CN105189579A - Method for preparing ethylene-vinyl acetate with low melt index - Google Patents
Method for preparing ethylene-vinyl acetate with low melt index Download PDFInfo
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- CN105189579A CN105189579A CN201480025338.0A CN201480025338A CN105189579A CN 105189579 A CN105189579 A CN 105189579A CN 201480025338 A CN201480025338 A CN 201480025338A CN 105189579 A CN105189579 A CN 105189579A
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- C07—ORGANIC CHEMISTRY
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- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/007—Esters of unsaturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
- C07C69/01—Vinyl esters
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Abstract
The present invention relates to a method for preparing an ethylene-vinyl acetate (EVA) having a melt index of 10 g/10min or less that includes: applying an electron beam with an exposure dose of 1 to 25 kGy to an ethylene-vinyl acetate resin composition including an ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt%. The ethylene-vinyl acetate prepared has a high vinyl acetate content to secure good properties with regard to transparency, elasticity, or the like, consequently having high processability and good mechanical properties such as a low melt index and thus can be applied to various industrial uses.
Description
Technical field
The present invention relates to the method that preparation has the ethylene-vinyl acetate of low-melt-index, more particularly, relate to the method that preparation has the ethylene-vinyl acetate of low-melt-index, it comprises ethene improved-vinyl acetate has high vinyl acetate content ethylene-vinyl acetate with preparation, to obtain the simple process about the superperformance of transparency, elasticity etc., therefore there is high processing characteristics and good mechanical property is applicable to various industrial use to make it, thus improve production efficiency and economic feasibility.
Background technology
Ethylene-vinyl acetate is the thermoplastic resin that one is applicable to various industrial use (as footwear, tackiness agent, coating, electric wire, flame-retardant compound, photovoltaic applications etc.).Particularly, ethylene-vinyl acetate containing at least vinyl acetate content of 18wt% obtains dispersiveness in good elasticity, inorganic additives and high transparency, and be therefore increasingly used for multiple use, as footwear foam materials, electric wire, flame-retardant compound and optoelectronic package material.
Needing especially to have in the footwear foam materials field of snappiness, low-gravity and high-flexibility, the use of ethylene-vinyl acetate is most important to obtaining good performance (as snappiness, low-gravity and high-flexibility, and competitive price).In addition, the vinyl acetate content of ethylene-vinyl acetate is tending towards rising, because higher vinyl acetate content can make these character more excellent.
Moreover the content of fire retardant must increase along with the object of the flame retardant resistance of raising flame-retardant compound.In order to make described ethylene-vinyl acetate have higher flame retardant resistance, the content of inorganic combustion inhibitor (as magnesium hydroxide, aluminium hydroxide ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.) has nothing for it but at least 40%.Because the consistency of ethylene-vinyl acetate and inorganics increases along with the growth of vinyl acetate content, increase the content of described vinyl acetate to utilize the inorganic combustion inhibitor of higher amount to be desirable.
There is with the growth of vinyl acetate content as the ethylene-vinyl acetate sheet of the packaged material of photovoltaic module the transparency of raising, thus obtain higher component efficiency.Therefore, the content of usual regulation vinyl acetate is more than 26%.
On the other hand, by the ethene of suitable blending ratio and vinyl acetate are added into high pressure or tubular reactor, and under high-temperature and high-pressure conditions, carry out polyreaction can prepare described ethylene-vinyl acetate.In this, when the amount of the vinyl acetate being added into described reactor increases, part vinyl acetate serves the effect of the telomer terminating reaction, may reduce the molecular weight of described ethylene-vinyl acetate.The ethylene-vinyl acetate of described lower molecular weight can cause higher melt index and lower melt strength.There is the ethylene-vinyl acetate of the vinyl acetate content of 33wt%, such as, there is the melt index of about 10 and the melt strength of about 30mN.
Increase the content of described vinyl acetate and the described higher melt index caused can cause the deterioration of mechanical property and processing characteristics.Therefore, there is the use of the conventional ethylene-vinyl acetate of high vinyl acetate content, advantage can be brought in snappiness, elasticity etc., but bring inferior position in mechanical property and processing characteristics.This is adding some limitation on described ethylene-vinyl acetate is separately in footwear foam materials, electric wire, flame-retardant compound etc.
