CA1273745A - Interpolymers of ethylene and unsaturated carboxylic acids - Google Patents
Interpolymers of ethylene and unsaturated carboxylic acidsInfo
- Publication number
- CA1273745A CA1273745A CA000456439A CA456439A CA1273745A CA 1273745 A CA1273745 A CA 1273745A CA 000456439 A CA000456439 A CA 000456439A CA 456439 A CA456439 A CA 456439A CA 1273745 A CA1273745 A CA 1273745A
- Authority
- CA
- Canada
- Prior art keywords
- comonomer
- interpolymer
- weight
- molecular weight
- boundary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
Homogeneous, random interpolymers of ethylene and lesser amounts by weight of olefinically-unsaturated comonomers are prepared in a substantially constant environment, substantially steady-state reaction mixture, in a well-stirred autoclave reactor, in continuous single-phase operation, using elevated synthesis conditions wherein the temperature and pressure are elevated to an amount high enough to approach, reach, or surpass the molecular weight distribution boundary.
Homogeneous, random interpolymers of ethylene and lesser amounts by weight of olefinically-unsaturated comonomers are prepared in a substantially constant environment, substantially steady-state reaction mixture, in a well-stirred autoclave reactor, in continuous single-phase operation, using elevated synthesis conditions wherein the temperature and pressure are elevated to an amount high enough to approach, reach, or surpass the molecular weight distribution boundary.
Description
3 ~J~3~L1 rj INTERPOLYMERS OF ETHYLENE AND
UNSA~URATED CARBOXYL I C AC IDS
BACKGROUND
Interpolymers of ethylene and unsatura~ed carboxylic acids, such as acrylic acid and methacrylic acid, are well known. This presen. disclosure pertains to such interpolymers when made under steady state conditions in stirred reactors at high pressure and elevated temperature and using a free-radical type initiator, in contradistinction to polymers made under non-steady state conditions or in non-stirred tu~ular lQ reactors sr in batch reactions, and in contradistinction to bloc~ copolymers or graft copolymers.
Patents which disclose interpolymerizations of ethylene and unsaturated carboxylic acids in a steady state reaction at high temperature and high pressure in a stirred reactor in the presence of a free-radical initiator are, e.g., Canadian Patent 655,298 (and its U.S. counterpart No. 4,351,931~:
U.S. 3,23g,370; U.S. 3,520,861; U.S. 3,658,741;
U.S. 3,884,857; U.S. 3,988,509; U.S. 4, 248,990; and U.S. 4,252,924.
U.S. 3,239l370 discloses a rar.dom copolymer-izat~on o ethylene with an unsaturated carboxylic C~ 60 -1-~ ~ ~3 ~
acid (e.g. acrylic acid) in a stirred autoclave operated at 16,000 psi, and 210C using a peroxy initiat~r, the so-formed copolymer being particularly useful as a coating for non-metallic substrates.
U.S. 3,520,861 discloses a substantially homogeneous, compositionally uniform, random coFoly~er of ethylene/unsaturated acid (e.g. acrylic acid, meth-acrylic acid, crotonic acid) prepared in a continuous manner in a stirred autoclave at high pressure and elevated temperature, using a free-radical initiator (such as a peroxide). The temperature of the polymer-ization is disclosed as being in the range of about 120C to about 300C, preferably about 150C to about 250C. The pressure of the polymerization is disclosed as being in the range of at least 1000 atmospheres, preferably between about 1000-3000 atmospheres, esp.
between 1100-1900 atmospheres.
Canadian Patent No. 655,298 and its U.S.
counterpart (U.S. 4,351,931) discloses homogeneous, compositionally uniform, random copolymers of ethylene and unsaturated carboxylic acids (e.g. acrylic acid) wherein said copolymer comprises at least about gO% by weight of ethylene with a melt index of 0.01 to 30 g/10 minutes. The copolymers are prepared in a well-stirred reactor at a pressure of at least 1000 atmospheres, at ~0-280C, using a free radical initiator, while maintaining the ratio of monomers (ethylene/acid) in the range of 10,000/1 to 50/1 by weight, the process being performed continuously by feeding monomers in, while removing reaction mixture, and maintaining a constant reaction environment.
C-31,56& -2-~ 4~
U.S. 3,658,741 discloses homogeneous copolymers of ethylene and unsaturated carboxyl-c z_ids and esters, prepared in the presence of a chain tra~sfer agent, a free radical catalyst, a temperature b-~ween 100C-300C and pressure between 100 and 1000 at~o-spheres, using turbulent agitation; the reactio-. is said to take place in the vapor phasP and prepa-es very low mol. wt. copol~mers.
U.S. 3,884,857 and U.S. 3,988,~09 disclose the preparation of copolymers, such as ethylene~acrylic acid copolymers in a continuous, high pressure, free-radical polymerization process, at 100-250C aL.d 1000-2500 atmospheres of pressure.
