CN1551892A - Ethylene alkyl acrylate copolymers with improved heat resistance - Google Patents
Ethylene alkyl acrylate copolymers with improved heat resistance Download PDFInfo
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- CN1551892A CN1551892A CNA028051327A CN02805132A CN1551892A CN 1551892 A CN1551892 A CN 1551892A CN A028051327 A CNA028051327 A CN A028051327A CN 02805132 A CN02805132 A CN 02805132A CN 1551892 A CN1551892 A CN 1551892A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention provides a copolymer of ethylene and at least 5 mol % of comonomer units derived from an alkyl acrylate or alkyl methacrylate, wherein the copolymer has a melt index of from 1 to 10,000 g/10 min, and a maximum peak melting temperature of at least 100 DEG C. The alkyl group of the alkyl acrylate or alkyl methacrylate can e a linear or branched C1 to C12 group, particularly n-butyl. The copolymer shows increased heat resistance as characterized by a temperature required to melt 50 % of the copolymer of at least 80 DEG C, a temperature required to melt 80 % of the copolymer of at least 100 DEG C, a temperature required to melt 100 % of the copolymer of at least 110 DEG C. The invention further provides a process for copolymerizing ethylene and an alkyl acrylate or alkyl methacrylate comonomer.
Description
1.
Invention field
The present invention relates to novel ethylene alkyl acrylate and ethylene methacrylic acid alkyl ester copolymer.Especially, the invention provides and have the improvement thermotolerance, as the multipolymer of the ethene of peak value melt temperature more and alkyl acrylate or alkyl methacrylate and the production method of multipolymer like this.These novel multipolymers are particularly suitable for as hotmelt, or as the component of hotmelt preparaton.
2.
Background
Ethene and comonomer such as alkyl acrylate or alkyl methacrylate or vinyl ester copolymerization have the polymkeric substance of different complete performances and attribute with generation, and this complete performance and attribute can not obtain from homopolymer self.When increasing the content of comonomer, some attributes such as bonding and low-temperature flexibility have significantly been improved.Yet, increasing co-monomer content and always cause lower peak value melt temperature, remarkable sometimes lower peak value melt temperature is particularly in the multipolymer that comprises more than about 5mol% comonomer.As an example, when co-monomer content increased, the remarkable reduction of commercially available ethylene vinyl acetate (EVA) and ethylene methyl acrylate (EMA) trade mark peak value display melt temperature was shown in Fig. 1 (prior art).These are the littler crystallite dimension of low peak melt temperature indication more, and this crystallite dimension is from shorter sequence (runs) uninterrupted in the main polymer chain, that repeat ethylene unit.Therefore, be difficult to adopt in addition the comonomer quantity of appropriateness to reach high-melting-point.
Also can significantly reduce the peak value fusing point by increasing melting index.Commercially available, the data presentation of nominal 28wt% vinyl acetate (VA) multipolymer, under the 2.3g/10min melting index about 73 ℃ to 63 ℃ reduction under the 420g/10min melting index, shown in Fig. 2 (prior art).Routine techniques is used in these observed trend indications, and high MI and high comonomer content multipolymer can have low-down fusing point.In hotmelt and some films or moulded parts, wherein thermotolerance and intensity are particularly importants, advantageously have following bonded multipolymer: high fusion index, high relatively co-monomer content and higher fusing point yet in some applications.
Be used to produce even ethylene acrylate copolymer continuously, the use of back mixing autoclave is disclosed in U.S. patent No.3,350,372.The copolymer resin that uses autoclave technology to produce is commercially available, and these resins are consistent with the trend of expectation.For example, as discussing more fully among the embodiment herein, under 32.5wt% n-butyl acrylate (9.5mol%), the peak value melt temperature of 330g/10min melting index ethylene n-butyl acrylate copolymer is determined deficiently, numerical value is about 58.7 ℃, this multipolymer from ExxonMobil Chemical with Enable
TMEN-33330 buys.The more low viscous trade mark, have the prediction melting index of about 900g/10min and from ExxonMobil Chemical with Enable
TMEN-33900 buys, have 58.1 ℃ in addition low peak melt temperature (seeing Table 1) more.
Manufacturers recognizes that the more low melting point of commercial copolymer is non-required restriction, and attempt development technique with the fusing point of the ethylene acrylate copolymer (EMA and EnBA) that is increased in continuously, produces in the high pressure autoclave (referring to as U.S. patent Nos.5,543,477 and 5,631,325).These technology cause having the multipolymer of following peak value melt temperature: this temperature is according to reports than about 7-10 ℃ of other conventional polymerization copolymerization object height of producing in autoclave.
First kind of commerce, the continuous processing that is used to produce ethylene alkyl acrylate and alkyl methacrylate multipolymer is the pipe reaction plumber skill (referring to US2,953,551) by Union Carbide exploitation.Known tubular reactor can the production melt temperature than the ethylene alkyl acrylate and the alkyl methacrylate multipolymer of the identical copolymerization object height of polymeric in the high pressure autoclave.Under identical molar percentage comonomer, compare with autoclave polymeric ethylene methyl acrylate copolymer, have high relatively peak value melt temperature by the commercially available ethylene ethyl acrylate copolymer of Union Carbide phase earlier 1960s production and selling.Yet, to use for some, the fusing point of the multipolymer that can obtain from these technology is lower still non-requiredly.
For further background information, referring to for example, WO00/58093, WO97/34939, US5,543,477, DE3217973, DE3404744, EP245773 and EP575873.
3.
General introduction
Be surprisingly found out that with in autoclave reactor or the similar multipolymer for preparing in the formerly known tube process compare, ethylene alkyl acrylate for preparing in tubular reactor or alkyl methacrylate multipolymer can show significantly higher peak value melt temperature, allow high-level relatively comonomer to introduce simultaneously.Therefore, the peak value melt temperature of multipolymer of the present invention surpasses those that obtain from conventional autoclave polymerization substantially.Even under higher n-butyl acrylate comonomer concentration (it should cause lower peak value melt temperature), the peak value melt temperature of product of the present invention is higher than U.S. patent Nos.5,543,477 and 5, disclosed improvement product and surpassing in 631,325 from U.S. patent No.5, the melting temperature upper limit that provides formula calculating in 631,325 is more than 8 ℃.
According to the present invention, being surprisingly found out that can be in the high pressure tubular reactors of using a plurality of decanting points of radical initiator, produce ethylene alkyl acrylate or alkyl methacrylate multipolymer, this multipolymer be characterized as the peak value melt temperature, high comonomer level and high fusion index optionally.The peak value melt temperature of multipolymer of the present invention, the peak value melt temperature height of the similar multipolymer that the conventional high pressure autoclave process technology of ratio use prepares arrives greater than 50 ℃ at least for 5 ℃, with at least 5 ℃ to similar 25 ℃ of the similar copolymerization object heights for preparing than the conventional high pressure tubular reactors of use (it is at a unique some injection initiator).
In one embodiment, the invention provides the ethene and the multipolymer of 5mol% comonomer unit at least, comonomer unit derived from propylene acid alkyl ester or alkyl methacrylate, wherein the melting index of multipolymer is 1-10,000g/10min and be at least 100 ℃ in the peak-peak melt temperature of this definition.The alkyl of alkyl acrylate or alkyl methacrylate can be linearity or branching C
1-C
12Group is as methyl, ethyl, butyl, hexyl and octyl group, particularly normal-butyl.Also can comprise other comonomer, as the part ester and the carbon monoxide of vinylformic acid, methacrylic acid, toxilic acid.The multipolymer indicating characteristic is the increase thermotolerance of following temperature: at least 80 ℃ the temperature that requires fusion 50% multipolymer, at least 100 ℃ the temperature that requires fusion 80% multipolymer, at least 110 ℃ the temperature that requires fusion 100% multipolymer.
In another embodiment, the invention provides the ethene and the multipolymer of 5mol% comonomer at least, comonomer comprises the first comonomer component and second comonomer component.The first comonomer component comprises alkyl acrylate, alkyl methacrylate or its mixture.Second comonomer component comprises the reactivity ratio r with respect to ethene
2Be 2 or littler, or 1.5 or littler, or 1.2 or littler, or about 1 monomer.Monomeric like this example comprises vinyl ester, as vinyl acetate, vinyl formate or propionate.The melting index of multipolymer is 1-10,000g/10min and be at least 80 ℃ in the peak-peak melt temperature of this definition.The alkyl of alkyl acrylate or alkyl methacrylate can be linearity or branching C
1-C
12Group is as methyl, ethyl, butyl, hexyl and octyl group, particularly normal-butyl.Also can comprise other comonomer, as the part ester and the carbon monoxide of vinylformic acid, methacrylic acid, toxilic acid.The multipolymer indicating characteristic is the increase thermotolerance of following temperature: at least 40 ℃ the temperature that requires fusion 50% multipolymer, at least 70 ℃ the temperature that requires fusion 80% multipolymer, at least 80 ℃ the temperature that requires fusion 100% multipolymer.
