CN102030910A - Method for preparing long chain branched polyethylene - Google Patents
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Abstract
The invention provides a method for preparing long chain branched polyethylene. The method comprises the following steps of: (1) irradiating a substrate polyethylene with high-energy electron beams or gamma-rays to obtain pre-irradiated polyethylene, wherein the irradiation dose is 1 to 20OkGy; (2) blending the pre-irradiated polyethylene obtained in the step (1) and the substrate polyethylene and uniformly stirring to obtain a premixture, wherein in the premixture, the pre-irradiated polyethylene accounts for 1 to 99 weight percent and the substrate polyethylene accounts for 99 to 1 weight percent; and (3) performing reaction extrusion on the premixture obtained in the step (2) to prepare the long chain branched polyethylene. The method is simple, feasible and low in cost; and the obtained long chain branched polyethylene has more sensitive shear thinning property and higher melt strength, is applied to multiple kinds of processing technology, has high processability and particularly has good application prospect in the fields of thin films and foaming.
Description
Technical field
The present invention relates to a kind of preparation method of long-chain branched polyethylene, specifically, relate to a kind of pre-irradiation technology that comprises and prepare the method for long-chain branched polyethylene.
Technical background
Commercial polyvinyl resin has the performance of various excellences, but but there is deficiency aspect melt strength and the processing characteristics, therefore for example promptly be that the linear polyethylene melt can not produce strain hardening when melting temperature is above, occur melt man-hour easily and subside and rupture adding.Again for example, linear low density polyethylene still has very high viscosity under high shear rate in the blown film process, make that to add moment of torsion in man-hour, melt temperature and die pressure all very big, cause melt to relax, be unfavorable for forming stable film bubble during blown film at the obvious of mouth mould place.In addition, also there are some other defectives in linear polyethylene under different melt-processed modes, edge warping appears in the coating procedure easily as extruding at a high speed, molten hanging down and inhomogeneous contraction taken place in the sheet material extrusion moulding easily, and is easy to occur the flowing instability phenomenon in the matrix material coextrusion processes.These deficiencies cause material property to descend and the ratio of defective goods increases, and have seriously limited the application of polyethylene at aspects such as extrusion-blown modling, coating, foaming.
It is generally acknowledged that introducing long chain branching on the linear polyethylene chain can address the above problem.The long chain branching linear polyethylene has the characteristics of plasticity of the elasticity of rubber like and thermoplastic resin concurrently, and (the high degree of branching is an elastomerics, reduced branching degree is a thermoplastic resin), it is low that it not only has density, the melt strength advantages of higher, and the puncture resistance of these goods is strong and dart impact strength also is improved.This is because long-chain branch can promote melt shear shinning behavior, the general linear polyethylene of the viscosity ratio of melt under high shear rate is low in other words, and the viscosity under low shear rate is than general linear polyethylene height, this is equivalent to the poly molecular weight distribution of broadening, therefore can improve Drawing abillity.Can not be attached in the backbone fold laminate structure fully than long-chain branch in addition, disturbed the folding of main chain, but can pass sheet intergranular transition layer and participate in another chain folded crystal, form sheet intergranular " frenulum " molecule, therefore improve the mechanical property of goods.Since when polymerization, be difficult to not only guarantee linear backbone increase in but also on main chain, introduce a certain amount of long branched chain, become the optimal path that improves polythene working property so adopt the post-modification method to prepare long-chain branched polyethylene, utilizing ionizing rays to introduce long-chain branch on the polyethylene main chain is exactly wherein a kind of important post-modification method.
The free radical yield that forms after the polyethylene raying is higher (can to reach 6-8mol/kg referring to Polymer Handbook, 2
NdEdition, 1957, by J.Brandrup), when if the screw extrusion press of employing sealing or Banbury mixer are directly extruded, under high pressure, high shear forces and secluding air state, the motion of polyethylene segment is accelerated, and the free radical probability of collision on the segment will increase greatly, therefore be easy to produce coupling and form branching and crosslinked, and degrade, the probability of oxidizing reaction will reduce.Just need control crosslinking reaction in the course of processing in order to increase long chain branching reaction as far as possible, reduce the collision between the free radical on the pre-irradiation polyethylene segment, this for pre-irradiation poly directly react to extrude add trade union and be difficult to realization.