U.S. 4,248,990 discloses copolymers, e.g.
ethylene/acrylic acid copolymers which are said to distinguish over the random copolymers o~ Canadian 655,298 and of U.S. 3,520,861 by virtue of being non-random. This non-randomness is said to be the result of operating the steady state, high pressure, stirred reactor at a pressure of from 0 to about 500 psi above, and at temperature of from 0-15C above, that needed to maintain a single phase reaction mixture at the given concentration of copolymer in the reaction mixture and at the given acid comonomer content of the copolymer.
U.S. 4,252,924 discloses the preparation of non-random copolymers, e.g. ethylene/acrylic acid copolymers in at least two constant environment, stirred autoclaves in series, each using a single phase reaction mixture, but where each succeeding autoclave is maintained at a temperature of at least 30C above that of the preceding autoclave.
~73~
In the ordinary course of events, operators of processes are not inclined to employ more energy (temperature and/
or pressure) than is deemed necessary to obtain a given product, in the absence of any recognized benefit to be derived from such additional expense. We have now found that there are unexpected benefits to be derived from employing more energy (temperature and pressure) than is generally deemed to be sufficient in the production of interpolymers of ethylene.
SU~IARY OF THE INVENTION
With reference to random interpolymers of ethylene and olefinically-unsaturated organic comonomers prepared in a well-stirred autoclave, in the presence of a free-radical initiator, under substantially constant conditions of temperature and pressure and substantially steady state, continuous operation, it has now been found, surprisingly and unexpectedly, that substantial and useful improvements are found by maintaining the synthesis conditions of temperature and pressure elevated high enough above the phase boundary that exists between the two-phase and single-phase conditions, for a given comonomer concentration and polymer concentration in the polymerization mixture, to closely approach, reach, andtor surpass the respective molecular weight distribution (~WD) boundary, i.e., the synthesis conditions at which the ratio of the weight average mol. wt./number average mol. wt. is at its maximum.
According to one aspect of the present invention there is provided a process for producing homogeneous, random inter-..~ ~
~73~
- 4a - 64693-3448 polymers comprising about 99~ to about 65% by weight of ethylene monomer and about 1% to about 35% by weight of at least one olefinically-unsaturated comonomer selected from the group com-prising unsatura-ted carboxylic acids, alkyl acrylates, alkyl meth-acrylates and vinyl esters, said process comprising interpoly-merizing the monomers in a substantially constant environment, under steady state conditions, in a single-phase reac~ion mixture, under the influence of a free-radical initiator, and in a well-stirred autoclave reactor operated in a continuous manner as the monomers are fed into the reactor and the reaction mixture iswithdrawn, said process being characterized by the use of synthesis conditions of a temperature and pressure which are elevated to a level high enough above the phase boundary between two-phase and single-phase operation such that the molecular weight distribution (MWD) boundary is approached, reached, or surpassed, the said molecular weight distribution boundary being the highest ratio of weight average molecular weight/number average molecular weight obtainable in single-phase operation, said elevated pressure being greater than 2000 psi above, and said elevated temperature being greater than 15C
above, the synthesis conditions required at the phase boundary for a given mixture of ethylene and comonomer, thereby producing an interpolymer having less gels, microgels and/or grain.
According to another aspect of the present invention, there is provided a process for producing substantially 1~73~
- 4b - 64693-3448 homogeneous, random interpolymers comprising about 99% to about 65~ by weight of ethylene monomer with about 1% to about 35% by weight of acrylic acid or methacrylic acid comonomer, said process comprising interpolymerizing the monomers in a well-stirred autoclave reactor operated in a continuous manner at steady state conditions using a free-radical polymerization initiator under substantially constant conditions of temperature, pressure, and flow rates, wherein the conditions of temperature and pressure re-quired to produce operation at the phase boundary are exceeded, respectively, by using a temperature of at least 15C above that at the phase boundary and a pressure of more than 2000 psi above that at the phase boundary, whereby the molecular weight distribution (MWD) boundary is reached or surpassed, thereby producing an interpolymer having less gels, microgels and/or grain.
According to a further aspect of the present invention there is provided a random, homogeneous, single-phase interpolymer product comprising about 65~ to about 99% by weight of ethylene monomer, the remaining percentage comprising at least one olefinically-unsaturated comonomer selected from the group com-prising unsaturated carboxylic acids, alkyl acrylates, alkyl methacrylates and vinyl esters, said interpolymer being further characterized as having a weight average molecular weight/number average molecular weight ratio as defined by the formula log ~MWw~=[Cl+(C2)(wt.fraction comonomer)]x(C4) ~MWn/
where MWW is the weight average molecular weight;
,~, 3~
- 4c - 64693-3448 MWn is the number average molecular weight;
Cl is the intercept of the wt. fraction comonomer versus log ~ w~ plot for a given comonomer, where nJmax.
w~ is the ratio of weight average molecular weight ~MWn~max.
to number average molecular weight at the MWD boundary for a given comonomer;
C2 is the slope of the wt. fraction comonomer versus 10 log ~MWw~ plot for a given comonomer;
nJmax.
