CN106928385A - The manufacture method of polyethylene or polyethylene vinylacetate copolymers - Google Patents
The manufacture method of polyethylene or polyethylene vinylacetate copolymers Download PDFInfo
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- CN106928385A CN106928385A CN201610533520.8A CN201610533520A CN106928385A CN 106928385 A CN106928385 A CN 106928385A CN 201610533520 A CN201610533520 A CN 201610533520A CN 106928385 A CN106928385 A CN 106928385A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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Abstract
The present invention provides through high-pressure free radical polymerization manufacture low density polyethylene (LDPE) or the method for polyethylene vinylacetate copolymers.The present invention relates to be defined the method to manufacture polyethylene or polyethylene vinylacetate copolymers to the radical initiator for putting into reactor, when the polyethylene and polyethylene vinylacetate copolymers resin of so manufacture are processed at high temperature, the generation of flake is inhibited, and can maintain senior exterior quality and can improve processing.
Description
Technical field
The present invention relates to polyethylene or the manufacture method of polyethylene vinyl acetate copolymer, it is related in more detail
The side of low density polyethylene (LDPE) or polyethylene vinyl acetate copolymer is manufactured in tube-type reactor by high-pressure free radical polymerization
When the polyethylene or polyethylene vinyl acetate copolymer resin of method, so manufacture are processed at high temperature, the generation of flake is obtained
Suppress, senior exterior quality can be maintained and processing can be improved.
Background technology
The polyethylene and polyethylene vinyl acetate copolymer resin manufactured by high-pressure free radical polymerization, the transparency
Excellent, processability is good, is widely used in the raw material of the purposes such as film, piece, electric wire, foaming product, injection moulding thing.High pressure is certainly
The method manufactured in tube-type reactor and the side manufactured in autoclave reactor are roughly divided into by base polymerization
Two kinds of method, basic manufacture method is widely known.
The polyethylene and polyethylene vinyl acetate copolymer resin manufactured with method for high pressure polymerization, in radical polymerization
Occur in journey as the cross-linking reaction of side reaction, therefore form gel or be referred to as the high molecular defect of flake, product can be damaged
The outward appearance of product.Diaphragm particularly in the electronic product for requiring high precision, the film for entering the coating of line number μ m-thick be extrusion coated,
It is most important demand characteristics without flake in the purposes such as high-voltage electrical line, solar energy sealing material.But on the other hand, gather
There is following characteristic in ethene and polyethylene vinyl acetate copolymer resin：Except being polymerized in manufacturing process, generation flake
Beyond approach, during being extruded at high temperature to be processed into film, piece, electric wire etc., due to hot and shearing (shear)
Free radical is produced, because the cross-linking reaction that free radical causes also increases flake.In general, adding on a small scale with vitro
Work is compared, even be processed with the manufacturing procedure of commercialization being processed under identical temperature conditionss, flake problem also can be serious
Much, because in the manufacturing procedure of commercialization, productivity is very important key element, it is desirable to increase productivity is carried out
Processing, therefore under such circumstances, the generation of heat and shearing (shear) is more serious, and the generation of flake also becomes more violent.Business
With passed through to prevent flake in the manufacturing procedure changed frequently with method be to reduce processing temperature, reduce process velocity,
Heat and shearing (shear) are reduced, but this productivity that there is a problem of product declines to a great extent.Resin more than flake is processed continuous
Production aspect there is also problem.Continuous process time is more long, and the flake that the decomposition, crosslinking inside extruder cause is produced more
Seriously, after the processing of certain hour, it is necessary to which the equipment of stopping is cleaned, therefore the damage of production loss and raw material and product is produced
Lose.
Disclose cleaning heat exchanger in Japan Patent JP4426221B9 publications, in an extruder using 53 microns with
Under accurate filter screen reduce the technology of flake.There is problems with the method：Although flake is reduced temporarily working, quilt
The flake of the Form of Polymer of filter screen filtration is detained and is persistently heated and decomposes, and is crosslinked, and if certain hour, flake is again
Secondary increase, therefore in order to periodically clean and the equipment that must stop, due to the increased extrusion load because of filter screen, existing to improve
Productive shortcoming.
