CN101532244A - Method for modifying ultrahigh molecular weight polyethylene fiber by plasma treatment - Google Patents
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Abstract
The invention relates to a method for modifying ultrahigh molecular weight polyethylene fiber by plasma treatment. The method comprises that: (1) a nanometer particle of silicon dioxide is prepared into an organic solvent or water solution of sol of which the mass percent is 0.01 to 15 percent, by an ultrasonic shock technique; or (2) a precursor solution of the organic-inorganic nanometer particle is subjected to hybridization reaction with the nanometer particle of silicon dioxide to prepare the nanometer silicon dioxide sol solution; (3) the sol solution is coated on the surface of the ultrahigh molecular weight polyethylene fiber by spraying or padding; and (4) the ultrahigh molecular weight polyethylene fiber is dried at a temperature of 10 to 150 DEG C, and the solvent is collected; and the ultrahigh molecular weight polyethylene fiber is introduced in a plasma atmosphere region by a plasma generator for plasma surface modification. The compound property between the treated ultrahigh molecular weight polyethylene fiber and the organic matrix materials is greatly improved; moreover, the method also has the advantages of simple process, good treatment effect, low cost, environmental protection and low energy consumption.
Description
Technical field
The invention belongs to the preparation field of surface modification of super-high molecular-weight polyethylene fiber surface, particularly relate to a kind of method of modifying ultrahigh molecular weight polyethylene fiber by plasma treatment.
Background technology
Ultra-high molecular weight polyethylene (UHMWPE) fiber is a kind of high-performance fiber that occurs after carbon fiber, aramid fiber.It is to be raw material with the ultra-high molecular weight polyethylene, process high-voltage solid-state extrusion, plasticising melt spinning method, surface crystallization growth method, super drawing or prepared such as local super drawing method, gel spinning-hot-drawing method, a kind of high-performance fiber with high strength, high-modulus.Its relative molecular mass is 1,000,000～6,000,000, molecular shape is the line style extended-chain configuration, the degree of orientation is near 100%, intensity is equivalent to about 15 times of high-quality steel, higher 2 times than carbon fiber, higher by 40% than aramid fiber, density is 0.97g/cm3, has also that UV resistant radiation, resistance to chemical attack, specific energy absorption height, dielectric constant are low, excellent properties such as the shock resistance that Electromgnetically-transparent rate height, coefficient of friction are low and outstanding, anti-cutting.Therefore, the UHMWPE fiber is an ideal material of making soft ballistic protective clothing, anti-stab clothing, lightweight bulletproof helmet, armoured van bulletproof armour, helicopter bulletproof armour, lightweight high-pressure bottle, space flight and aviation structural member, fishing net, racing boat, sailing boat, ski etc.But,, do not have stronger intermolecular force between fiber molecule because the UHMWPE fiber itself is the linear long-chain that is formed by nonpolar methylene; Fiber surface is chemical inertness, is difficult to form chemical bonding with resin; Highly crystalline that forms through super drawing and height-oriented and smooth surface that cause aborning.The acting in conjunction of all of these factors taken together makes the surface energy of fiber very little, is difficult to during as the reinforcing material of composite that to form good interface bonding with matrix resin.
Improve the interfacial adhesion strength between UHMWPE fiber and resin matrix, can carry out modification to fiber by methods such as surface-coated method, chemical reagent etch, Cement Composite Treated by Plasma modification, Corona discharge Treatment, photooxidation surface modification treatment, radiation grafting processing, make the activation of fiber inactive surfaces layer, introduce carboxyl, carbonyl, hydroxyl isopolarity group at nonpolar fiber surface.And the low-temperature plasma facture etc.Wherein the low-temperature plasma facture does not cause damage and environmental friendliness because it is efficiently rapid to the material key property, is subjected to paying close attention to widely.
The organic solution dipping polyethylene fiber that Chinese patent CN 1431358A improves simultaneously that high-tenacity polyethylene fibre is heat-resisting, the method for creep resistant and cementability utilizes photosensitizer and crosslinking agent to form, and then fiber carried out ultraviolet light irradiation cross-linking; Patent Int.C1D01MI5/00 (2006.01) proposes to handle the superhigh molecular weight polyethylene fibers that soaked the organic sulfonic acid molysite in a vacuum with intrinsic conducting polymer monomer pyrroles or thiophene and obtains fiber surface modification.