U.S. Pat 5508319 discloses a kind of method of utilizing radiotechnology to prepare long-chain branched polyethylene, thereby has improved the linear polyethylene extensional viscosity and the strain-hardening property of (comprising high density polyethylene(HDPE), linear low density polyethylene).Concrete grammar is at first to adopt gamma-rays or high energy electron irradiation under the absorption dose that is lower than 2.0Mrad (being 20kGy) resin to be carried out irradiation, and the volumetric concentration of oxygen will be lower than 15% in the radiation environment, and purpose is that minimizing active oxygen and material are subjected to the free radical reaction that produces behind the irradiation and reduce branching reaction efficient; Second step was enough time-shifts to be arranged and form branching being subjected to irradiated polyethylene to deposit the chain that made the free radical of generation in 2-30 minute in environment; Be the free radical deactivation process at last, can take thermal treatment (being higher than 60 ℃) or add radical scavenger (mercaptan compound) method elimination residue free radical, reduce with this crosslinked probability takes place.The melt tensile stress of the long-chain branched polyethylene of preparation has improved 1-4 doubly, and compares I by melt flow rate (MFR)
10/ I
2Increase show the molecular weight distribution broadening of resin and the improvement of processing characteristics.
Another U.S. Pat 4525257 discloses a kind of similar approach the narrow molecular weight distributions linear low density polyethylene has been carried out radiation treatment, improve the extensional viscosity and the shear viscosity of resin with this, irradiation dose is controlled between the 0.05Mrad to 2Mrad, but be subjected to irradiated polyethylene not remain free radical through the step of deactivating to reduce, this may cause partial cross-linked when high irradiation dose.
U.S. Pat 6887912 (B2) discloses the method that a kind of radiate linear polyethylene and common new LDPE (film grade) blend prepare foam material.The linear polyethylene that adopts comprises high density polyethylene(HDPE), linear low density polyethylene, on linear molecular chain, introduced long chain branching through after the radiation treatment, the product that obtains mixes with common new LDPE (film grade) again, and is compatible fully to determine it by the melting process of the hot analytical test intermingling material of DSC then.The blending foaming material abscess is even, nothing is subsided, and tearing toughness improves more than 25%.The problem that this blending foaming material exists is: 1, need to adopt two kinds of different structure polyethylene raw materials, so both increased the cost of selecting material, also want the irradiation dose (10-40kGy) of careful control line property polyethylene simultaneously, be unfavorable for blending technology and product performance in order to avoid produce gel; 2, intermingling material in use also might occur being separated and cause product performance to descend, therefore wherein irradiation linear polyethylene component concentration must be controlled at low ratio (is 20wt% as the high-content of irradiation linear low density polyethylene among the embodiment), guarantees the complete miscibility of material and obtains the preferable foamed products of performance with this.
From above-mentioned patent as can be seen: adopting method of radiating is the effective technology that linear polyethylene forms long chain branching, and the materials processing performance and the application performance that obtain are all good.But, need to reduce irradiation dose on the one hand and reduce oxygen concentration in the radiation environment in order to control poly radiation crosslinking and other side reaction; Need last handling process to eliminate the further reaction of residual free radical on the other hand, increased the complicacy of technology like this.
Summary of the invention
The inventor finds by great deal of experimental, adopt pre-irradiation polyethylene and matrix polyethylene blend reaction extrusion method, chain transfer and the branching reaction that can realize free radical carry out synchronously, when improving the free radical utilization ratio, also reduce irradiation and caused poly crosslinking degree, thereby the long-chain branched polyethylene that obtains has very sensitive shear shinning character and very high melt strength, also has favorable rigidity simultaneously, mechanical properties such as toughness, be adapted to various complete processings and have excellent machinability, especially better application prospect is arranged at film and foaming field.This preparation method also has advantages such as simple and easy to do, with low cost.