Disclosed in Japanese Laid-Open Patent JP2003231759A in the reactor input polymerization inhibitor come suppress polymerization-crosslinking
React so as to reduce the technology of flake.But, there is problems with the method：With the organic peroxy added as initiator
Thing direct reaction and exist generation colored byproducts side effect, extrusion processing when, particularly high temperature process when, produce article shaped
The phenomenon of xanthochromia.The concentration of organic peroxide is drastically reduced when additionally, there are polymerisation, and what polymerization was reduced asks
Topic.
The content of the invention
【Technical problem】
Increase because deteriorating caused flake it is an object of the present invention to provide when being processed by suppressing high temperature extrusion, so that
The polyethylene of processing property or the manufacturer of polyethylene vinyl acetate copolymer can be improved while maintenance high-quality
Method.
【Solution to problem】
In order to realize the purpose, the present invention provides the manufacture of a kind of polyethylene or polyethylene vinyl acetate copolymer
Method, it is characterised in that be that low density polyethylene (LDPE) or polyethylene vinyl acetate copolymerization are manufactured by high-pressure free radical polymerization
The method of thing, in the interval reactor of the reaction temperature comprising less than 230 DEG C, using 1 second half life temperature be 230 DEG C with
Under tertiary pentyl system organic peroxide as radical initiator.
【Invention effect】
It is bad because of resin by polyethylene produced by the present invention or polyethylene vinyl acetate copolymer in high temperature process
Flake increase is inhibited caused by changing, and can maintain few flake state.Therefore, it is not necessary to reduce temperature in order to ensure flake quality
Degree is processed or reduces speed of production, even if unclean equipment is also able to maintain that quality for a long time.Therefore, result is that have
The effect that processing property increases.It is special that the polyethylene and polyethylene vinyl acetate copolymer are particularly suitable for flake quality
The important electronics and diaphragm of optical articles, film be extrusion coated, high-voltage electrical line, the sealing material of solar energy module etc. are used
On the way.
Brief description of the drawings
Fig. 1 is the figure that diagram represents the tube-type reactor used in one embodiment of the present of invention.
Fig. 2 is to represent the polyethylene vinyl acetate copolymer for being manufactured by embodiment 2 and comparative example 3, is being represented
Processing temperature under when carrying out the processing of film, determine flake using AFC-100 flakes auto-counter and correspond to process time
Change.
Specific embodiment
The present invention is described more particularly below.But, this is the explanation carried out to be readily appreciated that the present invention, is not limited
The scope of the present invention.
The manufacture method of one embodiment of the present of invention is：By high-pressure free radical polymerization manufacture low density polyethylene (LDPE) or
The method of polyethylene vinyl acetate copolymer, in the interval reactor of the reaction temperature comprising less than 230 DEG C, uses 1 second
Clock half life temperature is less than 230 DEG C of tertiary pentyl system organic peroxide as radical initiator.
According to one embodiment of present invention, it is generally desirable to, the high-pressure free radical polymerisation reaction temperature 130~
340 DEG C, 2200~3500kg/cm of reaction pressure2Under conditions of carry out.
If minimum point temperature is less than 130 DEG C, initial reaction speed is excessively slow, to the conversion ratio reduction of polyethylene, anti-
Super high molecular weight chain should be formed the initial stage, gel is produced.If polymerization temperature is more than 340 DEG C, there is the decomposition reaction of polyethylene,
Runaway reaction can be caused.In addition, polymerization pressure is preferably 2200~3500kg/cm2If polymerization pressure is less than 2200kg/
cm2, then the reaction efficiency reduction of initiator, consumes a large amount of initiators, and the accessory substance of initiator is acted as the impurity of resin
With being to make the increased main cause of flake.In addition, less than 2200kg/cm2Pressure under, generate excessive short-chain branch and length
Side chain, making the density of film reduces, film-strength reduction, therefore is undesirable.Although the higher the better for polymerization pressure, but if exceeding
3500kg/cm2, then the generation of short-chain branch and long-chain branch is inhibited, and during processing film, machining load increases, and produces film mistake
In transparent problem.