In another embodiment, the invention provides the method for a kind of copolymerization of ethylene and alkyl acrylate or alkyl methacrylate comonomer, this method is included under the polymerizing condition and in the presence of one or more radical initiators, in high pressure tubular reactors, add the step that comprises the mixture that ethene and alkyl acrylate or alkyl methacrylate are at least a, to form ethylene alkyl acrylate or alkyl methacrylate multipolymer, wherein, preferably in tubular reactor, inject radical initiator at least three reaction zones at least two reaction zones along tubular reactor length.On the contrary, only in the single reaction district, provide monomer and comonomer to tubular reactor.Astoundingly, this method is produced and is had the temperature performance of improvement and the above-mentioned multipolymer of high comonomer content more.
In another embodiment, the invention provides ethylene alkyl acrylate or the alkyl methacrylate multipolymer of producing by the inventive method.
4.
The accompanying drawing summary
Fig. 1 (prior art) shows the DSC method 1 of definition herein of using, function as co-monomer content, for commercially available ethylene vinyl acetate (EVA) and ethylene methyl acrylate (EMA) multipolymer, by the peak value melt temperature of difference method scanning calorimetry (DSC) acquisition.
Fig. 2 (prior art) shows the use DSC method 1 of definition herein, as the function of copolymer melt index, for commercially available ethylene vinyl acetate (EVA) multipolymer, by the peak value melt temperature of difference method scanning calorimetry (DSC) acquisition.
Fig. 3 shows the DSC method 1 that use defines herein, dsc (DSC) thermogram of multipolymer of the present invention (embodiment 4) and correlated non-multipolymer of the present invention (Comparative Examples B).
Fig. 4 shows the DSC method 1 that use defines herein, dsc (DSC) thermogram of multipolymer of the present invention (embodiment 1) and correlated non-multipolymer of the present invention (Comparative Examples G).
Fig. 5 shows the DSC method 2 that use defines herein, compares dsc (DSC) thermogram of embodiment 2 multipolymers with the peak value melt temperature of the single-point tubular type multipolymer (Comparative Examples H) of about same comonomer content.
Fig. 6 shows the DSC method 1 that use defines herein, dsc (DSC) thermogram of multipolymer of the present invention ( embodiment 3,7 and 8) and conventional autoclave multipolymer (comparative example A).
5.
Describe in detail
Copolymer of the present invention is the copolymer of ethene and at least a comonomer, and wherein comonomer is alkyl acrylate or alkyl methacrylate. Suitable comonomer comprises acrylic acid and the methacrylate of C1-C12 linearity or branching alcohol, acrylic acid and the methacrylate of preferred C1-C8 linearity or branching alcohol. Be suitable for use as the preferred alkyl acrylate of comonomer or the example of alkyl methacrylate and comprise the just own ester of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid, acrylic acid 2-ethyl butyl ester and 2-EHA, and the acrylate of the new isomers of C5-C12 alcohol. Particularly preferred comonomer is n-butyl acrylate.
Copolymer can comprise at least 5mol%, preferred 5mol%-20mol%, 5mol%-15mol%, 6mol%-14mol%, or 7mol%-12mol% comonomer-derived unit. In one embodiment, copolymer comprises at least 5mol% or at least 6mol% or at least lower limit of 7mol% comonomer-derived unit, with the upper limit of 20mol% or 14mol% or 12mol% comonomer-derived unit, and the scope of imagination from any lower limit to any upper limit.
Alkyl acrylate or alkyl methacrylate monomer can use separately or use with mixture. Can optionally comprise the monomer that is not ethene and alkyl acrylate or alkyl methacrylate. These other monomers comprise vinyl esters, such as vinylacetate, and part ester and the carbon monoxide of monomer such as acrylic acid, methacrylic acid or maleic acid. Therefore, term " copolymer " comprises from two kinds as used herein, the polymer of three kinds or multiple comonomer preparation.
In some embodiments, copolymer comprises ethene, alkyl acrylate or alkyl methacrylate, or its mixture, and with respect to the reactivity ratio r of ethene2Be 2 or less, or 1.5 or less, or 1.2 or less, or about 1 comonomer. Exemplary comonomers with such reactivity ratio comprises vinyl esters, such as vinylacetate, vinyl formate and propionate. Reactivity ratio r2Be known in the art, for example be described in polymer science and engineering encyclopedia (Encyclopedia of Polymer Science and Engineering), Vol.6,401-403 page or leaf (1986) (John Wiley, New York), and encyclopedia of chemical technology (Encyclopedia of Chemical Technology, the 4th edition, Vol.17,718-719 page or leaf (1996) (John Wiley, New York).
Can in high pressure tubular reactors, produce ethylene alkyl acrylate of the present invention or alkyl methacrylate copolymer. High pressure tubular reactors for the production of ethylene alkyl acrylate or alkyl methacrylate copolymer is known, referring to such as U.S. patent No.2, and 953,551, the disclosure of the document is incorporated herein by reference in this purpose for the U.S. patent working. The present invention is not limited to any specific tubular reactor design, operating pressure or temperature variable, or initiator system, condition is that tubular reactor can be along at least two of reaction tubes, preferably at least three, and more preferably at least four positions, initator is injected reaction system.
Term " tubular type ethylene alkyl acrylate or alkyl methacrylate copolymer " is illustrated in many like this initators injections, the copolymer of producing in the high pressure tubular reactors as used herein.
Tubular reactor can be the strap clamp sleeve pipe or the pipe of elongation, common section or piece with proper strength and diameter.The length-to-diameter of typical tubular reactor is about 1000: 1-about 60,000: 1.Although can use the pressure that are higher than 3500 crust as required, tubular reactor is typically operated under the pressure of about 1000-3500 crust.
The temperature that keeps in the reactor is variable, and is mainly controlled and depended on the concrete initiator system of employing by the concrete initiator system that adopts.Temperature is generally about 100 ℃-350 ℃, and can change in different reaction zones.
The example that is applicable to the high pressure tubular reactors of production ethylene alkyl acrylate of the present invention or alkyl methacrylate multipolymer is shown in U.S. patent No.4,135,044, the disclosure of the document is incorporated herein by reference in this purpose for the U.S. patent working.If use U.S. patent No.4, the reactor shown in 135,044, preferred operations reactor and do not use the cold side linear flow.
In the presence of radical initiator, carry out polyreaction.Such initiator is being known in the art.The concrete non-limitative example of radical initiator comprises oxygen like this; Peroxide compound such as hydrogen peroxide, decanoyl peroxide, the peroxide neodecanoic acid tert-butyl ester, t-butylperoxy pivarate, peroxidation 3,5,5-trimethyl acetyl, diethyl peroxide, the peroxide-2 ethyl hexanoic acid tert-butyl ester, tert-butyl per(oxy)isobutyrate, benzoyl peroxide, tert-butyl peroxy acetate, t-butyl per(oxy)benzoate, di-t-butyl peroxide, peroxide neodecanoic acid tert-pentyl ester, peroxide PIVALIC ACID CRUDE (25) tert-pentyl ester, peroxide-2 ethyl hexanoic acid tert-pentyl ester and hydroperoxidation 1,1,3, the 3-tetramethyl butyl; Alkali metal persulphate, perborate and percarbonate; With azo-compound such as Diisopropyl azodicarboxylate.Preferred initiator is an organo-peroxide.Also can use the mixture of such initiator, can be used for different initiator injections with different initiators and/or different initiator mixture.Can adopt any suitable manner, as pure, be dissolved in suitable solvent, and/or mix with monomer or comonomer feed logistics, initiator is joined in the reactant flow.
As mentioned above, at least two positions, reactant flow is injected with initiator in preferably at least three positions and more preferably at least four positions.In preferred embodiments, monomer and comonomer are introduced tubular reactor in single position, make at second, third, the 4th and the other initiator of subsequent position inject, can't help the injection of any other ethene or comonomer to finish.