The purpose of this invention is to provide a kind of preparation method of long-chain branched polyethylene, may further comprise the steps:
(1) utilize high-power electron beam or gamma-radiation that the matrix polyethylene is carried out radiation treatment, obtain the pre-irradiation polyethylene, irradiation dose is 1～200kGy, is preferably 5～100kGy;
(2) pre-irradiation polyethylene and the matrix polyethylene that step (1) is obtained mixes, and stirs and obtain premixture, and wherein in premixture, the pre-irradiation polyethylene is 1～99%wt, and the matrix polyethylene is 99～1%wt; Preferred pre-irradiation polyethylene is 5～50%wt, and the matrix polyethylene is 95～50%wt;
(3) premixture that step (2) is obtained reacts and extrudes, and makes long-chain branched polyethylene.
Matrix polyethylene described in step of the present invention (1) and the step (2) is that density is 0.900～0.970g/cm
3Polyvinyl resin, comprise high-density polyethylene resin, linear low density polyethylene resin, ldpe resin.Preferred linear polyethylene resin (high-density polyethylene resin, linear low density polyethylene resin), more preferably linear low density polyethylene resin.Prepare these poly technologies and comprise vapor phase process, solution method, slurry process, catalyst system can be a Ziegler-Natta catalyst, also can adopt organic transition metal oxide catalyst, single site catalysts or metallocene catalyst.Linear polyethylene resin of the present invention is to be obtained by ethylene homo, or is obtained by any one or more than one monomer copolymerizable in ethene and propylene, butene-1, hexene-1,4-methyl-1-pentene, the octene-1; Linear low density polyethylene resin of the present invention is meant based on linear chain, contain a small amount of short branched chain and seldom or not contain long branched chain, the content of its short-and-medium branched chain is no more than 30/1000 carbon atom, as the polyethylene that is prepared in gas-phase process by the Ziegler-Natta catalyzer.
The selected linear polyethylene resin of the present invention is tasteless, odorless, nontoxic white powder or granular product, is preferably powdery product, and this helps directly carrying out post-modification from the raw material that poly-unit comes out handles, and reduces the extruding pelletization flow process.
Step of the present invention is carried out pre-irradiation to the matrix polyethylene in (1), the source of radiation that adopts comprises the gamma-radiation that high-power electron beam that high-energy electron accelerator produces or cobalt, caesium radioactive source produce, the gamma-radiation irradiation that preferably adopts radioactive source to produce in the present invention, gamma-radiation has characteristics such as penetrativity is strong, dose rate is low, continuity is good, is applicable to the radiation treatment of batch samples and various irregular samples.Gamma-radiation is by the radioactive nuleus element
60Co or
137The photon that produces during the Cs decay, energy is respectively 1.17MeV, 1.33MeV or 0.66MeV, these photons are absorbed by exposed material and its molecule generation are excited, and form ion, free radical isoreactivity group is used further to other reaction, the amount that forms active group is directly proportional with the radiating capacity that is absorbed (radiation dose).The fundamental unit of radiation dose is rad, and international unit generally adopts Gy (1Gy=100rad), the radiation dose that absorbs 1Gy represents that the irradiated material that is subjected to of 1kg has absorbed the radiating capacity of 1J, the irradiation dose that the present invention adopts is 1～200kGy, be preferably 5～100kGy, dose rate is 0.1～105kGy/h, is preferably 1～10kGy/h.
