CN101988266B - Method for improving surface bonding strength of high molecular weight polyethylene (UHMWPE) fibre - Google Patents
Method for improving surface bonding strength of high molecular weight polyethylene (UHMWPE) fibre Download PDFInfo
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Abstract
The invention relates to a method for improving the surface bonding strength of a high molecular weight polyethylene fibre, comprising the following steps of: putting the UHMWPE fibre into a solvent, the temperature of which is 60-135 DEG C, and swelling for 5-60 min to form a relatively loose and irregular swelling layer with a chain structure; then treating the swelling layer for 1-30 min in a phase solvent, the temperature of which is 70-100 DEG C and the concentration of which is 0.01-5 percent, so that the phase solvent diffuses into the swelling layer to form an out-phase coexisting subgrain areas on a high-crystallization core outer layer so as to further form a transition layer. By the method, resin has good wetting property for the surface of the transition layer, and meanwhile, reaction groups or polar groups in the resin have strong interaction with functional groups in the transition layer. The method keeps the performance, such as the strength of the fibre, basically not changed while improving the surface bonding strength of the fibre. Moreover, the method has simple process and convenience in operation and can be used for continuous industrial production.
Description
Technical field
The invention belongs to a kind of surface treatment modification field of synthetic fiber, relate in particular to the method for a kind of raising ultra-high molecular weight polyethylene (UHMWPE) fiber surface adhesive strength.
Background technology
Ultra-high molecular weight polyethylene (UHMWPE) fiber has the mechanical property of the incomparable excellence of other high-performance fibers.The intensity of superelevation, ultra high modulus, high-energy absorption, shock-resistant, low temperature resistant, electric insulation, excellent chemical resistance, weather resisteant, can see through X-ray and certain multiple excellent properties such as water proofing property, be widely used in the fields such as military affairs, space flight navigation engineering, high performance light composite material and high-grade leisure sports goods, such as shellproof protective materials, high-strength rope, composite, sports apparatus.
But the strand of superhigh molecular weight polyethylene fibers is linear structure, does not have phenyl ring isopolarity functional group, and intermolecular do not have a stronger intermolecular force (for example hydrogen bond); Fiber surface is chemical inertness, is difficult to form chemical bonding with resin; And, the smooth surface of fiber, surface energy is lower.Particularly in the fibre-resin composite, be difficult for producing stronger interaction force between fiber and the resin matrix, cause fiber and resin matrix between cementability relatively poor, thereby make the phenomenons such as the UHMWPE fibre reinforced composites in use easily come unstuck, matrix resin cracking, greatly limited the UHMWPE fiber in the particularly application in lightweight structural material field of composite.Therefore, fiber is carried out surface modification treatment, realize processing integrated method with Surface Polarization in the UHMWPE fibre forming process, the adhesive property that improves itself and resin matrix is an important subject.
Improve the interfacial adhesion strength between UHMWPE fiber and resin matrix, can carry out surface modification by methods such as chemical reagent oxidizes, Cement Composite Treated by Plasma, Corona discharge Treatment, photooxidation surface modification treatment or radiation grafting processing, make the activation of UHMWPE fiber surface layer, introduce carboxyl, carbonyl, hydroxyl isopolarity group at nonpolar fiber surface.
CN1035308A discloses a kind of method of the UHMWPE of raising fiber surface cementability, namely the UHMWPE fiber surface is carried out Cement Composite Treated by Plasma.But the method Effective Raise fiber is to wettability and the surface binded intensity of resin matrix, but this processing method needs higher vacuum, and less stable is difficult to realize the serialization suitability for industrialized production.
USP4870136 discloses a kind of method that improves ultra high molecular weight polyethylene fiber surface adhesive property.The method is first with a certain proportion of UHMWPE powder, radical initiator, silane compound and diluent melting mixing in screw machine, carry out the plasticizing melt spinning, cause the silanization graft reaction of finishing UHMWPE by heat in the spinning stage, then afterwards the fiber that spins is carried out hot-stretch in the medium of extractant and crosslinking agent, then in boiling water, finish cross-linking reaction.The adhesive property of the method gained fiber surface improves, but owing in the UHMWPE fiber spinning dope, having added a large amount of initators and graft compound and after graft reaction is finished, having stretched again, thereby cause the tensile fiber multiple lower, the mechanical property of gained UHMWPE fiber is also relatively poor.