Preferable feature of the invention, as radical initiator, preferably uses selected from tertiary pentyl system organic peroxy
More than a kind among compound.
It is particularly preferred that in being less than 230 DEG C of the reactor in reaction temperature interval with reaction temperature, using choosing
It is that more than a kind among less than 230 DEG C of tertiary pentyl system organic peroxide is used as free radical and draws from 1 second half life temperature
Hair agent.Half life temperature data is different and different according to the reaction environments such as pressure and solvent, generally by organic peroxide
Manufacturing enterprise provides.
The reaction temperature interval means to be present in the temperature range of inside reactor.Specifically, if by free radical
Initiator is injected into the reactor that there is monomer, then due to heat of polymerization, reaction temperature rises, therefore inside reactor is present
Low temperature is interval and high-temperature is interval.Among such temperature range, there is the reaction temperature area that reaction temperature is less than 230 DEG C
Between reactor in, as radical initiator, preferably use tertiary pentyl system organic peroxide, particularly 1 second half-life period
Temperature is less than 230 DEG C of tertiary pentyl system organic peroxide.
According to one embodiment of present invention, it is less than 230 DEG C of the organic mistake of tertiary pentyl system as 1 second half life temperature
Oxide, it is possible to use peroxidating 2 ethyl hexanoic acid tert-pentyl ester, peroxidating pivalic acid tert-pentyl ester, peroxidating neodecanoic acid tert-pentyl ester,
Peracetic acid tert-pentyl ester, isopropyl peroxide carbonic acid tert-pentyl ester, peroxidating -3,5,5- triethyl group caproic acid tert-pentyl esters etc..
Preferable feature of the invention, in the manufacture of polyethylene or polyethylene vinyl acetate copolymer, Ke Yijin
One step uses the organic peroxy for not damaging effect of the invention and can be used as tertiary pentyl system organic peroxide
Thing initiator.Its example has：The peroxidating pivalic acid tert-butyl ester, peroxy dicarbonate di-n-butyl, new peroxide tert-butyl caprate,
The peroxidating 2 ethyl hexanoic acid tert-butyl ester, peroxide acetic acid butyl ester, peroxidized t-butyl perbenzoate, di-tert-butyl peroxide,
T-butylcumylperoxide, 1,3- double (t-butylperoxyisopropyl) benzene, two t-amyl peroxy compounds, two tertiary hexyl peroxides
The tertiary own ester of compound, peroxidating 2 ethyl hexanoic acid and talkyl peropivalate etc., it is possible to use wherein optional more than a kind.
It is desirable that the tertiary pentyl system organic peroxy of minimum more than the 10 weight % containing reaction initiator total content
Compound.For no other reason than that：If containing below 10 weight %, can not fully suppress the cross-linking reaction of polymerization stage, Macromolecule
The formation of glue increases, thus the generation of flake increases, exterior quality reduction.
Foregoing organic peroxide can also only select a kind of material to use, as the efficiency of initiator according to temperature
And it is different, therefore in the case of the interval width of reaction temperature, in order to obtain optimum efficiency, two or more can be mixed to make
With.
In addition, for the Efficient Operation of initiator injection pump, foregoing organic peroxide can in a solvent dilute and
Use, the present invention uses common solvent, its species is not limited, preferably isoparaffin.
In manufacture method of the invention, usually used molecular weight regulator can be put into, the species of compound is not made
Limit.It is acetone, propionic aldehyde, methyl ethyl ketone, propylene, 1- butylene, isobutene, penta as the example of common molecular weight regulator
The olefin-based hydro carbons such as alkene, hexene, heptene, octene.These hydrocarbon molecules structures can include linear, branched structure or ring knot
Structure.Can include in the molecular structure of molecular weight regulator benzene structure, other double bond structure, aldehyde, ether, ester, carboxylic acid, alcohol, ketone,
The structures such as amine, sulphur.
In polyethylene of the invention and polyethylene vinyl acetate copolymer, do not damaging in the range of inventive nature, can
To add additive.As such additive, there are hindered phenol series antioxidant, phosphate system antioxidant, lactone system antioxygen
Agent, ethanol amine system antioxidant, HALS systems antioxidant, UV stabilizer, UV absorbents, nertralizer, anti-blocking agent, increasing are slided
Agent, nucleator, face material etc..