High-power electron beam that sub polyethylene subchain and above-mentioned source of radiation produce or gamma-radiation interact and dehydrogenation reaction take place and form free radical, these free radicals are uniformly distributed on the linear polyethylene chain, and the linear chain of polyethylene is easy to produce fold arrangement formation lamellar structure, platelet is further piled up the formation spherocrystal again, finally obtain the semicrystalline polymeric of crystallizing field and non-crystalline region coexistence, so the free radical that irradiation produces also is uniformly distributed in crystallizing field and the non-crystalline region thereupon.Reactions such as disproportionation, coupling not only can take place with the segment free movement and finally bury in oblivion in the free radical that forms on the non-crystalline region Polyethylene Chain, also form aldehyde radical, keto compounds with the combination with oxygen that is diffused into non-crystalline region easily in addition, this part free radical has also lost the possibility of further reaction; And the free radical that forms on the crystallizing field Polyethylene Chain can stable existence because sub-chain motion is limited among crystal layer, in the time of on being heated to the polyethylene melting temperature, along with crystallising part fusion and the crystallization segment motion that affranchises gradually, reactions such as branching, crosslinked, degraded and oxidation just can take place in the free radical on the crystallization segment.Reach " dilution " effect of free radical by high density free radical that the pre-irradiation polyethylene is carried to the poly chain transfer of matrix, will reduce the crosslinking reaction between the pre-irradiation polyethylene like this and realize that the long chain branching reaction is dominant between pre-irradiation polyethylene and matrix polyethylene.
In the step of the present invention (2) pre-irradiation polyethylene and matrix polyethylene mixed and stir and obtain premixture, stir and adopt manually stirring or adopt homogenizer to finish, wherein high-speed stirring speed stirs temperature in the kettle more fortunately below 50 ℃ between 1000 rev/mins to 10000 rev/mins.
In the step of the present invention (3) premixture reaction extruded and make long-chain branched polyethylene, temperature of reaction is the general processing temperature of polyethylene, selects not only guaranteeing the complete fusion of polyethylene but also can not make in the scope of its decomposition.Reaction is extruded the melt blending that is different from common forcing machine and is extruded, and has increased the high-shear engaged section in the extruder, and this helps the melting charge back mixing and improves the residence time and the mixed effect of material in equipment, also just helps branching reaction and carries out.Employed extruder is twin screw extruder, Banbury mixer etc.
The long branched chain of the long-chain branched polyethylene that the present invention prepares is the linear polyethylene molecular chain, the branched chain length range is 8-10000C, and these branched chains are that the binary that formed by any one or more than one monomer in Alathon or ethene and propylene, butene-1, hexene-1,4-methyl-1-pentene, the octene-1 or terpolymer are grafted on the matrix polyethylene backbone and form.Its melt flow index compares I
10/ I
2〉=10, and the I of ordinary lines property polyethylene
10/ I
2Be generally less than 10, most less than 5, visible long chain branching causes the shearing sensibility of material and non-Newtonianism obviously to increase, and therefore helps widening the process window of material and reduces production energy consumption.Melt strength 〉=the 20cN of long-chain branched polyethylene compares with the ordinary lines property polyethylene and to improve, and has increased melt relaxation time and stretch-proof performance to a certain extent.Long-chain branched polyethylene is with good melt processability and excellent mechanical property, be fit to be applied to produce fields such as film, fiber, sheet material, tubing, moulded parts, foaming product and wire cable insulating layer, be applied to blown film and foaming product field especially.
The present invention prepares long-chain branched polyethylene with pre-irradiation polyethylene and the matrix polyethylene method extruded of reaction that is mixed, the high density free radical that this method is carried the pre-irradiation polyethylene reaches " dilution " effect of free radical to the poly chain transfer of matrix, will reduce the crosslinking reaction between the pre-irradiation polyethylene like this, the polyethylene that obtains has very sensitive shear shinning character and very high melt strength, also has good rigidity simultaneously, mechanical properties such as toughness, this preparation method need not to add other chemical assistants just branching can take place, crosslinked, chemical reactions such as degraded, so the present invention has easy enforcement, with low cost, clean environment firendly, advantage such as energy-conservation.