Chinese patent literature CN1035308A discloses a kind of method of the UHMWPE of raising fiber surface cementability.It adopts the UHMWPE fiber surface to carry out the method for Cement Composite Treated by Plasma.The method can effectively improve wettability and the surperficial adhesive strength of fiber to resin matrix.But this method appointed condition requires high, and the industrialization difficulty is bigger, and deals with improperly fibrous mechanical property is significantly descended.
The surface modifying method of chromic acid agent treated UHMWPE fiber such as SilVerstein M.S., adhesive property has improved 6 times.But this method makes fiber surface be subjected to corrosion, and is bigger to the fibre strength influence.
American documentation literature USP6 172 163 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 crystallization and form one deck " molecular brush " again at fiber surface.After UHMWPE fiber of Chu Liing and the resin compounded, the fiber adhesive property is greatly improved in this way.But the same operation of this method is loaded down with trivial details, the process conditions harshness, and deal with the remarkable decline that also can cause the UHMWPE fibrous mechanical property improperly.
Chinese patent literature CN1693544A discloses a kind of method of the UHMWPE of raising fiber surface cementability.The method is that polar polymer is dissolved in the conventional extractant of UHMWPE gel spun fiber, make composite extractant, the UHMWPE gel spun fiber is extracted in composite extractant, back operation such as drawn is handled and is made the UHMWPE fiber that adhesive property improves a lot then again.Though this method can keep original intensity of UHMWPE fiber preferably, it is limited that the fiber adhesive strength improves degree, do not reach desirable and practical target.
American documentation literature LJSP5039549 and USP5755913 disclosed method are under plasma, ozone, corona discharge or ultraviolet irradiation, surface modifying method with some polar functionalities monomers (as acrylic acid, acrylamide, acrylonitrile etc.) in the grafting of UHMWPE fiber surface, can improve the surperficial adhesive property of UHMWPE fiber greatly, but this method operation is loaded down with trivial details, and the optimum process condition that grafting is handled is difficult to grasp, and industrial prospect is remote.
Chinese patent CN1035308A discloses a kind of method of the UHMWPE of raising fiber surface adhesive property, it is that the UHMWPE fiber surface is carried out Cement Composite Treated by Plasma, the method can effectively improve wettability and the surperficial adhesion strength of fiber to base-material commonly used, but the hot property and the croop property of fiber do not influenced.But this patent is not utilized nano material preparation colloidal sol technology, more do not mention and utilize the nano silicon dioxide sol technology to apply the UHMWPE fiber, particularly the UHMWPE fiber after nano silicon dioxide sol applies does not relate to through the above patent of method that plasma technique carries out surface modification again.
Low temperature plasma is a kind of plasma that is under the non-equilibrium thermodynamics state, wherein the energy of particle generally is about several to tens electron-volts, greater than material in conjunction with bond energy, can destroy the chemical bond of material fully and form new key, its energy is again far below the high energy radioactive ray, only relate to material surface, do not influence the bulk properties of material.Therefore, normal temperature, the atmospheric plasma physical efficiency improves the chemical reactivity of nano particle, uses plasma the UHMWPE fibrous material surface of coating nanometer silicon dioxide gel to be handled the physical and chemical modified of the material surface that can cause that conventional physical and chemical method can't realize.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of modifying ultrahigh molecular weight polyethylene fiber by plasma treatment, superhigh molecular weight polyethylene fibers and the composite performance between the organic basis material handled through the present invention have obtained improving greatly, this technology is simple, treatment effect good, cost is low, be difficult for causing environmental pollution, and can cut down the consumption of energy.
The method of a kind of modifying ultrahigh molecular weight polyethylene fiber by plasma treatment of the present invention comprises:
(1) nano SiO 2 particle being mixed with mass percent concentration through the ultrasonic oscillation technology is 0.01～15% the organic solvent or the sol solutions of water;
Or (2) pioneer's liquid of organic-inorganic nanometer and nano SiO 2 particle are made mass percent concentration through the hydridization reaction is 0.01～15% nano silicon dioxide sol liquid;
(3) above-mentioned sol solution is coated in the superhigh molecular weight polyethylene fibers surface, the method for painting method for spraying or padding;
(4) under 10～150 ℃, superhigh molecular weight polyethylene fibers is dried and the collection solvent, superhigh molecular weight polyethylene fibers is carried out plasma surface modification through plasma generator introducing plasma atmosphere district then, processing power is 10～15000w, and the time is 0.5～300 second; Superhigh molecular weight polyethylene fibers after handling is carried out online rolling in the automatic winding machine, regulate the Trace speed of superhigh molecular weight polyethylene fibers by the speed of regulating Scroll, needs according to different processing technologys, superhigh molecular weight polyethylene fibers is through the distance of plasma nozzle, and speed is adjusted accordingly.