Hereinafter, by one embodiment of the present of invention, reference picture 1 illustrates manufacture polyethylene or polyethylene-acetic acid second
The method of enoate copolymer.
According to one embodiment of present invention, the major part of cast polymerisation be divided into as shown in Figure 1 compressor reducer,
Reactor, seperator and extruder.
The mixed gas 1 of vinyl monomer or vinyl monomer and vinyl acetate monomer after refining are in 1 second compression device 2
It is compressed to about 200~300kg/cm2, 2,200 are compressed in 2 second compression devices 5 together with the recyclegas 13 for carrying out autoreactor
~3,500kg/cm2Afterwards, by the injecting reactor of reaction initiator 14~17, it is made to be polymerized.
The molecular weight regulator (3,4) of Molecular regulator amount can be further put into during this.Molecular weight regulator is also named
Make chain-transferring agent (chain transfer agent), on its species and performance, the document (J.Polymer of Mortimer
Science A-1, Vol8, Year1970, page1513) in be described in detail, enumerate if wherein several examples, have：Acetone,
The olefines such as the aldehydes such as the ketones such as methyl ethyl ketone, propionic aldehyde, propylene, isobutene, n-butene, hexene, octene, benzene, toluene, diformazan
Hydro carbons without effect group such as the thio alcohol such as the alcohols such as the aromatic compounds such as benzene, methyl alcohol, ethanol, mercaptan, butane etc..
Predetermined 2200~3500kg/cm of pressure is maintained in the reactor2, 130~340 DEG C of temperature and holdup time condition
And adjust reaction after, will contain polyethylene reaction product high pressure seperator 10 and low pressure seperator 11 be separated into macromolecule and
Unreacted monomer, the extruded machine of polyethylene separated by low pressure seperator is cut into graininess, the quilt as product
Packaging.
The place of the monomer in injection tube-type reactor has more than at one sometimes, and Fig. 1 shows single from two place injections
Body, the mode for putting on 4 grades of reactor to be polymerized.Monomer is injected into primary air 6, is warming up to by separate heater 8
After appropriate reaction temperature, it is polymerized into the 1st reactor (after 14).But, according to the present invention, as long as more than 1
Reactor, then it is several can, preferably carried out in the reactor more than 2.
Monomer after other compression is injected by secondary streamses 7, and appropriate reaction temperature is warming up to by separate heater 8
Afterwards, after mixing with the monomer/polymer of primary air, the 2nd reactor (after 15) is injected, is polymerized.
Then, it is polymerized in the 3rd reactor (after 16), the 4th reactor (after 17).
It is different according to operation, also either with or without the operation of secondary streamses 7, it can be understood as be not supplied to further except monomer anti-
Answer beyond device, carried out with the principle same with above-mentioned operation.
Now, in the 1st reactor to the 4th reactor, it is less than 230 DEG C to include reaction temperature simply by the presence of any one
The interval reactor of reaction temperature, it is possible to injected in the reactor radical initiator of the invention, i.e., 1 second half
The phase temperature of declining is less than 230 DEG C of tertiary pentyl system organic peroxide, is polymerized.When being manufactured by such method, even if
Processing is extruded by high temperature to be manufactured, it is also possible to provide flake few high-quality polyethylene or polyethylene vinyl acetate
Copolymer, goes for the important product of requirement flake quality.
Hereinafter, the physical property of the preferred embodiments of the present invention and each composition is described in detail, but this is to describe in detail to this
The degree that art personnel easily carry out an invention, is not meant to that technological thought of the invention and scope are so limited.
<Embodiment 1>
As shown in figure 1, manufacturing polyvinyl resin in 4 tube-type reactors of reactor.
After vinyl monomer and vinyl acetate monomer after being compressed by compressor reducer are preheating to reactor initial stage temperature,
It is injected into comprising in 4 tube-type reactors of conversion zone.