USP5039549 and USP5755913, under plasma, ozone, corona discharge or ultraviolet irradiation, monomer with some polar functionalities in the grafting of ultra high molecular weight polyethylene fiber surface, such as acrylic acid, acrylic amine, acrylonitrile etc., can greatly improve the surface binded performance of UHMWPE fiber, but the method operation is loaded down with trivial details, percent grafting is low, be difficult to grasp the optimum process condition that grafting is processed, the industrialization difficulty.
USP6172163 also discloses a kind of method that improves the fiber surface adhesive property.The method is to utilize poly high crystalline energy, adopts the method for pure physics, the unformed area of fiber surface is dissolved after again crystallization and form one deck " molecular brush " at fiber surface.Behind the UHMWPE fiber and resin compounded of processing in this way, the fiber adhesive property is greatly improved.But the same operation of the method is loaded down with trivial details, and process conditions are harsh, and deal with the remarkable decline that also can cause the UHMWPE fibrous mechanical property improperly.
Among the CN1693544A, the composite extractant that utilizes the polar functionalities polymer extracts processing to the ultra high molecular weight polyethylene gel spun fiber of spinning, can greatly improve the surface binded performance of fiber, and is simple to operate and do not need to add any equipment.The little molecule of this process using organosilan carries out modification to fiber in extraction process, be extruded easily in the drawing of fiber crystallization process, and it is limited that adhesive strength improves degree.
Silverstein M.S. etc. are at " the superhigh molecular weight polyethylene fibers surface property of acid etch and the relation between the caking property " (Composites Science and Technology, 1993,48 (1-4), 151-157) and the people such as Wu Yue at " the liquid oxidatively method is processed the ultra high molecular weight polyethylene fiber " (Journal of Functional Polymers, 1999,12 (4): 427) with agent treated UHMWPE such as chromic acid, discovery is after chromic acid is processed, the surface binded performance of UHMWPE is greatly improved, but this method makes fiber surface be subject to corrosion, cause fibrous mechanical property that larger loss is arranged, larger on the fibre strength impact.
The people such as Jia Guangxia are in " research of ultra high molecular weight polyethylene fiber cementability " (synthetic fiber industry, 1995, (6): 24-28) explored the copolymer (EVA) that in spinning solution, is blended into a certain proportion of ethene-vinyl acetate, then can make the improved UHMWPE fiber of surface binded performance through spinning, stretching, but the decline of the intensity of fiber is comparatively obvious.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method that improves superhigh molecular weight polyethylene fibers surface binded intensity, and can keep its mechanical properties of fiber constant simultaneously, this invention improves the wetting characteristics of the rear UHMWPE fiber surface of transition zone parcel.
The present invention solves the problems of the technologies described above the technical scheme of taking to be: a kind of method that improves superhigh molecular weight polyethylene fibers surface binded intensity, it acts on fiber surface by phase solvent, make between fiber and the resin and to form a transition zone that better wettability arranged, thereby improve the fiber surface adhesive strength, it is characterized in that step is followed successively by:
(1) solvent carries out swelling to the UHMWPE fiber in the situation of 60～135 ℃ of temperature, and swelling time is 5～60 minutes, and the formation chain structure is relatively loose, the swell layer of irregularity, forms a kind of skin-core structure;
(2) with UHMWPE fiber 1～30 minute processing time under 70～100 ℃ of temperature, in the phase solvent of mass concentration 0.01～5%, make the phase solvent diffusion in swell layer, in the outer subgrain zone that forms the out-phase coexistence of the kernel of highly crystalline, thereby form transition zone.So that resin has good wettability for the transition zone surface, can there be strong interaction in the reactive group in the resin or the functional group in polar group and the transition zone simultaneously.
Described solvent is decahydronaphthalene, paraffin oil, C
8～C
16N-alkane, perhaps isoparaffin, the perhaps mixture of above-mentioned solvent.
It is 10～60% haloflex that described phase solvent is selected from chlorinty, and preferred chlorinty is 30～40%; Average degree of polymerization is 650～1350 polyvinyl chloride, and preferred average degree of polymerization is 850～1100; Perhaps average degree of polymerization is 200～2000 Vingon, and preferred average degree of polymerization is 300～600 Vingon.
Preferred 70～100 ℃ of the swelling temperature that adopts in the described step (1); Preferred 10～30 minutes of swelling time.The concentration range 0.01～5% of the phase solvent that adopts in the described step (2), preferred 0.1～2%; Preferred 5～10 minutes of processing time.