C4 is a numerical value in the range of about 1.0 to about 0.1, representing conditions at, and beyond, the MWD
boundary, with C4 being equal to unity at the MWD boundary;
said interpolymer being further characterized as having a ratio of weight percent adjacent comonomer unit to total weight percent comonomer in the polymer of less than 0.44 and as having less gels, micro~els and/or grain.
According to a still further aspect of the present in-vention there is provided a process for producing homogeneous, random interpolymers of ethylene and lesser amounts by weight of olefinically-unsaturated organic monomers in a substantially con-stant environment, under substantially steady state conditions, in a single-phase reaction mixture, under the influence of a free-radical initiator, and in a well-stirred reactor operated in a continuous manner as monomers are fed into the reactor and re-action mixture is withdrawn, said process being characterized by the use of synthesis conditions of temperature and pres-sure which are elevated to a level high enough above the phase ~.~
- 4d - 64693-3448 boundary between two-phase and single-phase operation such that the molecular weight distribution bcundary is approached, reached or surpassed, the said molecular weight distribution boundary being the highest ratio of weight average molecular weight/number average molecular weight obtainable in single-phase operation.
According to a further aspect of the present invention there is provided a process for producing substantially homogene-ous, random interpolymers of ethylene with a lesser amount by weight of at least one copolymerizable ofefinically-unsaturated comonomer, said process being performed in a well-stirred auto-clave reactor operated in continuous manner at steady state con-ditions using a free-radical polymerization initiator under sub-stantially constant conditions of temperature, pressure, and -flow rates, wherein the conditions of temperature and pressure re-quired to produce operation at the phase boundary are e~ceeded, respectively, by using a temperature above that at the phase boun-dary and a pressure in a range of more than 500 up to 2,000 psi above that at the phase boundary.
According to another aspect of the present invention there is provided a random interpolymer having a molecular weight sufficient to form a film comprising at least 65% by weight of ethylene, the remaining percentage comprising at least one, ~,~-olefinically-saturated organic comonomer, wherein the microgel level is such that the interpolymer has a Gel Rating of 3 or less than 3.
According to further aspect of the present invention ~ ~7~
- 4e - 64693-3448 there is provided a melt extruded film comprising a random homogeneous, single-phase interpolymer of at least 65% by weight of ethylene and 35% by weight or less of at least one ~,~ -olefinically-unsaturated organic monomer, wherein the microgel level is such that, said interpolymer has a Gel Rating of 3 or less than 3.
Preferably the interpolymer has a Gel Rating of 2 or, more preferably, less than 1.
Preferably the interpolymers comprise from about 99% to about 88% by weight of ethylene units in the polymer chain.
DETAILED DESCRIPTIONS
Figure 1 is presen-ted as a visual aid for relating the present inventive concept.
~,'' ? ' ~ J
In Figure 1 it is shown that as the synthesis conditions are increased substantially beyond the conditions at which the phase boundary is exceed-d and at which single phase operation is achie~ed, there is found an increase in the ratio of weight averag-molecular weight (MWW~ to number average molecular weight (~Wn), i.e. a broadening of ~he ~D occurs, until a molecular weight distribution (~D) boundary is reached and then surpassed. Referring to Figure 1, the increase in the ratio of MWW/MWn is found to be accom-panied by beneficial changes in the properties o films and products made from copolymers which are prepared at temperatures above, and pressures well above, the synthesis conditions at which the phase boundary is reached, and also above the non-randomness ranye disclosed in U.S. 4,248,990; even further beneficial effects are found beyond the MWD boundary where the MWD
is found to decrease and the MW ~ n ratio is narrowing.
Whereas the present inventive concept is perceived as being broadly applicable to interpolymers of ethylene and olefinically-unsaturated organic comonomers, where ethylene comprises the majority amount of the monomer mixture, it is esp~cially appli-cable to acrylates, methacrylates, vinyl esters, and olefinically unsaturated carboxylic acids as comonomers.
It is most especially applicable, and preferably used, in prcparing polymers of ethylene interpolymerized with acrylic acid or methacrylic acid. The ensuing descrip-tions reflect Ihis preference of acrylic acid and methacrylic acid as comonomers.
This disclosure pertains to a process for preparing improved, homogeneous, random ethylene C-31,566 -5-L ~.~
copolymers, especially to improved copolymers o--ethylene and carboxylic acid comonomers. It is an objective of this invention to provide ethylene copolymers which are especially well suited for adhesive, coating ~nd/or packaging purposes and as extrusion resins. The objectives of the present invention are accomplished by preparing, especially, a copolymer of ethylene and 0.1-35 weight percent of an a,~-ethylenically unsaturated carboxylic acid (e.g., acrylic acid and methacrylic acid) having a melt index in the range of 0.01 to about 5000 g/10 min (AS~
D1238E). By "homogeneous, random", it is meant that substantially all of the copolymer molecules ha:e substantially the same chemical composition althougn their molecular weight can vary, and that the copolymer has a ratio of weight percent adjacent acid to total weight percent carboxylic acid in the copolymer less than 0.44 (as determined in accordance with U.S. 4,248,990).