Monomer be divided into the 1st reactor primary air and be directly entered the secondary streamses of the 2nd reactor and put into, with 55：
45 ratio input.Using propionic aldehyde or propylene as molecular weight regulator, the input ratio of primary air and secondary streamses is divided into 50：50
To inject.Molecular weight regulator injection rate is as shown in table 2.The species of the organic peroxide as reaction initiator and each composition
Composition ratio be shown in table 1 below, the polymerizing condition such as pressure, temperature, molecular weight regulator input amount in conversion zone at different levels
It is shown in table 2 below.
After reaction initiator is manufactured with the ratio shown in table 1, put into by the front end inlet of conversion zone at different levels,
Manufacture polyvinyl resin.Put into the reaction initiator of each reactor and adjust input amount for the reaction temperature met shown in table 2,
Relative to the reactant for ultimately generating, the amount of the overall reaction initiator of input is in 0.5kg- initiators/ton-reactant to 1.5kg-
Adjusted in the range of initiator/ton-reactant.
In it there is interval 1st reactor and 2nd reactor of the reaction temperature less than 230 DEG C, by 1 second half-life period temperature
Spend for 185 DEG C of peroxidating 2 ethyl hexanoic acid tert-pentyl ester (PO-5) together with tert-butyl group system organic peroxide with shown in table 1
Ratio mixes to use.
【Table 1】
Here, in the table, PO-1 is the peroxidating pivalic acid tert-butyl ester, and PO-2 is the peroxidating 2 ethyl hexanoic acid tert-butyl ester,
PO-3 is the trimethylhexanoate of peroxidating 3,5,5-, and PO-4 is di-tert-butyl peroxide, and PO-5 is peroxidating 2- ethyls
Caproic acid tert-pentyl ester, PO-6 is two t-amyl peroxy compounds.
【Table 2】
<Embodiment 2>
Manufactured according to the method same with foregoing embodiment 1, using as the ethene of monomer and vinyl acetate list
Body mixes input with the ratio shown in table 2, manufactures vinyl-vinyl acetate copolymer.230 DEG C are less than there is reaction temperature
It is 185 DEG C of peroxidating 2 ethyl hexanoic acid tert-pentyl ester by 1 second half life temperature in interval the 1st reactor and the 2nd reactor
Mix to use with the ratio shown in table 1 together with tert-butyl group system organic peroxide.By the stage of product particle, will make
For the SONGNOX-1076 (octadecyl 3- (3,5- di-t-butyl -4- hydrogen phenyl) propionate) of antioxidant is allocated as 400ppm
To be manufactured.
<Embodiment 3>
Manufactured according to the method same with foregoing embodiment 1, using as the ethene of monomer and vinyl acetate list
Body mixes input with the ratio shown in table 2, manufactures vinyl-vinyl acetate copolymer.230 DEG C are less than there is reaction temperature
It is 185 DEG C of peroxidating 2 ethyl hexanoic acid tert-pentyl ester by 1 second half life temperature in interval the 1st reactor and the 2nd reactor
Mix to use with the ratio shown in table 1 together with tert-butyl group system organic peroxide.By the stage of product particle, will make
For the SONGNOX-1076 (octadecyl 3- (3,5- di-t-butyl -4- hydrogen phenyl) propionate) of antioxidant is allocated as
1200ppm is manufactured.
<Comparative example 1>
Manufactured according to the method same with foregoing embodiment 1, as shown in table 1, do not use tertiary pentyl system organic
Peroxide and manufacture polyethylene using only tert-butyl group system organic peroxide.
<Comparative example 2>
Manufactured according to the method same with foregoing embodiment 1, from the 1st reactor to the 4th reactor, by 1 second
Half life temperature is that 251 DEG C of two t-amyl peroxy compounds are used in mixed way to manufacture polyethylene with the ratio shown in table 1.
<Comparative example 3>
Manufactured according to the method same with foregoing embodiment 1, using as the ethene of monomer and vinyl acetate list
Body mixes input with the ratio shown in table 2, manufactures vinyl-vinyl acetate copolymer.Reaction initiator be as shown in table 1,
Do not manufactured using only tert-butyl group system organic peroxide using tertiary pentyl system organic peroxide.By product particle
In the stage, will be adjusted as the SONGNOX-1076 of antioxidant (octadecyl 3- (3,5- di-t-butyl -4- hydrogen phenyl) propionate)
With being manufactured for 400ppm.
