing, obtain pellet, 110 ℃ of dryings are 24 hours in vacuum drying oven.This material can blow molding (as 500 milliliters container), and its tensile strength, thermotolerance, barrier etc. all do not change, and shock strength doubles than former nylon 6.
Embodiment 2:
With weight percent is 75% nylon 6; 1% ethylene glycol; 13% styrene-maleic anhydride copolymer (SMA); 10% ethylene-vinyl acetate copolymer (EVA); 1% Samarium trioxide; thorough mixing is even under homogenizer; the homogenizer rotating speed is 1000 rev/mins; mixed material is put into twin screw extruder to be processed; screw speed is 300 rev/mins; the screw rod charging zone; plasticizing zone; the membrana oralis temperature is respectively 220 ℃; 225 ℃, 230 ℃, 235 ℃; 235 ℃; 230 ℃, 225 ℃ and 220 ℃, material is about 2 minutes in the residence time of forcing machine; the material of extruding cools off in cooling tank; through the dicing machine pelletizing, obtain pellet, 110 ℃ of dryings are 30 hours in vacuum drying oven.This material can blow molding, and its tensile strength, thermotolerance etc. are identical with former nylon 6, and shock strength is higher than 6 three times of former nylon under the normal temperature, and low temperature impact strength is higher than former nylon 6 twices, and the oil impregnate rate is lower more than one times than nylon 6.
Claims (4)
1, a kind of preparation of composite nylon material capable of being blow moulded, it is characterized in that at weight percent be in the nylon 6 of 60-99.8%, add 0.1-39.9% chainextender or the polymkeric substance of functionalization and the rare earth oxide of 0.01-5%, be to mix the back on 500-8000 rev/min the homogenizer in twin screw extruder, to make pellet at rotating speed, extruder temperature is 160-320 ℃, rotating speed is 100-800 rev/min, the residence time of material in screw rod is 1-10 minute, the material of extruding is through cooling, pelletizing, then in baking oven 80-180 ℃ dry 10-30 hour.
2, as the said preparation of composite nylon material capable of being blow moulded of claim 1, it is characterized in that chainextender gets vulcabond TDI, p-Hydroxybenzoate, 4,4 '-isopropylidene double-basis phenol salicylate, salicylic acid phenyl ester, ethylene glycol, phenol, phenyloxalate DPO.
3, as the said preparation of composite nylon material capable of being blow moulded of claim 1, the polymkeric substance that it is characterized in that described functionalization is styrene-maleic anhydride copolymer SMA, ethylene-vinyl acetate copolymer EVA, maleic anhydride grafted polyethylene copolymer p E-g-MAH, maleic anhydride inoculated polypropylene copolymer p P-g-MAH, polyethylene acrylic acid grafts PE-g-AA, the polypropylene grafted thing PP-g-AA of vinylformic acid, glycidyl methacrylate-polyethylene graft copolymer GMA-g-PE, glycidyl methacrylate-polypropylene graft copolymer GMA-g-PP, maleic anhydride graft styrene-butadiene-styrene multipolymer MAH-g-SBS, maleic anhydride graft acrylonitrile-butadiene-styrene copolymer MAH-g-ABS.
