CN102582085B - Polyethylene self-reinforced composite material and preparation method thereof - Google Patents
Polyethylene self-reinforced composite material and preparation method thereof Download PDFInfo
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- CN102582085B CN102582085B CN201110453083.6A CN201110453083A CN102582085B CN 102582085 B CN102582085 B CN 102582085B CN 201110453083 A CN201110453083 A CN 201110453083A CN 102582085 B CN102582085 B CN 102582085B
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- polyethylene
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention discloses a polyethylene self-reinforced composite material and a preparation method thereof. The polyethylene self-reinforced composite material is prepared from polyethylene and polyethylene which is subjected to radiation micro-crosslinking. The method comprises the following steps of: (1) preparing the micro-crosslinked polyethylene; (2) preparing a masterbatch; (3) preparing a polyethylene blend; and (4) performing dynamic packing injection molding and the like. By the method, a self-reinforced structure of interlinked shish-kebab is formed inside the polyethylene composite material, so that the comprehensive performance of the material is enhanced; and compared with the polyethylene material without the micro-crosslinked polyethylene, the polyethylene self-reinforced composite material has the advantages that the tensile strength and modulus are improved obviously, the service life of the material can be prolonged, and the application range of the material is broadened.
Description
Technical field
The invention belongs to polymeric material field, relate to the preparation method of Self-reinforced Polyethylene macromolecular material.
Background technology
The physical and mechanical properties of polymer crystals Structure and morphology on polymeric material has important impact, is subject to increasing attention.Usually two kinds of crystal structures can be comprised: the orientation texture (shish-kebab, shish-kebab) that spherocrystal and flow-induction generate in semi-crystalline polymer goods.The former grows by platelet radial symmetric a kind of isotropic structure formed under static environment; The latter is the anisotropic structure formed under field of flow induction.Shish-kebab structure in goods imparts the mechanical property of material excellence, wear resistance and anti-fatigue performance etc., and therefore, the shish-kebab that generation ratio is larger and structure is more perfect in goods is all devoted in a lot of research.
Polyethylene is a kind of widely used semi-crystalline thermoplastic's macromolecular material, has good combination property, and the forming method of available general thermoplastic is processed.Its purposes is very extensive, is mainly used to manufacture film, container, pipeline, monofilament, electric wire, commodity etc., and can be used as the high-frequency insulation material of TV, radar etc.But, as a kind of general-purpose plastics, poly performance also improves a lot space to expand its scope of application.Such as, reduce shrinkage factor, improve strength and modulus, improve barrier property etc., these can go to consider from the angle of crystal structure.Polyethylene can generate shish-kebab structure in field of flow, and its ratio and degree of perfection depend on processing conditions, such as temperature, field of flow intensity, field of flow duration etc.But, for the polyethylene of molecular weight, also not necessarily shish-kebab structure can be formed under field of flow, mainly because field of flow is not unique decisive factor, poly molecular size range, in melt, macromolecular entangled state also can affect formation [the Tingzi Yan of shish-kebab structure, Baijin Zhao, Yuanhua Cong, Yuye Fang, Shiwang Cheng, Liangbin Li, Guoqiang Pan, Zijian Wang, Xiuhong Li, Fenggang Bian.Critical Strain for Shish-Kebab Formation.Macromolecules 2010, 43, 602-605]. current achievement in research thinks that the formation of shish structure mainly comes from the distortion of polymer melt network under field of flow substantially, the melt network that this intangibility twines more easily forms shish under field of flow, shish can grow nonparasitically upon another plant further and grow kebab crystal, and because intangibility twines and shish-kebab can be made to be connected with each other adding of network (just as one tree root).
In the pulsing packing injection molding process of routine, dynamic shearing self-reinforcing can obtain certain self-reinforced polyethylene, but shish-kebab ratio and organizational form are all undesirable.Other method, as the wild phases such as glass fibre, carbon fiber and whisker and matrix polymer compound also can be obtained composite reinforcing material, but this will bring the interface problems such as compatibility, reduce its scope of application.
Summary of the invention
In view of the above shortcoming of prior art, the object of the invention is to obtain a kind of Self-reinforced Polyethylene Composites preparation method, to obtain higher shish-kebab ratio, work in-process original position forms wild phase (interconnection shish-kebab structure), make wild phase and polymeric matrix have identical chemical constitution, the combination property of material is enhanced.