Embodiment
The invention will be further described below in conjunction with specific embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Testing method:
1, melt strength: according to the Rheotens type melt stretching rheometer test that German Gottfert company produces, the melt temperature out is 200 ℃, port mould diameter 2mm, melt stretching acceleration 20mm/s
2
2, melt flow rate (MFR): according to standard GB/T 3682-2000, probe temperature is 190 ℃, and load is 2.16kg and 10kg, is designated as I respectively
2And I
10
3, tensile strength: according to standard GB/T 1040.2-2006, specimen adopts compression molding, rate of extension 20mm/min.
4, modulus in flexure: according to standard GB/T 9341-2000, specimen adopts compression molding, test rate 2.0mm/min.
Embodiment 1
(Plant of Tianjin Petrochemical Company, DGH 1875, butene-1 copolymerization, density 0.918g/cm for line taking new LDPE (film grade) powder
3Melting index is 0.46g/10min) by obtaining the pre-irradiation polyethylene after the gamma-ray irradiation processing, irradiation carries out under air conditions, and absorption dose is 15kGy, 100g pre-irradiation polyethylene and 900g linear low density polyethylene powder mechanically mixing is carried out melt blending after evenly extrude.It is to finish in twin screw extruder that melt blending is extruded, screw diameter is 30mm, length-to-diameter ratio is 35.6, the temperature of forcing machine from feed zone to mouthful mould is set at 165 ℃, 180 ℃, 190 ℃, 200 ℃, 200 ℃, 200 ℃, 190 ℃ successively, engine speed is 300Hz, feed rate 8Hz finishes preparation process after circulator bath cooling of product process and the pelletizing.
The performance of the long-chain branched polyethylene that makes sees Table 1 and table 2.
Comparative Examples 1
Get embodiment 1 identical linear low density polyethylene powder 1000g and directly extrude processing, processing conditions is identical with embodiment 1.The linear low density polyethylene performance that obtains sees Table 1 and table 2.
Comparative Examples 2
Get embodiment 1 identical pre-irradiation linear low density polyethylene powder and directly extrude processing, pre-irradiation linear low density polyethylene of then 100g being extruded and 900g linear low density polyethylene powder are extruded processing after mixing again, obtain the long-chain branched polyethylene product of uneven distribution, i.e. long-chain branched polyethylene/poly mixture.It is all identical with embodiment 1 to extrude processing conditions for twice.
The performance of the long-chain branched polyethylene/polyethylene mixture that obtains sees Table 1 and table 2.
Embodiment 2
Get the identical linear low density polyethylene powder 50g of embodiment 1, by obtaining the pre-irradiation polyethylene after the gamma-ray irradiation processing, irradiation carries out under air conditions, absorption dose is 15kGy, extrudes reacting after above-mentioned pre-irradiation polyethylene and the direct pre-mixing of 900g linear low density polyethylene powder evenly.Reaction extrusion process is identical with embodiment 1, and product property sees Table 1 and table 2.
Embodiment 3
Get the identical linear low density polyethylene powder 150g of embodiment 1, by obtaining the pre-irradiation polyethylene after the gamma-ray irradiation processing, irradiation carries out under air conditions, absorption dose is 15kGy, extrudes reacting after above-mentioned pre-irradiation polyethylene and the direct pre-mixing of 850g linear low density polyethylene powder evenly.Reaction extrusion process is identical with embodiment 1, and product property sees Table 1 and table 2.
Embodiment 4
Get the identical linear low density polyethylene powder 950g of embodiment 1, by obtaining the pre-irradiation polyethylene after the gamma-ray irradiation processing, irradiation carries out under air conditions, absorption dose is 15kGy, extrudes reacting after above-mentioned pre-irradiation polyethylene and the direct pre-mixing of 50g linear low density polyethylene powder evenly.Reaction extrusion process is identical with embodiment 1, and product property sees Table 1 and table 2.
Embodiment 5
Get the identical linear low density polyethylene powder 50g of embodiment 1, by obtaining the pre-irradiation polyethylene after the gamma-ray irradiation processing, irradiation carries out under air conditions, absorption dose is 5kGy, extrudes reacting after above-mentioned pre-irradiation polyethylene and the direct pre-mixing of 950g linear low density polyethylene powder evenly.Reaction extrusion process is identical with embodiment 1, and product property sees Table 1 and table 2.