Also can be at conventional properties-correcting agent, as reacting under the chain-transfer agent existence.Typical chain-transfer agent comprise can not copolymerization chain-transfer agent, as radical of saturated aliphatic aldehyde, as formaldehyde, acetaldehyde or propionic aldehyde; Radical of saturated aliphatic ketone is as acetone, diethyl ketone and diamyl ketone; Radical of saturated aliphatic alcohol is as methyl alcohol, ethanol and propyl alcohol; Paraffinic hydrocarbons and naphthenic hydrocarbon such as pentane, hexane and hexanaphthene; Aromatic substance is as toluene, diethylbenzene and dimethylbenzene; With other compound such as propylene, tetracol phenixin and chloroform as chain terminator.Preferred chain-transfer agent can not copolymerization, especially preferably acetaldehyde.
Perhaps, but the chain-transfer agent of copolymerization, this chain-transfer agent comprises propylene, iso-butylene, 1-butylene etc., can be separately as a class use or with can not be used in combination by the copolymerization chain-transfer agent.But use the peak value melt temperature of the polymkeric substance of copolymerization chain-transfer agent preparation, usually less than forming and the accessible maximum value of reactor condition for the multipolymer that uses.
Tubular type ethylene alkyl acrylate of the present invention and alkyl methacrylate multipolymer are characterised in that following performance:
(a) total copolymerization monomer content: 5mol%-20mol%.These molar percentages are represented as monomer derived units in the multipolymer and comonomer-derived unit total mole number per-cent, comonomer-derived unit total mole number in the multipolymer.The other lower limit of comonomer-derived unit content can be at least 6%, at least 7%, or at least 8% (molar percentage).The special characteristic of multipolymer of the present invention is that a large amount of relatively comonomers can be introduced multipolymer, still keeps advantageous property described herein simultaneously.Comprising ethene, alkyl acrylate or alkyl methacrylate, with reactivity ratio with respect to ethene be 2 or the embodiment of littler comonomer (as vinyl ester) in, multipolymer of the present invention preferably includes 2mol% at least, or 3mol% at least, or 4mol% alkyl acrylate or alkyl methacrylate comonomer at least, at least 0.5mol%, or 1mol% at least, or 1.5mol% is 2 or littler comonomer for the reactivity ratio of ethene at least, and total copolymerization monomer content as mentioned above.
(b) melting index in g/10min is 1-10,000.The other lower limit of melting index can be 100g/10min at least, 300g/10min at least, 600g/10min at least, 900g/10min at least, 1500g/10min at least, or 2000g/10min at least.
(c) thermotolerance: at 60 ℃ of following fused per-cents.With respect to comparable conventional material, multipolymer of the present invention and their adhesive formulation of use show the thermotolerance that increases.For many application, because or in use, may require the thermotolerance under 60 ℃ with introducing the product of tackiness agent or being exposed to about at the most 60 ℃ temperature from the molding or the extruded product of copolymer in transportation, lay up period.Therefore, dsc (DSC) can be used for measuring 60 ℃ of following fused multipolymer quantity, as stable on heating indication.Use this to measure, in some embodiments, multipolymer of the present invention shows less than 40%, preferably less than 30% and be more preferably less than 25% at 60 ℃ of following fused per-cents.Comprising ethene, alkyl acrylate or alkyl methacrylate, with reactivity ratio with respect to ethene be 2 or the embodiment of littler comonomer (as vinyl ester) in, multipolymer of the present invention shows less than 70%, preferably less than 60% and be more preferably less than 50% at 60 ℃ of following fused per-cents.
(d) thermotolerance: the temperature under the % fusion.Stable on heating measuring in addition is the temperature of requirement fusion predetermined percentage multipolymer, and this temperature also can be by dsc measurement.Multipolymer of the present invention shows the increase thermotolerance with respect to the comparable multipolymer of routine, shown in embodiment herein; That is, require the multipolymer of higher temperature with the given per-cent of fusion.Use these to measure, in some embodiments, require the temperature of fusion 50% copolymer sample of the present invention to be at least 80 ℃, preferably at least 85 ℃ and more preferably at least 90 ℃; Require the temperature of fusion 80% copolymer sample of the present invention can be at least 100 ℃, preferably at least 105 ℃; Can be at least 110 ℃ with the temperature that requires fusion 100% copolymer sample of the present invention, preferably at least 115 ℃ and more preferably at least 120 ℃.Comprising ethene, alkyl acrylate or alkyl methacrylate, with reactivity ratio with respect to ethene be 2 or the embodiment of littler comonomer in, require the temperature of fusion 50% copolymer sample of the present invention to be at least 40 ℃, or at least 50 ℃ or at least 60 ℃; Can be at least 70 ℃ with the temperature that requires fusion 80% copolymer sample of the present invention, or at least 80 ℃ or at least 85 ℃; Can be at least 80 ℃ with the temperature that requires fusion 100% copolymer sample of the present invention, or at least 90 ℃, or at least 100 ℃.
(e) Vicat softening point: multipolymer of the present invention more another of high heat resistance is measured by Vicat softening point and is shown, the improvement ASTM program that Vicat softening point is described in the embodiment part from here uses the 200g load to replace the 1000g load measurement.Use this to measure, in some embodiments, the Vicat softening point of multipolymer of the present invention is at least 45 ℃, preferably at least 50 ℃, and more preferably at least 55 ℃ and still more preferably at least 60 ℃.Comprising ethene, alkyl acrylate or alkyl methacrylate and with respect to the reactivity ratio of ethene be 2 or the embodiment of littler comonomer in, the Vicat softening point of invention multipolymer is at least 30 ℃, or at least 35 ℃, or at least 40 ℃.
(f) peak value melt temperature (peak-peak melt temperature): with respect to having the conventional multipolymer that same general is formed, multipolymer of the present invention shows the more peak value fusing point by dsc measurement.At this use and the term " peak value fusing point " that uses in claims, " Tm " and " peak-peak melt temperature " is expressed as follows the temperature at peak: have the peak of high melting temperature, for example, 111.5 ℃ of peaks of following examples 2.Should be noted that in this regard maximum peak temperature can be positioned on the peak that appears on the DSC trace, is the higher temperature shoulder (shoulder) on Geng Dafeng, as shown in Figure 6, is 99.86 ℃ peak-peak melt temperature for embodiment 8.In some embodiments, the peak value fusing point of multipolymer of the present invention is at least 100 ℃, preferably at least 105 ℃, and more preferably at least 110 ℃.In some embodiments, with the even homogeneous copolymers of identical chemical constitution, compare at least 25 ℃ greatly of the peak value fusing points of multipolymer of the present invention as those the peak value melt temperature of in autoclave reactor, producing, preferably greatly at least 35 ℃ and more preferably greatly at least 50 ℃.Comprising ethene, alkyl acrylate or alkyl methacrylate and with respect to the reactivity ratio of ethene be 2 or the embodiment of littler comonomer in, the peak value fusing point of multipolymer of the present invention is at least 80 ℃, or at least 90 ℃ or at least 95 ℃.
(g) other numerical value: although provided concrete numerical value, should emphasize that multipolymer of the present invention can have other numerical value for above-mentioned physicals, as particularly, the numerical value of example among the embodiment herein.
(h) combination of performance: be to be understood that the required end-use that depends on multipolymer or tackiness agent, multipolymer of the present invention and the binder composition that comprises these multipolymers, the various combination that can have above performance.Such multipolymer with performance combination as embodiment institute example from here, is wondrous and unpredictable, that is, unknown up to now or expect to produce to have these performance combination of polymers.
Because improved thermotolerance and other favourable and wonderful performance, multipolymer of the present invention is suitable for use as hotmelt, or is applicable to the molding with improvement heatproof degree or the production of extruded product.Therefore, the goods that use these multipolymer manufacturings should be not easy to damage and also be not easy to be subjected to the influence of high-cycle fatigue when being exposed to higher temperature, and high-cycle fatigue produces heat in goods.In addition, multipolymer of the present invention also can be used for the hotmelt of following application: this application requiring is the basic maintenance of performance and intensity at high temperature.
6.