~O The copolyme-s of the present invention combine toughness, flexibility and chemical resistance with outstanding transparency, increased heat seal strength, improved hot tack strength, excellent extrusion coating properties and reduced microgel levels. One of the surprising attributes of ~he copolymers of the present invention is the outstanding transparency obtained at relatively low comonomer concentrations (i.e., <10 percent by wt.). At such low Goncentrations, the copolymers of the present invention exhibit transparency ordinarily achievable only at high acid concentrations or via the additional preparation step of acid-salt neutralization, e.g. as described in U.S. 3,264,272, U.S. 4,248,990, and U.S. 4,351,931.
C-31,56~ -6-Thus, these copolymers are extremely useful as high clarity blown films in such applications as fle~ible packaging where the additional advantages of exceptional draw-down, handleability, adhesiveness and prin.ability (without corona or other forms of pretreatment) as well as excellent processability are observed.
The interpolymers of this inve~tion can also be readily prepared with molecular weight distri~utions (determined by gel permeation chromatography, which may require esterification pretreatment) suitable for coating applications where improved draw rates, adhesion and heat seal strengths are observed.
The previous ethylene/carboxylic acid copoly-mers commonly known in the art normally exhibit poor blown film optical properties that preclude their widespread utilization in some packaging applications.
Therefore, the known art of acid-salt neutralization for the preparation of "ionomers" is sometimes e~ployed to confer substantial transparency to the acid copolymer.
However, ionomer preparation tends to compromise some of the bulk adhesiveness by "neutralizing" carboxyl or acid groups imparting the adhesion. Routinely, blown film converters, coaters and laminators must pretreat the ionomer product to regain adequate adhesion. Other disadvantages of the known route to transparent, adhesive film grade or coatir.g grade products is the fact that the ionomer is rheologically harder to process on conventional polyethylene extrusion equipment (i.e., ionomers draw high amperages and require additional extruder cooling) and is detrimentally moisture sensitive.
C-31,566 -7-~ 3 1~
The lack of transparency exhibited by co~er-cially known copolymers indicates that these products are characterized by comparatively broad molecular weight distributions and/or inadequate homogeneity.
Pieski and Sashihara (U.S. Patent 4,248,990) teach copolymer homogeneity as an attribute of single-phase synthesis. Therefore, to prepare the homogeneous (but non-random) copolymers of u.s. 4,248,9so, the position of the phase boundary (i.e., the transition from two-phase to single-phase reaction conditions) must be identified, and the reaction zone must be maintained in steady state at a reactor pressure of from 0 to about 500 psi above, and at a reactor temperature of from 0 to about 15C above, that transition point.
The improved homogeneity of the "single-phase"
products described in U~S. 4,248,990 is evidenced by lower levels of micro-gels or "grain" than comparable "two-phasel' products. However, these "single-phase"
products still possess a fair amount of grain due to their preparaticn at synthesis conditions in the close proximity of their respective phase boundaries. Such "single-phase" products will also show broader molecular weight distributions (than comparable "two-phase"
products) with a subse~uent decrease in transparency, and hence, require acid-salt neutralization to achieve the transparency needed for a variety of packaging applications. The broad molecular weight distributions sf these "single-phase" products, which are not offset by improved homogeneity, also result in a decrease in the maximum draw rate for film, filament, or coatings as compared to comparable two-phase products.
C-31,566 -8-~x~~
At synthesis temperatures and pressur~s a~ove the range specified by Pies~i and Sashihara, the resul-tant single-phase products are said to be random ~versus non~random) as indicated by lower ratios of percent adjacent acid to total weight percent carboxylic acid.
Such single-phase products (like those prepared at synthesis conditions in the specified range directly above the phase bou~dary) are assumed to possess increasingly broader molecular weight distributions as reactor temperature and pressures are progressi~lely increased.
With reference to Figure 1, which plots the MWW~MWn ratio vs. synthesis conditions, there is illus-trated a curve which reaches an apex that is labeled as the MWD boundary. Near the lower end of the curve corresponding to the lower end of the syn.hesis conditions, there is shown a phase boundary between two-phase conditions and single-phase conditions. The two-phase portion of the curve is labeled as 1. The non-random single-phase portion disclosed by Pieski and Sashihara (U.S. 4,248,990) is labeled as 2, and repre-sents the relative position of the curve (not drawn to scale) for copolymers made at 0-~00 psi above, and 0-15C above, the process conditions at which the phase boundary occurs. All the products made at syn~hesis conditions above the phase boundary are single-phase products. The part of th~ curve labeled as 3 represents the relative position of the curve between the non-random single-phase portion (2) and the ~D boundary which lies in the random single-phase portion. Beyond the MWD boundary there is a portion of the random single-phase curve labeled as 4 to represent products having a ratio falling approximately in the same range C-31,5~o -9-as portions 2 and 3, but which have unex~ected 'mproved properties. A curve portion 5 represents produ-ts having about the same ratios one would obtain at the two-phase conditions, but which are an appreciable improvement over the two-phase products. Still refer-ring to Figure 1, the product improvements foun~ on both sides of the MWD boundary, but substantially above the process conditions which give the non-rando.
products, are within the purview of the present invention, especially those products in portions 4 and 5 of the ratio curve.