Organic solvent in the described step (1) is a hexane, isopentane, pentane, benzinum, hexane, cyclohexane, isooctane, trifluoroacetic acid, trimethylpentane, pentamethylene, heptane, butyl chloride; Butyl chloride, trichloro-ethylene; Acetylene trichloride, carbon tetrachloride, chlorotrifluoroethane, propyl ether; Propyl ether, toluene, paraxylene, chlorobenzene, o-dichlorohenzene, diethyl ether; Ether, benzene, isobutanol, carrene, ethylene dichloride, n-butanol, butyl acetate; Butyl acetate, propyl alcohol, methylisobutylketone, oxolane, ethyl acetate, isopropyl alcohol, chloroform, methyl ethyl ketone, dioxanes, dioxane, dioxane, pyridine, acetone, nitromethane, acetate, acetonitrile, aniline, dimethyl formamide, methyl alcohol, ethylene glycol, n-octyl alcohol, n-hexyl alcohol, isobutanol, n-butanol, cyclohexanol, isopropyl alcohol, normal propyl alcohol, methyl alcohol, ethylene glycol, DAA, methyl-sulfoxide DMSO, acetone, ethyl acetate, benzinum, chloroform, oxolane, dioxane, DMF, carrene, carbon disulfide, oxolane, three fluoro acetate, trichloroethanes, ethyl acetate, butanone, glycol dimethyl ether, glycol monomethyl ether or butyl acetate;
Organic nanometer granule in the described step (2) is the organic compound of band reactive group, anthracene perylene, polydiacetylene, pyrazoline derivative organic nanocrystalline PDDP, DPP, DAP, poly-to styrene support PPV, thiophene oligomers, 1,4-two-(2-(5-phenyl oxygen nitrogen azoles base)) benzene, the pyrene organic molecule, the nano wire of anthracene, the nanotube of organic molecule pyrene, pyrene-polypyrrole, organic fluorescent dye Nile is red, ranadylic phthalocyanine, poly-to styrene support PPV, styrene St, oleic acid, carboxylic acid, isocyanic acid, polyisobutene acid, poly-butylacrylic acid, polymethylacrylic acid PMA, methacrylic acid, polymethyl, silane, methyl diphenylene diisocyanate, hexamethylene diisocyanate, the polyisocyanic acid phenyl ester, the toluene di-isocyanate(TDI) polyvinyl acetate, polyacrylate ACR, soap, methyl methacrylate MMA, the aluminic acid ester, titanate esters etc. contain ester group ester class, alcohols such as PVA polyvinyl alcohol, the organic molecule softex kw, silicon amide, polyaniline, N,N-dimethylacetamide, acyl Ammonias such as dimethyl formamide, polyoxyethylene lauryl ether, poly-N one isopropylacrylic acid amine grafted polystyrene, the PEG grafted polystyrene, PEG grafting polymethyl methacrylate, the polyethylene glycol grafted polystyrene;
Described inorganic nanoparticles is selected from that nano level metal, nanosize metal oxide, nanoscale are nonmetal, in the nanoscale nonmetal oxide one or more;
Described nano level metal is silver, copper or its mixture;
Described nanosize metal oxide is selected from one or more the mixture in the oxide of titanium, aluminium, zirconium, iron, tin, zinc, barium, nickel;
Nonmetal and the oxide of described nanoscale is selected from one or more the mixture in CNT, silica, imvite, the phosphorous oxides etc.;
Described plasma producing apparatus is all kinds of plasma generators, plasma atmosphere is produced by plasma generator, and be ejected into the plasma atmosphere that forms in the atmospheric environment of normal temperature, normal pressure via nozzle mechanism, be applied to industrialized mass;
Described plasma is selected from one or more in helium, argon gas or the functional gas, and wherein helium, argon gas mol ratio are 50%-99.99%, and functional gas is 0.001～30%, and the plasma of flowing through simultaneously forms the district and forms plasma atmosphere;
Described functional gas is SO
2Ammonia, oxygen, hydrogen, nitrogen, carbon tetrafluoride, carbon dioxide, methane CH4, ethane C2H6, propane C3H8, butane C4H10, pentane C5H12, hexane C6H14, heptane C7H16, octane C8H18, nonane C9H20, decane C10H22, hendecane C11H24, dodecane C12H26, tridecane C13H28, ethene (C2H4), propylene (C3H6), butylene (C4H8), amylene (C5H10), hexene (C6H12), allene (C3H4), butadiene (C4H6), isoprene (C5H8), hexatriene (C6H8), acetylene (C2H2), propine (C3H4), butine (C4H6), pentyne (C5H8), hexin (C6H10), heptyne (C7H12), octyne (C8H14), n-heptylacetylene (C9H16), decine (C10H18), undecyne (C11H20), tetrafluoroethylene and silane, various siloxane gas, acrylic acid, the steam of methacrylic acid or their composition gas.