<Comparative example 4>
Manufactured according to the method same with foregoing embodiment 1, using as the ethene of monomer and vinyl acetate list
Body mixes input with the ratio shown in table 2, manufactures vinyl-vinyl acetate copolymer.Reaction initiator be as shown in table 1,
Do not manufactured using only tert-butyl group system organic peroxide using tertiary pentyl system organic peroxide.By product particle
In the stage, will be adjusted as the SONGNOX-1076 of antioxidant (octadecyl 3- (3,5- di-t-butyl -4- hydrogen phenyl) propionate)
With being manufactured for 1200ppm.
<Experimental example>
To the polyvinyl resin and polyethylene vinyl acetate that are manufactured by foregoing embodiment 1~3 and comparative example 1~4
Each physical property of copolymer is measured, the results are shown in Table 3 below.In each embodiment, comparative example, the assessment item of each physical property and
Its assay method is as follows.
(1) melt index (Melt Index, MI)
：Determined under conditions of 190 DEG C, 2.16kg according to ASTM D1238 conditions.
(2) density of polyethylene
：According to ASTM D1505 conditions, after test film is boiled into 1 hour in 100 DEG C of boiling water, room temperature is cooled to,
After being placed 24 hours in thermostatic constant wet chamber, determined with density gradient method.
(3) vinyl acetate content in vinyl-vinyl acetate copolymer
：The vinyl acetate content in copolymer is determined according to FT-IR methods.
(4) flake corresponding with processing temperature
：For polyethylene or ethylene-vinyl acetate copolymer resin, in order to evaluate the increase of the flake under high temperature, 2
Implement film shaping at a temperature of more than individual to evaluate.Film with the PE30-CR9 casting films forming machine of OCS companies with 50 μ m thicks come
Manufacture, the big of gel is counted using film surface analyzer (Film surface analyzer) FSA-100 of OCS companies automatically
After small and number, wherein, counting reaches more than 200 μm of composite gel count, by the weight of the film of measured area, with every g's
Number is represented.Processing temperature when film is molded is represented on the basis of extruder barrel temperature and die head temperature.
【Table 3】
<Embodiment 1 and comparative example 1, the experimental result of comparative example 2>
As shown in table 3, the number of the flake of measure is respectively in embodiment 1, comparative example 1,2 at 180 DEG C of low temperature
0.19/g, 0.22/g, 0.25/g, relative number difference is similar within 30%, is 1/below g, is good
Alright.
It is being processed at 210 DEG C as a result, there is interval 1st reactor of the reaction temperature less than 230 DEG C and the 2nd anti-
In answering device, used 1 second half life temperature be in the embodiment 1 of 185 DEG C of peroxidating 2 ethyl hexanoic acid tert-pentyl ester be 0.35
Individual/g, increases to 1.8 times, but still is 1/below g, and good level is still in quality.
However, be 1.7/g in the comparative example 2 for only being manufactured with tert-butyl group system organic peroxide, and when processing for 180 DEG C
Compare, be significantly increased to 7.7 times.
Although using tertiary pentyl system organic peroxide, use what 1 second half-life period provided in the present invention
In the comparative example 2 of two t-amyl peroxy compounds outside scope, 210 DEG C processing results be 1.4/g, be significantly increased to
5.6 times.
Comparing more than, when the polyethylene manufactured with the method for the present invention is processed at high temperature, with comparative example phase
Than there is 3 times to 4 times of flake inhibition.
<The experimental result of embodiment 2 and comparative example 3>
As shown in table 3, the number in 180 DEG C of flakes of measure of low temperature is respectively 0.34 in embodiment 2 and comparative example 3
Individual/g, 0.32/g, be similar.But, in 200 DEG C of processing as a result, be 0.76/g in embodiment 2, slightly increase,
But it is 1.6/g in comparative example 3, is significantly increased.
Processed at 220 DEG C as a result, be 1.7/g in embodiment 2, and be further significantly increased in comparative example 3 to
15.3/g.During 200 DEG C of processing temperature, flake inhibition of the invention is 2.8 times, table of the present invention during 220 DEG C of processing temperature
Reveal 9 times of flake inhibition.