In accordance with the present invention, homogeneous, random single-phase ethylene copolymers with significantly improved transparency, heat seal strength and hot tack strength, and with molecular weight distributions similar to two-phase products, are readily prepared well above the position of the phase boundary and above the range of non-randomness disclosed in U.S. 4,248,990. Analogous to the phase boundary, we have found that there exists a transition boundary from broad molecular weight distributions to narrow molecular weight distributions. Unlike the phase boundary, the molecular weight distribution (MWD) boundary is not identified by the dramatic changes in initiator demand (efficiency), or by the significant changes in reactor stirrer motor amperage that are well-known to those skil~ed in the art. However, this position can be conveniently identified at a given comonomer concen-tration by observing the discontinuity in molecular weight distribution at a constant product melt index and comonomer concentration as synthesis conditions are changed in a manner to pass through the molecular weight dlstribution (Mv~) boundary (Figure 1). Before C-31,560 -10-JJ~
reaching this molecular weight distribution (MWD) boundary, random single-phase products exhibit broader molecular weight distributions than comparable two-phase products and non-random single-phase products. However, as the MWD boundary is approached, the random single-phase products will exhibit homogeneity that, surprisingly, offsets their broad molecular weight distributions and permits significantly improved transparency, heat seal strengths and drawdown rates. When synthesis conditions are increased further and/or progressively above the MWD boundary, the respective molecular weight distribution correspondingly narrows, i.e., the ratio of MWw/~1Wn decreases. Therefore, it is possible to conven-iently prepare "single-phase" products with molecular weight distributions equivalent to "two-phase" products by employing the appropriate synthesis conditions and consequently obtain additional product property improvements. The random single-phase products that are prepared under synthesis conditions at which the MMD
boundary is approached, reached, or surpassed are further distinguished from the previously known non-rand~m single-phase products, and the random two-phase products, in that the products of the present invention, at equivalent comonomer concentrations and polymer concentration in the polymerization mixture, will posses a ratio of weight average mol. wt. to number average mol.
wt. as defined by log( w ) = [Cl + (C2) (wt. fractlon comonomer)]x[C3 or C4]
MWn where MWW is the wt. ave. mol. wt., MWn is the no. ave. mol. wt., ~ ~ 7~
C1 is the intercept of the wt. fraction cc~onomer versus log ~ MWw ~ plot for a given comonomer ~ MW I
n ~max.
type, where ~ MWw ~ is the ratio of wt. ave.
n Jmax.
mol. wt. to no. ave. mol. wt. at the MwD
boundary for a given comonomer type, C2 is the slope of the wt. fraction comono~er versus log ~ MWw ~ plot for a given comonomer ~ MWn )max-type, C3 is a numerical value in the range of a~out O . 75 tG 1 . O, pr~ferably about O.85 to 2bout 1.0, and C4 is a numerical value in the range of about 1.0 to about 0.1, where C3 is employed at process conditions which produce products between the single-phase non-random range and the MWD boundary, and where C4 is employed at process conditions which produce products beyond the MWD boundary.
At the MWD boundary, both C3 and C4 are equal to unity.
Since product performance is intimately related to molecular weight distribution ~for example, narrow molecular weight distributions are generally requir~d for excellent copolymer transparency, and a relatively broad MWD is usually required for excellent extrusion coating properties), the ability to prepare a wide range of distinct distributions at a single product melt index allows the manufacture of products suitable for a wide range of film, coating, moldi~g and lami-nating applications.
C-31,56~ -12-7.;~5 Although the exact position of a ~ ~ boundary depends upon coMonomer concentration and a number of other variables, tests as above will demonstrate that the position is well above the corresponding phase boundary for the given comonomer concentration. For example, the MWD boundary occurs >2000 psi above, and >15 above, the phase boundary when producing an ethylenejacrylic acid copolymer containing nine percent acry7 ic acid by weight.
In addition to the ability to "tailor" the desired molecular weight distributions and achieve improved transparency and coating proper~ies, in accor-dance with the present invention, "single-phase"
products prepared just below, at, or above the ~D
boundary possess less microgels or grain than comparable "two-phase" products as well as less grain than the non-random, "single-phase" products prepared e.g. in U.S. 4,24~,990. In fact, at or above a corresponding MWD boundary, completely "grain-free" products can be readily prepared. This reduction in microgels or "grain" has an aesthetic appeal, and the presence of excessive amounts of grain can contribute to inadeguate heat seal and hot tack strengths, as well as promote delamination by compromising the adhesiveness. The improved heat seal ~nd hot tack strengths of these "single-phase" products is also an object of this invention.