The method overcoming the limitation of described ethylene-vinyl acetate comprises the subsequent reactions of the ethylene-vinyl acetate be prepared in the reactor, thus improves mechanical property and the processing characteristics of described ethylene-vinyl acetate.The method of modifying (for being mainly used in the method for described subsequent reactions) using superoxide is extruding reaction technique, comprise and ethylene-vinyl acetate resin and superoxide are added into forcing machine, in being reduction of described melt index and improve described melt strength.The method of modifying of described use superoxide with ethylene-vinyl acetate described in the mode modification of various combination, but can result in many problems, comprises huge power consumption, contamination, repacking, manufacturing deficiency etc.
The power consumption caused by the modified technique of described use superoxide and repacking are the principal elements of cost increase, and it becomes the commercial restriction of described ethylene-vinyl acetate.In addition, during described modified technique, the pollutent of introducing or generation can cause the quality problems of final ethylene-vinyl acetate product.
This means still there is the demand developed and prepare the simple and economical feasible method of ethylene-vinyl acetate, by ethylene-vinyl acetate described in the simple process of subsequent reactions, there is high vinyl acetate content, to obtain about transparency and elastic superperformance, and obtain high fondant-strength and good mechanical property, it is made to be applicable to large-scale industrial use, as footwear foam materials, tackiness agent etc.
Summary of the invention
[technical problem]
Therefore, the present invention is for providing a kind of method preparing the ethylene-vinyl acetate with low-melt-index, it comprises preparation and has the ethylene-vinyl acetate of high vinyl acetate content to obtain the simple modified technique of the superperformance about transparency, elasticity etc., therefore have high working property can and good mechanical property be applicable to various industrial use to make it, thus improve production efficiency and economic feasibility.
[technical scheme]
According to the present invention, provide a kind of method preparing the ethylene-vinyl acetate of the melt index with below 10g/10min, it comprises: the electron beam applying 1 to 25kGy irradiation dose is to the ethylene-vinyl acetate resin composition of ethylene-vinyl acetate resin comprising the vinyl acetate content with 15 to 50wt%.
Hereinafter, put up with the method that preparation has an ethylene-vinyl acetate (EVA) of low-melt-index according to an illustrative embodiment of the invention and give further detailed description.
According to an exemplary embodiment of the present invention, provide a kind of method preparing the ethylene-vinyl acetate of the melt index with below 10g/10min, it comprises: the electron beam applying 1 to 25kGy irradiation dose is to the ethylene-vinyl acetate resin composition of ethylene-vinyl acetate resin comprising the vinyl acetate content with 15 to 50wt%.
Tend to that there is low melt strength and high-melt index based on the ethylene-vinyl acetate with high vinyl acetate content, therefore there is the reality of the deterioration of mechanical property and processing characteristics, the present inventor have studied the preparation had about the superperformance of transparency, snappiness, elasticity etc. and the ethylene-vinyl acetate of good mechanical property and processing characteristics.Thereafter, the present inventor finds the ethylene-vinyl acetate causing having prepared the low-melt-index with below 10g/10min to the ethylene-vinyl acetate resin composition comprising the ethylene-vinyl acetate resin with high vinyl acetate content with the irradiation of the electron beam of specific irradiation dose, thus completes the present invention.
Especially, compared to using the conventional method of modifying of superoxide, the above-mentioned preparation method for ethylene-vinyl acetate result in little contamination during preparation process or manufacturing deficiency, and considerably less power consumption.In addition, the step opened packaging and repack can be omitted according to the preparation method of an illustrative embodiments, thus prepared the ethylene-vinyl acetate with high vinyl acetate content and low-melt-index in simple and economical feasible mode.
In addition, described preparation method can produce the ethylene-vinyl acetate with excellent mechanical properties (about melt strength, melt index, shear-thinning index, molecular weight distribution etc.), and described ethylene-vinyl acetate comprises the electron beam that applies to have a specific irradiation dose be improved to the simple modified technique of ethylene-vinyl acetate resin composition by means of only using.
Therefore, the ethylene-vinyl acetate that preparation method according to one exemplary embodiment provides has high vinyl acetate content and low-melt-index, it is made to be applicable to film formation, extrusion molding, foam molding etc., and demonstrate high shear-thinning index to maintain its shape under mild method, also under shearing force, reduce extrusion load, power consumption, pressure etc., therefore there is good mechanical property and processing characteristics.
On the other hand, preparation method according to one exemplary embodiment can comprise further: before the step applying electron beam, auxiliary mould spreads described ethylene-vinyl acetate resin composition out thickness to 1 to 16cm, or described ethylene-vinyl acetate resin composition is loaded in packing bag.