Pass through Scanning Electron Microscope photos reveal, the more undressed UHMWPE fiber of UHMWPE fiber surface was obviously coarse after (accompanying drawing 1, accompanying drawing 2) processed, but also without obvious etching and concavo-convex vestige, as seen the enhancing of this invention the adhesive strength of UHMWPE fiber, and very little on UHMWPE fibre strength impact.By the contact angle before and after the UHMWPE fibre modification as can be known, (subordinate list 1) UHMWPE fiber wettability improves significantly.
Compared with prior art, advantage of the present invention is:
(1) Intervention mechanism by transition zone, the compatilizer strand forms to have to be similar in its fiber surface finite depth grows nonparasitically upon another plant crystalline texture or forms the transition zone of winding arrangement with the PE chain, and then greatly strengthens the peel strength of UHMWPE fiber and matrix resin behind the transition zone parcel.
(2) the transition zone method is introduced bonding bottom by swelling action at fiber surface, can with the good combination of UHMWPE fiber continuous production technology, simple to operate, have industrialization prospect.
(3) owing to PE strand crystal structure is not caused whole destruction, thus little on the impact of fabric integer, therefore for other method of modifying, can keep to greatest extent the original intensity of fiber.
Description of drawings
Fig. 1 is the scanning electron microscope sem photo of undressed UHMWPE fiberboard;
Fig. 2 is the SEM photo of UHMWPE fiberboard after processing.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention, but embodiment does not limit the present invention.
Embodiment 1
It is 100 ℃ decahydronaphthalene swelling 10 minutes that the UHMWPE fiber is placed temperature, is 100 ℃ in temperature then, and mass concentration is to process 1 minute in 1% the haloflex solution, can make the superhigh molecular weight polyethylene fibers that the surface binded performance improves.
Embodiment 2
It is 100 ℃ decahydronaphthalene swelling 10 minutes that the UHMWPE fiber is placed temperature, is 100 ℃ in temperature then, and mass concentration is to process 2 minutes in 1% the haloflex solution, can make the superhigh molecular weight polyethylene fibers that the surface binded performance improves.
Embodiment 3
It is 90 ℃ decahydronaphthalene swelling 20 minutes that the UHMWPE fiber is placed temperature, is 90 ℃ in temperature then, and mass concentration is to process 1 minute in 1% the haloflex solution, can make the superhigh molecular weight polyethylene fibers that the surface binded performance improves.
Embodiment 4
It is 100 ℃ decahydronaphthalene swelling 10 minutes that the UHMWPE fiber is placed temperature, is 100 ℃ in temperature then, and mass concentration is to process 1 minute in 1% the polyvinyl chloride solution, can make the superhigh molecular weight polyethylene fibers that the surface binded performance improves.
Embodiment 5
It is 100 ℃ decahydronaphthalene swelling 10 minutes that the UHMWPE fiber is placed temperature, is 100 ℃ in temperature then, and mass concentration is to process 2 minutes in 1% the polyvinyl chloride solution, can make the superhigh molecular weight polyethylene fibers that the surface binded performance improves.
Embodiment 6
It is that the mass ratio of 90 ℃ decahydronaphthalene and n-dodecane is 9: 1 mixed solvent swelling 20 minutes that the UHMWPE fiber is placed temperature, then it is 90 ℃ in temperature, mass concentration is to process 1 minute in 1% the polyvinyl chloride solution, can make the superhigh molecular weight polyethylene fibers that the surface binded performance improves.
Embodiment 7
It is 100 ℃ paraffin oil swelling 10 minutes that the UHMWPE fiber is placed temperature, is 100 ℃ in temperature then, and mass concentration is to process 1 minute in 1% the haloflex solution, can make the superhigh molecular weight polyethylene fibers that the surface binded performance improves.
Embodiment 8
It is 100 ℃ paraffin oil swelling 10 minutes that the UHMWPE fiber is placed temperature, is 100 ℃ in temperature then, and mass concentration is to process 2 minutes in 1% the haloflex solution, can make the superhigh molecular weight polyethylene fibers that the surface binded performance improves.
Embodiment 9
It is 90 ℃ paraffin oil swelling 20 minutes that the UHMWPE fiber is placed temperature, is 90 ℃ in temperature then, and mass concentration is to process 1 minute in 1% the haloflex solution, can make the superhigh molecular weight polyethylene fibers that the surface binded performance improves.
Embodiment 10
It is that the mass ratio of 100 ℃ paraffin oil and decahydronaphthalene is 1: 1 mixed solvent swelling 10 minutes that the UHMWPE fiber is placed temperature, then it is 100 ℃ in temperature, mass concentration is to process 1 minute in 1% the polyvinyl chloride solution, can make the superhigh molecular weight polyethylene fibers that the surface binded performance improves.