The copolymers of the present invention can be conveniently prepared at reactor pressures from about 18,000 to about 50,000 psi and at reactor temper-atures from about 150 to about 350C so long as the phase boundary conditions are appreciably exceeded.
C-31,506 -13-~.
~ ~7,3 ~
The preferred reactor is a continuous autoclav~ witn a 1:1 to about a 16:1 L/D ratio. The reactor may consist of one or more reaction zone(s) by installing b-ffling systems common in the art; the reactor may be in series with one or more other reactors and the reactor may also be provided with one or more comonomer ent~y point(s) as described by British Patent 1,096,9-5.
Hence, when more than one reaction zone is employed, the reactor(s) can be maintained to provide an "intra-zone" and/or "interzone" constant environment or it isalso possible to operate in such a manner that a gradient of environments exists between and/or within the zones and/or reactors.
The products of this invention can be prepared with or without the use of solvents or hydrocar~ons as telogens and/or carriers for the comonomer(s) and/or initiator(s). These products are also useful as base resins for the preparation of ionic copolymers, known in the art as "Ionomers", wherefrom additional i~prove-ments in transparency, chemical resistance and hot tackstrength are readily obtained.
The gels that often characterize ethylene/car-boxylic acid interpolymers can be of many different shapes, varying sizes and of more than one origin. For instance, microgels or "grain" (i.e., very small and fine gels) are shown in accordznce with this disclosure to be an attribute of operating within and/or in the close proximity of a respective phase b~undary; large gels (i.e., gels >25~ in diameter) are usually an attribute or the result of thermal oxidation/degra-dation; however, microgels or "grain" can actually "seed" these larger gels.
~,~ J~37L~
In this disclosure, the following gel rating is used:
EAA GEL RATING*
Rating Criteria 0 No visible gels 1 Very few microgels
UNSA~URATED CARBOXYL I C AC IDS
BACKGROUND
Interpolymers of ethylene and unsatura~ed carboxylic acids, such as acrylic acid and methacrylic acid, are well known. This presen. disclosure pertains to such interpolymers when made under steady state conditions in stirred reactors at high pressure and elevated temperature and using a free-radical type initiator, in contradistinction to polymers made under non-steady state conditions or in non-stirred tu~ular lQ reactors sr in batch reactions, and in contradistinction to bloc~ copolymers or graft copolymers.
Patents which disclose interpolymerizations of ethylene and unsaturated carboxylic acids in a steady state reaction at high temperature and high pressure in a stirred reactor in the presence of a free-radical initiator are, e.g., Canadian Patent 655,298 (and its U.S. counterpart No. 4,351,931~:
U.S. 3,23g,370; U.S. 3,520,861; U.S. 3,658,741;
U.S. 3,884,857; U.S. 3,988,509; U.S. 4, 248,990; and U.S. 4,252,924.
U.S. 3,239l370 discloses a rar.dom copolymer-izat~on o ethylene with an unsaturated carboxylic C~ 60 -1-~ ~ ~3 ~
acid (e.g. acrylic acid) in a stirred autoclave operated at 16,000 psi, and 210C using a peroxy initiat~r, the so-formed copolymer being particularly useful as a coating for non-metallic substrates.
U.S. 3,520,861 discloses a substantially homogeneous, compositionally uniform, random coFoly~er of ethylene/unsaturated acid (e.g. acrylic acid, meth-acrylic acid, crotonic acid) prepared in a continuous manner in a stirred autoclave at high pressure and elevated temperature, using a free-radical initiator (such as a peroxide). The temperature of the polymer-ization is disclosed as being in the range of about 120C to about 300C, preferably about 150C to about 250C. The pressure of the polymerization is disclosed as being in the range of at least 1000 atmospheres, preferably between about 1000-3000 atmospheres, esp.
between 1100-1900 atmospheres.
Canadian Patent No. 655,298 and its U.S.
counterpart (U.S. 4,351,931) discloses homogeneous, compositionally uniform, random copolymers of ethylene and unsaturated carboxylic acids (e.g. acrylic acid) wherein said copolymer comprises at least about gO% by weight of ethylene with a melt index of 0.01 to 30 g/10 minutes. The copolymers are prepared in a well-stirred reactor at a pressure of at least 1000 atmospheres, at ~0-280C, using a free radical initiator, while maintaining the ratio of monomers (ethylene/acid) in the range of 10,000/1 to 50/1 by weight, the process being performed continuously by feeding monomers in, while removing reaction mixture, and maintaining a constant reaction environment.
C-31,56& -2-~ 4~
U.S. 3,658,741 discloses homogeneous copolymers of ethylene and unsaturated carboxyl-c z_ids and esters, prepared in the presence of a chain tra~sfer agent, a free radical catalyst, a temperature b-~ween 100C-300C and pressure between 100 and 1000 at~o-spheres, using turbulent agitation; the reactio-. is said to take place in the vapor phasP and prepa-es very low mol. wt. copol~mers.