Pass through plasma surface treatment, multiple physics, chemical change take place in the UHMWPE fibrous material surface of coating nanometer silicon dioxide gel, or produce etching and coarse, or the fine and close cross-linked layer of formation, or introducing contains the oxygen polar group, hydrophily, caking property and electrical property etc. are improved respectively, make material surface by nonpolar, difficult viscosity transfer to certain polarity is arranged, easy caking property, help bonding, coating.
Following physicochemical change takes place through the Cement Composite Treated by Plasma rear surface superhigh molecular weight polyethylene fibers of the present invention: the part chemical bond of the nano-material surface of (1) superhigh molecular weight polyethylene fibers surface and surface applied disconnects, and forms the high free radical of chemism; (2) free radical that exists with plasmoid rapidly and the combined with radical of the nano-material surface of superhigh molecular weight polyethylene fibers surface and surface applied, forms new chemical bond; (3) nano-material surface of superhigh molecular weight polyethylene fibers surface and surface applied is bombarded and etching, and microstructure helps the infiltration of organic basis material such as resin by smooth roughening.
Beneficial effect
(1) superhigh molecular weight polyethylene fibers handled of the present invention and the infiltration speed of matrix resin are improved, and the infiltration amount increases, and effect of impregnation may is improved, and the moulding process of its composite and whole synthesis performance are more optimized;
(2) this method is easy to operate, technology is simple, process velocity is fast, treatment effect is good, cost is low, be difficult for causing environmental pollution, and can cut down the consumption of energy.
Description of drawings
Fig. 1 is the process chart of the surface treatment method of superhigh molecular weight polyethylene fibers;
Fig. 2 is the contact angle photo through the superhigh molecular weight polyethylene fibers of helium plasma treatment;
Fig. 3 is the infared spectrum through the superhigh molecular weight polyethylene fibers of helium plasma treatment;
Fig. 4 is the contact angle photo through the superhigh molecular weight polyethylene fibers of oxygen plasma treatment
Fig. 5 is the infared spectrum through the superhigh molecular weight polyethylene fibers of oxygen plasma treatment;
Fig. 6 is the infrared difference spectrum through the superhigh molecular weight polyethylene fibers of helium plasma and oxygen plasma treatment.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The helium plasma treatment nano silicon dioxide sol applies superhigh molecular weight polyethylene fibers
As shown in Figure 1, it is 0.05% nano silicon dioxide sol that pending superhigh molecular weight polyethylene fibers 1 is immersed percent concentration along the gaily decorated basket cylindrical line of colloidal sol squeeze device 2, pad processing, then superhigh molecular weight polyethylene fibers is imported into drying unit 3, dry and collect solvent down at 60 ℃, the superhigh molecular weight polyethylene fibers 1 plasma atmosphere district that is introduced into plasma nozzle 4 carries out plasma surface modification and handles then, the fibre bundle upper surface is apart from nozzle distance 5MM, the fibre bundle lower surface is apart from nozzle＜20MM, 40 watts of power, 2 seconds processing times, superhigh molecular weight polyethylene fibers 1 after handling is carried out online rolling at automatic winding machine 5, regulate the Trace speed of superhigh molecular weight polyethylene fibers by the rotating speed of regulating Scroll.According to the needs of different processing technologys, superhigh molecular weight polyethylene fibers is through the distance of plasma nozzle, and speed is adjusted accordingly.