Embodiment
Characterizing and estimating in the following polymer properties feature, using following test procedure:
Measure melting index according to ASTM D-1238, but have following exception and explanation.For the sample of MI, use the condition 190/2.16 of ASTM method less than about 100g/10min.For the sample of MI greater than about 100g/10min, the MI of report is based on calculation formula, and this calculation formula is used for numerical associations with condition 125/0.325 to condition 190/2.16.For those samples, determine under 125 ℃ of melt temperatures and 0.325kg load, the time that plunger motion 25.4mm needs and this time are used for following formula to calculate the logarithm of melt flow rate under 190 ℃ and 2.16kg, and the antilogarithm of this numerical value is reported to melting index:
LogMI＝1.8311+0.8237log(928.4/g)，
Wherein t is the plunger motion time in second.With the unit of g/10min, or the suitable unit of the numeral of dg/min report melting index.
Use test method ASTM D3236 (rotating shaft 27), outside the employing in the following example, melt temperature is 190 ℃, measures melt viscosity.
Use is from the section measuring density (g/cm of print cutting
3), print is according to ASTM D-1292 program C compression molding, and is aging and measure according to ASTM D-1505 according to ASTM D-618 program A.
Use the FTIR program, the FTIR program is used calibration standard and the assignment numerical value of being measured by proton N MR, or by directly using proton N MR to measure co-monomer content.
From having the proton N MR spectrum of the temperature probe that is set at 120 ℃, measure the concentration of n-butyl acrylate in the ethylene n-butyl acrylate copolymer.Before data gathering, under 130 ℃, by the about 30mg sample of dissolving in about 3mL tetrachloroethane-d2, preparation sample.By will be between 3.5-4.5ppm the integral area in zone divided by two the factor, calculate the mole number of n-butyl acrylate.By the integral area from zone between the 0.5-3.0ppm deduct ten times of n-butyl acrylate mole numbers and with this result divided by four, calculate the mole number of ethene.
Also, measure the concentration of ethyl propenoate in the ethylene ethyl acrylate copolymer from having the proton N MR spectrum of the temperature probe that is set at 120 ℃.By will be between 3.5-4.5ppm the integral area in zone divided by two the factor, calculate the mole number of ethyl propenoate.By the integral area from zone between the 0.5-3.0ppm deduct six times of ethyl propenoate mole numbers and with this result divided by four, calculate the mole number of ethene.
Similar calculating well known in the art is used to measure the vinyl acetate between to for plastic ester concentration.
Be used to measure dsc (DSC) thermogram of following Several Parameters: as the peak value melt temperature, peak crystallization temperature is descended the temperature of 50%, 80% and 100% sample melted at 60 ℃ of following fused per-cents with at it, is measured by two kinds of methods." method 1 " use test method ASTM D-3417, difference is under the minimum and maximum temperature that is used to test, and uses 5 minute hold-time, replaces 10 minutes." method 2 " uses 10 minute hold-time by ASTM D-3417 regulation.
To the sample measurement Vicat softening point, sample is according to ASTM D-1928 program C compression molding, and aging and according to ASTM D-1525 according to ASTM D-618 program A, specified (Rate) B measures, and difference is to use non-standard 200g load replacement standard 1000g load.
Embodiment 1-5
, in the high pressure tubular reactors of disclosed tubular reactor, produce ethylene n-butyl acrylate copolymer of the present invention, but do not join the side logistics in the reactor in 135,044 similar in appearance to U.S. patent No.4 in design.Monomer have common commercial purity and without any measure to increase purity or to improve them by any way.The n-butyl acrylate monomer is not removed oxygen or shelf-stable agent.
Use following initiator mixture, initiated polymerization under indication quantity by weight: peroxide neodecanoic acid tert-pentyl ester, 39.5%, peroxide PIVALIC ACID CRUDE (25) tert-pentyl ester, 23.7%, and peroxide-2 ethyl hexanoic acid tert-pentyl ester, 36.8%.The 34.3wt% initiator mixture to the 65.7wt% solvent under, these materials are dissolved in hydrocarbon solvent.
Reactor output is held constant at 18.5 tonnes/hour.Reactor condition and production the results are shown in following table 1.In whole service, it is obvious not having noticeable response device or preheater fouling.In table 1, " LPS " and " HPS " represents light pressure separator and high-pressure separator respectively.The configuration tubular reactor is that 3 initiators inject or 4 initiators inject.The operation that dotted line "--" expression in the table 1 wherein only uses 3 initiators to inject.In following table 1, provide total initiator feed to the downstream decanting point.To distribute between them at all the initiator feed of each independent downstream decanting point, with the peak temperature that obtains representing.
Acetaldehyde is as the chain-transfer agent of all these samples.Discovery reaches the quantity of required melting index from the acetaldehyde fed speed of the device empirical Calculation of autoclave polymeric ethylene n-butyl acrylate far below actual needs.For embodiment 1-5, actual needs is more than the calculated flow rate of twice.
For the technology controlling and process purpose, by device quality control laboratory, use the FTIR method, check the concentration of n-butyl acrylate in the run duration embodiment multipolymer, developed the autoclave polymeric ethylene n-butyl acrylate copolymer that this method and common this method are used for preparing on same apparatus.This method requires suitable calibration standard to obtain accurate numerical value.The co-monomer content of embodiment multipolymer is also measured by above-mentioned proton N MR subsequently, and obtains lower numerical value.Proton N MR is absolute analytical procedure, and it does not require that any calibration standard is to determine accurate numerical value.Difference in the numerical value of being determined by two kinds of methods is represented, the infrared absorbency characteristics of the more crystalline tubular reactors of the present invention multipolymer is different from the infrared absorbency characteristics of the ethylene n-butyl acrylate copolymer of conventional autoclave produced.
Table 1: reactor condition
| ?????????????????????????? Embodiment | |||||
| ????1 | ????2 | ????3 | ????4 | ????5 | |
| Turnout (kg/hr) | ????5925 | ????5925 | ????5920 | ????7720 | ????7761 |
| Acetaldehyde amount (kg/hr) | ????61.4 | ????61.4 | ????59.1 | ????82.7 | ????52.7 |
| NBA measures (kg/hr) | ????1395 | ????1664 | ????1921 | ????2232 | ????2260 |
| Reactor pressure (MPa) | ????262 | ????262 | ????262 | ????276 | ????276 |
| The 1st temperature in (℃) | ????143 | ????143 | ????143 | ????143 | ????143 |
| The 2nd temperature in (℃) | ????157 | ????157 | ????157 | ????160 | ????157 |
| The 3rd temperature in (℃) | ????168 | ????168 | ????169 | ????157 | ????157 |
| The 4th temperature in (℃) | ????120 | ????119 | ????122 | ????157 | ????154 |
| The 1st peak temperature (℃) | ????216 | ????216 | ????216 | ????221 | ????221 |
| The 2nd peak temperature (℃) | ????224 | ????224 | ????224 | ????216 | ????216 |
| The 3rd peak temperature (℃) | ????232 | ????232 | ????232 | ????213 | ????213 |
| The 4th peak temperature (℃) | ????-- | ????-- | ????-- | ????207 | ????207 |
| Initiator feed amount: the 1st decanting point (kg/hr) | ????6.5 | ????6.5 | ????6.5 | ????7.9 | ????8.4 |
| Initiator feed amount: the summation of all downstream decanting points (kg/hr) | ????19.4 | ????19.4 | ????19.4 | ????23.4 | ????25.2 |
| The LPS polymer temperature (℃) | ????117 | ????118 | ????121 | ????113 | ????127 |
| LPS pressure (kPa) | ????73.1 | ????74.5 | ????78.6 | ????137.9 | ????144.8 |
| The HPS temperature (℃) | ????161 | ????160 | ????161 | ????176 | ????176 |
| HPS pressure (MPa) | ????30.4 | ????30.4 | ????30.4 | ????30.5 | ????30.4 |
| Pack-out?MI(dg/min) | ????-- | ????-- | ????-- | ????-- | ????364 |
| Pack-out viscosity (mPas) | ????2575 | ????2912 | ????4475 | ????11070 | ????-- |
| NBA (wt%) by FTIR mensuration * | ????27.36 | ????31.18 | ????35.11 | ????35.75 | ????36.47 |
*For the correct value of measuring by proton N MR, referring to table 2
These embodiment comprise the high-caliber relatively n-butyl acrylate comonomer that surpasses 10mol% from about 7mol%-.Melting index arrives above 2500 of prediction for the low value of about 364g/10min; For grade, be used to replace melting index 190 ℃ melt viscosities greater than 330MI.Melt viscosity is high to about 48, and 000mPas is to being low to moderate about 2400mPas.