The present invention also aims to, a kind of Self-reinforced Polyethylene Composites is provided, make its inside have the self-reinforced structure of interconnection shish-kebab (ihterlinked shish-kebab).
The object of the invention is by following means realize:
A preparation method for Self-reinforced Polyethylene Composites, with polyethylene and through the micro-crosslinked polyethylene of radiation for Self-reinforced Polyethylene Composites prepared by raw material, comprise following processing step:
(1) micro-crosslinked polyethylene preparation: polyethylene powder or pellet are carried out radiation micro-crosslinked, dosage is less than 20kGy, obtains micro-crosslinked polyethylene;
(2) master batch processing: add in xylene solution after micro-crosslinked polyethylene obtained by step (1) accounting for masterbatch total amount 5 ~ 85% is mixed with the uncrosslinked pure polyethylene of surplus, solution mixing is carried out, until form the solution of homogeneous phase under heating and stirring condition; Being injected in methyl alcohol by gained solution makes polyethylene separate out, and obtains masterbatch after filtration with after heat drying; The moisture weight content of described masterbatch is less than 0.01%;
(3) polyethylene blend preparation: extruded by gained masterbatch melt blending in double screw extruder in step 2, carries out pelletizing after the material strip extruded being immersed cold water cooling, obtains the polyethylene blend containing a small amount of micro-crosslinked polyethylene uniformly;
(4) pulsing packing injection mo(u)lding: the polyethylene products polyethylene blend drying that (3) are obtained being carried out afterwards pulsing packing injection mo(u)lding self-reinforcing with Vibration Injection Molding mould, the barrel temperature of injection machine is 140 ~ 210 DEG C, nozzle temperature 190 ~ 210 DEG C, mold hot flow temperature is 180 ~ 200 DEG C, and mold temperature is 20 ~ 50 DEG C.
The present invention improves condensed state structure to improve its physical and mechanical properties from the angle of crystallization.The ratio that a small amount of micro-crosslinked polyethylene improves shish-kebab is added in base polyethylene, and Shearing Flow is applied in process, then the microstructure of goods is regulated and controled by controlling actual processing flow field parameter, make the shish-kebab that formed in polyethylene more, structure is more perfect, thus improves its combination property.There is following obvious advantage:
1, the shortcoming that shish-kebab ratio that polyethylene formed in field of flow is lower is overcome, a small amount of micro-crosslinked polyethylene is added in base polyethylene, a large amount of shish-kebabs can be formed in field of flow, the low molecular weight polyethylene of shish-kebab particularly can not be generated for itself, higher shish-kebab ratio can be obtained, and be interconnection shish-kebab, advantage is more obvious.
2, utilize the dynamic shearing field of flow in pulsing packing hot runner mould, the ratio of shish-kebab can be improved, improve the structure of crystal, and then improve its serviceability.
3, the material in the present invention is all polyethylene, do not add other polymeric material, belong to self-reinforcing, work in-process original position forms wild phase (interconnection shish-kebab structure), wild phase and polymeric matrix have identical chemical constitution, therefore not Presence of an interface problem.Ensure that the unicity of material, can be used for occasion material being had to particular requirement.
Accompanying drawing is described as follows:
Fig. 1 is the electron scanning micrograph of spherocrystal in the embodiment of the present invention;
Fig. 2 is the illustraton of model of shish-kebab;
Fig. 3 is the electron scanning micrograph of shish-kebab in the embodiment of the present invention 2;
Fig. 4 is pulsing packing injection forming mold schematic diagram.
Fig. 5 is the electron micrograph of composite (embodiment 2) the oscillating packing injection sample sandwich layer adding a small amount of crosslinked polyethylene.
The formula of table one embodiment 1 ~ 9 and comparative example 1.
Table two embodiment 1 ~ 9 and the tensile property of comparative example 1 under different injecting condition.
Detailed description of the invention
Embodiment given below is specifically described the present invention.What be necessary to herein means out is that following examples are only for the present invention is further illustrated; can not be interpreted as limiting the scope of the invention, the nonessential improvement that this art skilled person makes the present invention according to the invention described above content and adjustment still belong to protection scope of the present invention.Material polyethylene is the high density polyethylene (HDPE) that MFR is greater than 20g/10min in the examples below, can be powder or pellet.