In other words, auxiliary mould spreads described ethylene-vinyl acetate resin composition out thickness to 1 to 16cm, then with 1 to 25kGy irradiation dose irradiation under electron beam; Or described ethylene-vinyl acetate resin composition is loaded in wrapping paper, then with the irradiation of 1 to 25kGy irradiation dose under electron beam.The height being meant to bottom to the top of the described ethylene-vinyl acetate resin composition spread out on the bottom of described auxiliary mould of term " thickness " used herein.
Described auxiliary mould can be the arbitrary known mould that this area is commonly used, and comprises, such as, and metal, paper, polymeric film, timber, plastics etc.
Described wrapping paper can be the conventional arbitrary well known materials in this area, and is not particularly limited, and comprises, such as, and polyolefin film, woven yarn, paper, enamelled paper, paper, fabric etc. with lining form.
Described polyolefin film can be by, such as, prepared by Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra-low density polyethylene (VLDPE), high density polyethylene(HDPE) (HDPE), polypropylene (PP), the elastomerics based on ethene, the plastomer based on ethene, the elastomerics based on propylene, the plastomer based on propylene or their mixture.
On the other hand, apply the step of electron beam to described packing bag by described packing bag being placed on the forwarder of metal deflector roll or metal die form, and described forwarder is realized through the irradiation zone of electron beam.Along with continuing of electron beam irradiation, the temperature of described metal deflector roll or mould raises, and described packing bag is melted, and its inclusion can flow in described packing bag, or is bonded on described forwarder.For avoiding this problem, desirably adopt the material be made up of at high temperature stable material of main part.
The gross weight of described packing bag does not do special restriction, but conveniently transports, and it can be below 1000kg.Described packing bag is transported by manpower or machinery.In this, the gross weight of described packing bag can be limited according to the type of the instrument of transport.The weight that term " gross weight of packing bag " used herein refers to described ethylene-vinyl acetate resin composition adds the weight of described packing bag.When transporting packing bag with machinery, can will have about below 1000kg, the ethylene-vinyl acetate resin composition being preferably the weight of below 500 to 600kg loads in Shipping Sack (Flecon) or cardboard (Carton) bag.When transporting packing bag with manpower, the gross weight of described packing bag can be about below 50kg, is preferably about 5 to 50kg, is more preferably about 10 to 40kg.
Described auxiliary mould or described packing bag do not do special restriction in size and dimension.Preferably, described height is the steady state value of more than 1cm, and described shape is designed to allow described ethylene-vinyl acetate resin composition and spreads out to predetermined thickness or be loaded into.
The preparation method of ethylene-vinyl acetate according to one exemplary embodiment comprises: on auxiliary mould, spread described ethylene-vinyl acetate resin composition out, or loaded in packing bag, then by making described auxiliary mould or described packing bag come to apply electron beam to described ethylene-vinyl acetate resin composition through electron beam irradiation, thus the performance of described ethylene-vinyl acetate is improved, and do not need specific additional step, as packaging or the use of properties-correcting agent (as superoxide).This makes it can prepare ethylene-vinyl acetate in simple and economical feasible mode.
Especially, compared to the ordinary method using superoxide to prepare ethylene-vinyl acetate, preparation method of the present invention result in considerably less power consumption, and improves operating rate to as high as at least 700kg is per hour.
Described ethylene-vinyl acetate resin composition is loaded in electron beam irradiation, accepts the irradiation of electron beam.When loading the described ethylene-vinyl acetate resin composition in packing bag and accepting the irradiation of electron beam, can determine that described packing bag is standing upright or lies on one's side according to the shape of described electron beam irradiation and position; Preferably, described packing bag can lie upon its side and pass through from described electron beam.
Described electron beam can be put on the one or both sides of described ethylene-vinyl acetate resin composition.Preferably, when described ethylene-vinyl acetate resin composition is thin, apply the side of described electron beam to described ethylene-vinyl acetate resin composition, or when described ethylene-vinyl acetate resin composition is thick, be applied to the both sides of described ethylene-vinyl acetate resin composition.The irradiation one or many of described electron beam can be implemented on the both sides of described ethylene-vinyl acetate resin composition or side.
The ethylene-vinyl acetate resin of the vinyl acetate content of described 15 to the 50wt% of having can have stretching rheometer (Rheotens) melt strength of 1 to 30mN.The ethylene-vinyl acetate resin of the vinyl acetate content of described 15 to the 50wt% of having also can have at least 15g/10min, is preferably the melt index (190 DEG C, 2.16kg) of at least 20g/10min.Described ethylene-vinyl acetate resin has pole low melt strength and high melt index, therefore has poor processing characteristics and processability, but by with the irradiation dose irradiation of specified range in electron beam by its modification, to obtain excellent performance.