Table 2 show tags is the composition of the multipolymer of embodiment 1-5, melt viscosity (or melting index I
2.16) and density.
Table 2: the physicals of tubular type EnBA multipolymer
| ?????????????????????????? Embodiment No. | |||||
| ????1 | ????2 | ????3 | ????4 | ????5 | |
| Melt viscosity (mPas under 190 ℃) | ??2435 | ??2870 | ??4275 | ??11,470 | ??48,000 |
| MI(g/10min) | ??n/a * | ??n/a * | ??n/a * | ??n/a * | ??364 |
| Density (g/cm 3) | ??0.938 | ??0.938 | ??0.938 | ??0.941 | ??0.941 |
| nBA(mol％) (a) | ??6.90 | ??8.10 | ??9.32 | ??9.33 | ??9.42 |
| nBA(wt％) (b) | ??25.30 | ??28.71 | ??31.97 | ??31.98 | ??32.22 |
*Inapplicable
(a)Obtain by NMR
(b)Calculate from mol% by NMR
By difference method scanning calorimetry (DSC), use above-mentioned two kinds of methods (" method 1 " and " method 2 ") to measure the performance of multipolymer.Use the performance of two kinds of methods to see Table 3 and 4 respectively.
Table 3: the DSC performance of tubular type EnBA multipolymer (method 1)
| ?????????????????????????????????????????? Embodiment No. | |||||
| ????1 | ????2 | ????3 | ????4 | ????5 | |
| DSC peak value Tm (℃) (a) | ????108.0 ????112.0 | ????107.7 ????111.4 | ????105.9 ????110.5 | ??109.3 ??113.3 | ??108.8 ??113.3 |
| DSC peak value Tc (℃) | ????96.1 | ????95.1 | ????92.0 | ??94.4 | ??91.7 |
| Melting heat (J/g) | ????86.8 | ????72.8 | ????60.5 | ??72.7 | ??75.2 |
| Melting heat (J/g) | ????-65.3 | ????-60.5 | ????-85.4 | ??-60.7 | ??-78.5 |
| At 60 ℃ of following fused % | ????22.8 | ????26.4 | ????17.5 | ??20.2 | ??23.3 |
| T under 50% fusion (℃) | ????88.5 | ????86.5 | ????91.5 | ??92.0 | ??92.5 |
| T under 80% fusion (℃) | ????107.5 | ????106.5 | ????106.3 | ??109.5 | ??110.0 |
| T under 100% fusion (℃) | ????123 | ????120 | ????116 | ??119 | ??124 |
| Dimension card SP (℃) | ????69.1 | ????60.9 | ????54.4 | ??63.6 | ??63.5 |
(a)Observe two peaks
Table 4: the DSC performance of tubular type EnBA multipolymer (method 2)
| ????????????????????????????????????????????? Embodiment No. | |||||
| ????1 | ????2 | ????3 | ????4 | ????5 | |
| The DSC melting peak (℃) (a) | ????112.3 ????108.2 ????88.88 | ????111.5 ????107.4 ????88.88 | ????110.6 ????106.0 ????88.88 | ??113.6 ??109.4 ??90.69 | ??113.2 ??109.3 ??91.86 |
| The DSC peak crystallization (℃) | ????97.00 | ????96.32 | ????93.11 | ??95.33 | ??93.45 |
| Melting heat (J/g) | ????85.9 | ????73.3 | ????65.7 | ??65.2 | ??64.4 |
| Melting heat (J/g) | ????-103 | ????-93.1 | ????-82.6 | ??-84.4 | ??-85.2 |
| At 60 ℃ of following fused % | ????24.6 | ????25.3 | ????27.8 | ??20.8 | ??20.6 |
| T under 50% fusion (℃) | ????88.3 | ????87.6 | ????85.5 | ??94.7 | ??96.6 |
| T under 80% fusion (℃) | ????107.8 | ????107.0 | ????106.1 | ??110.2 | ??110.4 |
| T under 100% fusion (℃) | ????116.5 | ????115.9 | ????115.6 | ??117.9 | ??118.4 |
(a)Observe 3 peaks
In table 4,, be reported to three peaks for DSC melting peak numerical value.According to DSC curve shown in Figure 5, with these " peak " assignment.For example, with reference to figure 5 and table 4, the DSC trace of embodiment 2 is presented at small peak and the overlapping peaks under about 107 ℃ and 111 ℃ under 89 ℃.These are three peaks of report in table 4.
Use abundant back mixing, the high pressure autoclave prepares comparative example A and B, has the ethylene n-butyl acrylate copolymer of indication melt viscosity and co-monomer content with formation.The closest respectively embodiment 5 and 4 of being comparable to of comparative example A and B.The test ethylene n-butyl acrylate copolymer that Comparative Examples C and D are produced in fully back mixing, high pressure autoclave by ExxonMobilChemical.Comparative Examples E, F and G are by the commercially available ethylene ethyl acrylate copolymer of Union Carbide Corporation (Subsidiary Company of DowChemical Company) preparation and are expressed as DPD-6169NT, DPD-6182 and DPD-9169 respectively.With embodiment 6-11 in preparation Comparative Examples H in the relevant following high pressure tubular reactors, difference is only to use single-point to inject.The composition of these Comparative Examples, density and melt viscosity capability see Table 5.
Table 5: the performance of contrast multipolymer
| Comparative Examples No. | ||||||||
| ????A | ????B | ????C | ????D | ????E | ????F | ????G | ????H | |
| Melt viscosity (mPas under 190 ℃) | -- | 8337 * | ??-- | ??-- | ??-- | ??-- | ??-- | ??3720 |
| MI(g/10min) | 330 | est?900 | ??1.75 | ??7.25 | ??6.25 | ??1.32 | ??20.85 | ??-- |
| Density (g/cm 3) | 0.922 * | 0.919 * | ??-- | ??-- | ??-- | ??-- | ??-- | ??0.9344 |
| Co-monomer content (mol%) (a) | 9.53 | 9.53 | ??9.63 | ??7.30 | ??5.53 | ??4.43 | ??5.83 | ??5.83 |
| nBA(wt％) (b) | 32.5 * | 32.5 * | ??32.75 | ??26.46 | ??n/a | ??n/a | ??n/a | ??27.97 |
| Ethyl propenoate (wt%) (c) | n/a | n/a | ??n/a | ??n/a | ??17.3 | ??14.2 | ??18.1 | ??n/a |
--do not have measurement or unavailable
*Data from trade mark data sheet
N/a=is inapplicable
(a)From corresponding weight percent comonomer numerical evaluation
(b)Obtain by FTIR
(c)Obtain by NMR
By difference method scanning calorimetry (DSC), use above-mentioned two kinds of methods (" method 1 " and " method 2 ") to measure the performance of Comparative Examples.Use the performance of two kinds of methods to see Table 6 and 7 respectively.