Fig. 2 is film surface analyzer (the Film surface analyzer) FSA-100 for utilizing OCS to embodiment 2 and ratio
Flake corresponding with film process time change compared with example 3 carries out the result of automatic counting.
As shown in Figure 2, it is known that：In embodiment 2, even 220 DEG C of processing temperature also carries out film processing with the level of stabilization,
But in comparative example 3, elapsed time is more long, then flake correspondingly increases with the time, as the state for being difficult to maintain long-term quality.
<The experimental result of embodiment 3 and comparative example 4>
As shown in table 3, the number of 180 DEG C of flakes of measure of low temperature is respectively 0.67 in embodiment 3 and comparative example 4
Individual/g, 0.68/g, be similar.But, in 210 DEG C of processing as a result, slightly increase to 1.4/g in embodiment 3, but
It is significantly increased in comparative example 3 to 2.6/g.In the embodiment 3 manufactured with the method for the present invention, compared with comparative example 4, there are 2 times
Flake inhibition.
Therefore, the polyethylene and polyethylene vinyl acetate copolymer for being manufactured by manufacture method of the invention are shown
Suppress flake generation during extrusion processing at high temperature, there is provided the excellent effect of the few film of flake.The height few in order to manufacture flake
Quality thin film can not also be processed at low temperature, therefore with processing temperature is improved to high-quality product, reduce machine utilization, can
To improve productive excellent effect.
Claims (7)
1. the manufacture method of polyethylene or polyethylene vinyl acetate copolymer, it is characterised in that
It is the method that low density polyethylene (LDPE) or polyethylene vinyl acetate copolymer are manufactured by high-pressure free radical polymerization,
In the interval reactor of the reaction temperature comprising less than 230 DEG C,
The tertiary pentyl system organic peroxide for being less than 230 DEG C using 1 second half life temperature is used as radical initiator.
2. the manufacture method of polyethylene according to claim 1 or polyethylene vinyl acetate copolymer, its feature exists
In,
The high-pressure free radical is aggregated in 130~340 DEG C of reaction temperature, 2200~3500kg/cm of reaction pressure2Under conditions of enter
OK.
3. the manufacture method of polyethylene according to claim 1 or polyethylene vinyl acetate copolymer, its feature exists
In,
As tertiary pentyl system organic peroxide, from by peroxidating 2 ethyl hexanoic acid tert-pentyl ester, peroxidating pivalic acid uncle penta
Ester, peroxidating neodecanoic acid tert-pentyl ester, peracetic acid tert-pentyl ester, isopropyl peroxide carbonic acid tert-pentyl ester, peroxidating -3,5,5- three
More than a kind is selected in the group of thylhexoic acid tert-pentyl ester composition.
4. the manufacture method of polyethylene according to claim 1 or polyethylene vinyl acetate copolymer, its feature exists
In,
As the radical initiator, further comprising selected from by the peroxidating pivalic acid tert-butyl ester, peroxy dicarbonate two just
Butyl ester, new peroxide tert-butyl caprate, the peroxidating 2 ethyl hexanoic acid tert-butyl ester, peroxide acetic acid butyl ester, perbenzoic acid
The tert-butyl ester, di-t-butyl peroxide, t-butylcumylperoxide, 1,3- double (t-butylperoxyisopropyl) benzene, two uncles penta
Base peroxide, two tertiary hexyl peroxide, the tertiary own ester of peroxidating 2 ethyl hexanoic acid and talkyl peropivalate composition
More than a kind in group.
5. the manufacture method of polyethylene according to claim 1 or polyethylene vinyl acetate copolymer, its feature exists
In,
The radical initiator is used after being diluted in isoparaffin.
6. the manufacture method of polyethylene according to claim 1 or polyethylene vinyl acetate copolymer, its feature exists
In,
The reactor is tube-type reactor.