Embodiment 11
It is 100 ℃ paraffin oil swelling 10 minutes that the UHMWPE fiber is placed temperature, is 100 ℃ in temperature then, and mass concentration is to process 2 minutes in 1% the polyvinyl chloride solution, can make the superhigh molecular weight polyethylene fibers that the surface binded performance improves.
Embodiment 12
It is that the mass ratio of 90 ℃ paraffin oil and dimethylbenzene is 4: 1 mixed solvent swelling 20 minutes that the UHMWPE fiber is placed temperature, then it is 90 ℃ in temperature, mass concentration is to process 1 minute in 1% the polyvinyl chloride solution, can make the superhigh molecular weight polyethylene fibers that the surface binded performance improves.
Can find out by ESEM Fig. 1,2, it is obviously coarse than the undressed UHMWPE fiber of Fig. 1 that Fig. 2 processes rear UHMWPE fiber surface, but also without obvious etching and concavo-convex vestige, as seen this invention has strengthened the adhesive strength of UHMWPE fiber, and little to UHMWPE fiber injury itself.
Before and after the table 1 UHMWPE fibre modification to the contact angle of ethylene glycol (°)
| The embodiment numbering | Before the modification | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 |
| Contact angle | 87 | 76 | 73 | 79 | 78 | 77 | 78 | 76 | 75 | 77 | 74 | 76 | 77 |
By as seen from Table 1, the UHMWPE fiber drops to below 80 ° from untreated 87 ° the contact angle of ethylene glycol, and UHMWPE fiber wettability improves significantly.
Claims (6)
1. method that improves superhigh molecular weight polyethylene fibers surface binded intensity is characterized in that step is followed successively by:
(1) solvent carries out swelling to the UHMWPE fiber in the situation of 60～135 ℃ of temperature, and swelling time is 5～60 minutes, and the formation chain structure is relatively loose, the swell layer of irregularity, forms a kind of skin-core structure;
(2) with UHMWPE fiber 1～30 minute processing time under 70～100 ℃ of temperature, in the compatilizer of mass concentration 0.01～5%, make the compatilizer diffusion in swell layer, in the outer subgrain zone that forms the out-phase coexistence of the kernel of highly crystalline, thereby form transition zone;
It is 10～60% haloflex that described compatilizer is selected from chlorinty, average degree of polymerization is 650～1350 polyvinyl chloride, perhaps average degree of polymerization is 200～2000 Vingon, and the solvent in the compatilizer is decahydronaphthalene, toluene, dimethylbenzene, paraffin oil, C
8～C
16N-alkane, perhaps C
8～C
16Isoparaffin, the perhaps mixture of above-mentioned two or more solvents.
2. a kind of method that improves superhigh molecular weight polyethylene fibers surface binded intensity according to claim 1, it is characterized in that: described solvent is decahydronaphthalene, toluene, dimethylbenzene, paraffin oil, C
8～C
16N-alkane, perhaps C
8～C
16Isoparaffin, the perhaps mixture of above-mentioned two or more solvents.
3. a kind of method that improves superhigh molecular weight polyethylene fibers surface binded intensity according to claim 2, it is characterized in that: it is 30～40% haloflex that described compatilizer is selected from chlorinty, average degree of polymerization is 850～1100 polyvinyl chloride, and perhaps average degree of polymerization is 300～600 Vingon.
4. a kind of method that improves superhigh molecular weight polyethylene fibers surface binded intensity according to claim 1, it is characterized in that: described swelling time is 10～30 minutes.
5. a kind of method that improves superhigh molecular weight polyethylene fibers surface binded intensity according to claim 1, it is characterized in that: the concentration of described compatilizer is 0.1～2%.
6. a kind of method that improves superhigh molecular weight polyethylene fibers surface binded intensity according to claim 1 is characterized in that: 5～10 minutes described processing times.
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| CN107245225B (en) * | 2017-06-08 | 2019-08-06 | 宁波大学 | A kind of haloflex/ultra high molecular weight polyethylene fiber composite material and preparation method |
| CN109662354B (en) * | 2018-12-28 | 2020-12-11 | 宁波三同编织有限公司 | Health-care elastic cotton-flax underwear and preparation method thereof |
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| CN101457476A (en) * | 2007-12-14 | 2009-06-17 | 上海化工研究院天地科技发展有限公司 | Ultra-high molecular weight polyethylene fiber surface treatment method |
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