The ethylene-vinyl acetate (EVA) so obtained can have below 10g/10min, is preferably the melt index (190 DEG C, 2.16kg) of 0.01 to 5g/10min.Especially, when the melt index of described EVA is less than 0.01g/10min, it has so high intensity in molten state so that substantially increases and extrudes moment of torsion, and becomes and be difficult to extract out, and it may increase difficulty in the execution of foaming, film forming, plate forming, compound etc.
Described melt index is relevant to molecular weight.Therefore, described vinyl acetate serves the effect of telomer (such as, reaction terminating agent), to have the molecular weight of the ethylene-vinyl acetate of high vinyl acetate content described in reducing and to improve described melt index.This can cause the reduction of mechanical property and processing characteristics.Otherwise, even if the ethylene-vinyl acetate that preparation method according to one exemplary embodiment obtains has the high vinyl acetate content of 15 to 50wt%, the low-melt-index of below 10g/10min also can be had.This can overcome the above-mentioned limitation about mechanical property and processing characteristics.
The ethylene-vinyl acetate so obtained can have at least 30mN, be preferably 30 to 150mN stretching rheometer (
) melt strength (170 DEG C).There is ethylene-vinyl acetate elasticity and the intensity difference in the molten state of the melt strength being less than 30mN, formed during foam molding process and growth bubble difficulty, therefore it is made fully not formed spongy, and at high temperature shape-retentivity is poor during injection/extrusion moulding process, therefore it can not be molded with required shape.
Further, the ethylene-vinyl acetate of so preparation can have ARES (150 DEG C, 15% strain) the shear-thinning index of 4 to 25.Described shear-thinning index is defined as the ratio of the viscosity under 1 radian per second and the viscosity under 100 radian per seconds.The viscosity that higher shear-thinning exponential representation is higher under lower shear-stress and viscosity lower under higher shear-stress.The ethylene-vinyl acetate with the ARES shear-thinning index in the scope of above-mentioned restriction has so high viscosity to maintain its shape and not deform under relatively low shear-stress, viscosity with bending down at relative high shear-stress, thus reduces extrusion load and power consumption.
In addition, prepared ethylene-vinyl acetate can have at least 10, is preferably the molecular weight distribution of 10 to 50.Molecular weight distribution in limited range is more much higher than the molecular weight distribution with the ethylene-vinyl acetate resin of the vinyl acetate content of 15 to 50wt% before the irradiation accepting electron beam.This illustrate adopt use the modification of irradiation of electron beam can cause producing the molecular weight distribution with wide region and suitably obtain high physical strength and the ethylene-vinyl acetate of processing characteristics.
On the other hand, described ethylene-vinyl acetate resin composition can comprise additive further, as photoreactivity monomer, antioxidant, slip(ping)agent, antiblocking agent, ultra-violet stabilizer, reaction promoter or their mixture.
Described antioxidant can improve thermostability and the oxidative stability of prepared ethylene-vinyl acetate.More particularly, described antioxidant can be based on the antioxidant of phenol, the non-antioxidant based on phenol or their mixture.Preferably, be conceived to reduce the reduction of complex viscosity and shear-thinning exponential sum and make to fade and minimize, adopt the non-antioxidant based on phenol.
Antioxidant based on phenol used herein is the conventional known antioxidant in this area and without any restriction.The specific examples of the described antioxidant based on phenol can comprise: octadecyl-3-(3; 5-di-t-butyl-4-hydroxyphenyl)-propionic ester, butylhydroxy toluene, tetramethylolmethane four (3-(3; 5-di-tert-butyl-hydroxy phenyl) propionic ester), 2'; two [[3-[3,5-di-tert-butyl-hydroxy phenyl] propionyl]] the propionyl hydrazines of 3-or their mixture.
The non-antioxidant based on phenol used herein is the conventional known antioxidant in this area and without any restriction.The specific examples of the described non-antioxidant based on phenol can comprise: three (2, 4-di-tert-butyl-phenyl) phosphorous acid ester, 4, 4'-thiobis (the 6-tertiary butyl-meta-cresol), two-(2, 4-DI-tert-butylphenol compounds) pentaerythritol diphosphites, the 2-tertiary butyl-6-methyl-4-(3-((2, 4, 8, 10-tetra-tert dibenzo [d, f] [1, 3, 2] Delnav suberane-6-bases) oxygen base) propyl group) phenol (2-(tert-butyl)-6-methyl-4-(3-((2, 4, 8, 10-tetrakis (tert-butyl) dibenzo [d, f] [1, 3, 2] dioxaphosphepin-6-yl) oxy) propyl) phenol), two (2, 4-di-t-butyl-6-aminomethyl phenyl)-ethyl-phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester or their mixtures.