Embodiment 6
Get the identical linear low density polyethylene powder 100g of embodiment 1, by obtaining the pre-irradiation polyethylene after the gamma-ray irradiation processing, irradiation carries out under air conditions, absorption dose is 5kGy, extrudes reacting after above-mentioned pre-irradiation polyethylene and the direct pre-mixing of 900g linear low density polyethylene powder evenly.Reaction extrusion process is identical with embodiment 1, and product property sees Table 1 and table 2.
Embodiment 7
Get the identical linear low density polyethylene powder 150g of embodiment 1, by obtaining the pre-irradiation polyethylene after the gamma-ray irradiation processing, irradiation carries out under air conditions, absorption dose is 5kGy, extrudes reacting after above-mentioned pre-irradiation polyethylene and the direct pre-mixing of 850g linear low density polyethylene powder evenly.Reaction extrusion process is identical with embodiment 1, and product property sees Table 1 and table 2.
Embodiment 8
Get the identical linear low density polyethylene powder 50g of embodiment 1, by obtaining the pre-irradiation polyethylene after the gamma-ray irradiation processing, irradiation carries out under air conditions, absorption dose is 50kGy, extrudes reacting after above-mentioned pre-irradiation polyethylene and the direct pre-mixing of 950g linear low density polyethylene powder evenly.Reaction extrusion process is identical with embodiment 1, and product property sees Table 1 and table 2.
Embodiment 9
Get the identical linear low density polyethylene powder 100g of embodiment 1, by obtaining the pre-irradiation polyethylene after the gamma-ray irradiation processing, irradiation carries out under air conditions, absorption dose is 50kGy, extrudes reacting after above-mentioned pre-irradiation polyethylene and the direct pre-mixing of 900g linear low density polyethylene powder evenly.Reaction extrusion process is identical with embodiment 1, and product property sees Table 1 and table 2.
Embodiment 10
Get the identical linear low density polyethylene powder 150g of embodiment 1, by obtaining the pre-irradiation polyethylene after the gamma-ray irradiation processing, irradiation carries out under air conditions, absorption dose is 50kGy, extrudes reacting after above-mentioned pre-irradiation polyethylene and the direct pre-mixing of 850g linear low density polyethylene powder evenly.Reaction extrusion process is identical with embodiment 1, and product property sees Table 1 and table 2.
Table 1
Table 2
From the embodiment of table 1 and Comparative Examples data as can be seen, the melt flow index of long-chain branched polyethylene of the present invention is than obviously increasing, and melt strength also significantly improves, and proves that thus this polyethylene has better shearing sensibility and better processability energy.It can also be seen that from table 2 that in addition the mechanical property of long-chain branched polyethylene of the present invention also has raising.
Claims (5)
1. the preparation method of a long-chain branched polyethylene may further comprise the steps:
(1) utilize high-power electron beam or gamma-radiation that the matrix polyethylene is carried out radiation treatment, obtain the pre-irradiation polyethylene, irradiation dose is 1～200kGy;
(2) pre-irradiation polyethylene and the matrix polyethylene that step (1) is obtained mixes, and stirs and obtain premixture, and wherein in premixture, the pre-irradiation polyethylene is 1～99%wt, and the matrix polyethylene is 99～1%wt;
(3) premixture that step (2) is obtained reacts and extrudes, and makes long-chain branched polyethylene.
2. the preparation method of a kind of long-chain branched polyethylene according to claim 1 is characterized in that, the irradiation dose described in the step (1) is 5～100kGy.
3. the preparation method of a kind of long-chain branched polyethylene according to claim 1 is characterized in that, in described premixture, wherein the pre-irradiation polyethylene is 5～50%wt in the step (2), and the matrix polyethylene is 95～50%wt.