Table 6: the DSC performance of Comparative Examples (method 1)
| Comparative Examples No. | ||||||||
| ??A | ??B | ??C | ??D | ??E | ??F | ??G | ????H | |
| DSC peak value Tm (℃) (a) | 58.7 18 | ?58.0 ?30 | ?67.6 | ?78.4 ?65.2 | ?97.4 ?84.8 | ?99.5 ?87.7 | ?96.9 ?83.2 | ??? (c) |
| DSC peak value Tc (℃) (b) | 42.2 | ?43.1 | ?51.7 | ?63.0 ?35.6 | ?79.2 ?46.6 | ?81.7 ?50.1 | ?78.1 ?44.4 | ??? (c) |
| Melting heat (J/g) | 49.9 | ?40.3 | ?33.1 | ?51.3 | ?64.6 | ?76.6 | ?60.5 | ??? (c) |
| Melting heat (J/g) | -26.9 | ?-30.6 | -35.2 | -53.7 | -76.2 | ?-88.7 | ?-73.6 | ??? (c) |
| At 60 ℃ of following fused % | 87.3 | ?85.3 | ?68.3 | ?46.3 | ?22.3 | ?20.3 | ?22.2 | ??? (c) |
| T under 50% fusion (℃) | 23.8 | ?35.6 | ?50.0 | ?61.5 | ?83.2 | ?85.9 | ?90.2 | ??? (c) |
| T under 80% fusion (℃) | 53.6 | ?56.7 | ?64.9 | ?76.1 | ?97.1 | ?99 | ?97.3 | ??? (c) |
| T under 100% fusion (℃) | 82 | ?84 | ?76 | ?86 | ?107 | ?108 | ?107 | ??? (c) |
| Dimension card SP under 200g (℃) | 41 * | ?37 * | ?55.4 | ?66.8 | ?83.7 | ?92.5 | ?78.3 | ??51.9 |
*Data from trade mark data sheet
(a)Except that sample C, observe two peaks
(b)For sample D, E, F and G observe two peaks
(c)Not by 1 test of DSC method
Table 7: the DSC performance of Comparative Examples (method 2)
| Comparative Examples No. | ||||||||
| ??A | ??B | ??C | ??D | ??E | ??F | ??G | ????H | |
| DSC peak value Tm (℃) | 60.94 29.38 | ?58.05 ?27.59 | ?65.61 | ?76.95 ?61.20 | ?97.89 ?83.70 | ?99.93 ?87.60 | ?97.41 ?82.70 | ??100.1 (c)??96.04 ??74.80 |
| DSC peak value Tc (℃) | 46.33 16.42 | ?45.73 ?15.40 | ?50.58 ?26.99 | ?62.41 ?33.80 | ?80.1 ?48.0 | ?82.46 ?51.20 | ?79.27 ?45.29 | ??81.78 ??74.76 ??42.28 |
| Melting heat (J/g) | 44.9 | ?37.5 | ?55.4 | ?73.2 | ?81.6 | ?94.1 | ?79.2 | ??69.4 |
| Melting heat (J/g) | -44.6 | -47.1 | -51.6 | -69.3 | -99.7 | -110.8 | ?-95.0 | ??-84.4 |
| At 60 ℃ of following fused % | 83.1 | ?85.8 | ?74.6 | ?59.2 | ?34.5 | ??31.0 | ??36.0 | ??40.7 |
| T under 50% fusion (℃) | 33.0 | ?31.7 | ?41.9 | ?53.3 | ?75.5 | ??79.2 | ??74.3 | ??69.5 |
| T under 80% fusion (℃) | 57.8 | ?55.9 | ?63.4 | ?73.6 | ?96.1 | ??98.1 | ??95.8 | ??95.0 |
| T under 100% fusion (℃) | 81.5 | ?80.9 | ?86.9 | ?94.8 | ?107.5 | ??108.7 | ??108.0 | ??107.0 |
(a)Shoulder on the high temperature side of main melting peak
Embodiment 6-11
Above program description the preparation of embodiment 1-5.Use similar program and condition with preparation Comparative Examples H and embodiment 6-11.In embodiment 6, use 4 injections.In embodiment 7-11, use 3 injections.In Comparative Examples H, only use single-point to inject.In embodiment 6-11, monomer mixture comprises ethene, n-butyl acrylate and vinyl acetate.The reactor output of these embodiment be the 21.3-23.0 metric ton per hour.Processing condition see Table 8.
Table 8
| Embodiment No. | |||||||
| ????6 | ????7 | ????8 | ????9 | ????10 | ????11 | ????H | |
| Turnout (lb/hr) | ??13000 | ???12720 | ???12590 | ???12618 | ???11546 | ???11209 | ???5220 |
| Acetaldehyde amount (lb/hr) | ??116 | ???102 | ???104 | ???108 | ???90 | ???93 | ???20 * |
| NBA measures (lb/hr) | ??2379 | ???2465 | ???3010 | ???3650 | ???2025 | ???2030 | ???1595 |
| VA measures (lb/hr) | ??1957 | ???1645 | ???1140 | ???840 | ???1190 | ???445 | ???0 |
| Reactor pressure (kpsig) | ??36.0 | ???36.0 | ???36.0 | ???36.0 | ???36.0 | ???36.0 | ???36.0 |
| The 1st temperature in (°F) | ??275 | ???310 | ???310 | ???310 | ???310 | ???310 | ???310 |
| The 2nd temperature in (°F) | ??280 | ???310 | ???310 | ???310 | ???310 | ???310 | ???310 |
| The 3rd temperature in (°F) | ??305 | ???310 | ???310 | ???310 | ???310 | ???310 | ???310 |
| The 4th temperature in (°F) | ??325 | ???-- | ???-- | ???-- | ???-- | ???-- | ???-- |
| The 1st peak temperature (°F) | ??435 | ???430 | ???430 | ???430 | ???430 | ???430 | ???430 |
| The 2nd peak temperature (°F) | ??435 | ???420 | ???420 | ???420 | ???420 | ???420 | ???420 |
| The 3rd peak temperature (°F) | ??410 | ???420 | ???420 | ???420 | ???420 | ???420 | ???420 |
| The 4th peak temperature (°F) | ??395 | ???-- | ???-- | ???-- | ???-- | ???-- | ???-- |
| Initiator consumes (gal/hr) | ??20.5 | ???19.4 | ???18.0 | ???20.8 | ???16.0 | ???16.5 | ???11.5 |
| The LPS polymer temperature (°F) | ??240 | ???246 | ???246 | ???246 | ???210 | ???255 | ???236 |
| LPS pressure (psi) | ??13 | ???12.8 | ???12.9 | ???12.0 | ???12.0 | ???12.5 | ???9.5 |
| The HPS polymer temperature (°F) | ??305 | ???316 | ???314 | ???314 | ???311 | ???311 | ???289 |
| HPS pressure (kpsig) | ??3935 | ???3990 | ???3960 | ???3960 | ???3875 | ???3850 | ???4160 |
| Pack-out viscosity (cp) | ??2,805 | ???2,520 | ???2,785 | ???2,535 | ???2,820 | ???2,685 | ???3,720 |
| NBA (wt%) by NMR | ??17.77 | ???18.80 | ???23.90 | ???28.92 | ???17.53 | ???18.10 | ???27.97 |
| VA (wt%) by NMR | ??9.66 | ???9.98 | ???6.50 | ???3.88 | ???6.95 | ???3.93 | ???0 |
*Estimated value
In embodiment 6-11, use method for preparing ethene, the multipolymer of n-butyl acrylate and vinyl acetate.The performance of these multipolymers of the present invention sees Table 9.All dsc measurements of multipolymer are carried out in attention according to aforesaid method 2.
Table 9: the performance of tubular type EnBAVA multipolymer
| Embodiment No. | ||||||
| ????6 | ????7 | ????8 | ????9 | ????10 | ????11 | |
| Melt viscosity (mPas under 190 ℃) | ????2805 | ????2520 | ????2785 | ????2535 | ????2820 | ????2685 |
| Density (g/cm 3) | ????0.9413 | ????0.9415 | ????0.9400 | ????0.9400 | ????0.9398 | ????0.9392 |
| nBA(mol％) (a) | ????4.92 | ????5.23 | ????6.74 | ????8.57 | ????4.90 | ????4.76 |
| nBA(wt％) (b) | ????17.83 | ????18.8 | ????23.74 | ????29.24 | ????18.04 | ????18.1 |
| VA(mol％) | ????4.10 | ????4.13 | ????2.75 | ????1.63 | ????3.25 | ????1.54 |
| VA(wt％) | ????9.99 | ????9.98 | ????6.52 | ????3.73 | ????8.04 | ????3.93 |
| Total copolymerization monomer content (mol%) | ????9.02 | ????9.36 | ????9.49 | ????10.2 | ????8.15 | ????6.3 |
| The DSC melting peak (℃) | ????96.15 (c)????92.15 ????67.16 | ????95.48 (c)????90.44 ????63.47 | ????99.86 (c)????95.71 ????72.42 | ????104.7 ????99.78 ????79.77 | ????99.66 (c)????95.37 ????74.21 | ????106.8 ????102.1 ????83.1 |
| The DSC peak crystallization (℃) | ????76.88 | ????75.18 | ????81.62 | ????87.04 | ????81.79 | ????89.06 |
| Melting heat (J/g) | ????72.8 | ????71.3 | ????66.0 | ????54.5 | ????81.6 | ????93.7 |
| Melting heat (J/g) | ????-91.9 | ????-83.1 | ????-80.9 | ????-74.5 | ????-93.8 | ????-109.6 |
| At 60 ℃ of following fused % | ????43.9 | ????47.1 | ????40.5 | ????35.1 | ????41.3 | ????31.9 |
| T under 50% fusion (℃) | ????65.9 | ????62.7 | ????69.5 | ????75.4 | ????68.4 | ????78.9 |
| T under 80% fusion (℃) | ????91.2 | ????89.1 | ????94.7 | ????98.9 | ????94.0 | ????101.7 |
| T under 100% fusion (℃) | ????104.1 | ????102.9 | ????107.3 | ????110.4 | ????106.3 | ????112.2 |
| Dimension card SP under the 200g load (℃) | ????53.0 | ????49.4 | ????50.9 | ????44.1 | ????57.3 | ????69.5 |
(a)From corresponding weight percent comonomer numerical evaluation
(b)By
1H NMR obtains
(c)Shoulder on main melting peak high temperature side
The improvement of multipolymer thermal characteristics of the present invention is showed by following aspect: the increase of (1) peak value melt temperature; (2) at each observed value how many polymer melts are arranged along each point of DSC trace; (3) increase of Vicat softening point under the 200g load.