Relative to the described ethylene-vinyl acetate resin composition of 100 weight parts, described antioxidant can 0.01 to 0.5 weight part amount use.The pole low levels of described antioxidant can cause the ethylene-vinyl acetate preparing oxidative stability of going on business, and the high content of described antioxidant greatly reduces the efficiency the variable color that may cause described ethylene-vinyl acetate that use the modification of electron beam.
Described ethylene-vinyl acetate resin composition can comprise ultra-violet stabilizer further, and it not only can maintain thermostability and the oxidative stability of prepared ethylene-vinyl acetate, can prevent again the efficiency of the modification using electron beam from reducing.Ultra-violet stabilizer used herein is preferably the known ultra-violet stabilizer based on bulky amine that this area is commonly used.The described ultra-violet stabilizer based on bulky amine can keep the effect of the modification of the ethylene-vinyl acetate using electron beam well, thus makes the irradiation dose meeting the required electron beam needed for performance be low irradiation dose.This prepares ethylene-vinyl acetate with allowing its economical and efficient.
The specific examples of described ultra-violet stabilizer can comprise: Succinic acid dimethylester and 4-hydroxyl-2,2,6, the polymkeric substance, two (2,2,6 of 6-tetramethyl--1-piperidine ethanol, 6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, poly-[6-[(1,1,3,3-tetramethyl butyl) amino]-1,3,5-triazine-2,4-bis-base] [(2,2,6,6-tetramethyl--4-piperidyl) imino-] hexa-methylene [2,2,6,6-tetramethyl--4-piperidyl) imino-]] or their mixture.Relative to the described ethylene-vinyl acetate resin composition of 100 weight parts, the described ultra-violet stabilizer of the amount of 0.01 to 0.5 weight part can be comprised.
Antiblocking agent used herein can be the conventional known compound in this area of the viscosity controlling described ethylene-vinyl acetate particle and without any restriction.The specific examples of described antiblocking agent can comprise: oleylamide, stearylamide, erucicamide, ethylenebisstearamide, ethylenebis-oleylamide or their mixture.Relative to the described ethylene-vinyl acetate resin composition of 100 weight parts, the described antiblocking agent of the amount of 0.02 to 0.5 weight part can be comprised.The change of color during the high content of described antiblocking agent may cause using the modifying process of electron beam, and the pole low levels of described antiblocking agent causes particle to stick together.Therefore, preferably described antiblocking agent is comprised with the amount of above-mentioned limited range.
Described photoreactivity monomer plays a role as the auxiliary agent of the modification using electron beam, and it helps to use the modifying process of electron beam efficiently to complete.The specific examples of described photoreactivity monomer can comprise: vinylformic acid, acrylate, methacrylic acid, methacrylic ester, double bond containing dicarboxylic acid, double bond containing dicarboxylic ester, double bond containing dicarboxylic anhydride, silane coupling agent or their mixture.
In the example of described photoreactivity monomer, described dicarboxylic acid can be toxilic acid, phthalic acid, methylene-succinic acid, citraconic acid, alkenyl succinic acid, cis-1,2,3,6-tetrahydrophthalic acid or 4-methyl isophthalic acid, 2,3,6-tetrahydrophthalic acid; Described (methyl) acrylic compound can be vinylformic acid, methacrylic acid, vinylacetic acid, vinyl acetate, methyl-acrylic acid, ethyl-vinylformic acid, butyl-vinylformic acid, methyl-methacrylic acid, Ethyl-Methyl vinylformic acid, glycidyl acrylate or glycidyl methacrylate; And described silane coupling agent can be vinyltrimethoxy silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-acryloxypropyl Trimethoxy silane or acryloyloxymethyl Trimethoxy silane.
Described ethylene-vinyl acetate resin composition is by comprising for using the auxiliary agent of the modification of electron beam to improve the efficiency of electron beam irradiation.This allows its preparation to have the ethylene-vinyl acetate of polar group (introducing the mechanical property improving adhesivity and improve about melt strength or shear-thinning index).Relative to the described ethylene-vinyl acetate resin composition of 100 weight parts, the described photoreactivity monomer of the amount of 0.1 to 3 weight part can be comprised.