4,, it is characterized in that described rare earth oxide is cerium oxide, lanthanum trioxide, Samarium trioxide, Praseodymium trioxide, Yangization Nd, europium sesquioxide as the said preparation of composite nylon material capable of being blow moulded of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021360952A CN1176998C (en) | 2002-07-18 | 2002-07-18 | Prepn. of composite nylon material capable of being blow moulded |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021360952A CN1176998C (en) | 2002-07-18 | 2002-07-18 | Prepn. of composite nylon material capable of being blow moulded |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1389515A true CN1389515A (en) | 2003-01-08 |
| CN1176998C CN1176998C (en) | 2004-11-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021360952A Expired - Fee Related CN1176998C (en) | 2002-07-18 | 2002-07-18 | Prepn. of composite nylon material capable of being blow moulded |
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| CN (1) | CN1176998C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805516A (en) * | 2010-03-17 | 2010-08-18 | 浙江俊尔新材料有限公司 | Nylon 6 slice prepared by using waste fishing net and preparation method thereof |
| CN102399425A (en) * | 2010-09-09 | 2012-04-04 | 上海日之升新技术发展有限公司 | Electromagnetic-radiation-resisting rare earth oxide polymer composite material and preparation method thereof |
| CN103254635A (en) * | 2013-03-15 | 2013-08-21 | 东风(十堰)非金属部件有限公司 | Rare earth modified toughening nylon material and its preparation method |
| CN104119635A (en) * | 2013-04-25 | 2014-10-29 | 上海杰事杰新材料(集团)股份有限公司 | ABS / PA6 material for extrusion technology and preparation method thereof |
| CN104119634A (en) * | 2013-04-25 | 2014-10-29 | 上海杰事杰新材料(集团)股份有限公司 | Weather-proof ABS / PA6 material for flame retardation extrusion technology and preparation method thereof |
| CN104177822A (en) * | 2014-07-22 | 2014-12-03 | 上海日晶工程塑料科技有限公司 | Injection-molding-grade nylon 6 composite material and application thereof |
| CN106336654A (en) * | 2016-07-27 | 2017-01-18 | 温州市赢创新材料技术有限公司 | Heat conductive polyamide material |
| CN109467920A (en) * | 2018-12-19 | 2019-03-15 | 天津金发新材料有限公司 | 6 composition of automobile pipeline tri-dimensional blow moulding fiber glass reinforced polyamide and preparation method thereof |
| CN109721928A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polypropene composition and its preparation method and application |
| CN109852048A (en) * | 2019-01-04 | 2019-06-07 | 江苏理工学院 | A kind of PA6 modified composite material and preparation method thereof |
-
2002
- 2002-07-18 CN CNB021360952A patent/CN1176998C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805516B (en) * | 2010-03-17 | 2012-01-25 | 浙江俊尔新材料有限公司 | Nylon 6 slice prepared by using waste fishing net and preparation method thereof |
| CN101805516A (en) * | 2010-03-17 | 2010-08-18 | 浙江俊尔新材料有限公司 | Nylon 6 slice prepared by using waste fishing net and preparation method thereof |
| CN102399425A (en) * | 2010-09-09 | 2012-04-04 | 上海日之升新技术发展有限公司 | Electromagnetic-radiation-resisting rare earth oxide polymer composite material and preparation method thereof |
| CN103254635B (en) * | 2013-03-15 | 2015-07-15 | 东风(十堰)非金属部件有限公司 | Rare earth modified toughening nylon material and its preparation method |
| CN103254635A (en) * | 2013-03-15 | 2013-08-21 | 东风(十堰)非金属部件有限公司 | Rare earth modified toughening nylon material and its preparation method |
| CN104119635A (en) * | 2013-04-25 | 2014-10-29 | 上海杰事杰新材料(集团)股份有限公司 | ABS / PA6 material for extrusion technology and preparation method thereof |
| CN104119634A (en) * | 2013-04-25 | 2014-10-29 | 上海杰事杰新材料(集团)股份有限公司 | Weather-proof ABS / PA6 material for flame retardation extrusion technology and preparation method thereof |
| CN104177822A (en) * | 2014-07-22 | 2014-12-03 | 上海日晶工程塑料科技有限公司 | Injection-molding-grade nylon 6 composite material and application thereof |
| CN106336654A (en) * | 2016-07-27 | 2017-01-18 | 温州市赢创新材料技术有限公司 | Heat conductive polyamide material |
| CN106336654B (en) * | 2016-07-27 | 2018-09-11 | 温州市赢创新材料技术有限公司 | A kind of heat conduction polyamide material |
| CN109721928A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polypropene composition and its preparation method and application |
| CN109467920A (en) * | 2018-12-19 | 2019-03-15 | 天津金发新材料有限公司 | 6 composition of automobile pipeline tri-dimensional blow moulding fiber glass reinforced polyamide and preparation method thereof |
| CN109852048A (en) * | 2019-01-04 | 2019-06-07 | 江苏理工学院 | A kind of PA6 modified composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1176998C (en) | 2004-11-24 |
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