The peak value melt temperature of the embodiment of the invention 4 and 5 multipolymers, higher 50 ℃ or bigger than the peak value melt temperature of corresponding comparative example A and B, as shown in Figure 3.In addition, can in Fig. 4, find out improvement with respect to conventional tubular reactor EEA multipolymer.Fig. 5 demonstration is compared the more peak value melt temperature of embodiment 2 multipolymers with the single-point tubular type multipolymer peak value melt temperature of about same comonomer content.
As discussed abovely like that, require 60 ℃ thermotolerance, because or in use, product may be exposed to high temperature to this temperature in transportation, lay up period for many application.The improved thermotolerance of lower percentages show at 60 ℃ of following molten polymers.The result of embodiment 1-5 shows when sample is heated to 60 ℃, and the polymer melt less than about 25%, and when reaching identical temperature is more than 85% comparative example A and B and more than 45% Comparative Examples C and D fusion.Astoundingly, this relatively in the embodiment of the invention (embodiment 1-5) show that similar in appearance to Comparative Examples E the performance of F and G arrives 15% or more greater than twice comonomer concentration (based on mole) although the embodiment of the invention comprises at least; This situation with expectation is opposite, and this is because higher co-monomer content should cause the poorer performance in this measures.
Can aspect following, find out the stable on heating similar improvement of embodiment: compare with the temperature that needs fusion comparable measure comparative example A-D, need the remarkable higher temperature of the fusion 50,80 and 100% embodiment of the invention.At the embodiment of the invention and Comparative Examples E, the significant difference of performance is the temperature that needs fusion 100% sample between F and the G.
In the increase of Vicat softening point, find out more the third indication of high heat resistance of product of the present invention, use non-standard 200g load to replace the 1000g load measurement Vicat softening point of in ASTM D-1525, stipulating.(all embodiment of the invention and comparative example A and B, too soft and can not use the 1000g Road test). Embodiment 4 and 5 result are than high about 20 ℃ of corresponding comparative example A and B.
With respect to comparative example A-D, the present invention's (embodiment 6-11) ethylene n-butyl acrylate vinyl acetate (EnBAVA) multipolymer also has improved thermotolerance.This by the increase of DSC melting peak and on the DSC trace each fused quantity of material shown.Fig. 6 shows the present invention (embodiment 3) EnBA multipolymer, the increase peak value melt temperature of the present invention's (embodiment 7 and 8) EnBAVA multipolymer and conventional autoclave multipolymer (comparative example A).Although the viscosity ratio embodiment 6-11 height of A and B, comparing embodiment 6-11 and comparative example A and B also find the Vicat softening point that increases; Vicat softening point known in the art significantly increases with the viscosity of polymkeric substance, therefore improvement or even more noticeable.Comparative Examples C and D, their viscosity very high (typical range that surpasses the instrument that is used to measure embodiment viscosity far away), its Vicat softening point is in the scope of embodiment 1-11.
The extensive stock name this by
TMThe symbol indication, the expression title can be by the trade mark privileges protection of determining.Some such titles also can be the registered trademarks in various authorities.
All patents, test procedure and other citing document herein that comprises priority documents are incorporated herein by reference following degree fully: so open inconsistent and be used for wherein not allowing all authorities of introducing like this with the present invention.
Claims (54)
1. one kind comprises the ethene and the multipolymer of 5mol% comonomer unit at least, this comonomer unit derived from propylene acid alkyl ester, alkyl methacrylate or its mixture, and wherein multipolymer has:
(i) 1-10, the melting index of 000g/10min;
(ii) at least 100 ℃ peak-peak melt temperature; With
(iii) at least 80 ℃ the temperature that requires fusion 50% multipolymer.
2. the multipolymer of claim 1, wherein melting index is at least 100g/10min.
3. the multipolymer of claim 1, wherein melting index is at least 300g/10min.
4. the multipolymer of claim 1, wherein melting index is at least 600g/10min.
5. the multipolymer of claim 1, wherein melting index is at least 900g/10min.
6. the multipolymer of claim 1, wherein melting index is at least 1500g/10min.
7. the multipolymer of claim 1, wherein melting index is at least 2000g/10min.
8. the multipolymer of claim 1, wherein multipolymer comprises the comonomer unit of 6mol% at least, this comonomer unit derived from propylene acid alkyl ester or alkyl methacrylate.
9. the multipolymer of claim 1, wherein multipolymer comprises the comonomer unit of 7mol% at least, this comonomer unit derived from propylene acid alkyl ester or alkyl methacrylate.
10. the multipolymer of claim 1, wherein multipolymer comprises the comonomer unit of 8mol% at least, this comonomer unit derived from propylene acid alkyl ester or alkyl methacrylate.
11. the multipolymer of claim 1, wherein multipolymer comprises the comonomer unit of 9mol% at least, this comonomer unit derived from propylene acid alkyl ester or alkyl methacrylate.
12. the multipolymer of claim 1, wherein the peak-peak melt temperature of multipolymer is at least 105 ℃.
13. the multipolymer of claim 1, wherein the peak-peak melt temperature of multipolymer is at least 110 ℃.
14. the multipolymer of claim 1 wherein requires the temperature of fusion 50% multipolymer to be at least 85 ℃.
15. the multipolymer of claim 1 wherein requires the temperature of fusion 50% multipolymer to be at least 90 ℃.
16. the multipolymer of claim 1 wherein requires the temperature of fusion 80% multipolymer to be at least 100 ℃.
17. the multipolymer of claim 16 wherein requires the temperature of fusion 80% multipolymer to be at least 105 ℃.
18. the multipolymer of claim 1 wherein requires the temperature of fusion 100% multipolymer to be at least 110 ℃.
19. the multipolymer of claim 18 wherein requires the temperature of fusion 100% multipolymer to be at least 115 ℃.
20. the multipolymer of claim 18 wherein requires the temperature of fusion 100% multipolymer to be at least 120 ℃.
21. the multipolymer of claim 1, wherein the alkyl of alkyl acrylate or alkyl methacrylate is linearity or branching C
1-C
12Group.
22. the multipolymer of claim 1, wherein alkyl acrylate is selected from the just own ester of methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, vinylformic acid, vinylformic acid 2-ethyl butyl ester and 2-EHA.
23. the multipolymer of claim 1, wherein alkyl acrylate is a n-butyl acrylate.
24. the multipolymer of claim 1 further comprises the polymeric comonomer unit, part ester, carbon monoxide or its mixture of this comonomer unit derived from propylene acid, methacrylic acid, toxilic acid.
25. the ethene and the multipolymer of 5mol% comonomer at least, this comonomer comprises the first comonomer component and second comonomer component, the first comonomer component comprises alkyl acrylate, alkyl methacrylate or its mixture, and second comonomer component comprises the reactivity ratio r with respect to ethene
2Be 2 or littler compound, wherein multipolymer has:
(i) 1-10, the melting index of 000g/10min;
(ii) at least 80 ℃ peak-peak melt temperature; With
(iii) at least 40 ℃ the temperature that requires fusion 50% multipolymer.
26. the multipolymer of claim 25, wherein melting index is at least 100g/10min.
27. the multipolymer of claim 25, wherein melting index is at least 300g/10min.
28. the multipolymer of claim 25, wherein melting index is at least 600g/10min.
29. the multipolymer of claim 25, wherein melting index is at least 900g/10min.
30. the multipolymer of claim 25, wherein melting index is at least 1500g/10min.
31. the multipolymer of claim 25, wherein melting index is at least 2000g/10min.
32. the multipolymer of claim 25, wherein multipolymer comprises the first comonomer unit of 3mol% at least and second comonomer unit of 1mol% at least.