Reaction promoter used herein can comprise linking agent and the crosslinking coagent of peroxide types.The specific examples of described peroxide cross-linking agent can comprise dicumyl peroxide, 1, 1-bis-(t-butyl peroxy)-3, 3, 5-trimethyl-cyclohexane, two (2-tert-butyl-peroxy sec.-propyl)-benzene, butyl-4, 4-bis-(tertiary butyl dioxy base) valerate, two (2, 4-dichloro-benzoyl base)-superoxide, two (2, 4-dichloro-benzoyl base)-superoxide, dibenzoyl peroxide, t-butyl per(oxy)benzoate, t-butylcumylperoxide, 2, 5-dimethyl-2, 5-bis-(t-butyl peroxy) hexane, ditertiary butyl peroxide, 2, 5-dimethyl-2, 5-bis-(t-butyl peroxy)-3-hexin or their mixture.The specific examples of described crosslinking coagent can comprise triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethyl propane trimethacrylate, Vinylstyrene, Ethylene-glycol-dimethacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate or their mixture.
Also have, except described ethylene-vinyl acetate resin, described ethylene-vinyl acetate resin composition can comprise further: containing the ethylene copolymer of ethylene-vinyl acetate copolymer, metallocene polypropylene, metallocene polyethylene, Z-N (Ziegler-Natta) polyethylene, Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE), thermoplastic polyethylene's elastomerics, thermoplastic polyethylene's plastomer or their mixture.
[beneficial effect]
According to the present invention, the preparation method of the ethylene-vinyl acetate of low-melt-index can be provided, described method is by comprising the easy steps of modification to obtain the good performance about transparency, elasticity etc. in the preparation of the ethylene-vinyl acetate with high vinyl acetate content, improve production efficiency and economic feasibility, and allow good processing characteristics, but also showing good mechanical property, this makes described ethylene-vinyl acetate be applicable to various industrial use.
Accompanying drawing explanation
Fig. 1 shows the chart of the molecular weight distribution in embodiment 5 as the function of the irradiation dose of electron beam.
Embodiment
Hereinafter, the present invention is described in further detail with reference to following examples, and the embodiment provided for exemplary illustration of the present invention, and is not intended to limit scope of the present invention.
[EXPERIMENTAL EXAMPLE 1] is according to the measurement of the penetration depth of the electron beam of beam energy
By the beam energy of 2.5MeV or 10MeV with until the sweep length of 60kW puts on vertical direction.Then based on the reference irradiation dose of the beam energy of 25KGy, the actual irradiation dose of the electron beam of the function as penetration depth is measured.That measures the results are shown in table 1.
[table 1]
As can be seen from Table 1, maximum penetration is the 8cm under 3.2cm and 10MeV under 2.5MeV.Because the both sides irradiation herein illustrating electron beam can realize the degree of depth of 16cm under the degree of depth of 6.4cm under 2.5MeV and 10MeV.
[embodiment 1] is according to the melt index of the irradiation dose of vinyl acetate content and electron beam
Above 60g/10min will be had (at 190 DEG C in metal tray (100cm × 100cm × 10cm), melt index 2.16kg) and 40% the ethylene-vinyl acetate (EVA) of vinyl acetate (VA) content, and the EVA with the melt index of 30g/10min (at 190 DEG C, 2.16kg) and the VA content of 33% spreads the uniform thickness to 3 to 4cm out.Then, the melt index of the irradiation dose according to electron beam is measured.That measures the results are shown in table 2.
[table 2]
As can be seen from Table 2, the melt index of ethylene-vinyl acetate (EVA) reduces along with the increase of the irradiation dose of electron beam.
* the measuring process of melt index:
The hole of 2.096mm diameter is arranged in the cylinder of melt index survey meter at 190 DEG C, and loads the EVA of 4 to 5g in described cylinder.In the described cylinder with piston, the counterweight of 2.16kg is placed on described piston with applying load on described EVA.By the EVA preheating in described cylinder about 5 minutes, and measure the amount of the EVA fallen from described cylinder in a minute.It is the amount of the EVA fallen from described cylinder in 10 minutes by the quantitative change of this EVA.