Embodiment 1-9.
1, micro-crosslinked polyethylene is prepared: polyethylene is carried out radiation micro-crosslinked, dosage 5 ~ 10kGy.
2, preparation is containing the masterbatch of micro-crosslinked polyethylene: add in xylene solution by micro-crosslinked polyethylene of 20% and 80% uncrosslinked polyethylene, solution mixing is carried out under heating and stirring condition, heating-up temperature 100 DEG C, mixing speed 1000 ~ 3000RPM, more than half an hour time, until form the solution of homogeneous phase.Be injected in the methyl alcohol of room temperature by gained solution, methyl alcohol volume is 5 ~ 6 times of solution, polyethylene is separated out, then filters, and by much filtrate at 80 ~ 100 DEG C dry 8 ~ 12 hours, makes moisture weight content be less than 0.01%.
3, preparation is containing the polyethylene blend of a small amount of micro-crosslinked polyethylene: after dry for gained in the polyethylene of at least 85% (specifically filling a prescription in table one) and step 2 thing mechanical mixture, be placed in double screw extruder melt blending to extrude, obtain the polyethylene blend containing a small amount of micro-crosslinked polyethylene uniformly.First three section of extruder barrel and die temperature are set as 150,170,200 respectively, 190 DEG C, screw speed 60 ~ 120RPM, the material strip extruded are immersed temperature lower than forcing the rear pelletizing of cooling in the cooling water of 25 DEG C.Finally that poly blend pellet is dry at 80 ~ 100 DEG C, make moisture weight content be less than 0.01%.
4, pulsing packing injection mo(u)lding: then add in the injection machine being provided with pulsing packing injection mold by dried blend pellet, injection mo(u)lding is containing the self-reinforcing goods of shish-kebab structure.Compared with common injection mo(u)lding, be characterized in after mold filling, oscillatory shear effect to be applied to melt in mold cavity, promote molecular chain orientation, generate the self-reinforced structures such as shish-kebab.Injecting machine material tube temperature 150 ~ 210 DEG C, nozzle temperature 200 DEG C, hot flow path temperature 190 DEG C, mold temperature 40 DEG C.Pulsing packing oil cylinder working-pressure 5MPa, oil cylinder piston vibration frequency 0.3Hz.Fig. 4 is typical pulsing packing injection molding apparatus: 1-barrel, 2,12-hot flow path, 3,11-piston, 4,10-oil cylinder, 5,9-melt chamber, and 6-cast gate, 7-die cavity, 8-air adiabatic pad.Have lasting shear action by the reciprocating motion of piston 3 and 10 to melt in die cavity at the packing stage of injection moulding process, consequently polymer molecular chain produces orientation and freezes, and therefore goods have higher strength and modulus.
When reality is implemented, the technological parameter in step (3) can have the change of certain amplitude, and the barrel of screw extruder and die temperature should set and can be between 140 DEG C ~ 210 DEG C, and screw speed is less than 200 turns/min, and the temperature of cooling water is lower than 35 DEG C.Experiment also shows, when preparing masterbatch, micro-crosslinked polyethylene has larger material variable range with the uncrosslinked pure polyethylene of surplus.When other condition of upper embodiment is constant, micro-crosslinked polyethylene weight is 5 ~ 85%, and accordingly, the uncrosslinked pure polyethylene of surplus is in 15 ~ 95% scopes, and product all has the effect required by the present invention.
Comparative example 1
By the component proportion that comparative example in table one 1 provides, by material oscillating packing injection molding, prepare pure HDPE goods for Performance comparision.
The present invention also adopts SEM to observe to the microscopic pattern of composite polyethylene material, the results are shown in accompanying drawing 1, Fig. 3 and Fig. 5.Shown in Fig. 1 is do not strengthen the sandwich layer of sample and the structure in intermediate layer, and its crystal is mainly spherocrystal.Fig. 3 is the crystal structure in the intermediate layer of the Dynamic contrast enhance sample that with the addition of a small amount of crosslinked polyethylene, can find out, under the effect of oscillatory shear, define interconnection shish-kebab structure in sample, PE platelet is along flow direction orientation.After with the addition of a small amount of crosslinked polyethylene as can be seen from Figure 5, also there is interconnection shish-kebab in the sandwich layer of composite, and this is the immanent cause that is improved of the performance of material just also.