U.S. 3,884,857 and U.S. 3,988,~09 disclose the preparation of copolymers, such as ethylene~acrylic acid copolymers in a continuous, high pressure, free-radical polymerization process, at 100-250C aL.d 1000-2500 atmospheres of pressure.
U.S. 4,248,990 discloses copolymers, e.g.
ethylene/acrylic acid copolymers which are said to distinguish over the random copolymers o~ Canadian 655,298 and of U.S. 3,520,861 by virtue of being non-random. This non-randomness is said to be the result of operating the steady state, high pressure, stirred reactor at a pressure of from 0 to about 500 psi above, and at temperature of from 0-15C above, that needed to maintain a single phase reaction mixture at the given concentration of copolymer in the reaction mixture and at the given acid comonomer content of the copolymer.
U.S. 4,252,924 discloses the preparation of non-random copolymers, e.g. ethylene/acrylic acid copolymers in at least two constant environment, stirred autoclaves in series, each using a single phase reaction mixture, but where each succeeding autoclave is maintained at a temperature of at least 30C above that of the preceding autoclave.
~73~
In the ordinary course of events, operators of processes are not inclined to employ more energy (temperature and/
or pressure) than is deemed necessary to obtain a given product, in the absence of any recognized benefit to be derived from such additional expense. We have now found that there are unexpected benefits to be derived from employing more energy (temperature and pressure) than is generally deemed to be sufficient in the production of interpolymers of ethylene.
SU~IARY OF THE INVENTION
With reference to random interpolymers of ethylene and olefinically-unsaturated organic comonomers prepared in a well-stirred autoclave, in the presence of a free-radical initiator, under substantially constant conditions of temperature and pressure and substantially steady state, continuous operation, it has now been found, surprisingly and unexpectedly, that substantial and useful improvements are found by maintaining the synthesis conditions of temperature and pressure elevated high enough above the phase boundary that exists between the two-phase and single-phase conditions, for a given comonomer concentration and polymer concentration in the polymerization mixture, to closely approach, reach, andtor surpass the respective molecular weight distribution (~WD) boundary, i.e., the synthesis conditions at which the ratio of the weight average mol. wt./number average mol. wt. is at its maximum.
According to one aspect of the present invention there is provided a process for producing homogeneous, random inter-..~ ~
~73~
- 4a - 64693-3448 polymers comprising about 99~ to about 65% by weight of ethylene monomer and about 1% to about 35% by weight of at least one olefinically-unsaturated comonomer selected from the group com-prising unsatura-ted carboxylic acids, alkyl acrylates, alkyl meth-acrylates and vinyl esters, said process comprising interpoly-merizing the monomers in a substantially constant environment, under steady state conditions, in a single-phase reac~ion mixture, under the influence of a free-radical initiator, and in a well-stirred autoclave reactor operated in a continuous manner as the monomers are fed into the reactor and the reaction mixture iswithdrawn, said process being characterized by the use of synthesis conditions of a temperature and pressure which are elevated to a level high enough above the phase boundary between two-phase and single-phase operation such that the molecular weight distribution (MWD) boundary is approached, reached, or surpassed, the said molecular weight distribution boundary being the highest ratio of weight average molecular weight/number average molecular weight obtainable in single-phase operation, said elevated pressure being greater than 2000 psi above, and said elevated temperature being greater than 15C
above, the synthesis conditions required at the phase boundary for a given mixture of ethylene and comonomer, thereby producing an interpolymer having less gels, microgels and/or grain.
According to another aspect of the present invention, there is provided a process for producing substantially 1~73~
- 4b - 64693-3448 homogeneous, random interpolymers comprising about 99% to about 65~ by weight of ethylene monomer with about 1% to about 35% by weight of acrylic acid or methacrylic acid comonomer, said process comprising interpolymerizing the monomers in a well-stirred autoclave reactor operated in a continuous manner at steady state conditions using a free-radical polymerization initiator under substantially constant conditions of temperature, pressure, and flow rates, wherein the conditions of temperature and pressure re-quired to produce operation at the phase boundary are exceeded, respectively, by using a temperature of at least 15C above that at the phase boundary and a pressure of more than 2000 psi above that at the phase boundary, whereby the molecular weight distribution (MWD) boundary is reached or surpassed, thereby producing an interpolymer having less gels, microgels and/or grain.
According to a further aspect of the present invention there is provided a random, homogeneous, single-phase interpolymer product comprising about 65~ to about 99% by weight of ethylene monomer, the remaining percentage comprising at least one olefinically-unsaturated comonomer selected from the group com-prising unsaturated carboxylic acids, alkyl acrylates, alkyl methacrylates and vinyl esters, said interpolymer being further characterized as having a weight average molecular weight/number average molecular weight ratio as defined by the formula log ~MWw~=[Cl+(C2)(wt.fraction comonomer)]x(C4) ~MWn/
where MWW is the weight average molecular weight;
,~, 3~
- 4c - 64693-3448 MWn is the number average molecular weight;
Cl is the intercept of the wt. fraction comonomer versus log ~ w~ plot for a given comonomer, where nJmax.
w~ is the ratio of weight average molecular weight ~MWn~max.
to number average molecular weight at the MWD boundary for a given comonomer;
C2 is the slope of the wt. fraction comonomer versus 10 log ~MWw~ plot for a given comonomer;
nJmax.