Superhigh molecular weight polyethylene fibers surface treatment effect: contact angle photo such as Fig. 2, infared spectrum such as Fig. 3.
Embodiment 2
The oxygen plasma treatment nano silicon dioxide sol applies superhigh molecular weight polyethylene fibers
As shown in Figure 1, it is 0.05% nano silicon dioxide sol that pending superhigh molecular weight polyethylene fibers 1 is immersed percent concentration along the gaily decorated basket cylindrical line of colloidal sol squeeze device 2, pad processing, then superhigh molecular weight polyethylene fibers is imported into drying unit 3, dries and collect solvent down at 110 ℃.The superhigh molecular weight polyethylene fibers 1 plasma atmosphere district that is introduced into plasma nozzle 4 carries out plasma surface modification and handles then, the fibre bundle upper surface is apart from nozzle distance 5MM, the fibre bundle lower surface is apart from nozzle＜20MM, 40 watts of power, 2 seconds processing times, superhigh molecular weight polyethylene fibers 1 after handling is carried out online rolling at automatic winding machine 5, regulate the Trace speed of carbon fiber by the rotating speed of regulating Scroll.According to the needs of different processing technologys, superhigh molecular weight polyethylene fibers is through the distance of plasma nozzle, and speed is adjusted accordingly.
Superhigh molecular weight polyethylene fibers surface treatment effect: contact angle photo such as Fig. 4, infared spectrum such as Fig. 5.
Claims (8)
1. the method for a modifying ultrahigh molecular weight polyethylene fiber by plasma treatment comprises:
(1) nano SiO 2 particle being mixed with mass percent concentration through the ultrasonic oscillation technology is 0.01～15% the organic solvent or the sol solutions of water;
Or (2) pioneer's liquid of organic-inorganic nanometer and nano SiO 2 particle are made mass percent concentration through the hydridization reaction is 0.01～15% nano silicon dioxide sol liquid;
(3) above-mentioned sol solutions is coated in the superhigh molecular weight polyethylene fibers surface, the method for painting method for spraying or padding;
(4) at 10～150 ℃ superhigh molecular weight polyethylene fibers is dried and the collection solvent, superhigh molecular weight polyethylene fibers is introduced into the plasma atmosphere district through plasma generator and carries out plasma surface modification then, processing power is 10～15000w, and the time is 0.5～300 second; Superhigh molecular weight polyethylene fibers after handling is carried out online rolling in the automatic winding machine, regulate the Trace speed of superhigh molecular weight polyethylene fibers by the speed of regulating Scroll.
2. the method for a kind of modifying ultrahigh molecular weight polyethylene fiber by plasma treatment according to claim 1, it is characterized in that: the organic solvent in the described step (1) is a hexane, isopentane, pentane, benzinum, hexane, cyclohexane, isooctane, trifluoroacetic acid, trimethylpentane, pentamethylene, heptane, butyl chloride; Butyl chloride, trichloro-ethylene; Acetylene trichloride, carbon tetrachloride, chlorotrifluoroethane, propyl ether; Propyl ether, toluene, paraxylene, chlorobenzene, o-dichlorohenzene, diethyl ether; Ether, benzene, isobutanol, carrene, ethylene dichloride, n-butanol, butyl acetate; Butyl acetate, propyl alcohol, methylisobutylketone, oxolane, ethyl acetate, isopropyl alcohol, chloroform, methyl ethyl ketone, dioxanes, dioxane, dioxane, pyridine, acetone, nitromethane, acetate, acetonitrile, aniline, dimethyl formamide, methyl alcohol, ethylene glycol, n-octyl alcohol, n-hexyl alcohol, isobutanol, n-butanol, cyclohexanol, isopropyl alcohol, normal propyl alcohol, methyl alcohol, ethylene glycol, DAA, methyl-sulfoxide DMSO, acetone, ethyl acetate, benzinum, chloroform, oxolane, dioxane, DMF, carrene, carbon disulfide, oxolane, three fluoro acetate, trichloroethanes, ethyl acetate, butanone, glycol dimethyl ether, glycol monomethyl ether or butyl acetate.