4. the preparation method of a kind of long-chain branched polyethylene according to claim 1 is characterized in that, the matrix polyethylene described in step (1) and the step (2) is high density polyethylene(HDPE), new LDPE (film grade) or linear low density polyethylene.
5. the preparation method of a kind of long-chain branched polyethylene according to claim 4 is characterized in that, described matrix polyethylene is a linear low density polyethylene.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103515463A (en) * | 2012-06-27 | 2014-01-15 | 住友化学株式会社 | Film used for solar cell backboard, solar cell backboard and solar cell module |
| CN104974419A (en) * | 2014-04-14 | 2015-10-14 | 中国石化扬子石油化工有限公司 | Foamed polypropylene pre-mixed material and preparation method thereof |
| CN106479037A (en) * | 2015-08-26 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of method of polypropylene toughening |
| CN107200918A (en) * | 2017-07-12 | 2017-09-26 | 肇庆市东盛益源包装材料有限公司 | A kind of PE heat shrink films and preparation method thereof |
| CN108463496A (en) * | 2016-01-12 | 2018-08-28 | Sabic环球技术有限责任公司 | The injection molding product of foaming |
| CN108611006A (en) * | 2016-12-19 | 2018-10-02 | 上海海优威新材料股份有限公司 | Caking property protective film of cross-linking radiation and preparation method thereof |
| CN109762229A (en) * | 2018-12-24 | 2019-05-17 | 浙江万里新材料科技有限公司 | A kind of Radiation Crosslinked Polyethylene foam material and preparation method thereof |
| CN111484676A (en) * | 2020-06-13 | 2020-08-04 | 厦门毅兴行塑胶原料有限公司 | Toughness-improved polypropylene and preparation method thereof |
| CN112280184A (en) * | 2020-11-10 | 2021-01-29 | 中嘉卫华（固安）新材料科技有限公司 | Electron irradiation crosslinking foaming polypropylene heat preservation belt and preparation method thereof |
| CN115806704A (en) * | 2022-12-23 | 2023-03-17 | 常州市聚智新材料科技股份有限公司 | Hardened polyethylene foam and preparation method thereof |
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Cited By (11)
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| CN103515463A (en) * | 2012-06-27 | 2014-01-15 | 住友化学株式会社 | Film used for solar cell backboard, solar cell backboard and solar cell module |
| CN104974419A (en) * | 2014-04-14 | 2015-10-14 | 中国石化扬子石油化工有限公司 | Foamed polypropylene pre-mixed material and preparation method thereof |
| CN106479037A (en) * | 2015-08-26 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of method of polypropylene toughening |
| CN108463496A (en) * | 2016-01-12 | 2018-08-28 | Sabic环球技术有限责任公司 | The injection molding product of foaming |
| CN108463496B (en) * | 2016-01-12 | 2021-03-23 | Sabic环球技术有限责任公司 | Foamed injection molded article |
| CN108611006A (en) * | 2016-12-19 | 2018-10-02 | 上海海优威新材料股份有限公司 | Caking property protective film of cross-linking radiation and preparation method thereof |
| CN107200918A (en) * | 2017-07-12 | 2017-09-26 | 肇庆市东盛益源包装材料有限公司 | A kind of PE heat shrink films and preparation method thereof |
| CN109762229A (en) * | 2018-12-24 | 2019-05-17 | 浙江万里新材料科技有限公司 | A kind of Radiation Crosslinked Polyethylene foam material and preparation method thereof |
| CN111484676A (en) * | 2020-06-13 | 2020-08-04 | 厦门毅兴行塑胶原料有限公司 | Toughness-improved polypropylene and preparation method thereof |
| CN112280184A (en) * | 2020-11-10 | 2021-01-29 | 中嘉卫华（固安）新材料科技有限公司 | Electron irradiation crosslinking foaming polypropylene heat preservation belt and preparation method thereof |
| CN115806704A (en) * | 2022-12-23 | 2023-03-17 | 常州市聚智新材料科技股份有限公司 | Hardened polyethylene foam and preparation method thereof |
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Application publication date: 20110427 |