[embodiment 2] is according to the melt index of the thickness of vinyl acetate content and EVA composition
60g/10min will be had (at 190 DEG C, melt index 2.16kg) and 40% the ethylene-vinyl acetate (EVA) of vinyl acetate (VA) content, and the EVA with the melt index of 30g/10min (at 190 DEG C, 2.16kg) and the VA content of 33% loads in the polyolefine packing bag prepared primarily of LLDPE to the thickness of table 3 regulation and weight.Then, the melt index of described EVA is measured.After the two-sided irradiation of described EVA composition to 6.3cm thickness, the thickness piece of described EVA composition is decided to be 12cm.
[table 3]
[embodiment 3] is according to the change of the melt index of the irradiation dose of electron beam
Make the EVA with 40%VA content accept the irradiation of electron beam with different irradiation dose, then about melt strength (
170 DEG C) measure.That measures the results are shown in table 4.
[table 4]
| The irradiation dose (kGy) of electron beam | Melt strength (mN) | |
| Embodiment 3-1 | 5 | 30 |
| Embodiment 3-2 | 10 | 135 |
| Embodiment 3-3 | 15 | 1200 |
| Comparative example 3-1 | 0 | 4.2 |
* melt strength (
170 DEG C) measuring process:
Described melt strength is with the Rheotens71.97 device measuring being connected to capillary rheometer.In the capillary cylinder of 15mm diameter, ethylene-vinyl acetate is melted in about 4 minutes at 170 DEG C, and pass the kapillary of 32mn length and 1.0mm diameter by the piston declined with the speed of 3mm per minute.Through the ethylene-vinyl acetate of the melting in aperture then through being positioned at 150mm and with 3mm/s below
2acceleration engage each other between two wheels of rotation.
As can be seen from Table 4, the EVA not accepting the comparative example 3-1 of the irradiation of electron beam only has the melt strength of 4.2mN, is not high enough to the purposes allowing described EVA for extrusion moulding, injection molding, foaming etc.Otherwise, accept the melt strength that there is the embodiment 3-1 of the irradiation of the electron beam of the irradiation dose of 5kGy, 10kGy or 15kGy, the EVA of 3-2 and 3-3 has at least 30mN, be high enough to and make described EVA can be used for film forming, extrusion moulding, foaming etc.
[embodiment 4] is according to the change of the shear-thinning index of the EVA of the irradiation dose of electron beam
Make the EVA with 40%VA content accept the irradiation of electron beam, then about shear-thinning index (
170 DEG C, 15% strain) measure.That measures the results are shown in table 5.Described shear-thinning index is defined as the ratio of the viscosity under 1 radian per second and the viscosity under 100 radian per seconds.The viscosity that higher shear-thinning exponential representation is higher under lower shear-stress and viscosity lower under high shear-stress.
* shear-thinning index=(viscosity under 1 radian per second)/(viscosity under 100 radian per seconds)
[table 5]
| The irradiation dose (kGy) of electron beam | Shear-thinning index | |
| Embodiment 4-1 | 5 | 4.9 |
| Embodiment 4-2 | 10 | 7.1 |
| Embodiment 4-3 | 15 | 10.2 |
| Comparative example 4-1 | 0 | 2.6 |
As can be seen from Table 5, the EVA of comparative example 4-1 has the shear-thinning index of 2.6, almost can not demonstrate shear-thinning effect, and accept there is the embodiment 4-1 of the irradiation of the electron beam of the irradiation dose of 5 to 15kGy, the EVA of 4-2 and 4-3 have 4.9 to 10.2 shear-thinning index, describe good processing characteristics.
[embodiment 5] changes according to the PDI of the irradiation dose of electron beam
Make the EVA with 40%VA content accept the irradiation of electron beam, then carry out measuring to calculate molecular weight distribution about molecular weight.That measures the results are shown in table 6 and Fig. 1.Described molecular weight distribution is defined as weight-average molecular weight divided by number-average molecular weight.
[table 6]
| The irradiation dose (kGy) of electron beam | PDI | |
| Embodiment 5-1 | 5 | 11.2 |
| Embodiment 5-2 | 10 | 22.9 |
| Embodiment 5-3 | 15 | 14.3 |
| Comparative example 5-1 | 0 | 4.8 |
As can be seen from table 6 and Fig. 1, compared to the EVA of irradiation not accepting electron beam, accept the embodiment 5-1 of the irradiation of electron beam, the EVA of 5-2 and 5-3 shows higher PDI value and broader molecular weight distribution, thus obtain suitable physical strength and processing characteristics.
Claims (15)
1. prepare a method for the ethylene-vinyl acetate (EVA) of the melt index with below 10g/10min, comprising:
The electron beam applying 1 to 25kGy irradiation dose is to the ethylene-vinyl acetate resin composition of ethylene-vinyl acetate resin comprising the vinyl acetate content with 15 to 50wt%.