33. the multipolymer of claim 25, wherein multipolymer comprises total copolymerization monomeric unit of 7mol% at least.
34. the multipolymer of claim 25, wherein the peak-peak melt temperature of multipolymer is at least 90 ℃.
35. the multipolymer of claim 25, wherein the peak-peak melt temperature of multipolymer is at least 95 ℃.
36. the multipolymer of claim 25 wherein requires the temperature of fusion 50% multipolymer to be at least 50 ℃.
37. the multipolymer of claim 25 wherein requires the temperature of fusion 50% multipolymer to be at least 60 ℃.
38. the multipolymer of claim 25 wherein requires the temperature of fusion 80% multipolymer to be at least 70 ℃.
39. the multipolymer of claim 38 wherein requires the temperature of fusion 80% multipolymer to be at least 80 ℃.
40. the multipolymer of claim 38 wherein requires the temperature of fusion 80% multipolymer to be at least 85 ℃.
41. the multipolymer of claim 25 wherein requires the temperature of fusion 100% multipolymer to be at least 80 ℃.
42. the multipolymer of claim 41 wherein requires the temperature of fusion 100% multipolymer to be at least 90 ℃.
43. the multipolymer of claim 41 wherein requires the temperature of fusion 100% multipolymer to be at least 100 ℃.
44. the multipolymer of claim 25, wherein the alkyl of alkyl acrylate or alkyl methacrylate is linearity or branching C
1-C
12Group.
45. the multipolymer of claim 25, wherein alkyl acrylate is selected from the just own ester of methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, vinylformic acid, vinylformic acid 2-ethyl butyl ester and 2-EHA.
46. the multipolymer of claim 25, wherein alkyl acrylate is a n-butyl acrylate.
47. the multipolymer of claim 25, wherein reactivity ratio r
2Be 1.5 or littler.
48. the multipolymer of claim 25, wherein reactivity ratio r
2Be 1.2 or littler.
49. the multipolymer of claim 25, wherein second comonomer component comprises vinyl ester.
50. the multipolymer of claim 49, therein ethylene base ester is a vinyl acetate.
51. method of producing the multipolymer of ethene and alkyl acrylate or alkyl methacrylate, this method is included under the polymerizing condition and in the presence of radical initiator, in high pressure tubular reactors, add the monomer mixture that comprises ethene and at least a alkyl acrylate or alkyl methacrylate, to form ethylene alkyl acrylate or alkyl methacrylate multipolymer, wherein along radical initiator to tubular reactor in being provided in two reaction zones of tubular reactor length at least and only in the single reaction district, providing monomer mixture to tubular reactor.
52. method of producing the multipolymer of ethene and alkyl acrylate or alkyl methacrylate, this method is included under the polymerizing condition and in the presence of radical initiator, in high pressure tubular reactors, add the monomer mixture that comprises ethene and at least a alkyl acrylate or alkyl methacrylate, to form ethylene alkyl acrylate or alkyl methacrylate multipolymer, wherein along in tubular reactor, providing radical initiator at least three reaction zones of tubular reactor length.
53. the multipolymer of producing by the method for claim 51.
54. the multipolymer of producing by the method for claim 52.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US26300201P | 2001-01-19 | 2001-01-19 | |
| US60/263,002 | 2001-01-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1551892A true CN1551892A (en) | 2004-12-01 |
Family
ID=22999976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA028051327A Pending CN1551892A (en) | 2001-01-19 | 2002-01-18 | Ethylene alkyl acrylate copolymers with improved heat resistance |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1409559A4 (en) |
| JP (1) | JP2004527595A (en) |
| KR (1) | KR20030072600A (en) |
| CN (1) | CN1551892A (en) |
| AU (1) | AU2002243591A1 (en) |
| CA (1) | CA2435284A1 (en) |
| TW (1) | TW593358B (en) |
| WO (1) | WO2002057354A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054715A (en) * | 2012-04-13 | 2019-07-26 | 埃克森美孚化学专利公司 | The manufacturing method of polyethylene polymer and polymer composition containing polar comonomers |
| CN114555655A (en) * | 2019-07-31 | 2022-05-27 | 陶氏环球技术有限责任公司 | Ethylene-based polymer compositions with branching |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040266927A1 (en) * | 2003-06-27 | 2004-12-30 | Prejean George Wyatt | Filled blends of tubular reactor produced ethylene/alkyl acrylate copolymers modified with organic acids |
| WO2009114661A1 (en) | 2008-03-13 | 2009-09-17 | Dow Global Technologies Inc. | Long chain branched (lcb), block or interconnected copolymers of ethylene in combination with one other polymer |
| KR102502365B1 (en) * | 2014-11-13 | 2023-02-23 | 다우 글로벌 테크놀로지스 엘엘씨 | Lubricant compositions for improved high pressure free-radical polymerizations |
| KR102334926B1 (en) * | 2017-07-31 | 2021-12-07 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | High Pressure Polymerization Method for Making Ethylene Copolymer |
| WO2024116909A1 (en) * | 2022-11-30 | 2024-06-06 | 住友化学株式会社 | Ethylene-(meth)acrylate copolymer, method for producing same, and composition |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3217973A1 (en) * | 1982-05-13 | 1983-11-17 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING COPOLYMERISATES OF ETHYLENE WITH ACRYLIC ACID ESTERS IN A TWO-ZONE REACTOR AT PRESSURES ABOVE 500 BAR |
| DE3404744A1 (en) * | 1984-02-10 | 1985-08-14 | Basf Ag, 6700 Ludwigshafen | COPOLYMERISATES OF ETHYLENE WITH COMONOMERS CONTAINING CARBOXYL GROUPS |
| US4764546A (en) * | 1986-04-25 | 1988-08-16 | Sumitomo Chemical Co., Ltd. | Filler-containing polypropylene resin composition and process for producing the same |
| US4988781A (en) * | 1989-02-27 | 1991-01-29 | The Dow Chemical Company | Process for producing homogeneous modified copolymers of ethylene/alpha-olefin carboxylic acids or esters |
| US5234986A (en) * | 1992-03-02 | 1993-08-10 | E. I. Du Pont De Nemours And Company | Hot-melt adhesives for PVC with good high temperature utility |
| US5482977A (en) * | 1995-05-08 | 1996-01-09 | Eastman Chemical Company | Foamable branched polyesters |
| US6388026B1 (en) * | 1997-08-05 | 2002-05-14 | S. C. Johnson Commercial Markets, Inc. | Process for the preparation of macromers |
| US6294264B1 (en) * | 1999-03-30 | 2001-09-25 | Cryovac, Inc. | Oriented cook-in film with good interply adhesion |
-
2002
- 2002-01-18 WO PCT/US2002/001471 patent/WO2002057354A2/en active Application Filing
- 2002-01-18 EP EP02709086A patent/EP1409559A4/en not_active Withdrawn
- 2002-01-18 CN CNA028051327A patent/CN1551892A/en active Pending
- 2002-01-18 JP JP2002558422A patent/JP2004527595A/en active Pending
- 2002-01-18 CA CA002435284A patent/CA2435284A1/en not_active Abandoned
- 2002-01-18 KR KR10-2003-7009597A patent/KR20030072600A/en not_active Application Discontinuation
- 2002-01-18 AU AU2002243591A patent/AU2002243591A1/en not_active Abandoned
- 2002-01-21 TW TW091100875A patent/TW593358B/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054715A (en) * | 2012-04-13 | 2019-07-26 | 埃克森美孚化学专利公司 | The manufacturing method of polyethylene polymer and polymer composition containing polar comonomers |
| CN110054715B (en) * | 2012-04-13 | 2022-03-25 | 埃克森美孚化学专利公司 | Polyethylene polymers containing polar comonomers and process for making polymer compositions |
| CN114555655A (en) * | 2019-07-31 | 2022-05-27 | 陶氏环球技术有限责任公司 | Ethylene-based polymer compositions with branching |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1409559A2 (en) | 2004-04-21 |
| TW593358B (en) | 2004-06-21 |
| WO2002057354A2 (en) | 2002-07-25 |
| KR20030072600A (en) | 2003-09-15 |
| JP2004527595A (en) | 2004-09-09 |
| EP1409559A4 (en) | 2004-06-02 |
| AU2002243591A1 (en) | 2002-07-30 |
| CA2435284A1 (en) | 2002-07-25 |
| WO2002057354A3 (en) | 2004-02-26 |
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