Table two have expressed embodiment 1 ~ 9 and the tensile property of comparative example 1 under different injecting condition.
In order to investigate the mechanical property of prepared composite polyethylene material, utilize the performance of tester for elongation to the Static and dynamic sample of each embodiment and comparative example to measure according to the method provided in ASTM D-638, the results are shown in Table 2.Rate of extension is 10mm/min, and probe temperature is room temperature (23 DEG C).
Claims (2)
1. a preparation method for Self-reinforced Polyethylene Composites, with polyethylene and through the micro-crosslinked polyethylene of radiation for Self-reinforced Polyethylene Composites prepared by raw material, comprise following processing step:
(1) micro-crosslinked polyethylene preparation: polyethylene powder or pellet are carried out radiation micro-crosslinked, dosage is less than 20kGy, obtains micro-crosslinked polyethylene;
(2) master batch processing: add in xylene solution after micro-crosslinked polyethylene obtained by step (1) accounting for masterbatch total amount 5 ~ 85% is mixed with the uncrosslinked pure polyethylene of surplus, solution mixing is carried out, until form the solution of homogeneous phase under heating and stirring condition; Being injected in methyl alcohol by gained solution makes polyethylene separate out, and obtains masterbatch after filtration with after heat drying; The moisture weight content of described masterbatch is less than 0.01%;
(3) polyethylene blend preparation: gained masterbatch melt blending in double screw extruder in step (2) is extruded, carry out pelletizing after the material strip extruded being immersed cold water cooling, obtain the polyethylene blend containing a small amount of micro-crosslinked polyethylene uniformly;
(4) pulsing packing injection mo(u)lding: the polyethylene products polyethylene blend drying that step (3) is obtained being carried out afterwards pulsing packing injection mo(u)lding self-reinforcing with Vibration Injection Molding mould, the barrel temperature of injection machine is 140 ~ 210 DEG C, nozzle temperature 190 ~ 210 DEG C, mold hot flow temperature is 180 ~ 200 DEG C, and mold temperature is 20 ~ 50 DEG C; Described material polyethylene is the high density polyethylene (HDPE) that MFR is greater than 20g/10min; In step (3), the barrel of described screw extruder and die temperature should be set as that between 140 DEG C ~ 210 DEG C, screw speed is less than 200 turns/min, and the temperature of cooling water is lower than 35 DEG C.
2. the Self-reinforced Polyethylene Composites that method is obtained according to claim 1, is characterized in that, described self-reinforced polyethylene composite inner has the self-reinforced structure of interconnection shish-kebab.
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| CN106589525A (en) * | 2016-11-28 | 2017-04-26 | 安徽瑞研新材料技术研究院有限公司 | Antistatic polyethylene self reinforced composite material |
| CN109503916B (en) * | 2018-07-13 | 2021-07-02 | 四川大学 | High-strength hydrostatic-pressure-resistant polyethylene pipe and preparation method thereof |
| CN109256239B (en) * | 2018-07-28 | 2020-10-16 | 郑州大学 | Poly (3-hexylthiophene) conductive network structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6461644B1 (en) * | 1996-03-25 | 2002-10-08 | Richard R. Jackson | Anesthetizing plastics, drug delivery plastics, and related medical products, systems and methods |
| CN101679696A (en) * | 2007-05-18 | 2010-03-24 | 住友化学株式会社 | Ethylene polymer composition and film |
| CN101824178A (en) * | 2010-04-06 | 2010-09-08 | 湖北众联塑业有限公司 | Method for reducing flow rate of polyethylene melt |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6461644B1 (en) * | 1996-03-25 | 2002-10-08 | Richard R. Jackson | Anesthetizing plastics, drug delivery plastics, and related medical products, systems and methods |
| CN101679696A (en) * | 2007-05-18 | 2010-03-24 | 住友化学株式会社 | Ethylene polymer composition and film |
| CN101824178A (en) * | 2010-04-06 | 2010-09-08 | 湖北众联塑业有限公司 | Method for reducing flow rate of polyethylene melt |
Non-Patent Citations (1)
| Title |
|---|
| 微交联聚乙烯网络对聚乙烯流动诱导结晶过程的影响;雷军等;《2011年全国高分子学术论文报告会》;20110928;第364页 * |
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