2. method according to claim 1, described method comprises further: before the step applying electron beam,
Auxiliary mould is spread out the thickness of described ethylene-vinyl acetate resin composition to 1 to 16cm, or
Described ethylene-vinyl acetate resin composition is loaded in packing bag.
3. method according to claim 2, wherein, described packing bag be selected from polyolefin film, woven yarn, paper, enamelled paper, with the paper of lining form and fabric.
4. method according to claim 3, wherein, described polyolefin film adopts at least one be selected from Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra-low density polyethylene (VLDPE), high density polyethylene(HDPE) (HDPE), polypropylene (PP), the elastomerics based on ethene, the plastomer based on ethene, the elastomerics based on propylene and the plastomer based on propylene to make.
5. method according to claim 2, wherein, the gross weight of described packing bag is below 1000kg.
6. method according to claim 1, wherein, puts on the one or both sides of described ethylene-vinyl acetate resin composition by described electron beam.
7. method according to claim 1, wherein, described in there is the vinyl acetate content of 15 to 50wt% ethylene-vinyl acetate resin there is the Rheotens melt strength of 1 to 30mN.
8. method according to claim 1, wherein, described in there is the vinyl acetate content of 15 to 50wt% ethylene-vinyl acetate resin there is the melt index (190 DEG C, 2.16kg) of at least 15g/10min.
9. method according to claim 1, wherein, the ethylene-vinyl acetate of preparation has the melt index of 0.01 to 5g/10min.
10. method according to claim 1, wherein, the ethylene-vinyl acetate of preparation has the Rheotens melt strength of at least 30mN.
11. methods according to claim 1, wherein, the ethylene-vinyl acetate of preparation has the ARES shear-thinning index of 4 to 25.
12. methods according to claim 1, wherein, the ethylene-vinyl acetate of preparation has the molecular weight distribution of at least 10.
13. methods according to claim 1, wherein, described ethylene-vinyl acetate resin composition comprises at least one additive be selected from photoreactivity monomer, antioxidant, slip(ping)agent, antiblocking agent, ultra-violet stabilizer and reaction promoter further.
14. methods according to claim 13, wherein, described photoreactivity monomer comprises at least one be selected from vinylformic acid, acrylate, methacrylic acid, methacrylic ester, double bond containing dicarboxylic acid, double bond containing dicarboxylic ester, double bond containing dicarboxylic anhydride and silane coupling agent.
15. methods according to claim 1, wherein, described ethylene-vinyl acetate resin composition comprises at least one fluoropolymer resin be selected from containing in the ethylene copolymer of ethylene-vinyl acetate copolymer, metallocene polypropylene, metallocene polyethylene, Ziegler-Natta polyethylene, Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE), thermoplastic polyethylene's elastomerics and thermoplastic polyethylene's plastomer further.
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| KR1020140032236A KR20140132667A (en) | 2013-05-08 | 2014-03-19 | Method for ethylenevinylacetate with low melt index |
| PCT/KR2014/003731 WO2014181991A1 (en) | 2013-05-08 | 2014-04-28 | Method for preparing ethylene-vinyl acetate with low melt index |
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| KR102309428B1 (en) * | 2018-11-26 | 2021-10-05 | 주식회사 엘지화학 | Ethylene vinyl acetate copolymer and method for preparing the same |
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| JPH06336525A (en) * | 1993-04-01 | 1994-12-06 | Sekisui Chem Co Ltd | Production of interlayer for laminated glass |
| CN101565526A (en) * | 2009-05-13 | 2009-10-28 | 深圳市长园集团股份有限公司 | Thermal anti-oxidation radiation resistance polyolefine thermal contraction material and preparation method thereof |
| US20110031657A1 (en) * | 2009-08-04 | 2011-02-10 | E-Beam Services, Inc. | Electron Beam Irradiation of Bulk Material Solids |
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|---|---|---|---|---|
| JPH06336525A (en) * | 1993-04-01 | 1994-12-06 | Sekisui Chem Co Ltd | Production of interlayer for laminated glass |
| CN101565526A (en) * | 2009-05-13 | 2009-10-28 | 深圳市长园集团股份有限公司 | Thermal anti-oxidation radiation resistance polyolefine thermal contraction material and preparation method thereof |
| US20110031657A1 (en) * | 2009-08-04 | 2011-02-10 | E-Beam Services, Inc. | Electron Beam Irradiation of Bulk Material Solids |
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