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Method for polymerizing and grafting polyethylene surface light-initiated controllable free radical with ultrahigh molecular weight

An ultra-high molecular weight, polyethylene technology, applied in the field of surface chemical modification of high molecular polymer materials, can solve the problems of difficult continuity treatment, easy attenuation of fiber surface bonding properties, and many side reactions, so as to improve the hydrophilicity. The effect of high adhesion and adhesion properties, low UV intensity, and product purity

Active Publication Date: 2012-06-20
SHANGHAI RES INST OF CHEM IND +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0010] 3. Low-temperature plasma treatment has the advantages of good environmental protection, good modification effect, and simple method, but the cost is high, it is difficult to achieve continuous treatment, and there is also the problem of attenuation of modification effect
[0011] 4. Photografting modification. At present, the commonly used radiation source is ultraviolet light, which has the advantages of good environmental protection, low cost, good modification effect, almost no effect on mechanical properties, and long-term modification effect. The photografting modification method carried out is not easy to control, and there are many side reactions, the grafting efficiency is low, and the homopolymer is obviously produced.
The results show that after corona treatment, the oxygen content on the surface of UHMWPE fiber increases, the number and types of oxygen-containing groups increase, the surface wettability is improved, and the interfacial bond strength (τs) between the fiber and the matrix increases by 535%. The shear strength of the short beam has been increased by more than 40%, but the bonding performance of the fiber surface treated by this method is easy to decay, and it is not easy to store for a long time
[0016] Liang Guozheng et al. [Applied Surface Science, 2006, 253(2): 668-673] of Northwestern Polytechnical University in China found that the monofilament of UHMWPE fiber after grafting was pulled out through liquid-phase UV irradiation grafting of acrylamide (AM). The strength and interlayer shear strength of the interface are greatly improved, reaching 16.9MPa for epoxy resin ILLS, and 19.4MPa for special vinyl resin, but the reaction time of this method is longer
[0017] Chinese patent CN1035308A discloses a method for improving the surface bonding properties of UHMWPE fibers, which uses plasma to treat the surface of ultra-high molecular weight polyethylene fibers, and the wettability and surface bonding properties of the modified fibers to common substrates Both are greatly strengthened, but the cost of this method is high, and it is not easy to realize continuous production, and improper operation may easily cause the decline of fiber mechanical properties

Method used

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  • Method for polymerizing and grafting polyethylene surface light-initiated controllable free radical with ultrahigh molecular weight
  • Method for polymerizing and grafting polyethylene surface light-initiated controllable free radical with ultrahigh molecular weight
  • Method for polymerizing and grafting polyethylene surface light-initiated controllable free radical with ultrahigh molecular weight

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Experimental program
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Effect test

Embodiment 1

[0048] Under the protection of nitrogen, the ultra-high molecular weight polyethylene film was swelled in n-heptane for 6 hours, and then extracted with acetone for 6 hours to obtain a pretreated ultra-high molecular weight polyethylene film. The pretreated film was soaked in diphenyl Methanone (concentration 1%) in the acetone / n-heptane (acetone / n-heptane weight ratio 1: 4) solution 2h, then be placed in the quartz tube and react 20min under nitrogen atmosphere, the sample infrared spectrum after reaction is as follows figure 1 As shown, after ultraviolet irradiation, the absorption peaks of benzene ring appeared at 1654, 1586 and 752nm.

Embodiment 2

[0050] Under the protection of nitrogen, the ultra-high molecular weight polyethylene fibers were swelled in n-heptane for 24 hours, and then extracted with acetone for 10 hours to obtain pretreated ultra-high molecular weight polyethylene fibers. The pretreated fibers were soaked in diphenyl Methanone / xanthone (benzophenone / xanthone weight ratio 4:1, concentration 10%) in acetone / n-heptane (acetone / n-heptane weight ratio 4:1) solution for 24h, then Placed in a quartz tube and reacted for 120min under a nitrogen atmosphere, the UV absorption spectrum of the reacted sample is as follows: figure 2 As shown, the UHMWPE-SP fiber has an obvious absorption peak at 280nm, but the blank fiber sample does not, and the absorption peak at 280nm is the ultraviolet absorption peak of the benzene ring.

Embodiment 3

[0052] Under the protection of nitrogen, the ultra-high molecular weight polyethylene fibers were swelled in n-heptane for 12 hours, and then extracted with acetone for 8 hours to obtain pretreated ultra-high molecular weight polyethylene fibers. The pretreated fibers were soaked in diphenyl Methanone (concentration 5%) in acetone / tetrahydrofuran (acetone / tetrahydrofuran weight ratio 2: 1) solution for 12h, then placed in a quartz tube and reacted for 60min under a nitrogen atmosphere, the sample py-GC-MS spectrum after the reaction is as follows image 3 As shown, the benzene ring and toluene fragment ion flow in the Py-GC-MS spectrum is the fragment ion flow of the photosensitive group in UHMWPE-SP.

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Abstract

The invention discloses a method for polymerizing and grafting a polyethylene surface light-initiated controllable free radical with ultrahigh molecular weight. The method comprises the following steps of: putting a pretreated polyethylene substrate with ultrahigh molecular weight into a photosencitizer solution; radiating with ultraviolet rays to form a surface photosensitive group; soaking in a riveted monomer solution for reacting; initiating the grafting reaction of the light-initiated riveting monomer through ultraviolet radiation; treating the grafted polyethylene substrate with ultrahigh molecular weight by using a light-initiated transfer terminator; and forming an active tail end which can be used for initiating through ultraviolet rays on treated substrate, wherein the active tail end has high initiation performance, is controllable, and can be used for further initiating controllable free radical polymerizing and grafting of other active monomers, so that the bonding performance and hydrophilicity of the polyethylene substrate with ultrahigh molecular weight are greatly improved.

Description

technical field [0001] The invention relates to a method for surface chemical modification of high molecular polymer materials, in particular to a method for surface polymerization graft modification of ultra-high molecular weight polyethylene materials. Background technique [0002] Ultra-high molecular weight polyethylene (UHMWPE) is a thermoplastic engineering plastic with a linear structure and excellent comprehensive properties. The world's first industrialized production was realized in 1957 by Allied Chemical Company of the United States. Since then, Hoechst Company of Germany, Hercules Company of the United States, and Mitsui Petrochemical Company of Japan have also been put into industrial production one after another. my country successfully developed it in 1964 and put it into industrialized production. Due to the conditions at that time, the molecular weight of the product was about 1.5 million. With the advancement of technology, the current molecular weight of ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08J7/18C08J7/12C08J7/02
Inventor 李志麦永懿吴向阳张炜赵春保王新威
Owner SHANGHAI RES INST OF CHEM IND
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