7. the manufacture method of polyethylene according to claim 6 or polyethylene vinyl acetate copolymer, its feature exists
In,
The reactor is made up of the reactor of more than 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2015-0188739 | 2015-12-29 | ||
| KR1020150188739A KR101757565B1 (en) | 2015-12-29 | 2015-12-29 | Method for manufacturing polyethylene or polyethylene vinylacetate copolymer |
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| CN106928385A true CN106928385A (en) | 2017-07-07 |
| CN106928385B CN106928385B (en) | 2020-01-07 |
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| JP (1) | JP6283714B2 (en) |
| KR (1) | KR101757565B1 (en) |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204637A (en) * | 2019-06-21 | 2019-09-06 | 中国神华煤制油化工有限公司 | Tubular process high pressure prepare low crystal point polyethylene method and low crystal point polyethylene |
| CN110891986A (en) * | 2017-11-03 | 2020-03-17 | Lg化学株式会社 | Process for preparing ethylene-vinyl acetate copolymer |
| CN112239517A (en) * | 2019-07-19 | 2021-01-19 | 旭化成株式会社 | Ethylene-vinyl acetate copolymer resin and film |
| CN115636889A (en) * | 2021-07-19 | 2023-01-24 | 中国石油天然气股份有限公司 | Preparation method of LDPE resin for film product |
| TWI811924B (en) * | 2021-03-08 | 2023-08-11 | 日商旭化成股份有限公司 | Ethylene-vinyl acetate copolymer, moldings, sheets and foams containing it |
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| KR102055982B1 (en) * | 2017-10-20 | 2020-01-22 | 한화토탈 주식회사 | Ethylenevinylacetate copolymer for solar light, the method of preparing the same, and Encapsulant sheet for solar cell employing the same |
| KR101948445B1 (en) | 2017-11-28 | 2019-02-14 | 한화토탈 주식회사 | Polymer manufacturing method for producing polyethylene homopolymer or polyethylene vinyl acetate copolymer |
| JP7110625B2 (en) * | 2018-03-02 | 2022-08-02 | 日本ポリエチレン株式会社 | Resin composition for extrusion lamination, laminate, and method for producing laminate |
| JP7445032B2 (en) * | 2022-02-02 | 2024-03-06 | 旭化成株式会社 | Ethylene-vinyl acetate copolymer resin, film, molded product, foam, and sheet |
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| CN110891986A (en) * | 2017-11-03 | 2020-03-17 | Lg化学株式会社 | Process for preparing ethylene-vinyl acetate copolymer |
| US11603420B2 (en) | 2017-11-03 | 2023-03-14 | Lg Chem, Ltd. | Method for preparing ethylene vinylacetate copolymer |
| CN110891986B (en) * | 2017-11-03 | 2023-07-18 | Lg化学株式会社 | Process for preparing ethylene-vinyl acetate copolymer |
| CN110204637A (en) * | 2019-06-21 | 2019-09-06 | 中国神华煤制油化工有限公司 | Tubular process high pressure prepare low crystal point polyethylene method and low crystal point polyethylene |
| CN110204637B (en) * | 2019-06-21 | 2021-08-17 | 中国神华煤制油化工有限公司 | Method for preparing low-crystalline-point polyethylene under high pressure by tubular method and low-crystalline-point polyethylene |
| CN112239517A (en) * | 2019-07-19 | 2021-01-19 | 旭化成株式会社 | Ethylene-vinyl acetate copolymer resin and film |
| CN112239517B (en) * | 2019-07-19 | 2024-01-09 | 旭化成株式会社 | Ethylene-vinyl acetate copolymer resin and film |
| TWI811924B (en) * | 2021-03-08 | 2023-08-11 | 日商旭化成股份有限公司 | Ethylene-vinyl acetate copolymer, moldings, sheets and foams containing it |
| CN115636889A (en) * | 2021-07-19 | 2023-01-24 | 中国石油天然气股份有限公司 | Preparation method of LDPE resin for film product |
| CN115636889B (en) * | 2021-07-19 | 2024-03-01 | 中国石油天然气股份有限公司 | Preparation method of LDPE resin for film product |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6283714B2 (en) | 2018-02-21 |
| JP2017119816A (en) | 2017-07-06 |
| CN106928385B (en) | 2020-01-07 |
| KR20170078338A (en) | 2017-07-07 |
| KR101757565B1 (en) | 2017-07-12 |
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