3. the method for a kind of modifying ultrahigh molecular weight polyethylene fiber by plasma treatment according to claim 1, it is characterized in that: the organic nanometer granule in the described step (2) is the organic compound of band reactive group, anthracene perylene, polydiacetylene, pyrazoline derivative organic nanocrystalline PDDP, DPP, DAP, poly-to styrene support PPV, thiophene oligomers, 1,4-two-(2-(5-phenyl oxygen nitrogen azoles base)) benzene, the pyrene organic molecule, the nano wire of anthracene, the nanotube of organic molecule pyrene, pyrene-polypyrrole, organic fluorescent dye Nile is red, ranadylic phthalocyanine, poly-to styrene support PPV, styrene St, oleic acid, carboxylic acid, isocyanic acid, polyisobutene acid, poly-butylacrylic acid, polymethylacrylic acid PMA, methacrylic acid, polymethyl, silane, methyl diphenylene diisocyanate, hexamethylene diisocyanate, the polyisocyanic acid phenyl ester, the toluene di-isocyanate(TDI) polyvinyl acetate, polyacrylate ACR, soap, methyl methacrylate MMA, the aluminic acid ester, titanate esters etc. contain ester group ester class, alcohols such as PVA polyvinyl alcohol, the organic molecule softex kw, silicon amide, polyaniline, N,N-dimethylacetamide, acyl Ammonias such as dimethyl formamide, polyoxyethylene lauryl ether, poly-N one isopropylacrylic acid amine grafted polystyrene, the PEG grafted polystyrene, PEG grafting polymethyl methacrylate, the polyethylene glycol grafted polystyrene.
4. the method for a kind of modifying ultrahigh molecular weight polyethylene fiber by plasma treatment according to claim 1 is characterized in that: the inorganic nanoparticles in the described step (2) is selected from that nano level metal, nanosize metal oxide, nanoscale are nonmetal, one or more the mixture in the nanoscale nonmetal oxide.
5. the method for a kind of modifying ultrahigh molecular weight polyethylene fiber by plasma treatment according to claim 4 is characterized in that: described nano level metal is silver, copper or its mixture; Described nanosize metal oxide is selected from one or more the mixture in the oxide of titanium, aluminium, zirconium, iron, tin, zinc, barium, nickel; Nonmetal and the oxide of described nanoscale is selected from one or more the mixture in CNT, silica, imvite, the phosphorous oxides.
6. the method for a kind of modifying ultrahigh molecular weight polyethylene fiber by plasma treatment according to claim 1, it is characterized in that: the plasma producing apparatus in the described step (3) is all kinds of plasma generators, plasma atmosphere is produced by plasma generator, and is ejected into the plasma atmosphere that forms in the atmospheric environment of normal temperature, normal pressure via nozzle mechanism.
7. the method for a kind of modifying nanometer sol ultrahigh molecular weight polyethylene fiber by plasma treatment according to claim 1, it is characterized in that: the plasma in the described step (3) is selected from one or more in helium, argon gas or the functional gas, wherein helium, argon gas mol ratio are 50%-99.99%, functional gas is 0.001～30%, and the plasma of flowing through simultaneously forms the district and forms plasma atmosphere.
8. the method for a kind of modifying nanometer sol ultrahigh molecular weight polyethylene fiber by plasma treatment according to claim 7, it is characterized in that: described functional gas is SO
2Ammonia, oxygen, hydrogen, nitrogen, carbon tetrafluoride, carbon dioxide, methane CH4, ethane C2H6, propane C3H8, butane C4H10, pentane C5H12, hexane C6H14, heptane C7H16, octane C8H18, nonane C9H20, decane C10H22, hendecane C11H24, dodecane C12H26, tridecane C13H28, ethene (C2H4), propylene (C3H6), butylene (C4H8), amylene (C5H10), hexene (C6H12), allene (C3H4), butadiene (C4H6), isoprene (C5H8), hexatriene (C6H8), acetylene (C2H2), propine (C3H4), butine (C4H6), pentyne (C5H8), hexin (C6H10), heptyne (C7H12), octyne (C8H14), n-heptylacetylene (C9H16), decine (C10H18), undecyne (C11H20), tetrafluoroethylene and silane, various siloxane gas, acrylic acid, the steam of methacrylic acid or their composition gas.
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