C4 is a numerical value in the range of about 1.0 to about 0.1, representing conditions at, and beyond, the MWD
boundary, with C4 being equal to unity at the MWD boundary;
said interpolymer being further characterized as having a ratio of weight percent adjacent comonomer unit to total weight percent comonomer in the polymer of less than 0.44 and as having less gels, micro~els and/or grain.
According to a still further aspect of the present in-vention there is provided a process for producing homogeneous, random interpolymers of ethylene and lesser amounts by weight of olefinically-unsaturated organic monomers in a substantially con-stant environment, under substantially steady state conditions, in a single-phase reaction mixture, under the influence of a free-radical initiator, and in a well-stirred reactor operated in a continuous manner as monomers are fed into the reactor and re-action mixture is withdrawn, said process being characterized by the use of synthesis conditions of temperature and pres-sure which are elevated to a level high enough above the phase ~.~
- 4d - 64693-3448 boundary between two-phase and single-phase operation such that the molecular weight distribution bcundary is approached, reached or surpassed, the said molecular weight distribution boundary being the highest ratio of weight average molecular weight/number average molecular weight obtainable in single-phase operation.
According to a further aspect of the present invention there is provided a process for producing substantially homogene-ous, random interpolymers of ethylene with a lesser amount by weight of at least one copolymerizable ofefinically-unsaturated comonomer, said process being performed in a well-stirred auto-clave reactor operated in continuous manner at steady state con-ditions using a free-radical polymerization initiator under sub-stantially constant conditions of temperature, pressure, and -flow rates, wherein the conditions of temperature and pressure re-quired to produce operation at the phase boundary are e~ceeded, respectively, by using a temperature above that at the phase boun-dary and a pressure in a range of more than 500 up to 2,000 psi above that at the phase boundary.
According to another aspect of the present invention there is provided a random interpolymer having a molecular weight sufficient to form a film comprising at least 65% by weight of ethylene, the remaining percentage comprising at least one, ~,~-olefinically-saturated organic comonomer, wherein the microgel level is such that the interpolymer has a Gel Rating of 3 or less than 3.
According to further aspect of the present invention ~ ~7~
- 4e - 64693-3448 there is provided a melt extruded film comprising a random homogeneous, single-phase interpolymer of at least 65% by weight of ethylene and 35% by weight or less of at least one ~,~ -olefinically-unsaturated organic monomer, wherein the microgel level is such that, said interpolymer has a Gel Rating of 3 or less than 3.
Preferably the interpolymer has a Gel Rating of 2 or, more preferably, less than 1.
Preferably the interpolymers comprise from about 99% to about 88% by weight of ethylene units in the polymer chain.
DETAILED DESCRIPTIONS
Figure 1 is presen-ted as a visual aid for relating the present inventive concept.
~,'' ? ' ~ J
In Figure 1 it is shown that as the synthesis conditions are increased substantially beyond the conditions at which the phase boundary is exceed-d and at which single phase operation is achie~ed, there is found an increase in the ratio of weight averag-molecular weight (MWW~ to number average molecular weight (~Wn), i.e. a broadening of ~he ~D occurs, until a molecular weight distribution (~D) boundary is reached and then surpassed. Referring to Figure 1, the increase in the ratio of MWW/MWn is found to be accom-panied by beneficial changes in the properties o films and products made from copolymers which are prepared at temperatures above, and pressures well above, the synthesis conditions at which the phase boundary is reached, and also above the non-randomness ranye disclosed in U.S. 4,248,990; even further beneficial effects are found beyond the MWD boundary where the MWD
is found to decrease and the MW ~ n ratio is narrowing.
Whereas the present inventive concept is perceived as being broadly applicable to interpolymers of ethylene and olefinically-unsaturated organic comonomers, where ethylene comprises the majority amount of the monomer mixture, it is esp~cially appli-cable to acrylates, methacrylates, vinyl esters, and olefinically unsaturated carboxylic acids as comonomers.
It is most especially applicable, and preferably used, in prcparing polymers of ethylene interpolymerized with acrylic acid or methacrylic acid. The ensuing descrip-tions reflect Ihis preference of acrylic acid and methacrylic acid as comonomers.
This disclosure pertains to a process for preparing improved, homogeneous, random ethylene C-31,566 -5-L ~.~
copolymers, especially to improved copolymers o--ethylene and carboxylic acid comonomers. It is an objective of this invention to provide ethylene copolymers which are especially well suited for adhesive, coating ~nd/or packaging purposes and as extrusion resins. The objectives of the present invention are accomplished by preparing, especially, a copolymer of ethylene and 0.1-35 weight percent of an a,~-ethylenically unsaturated carboxylic acid (e.g., acrylic acid and methacrylic acid) having a melt index in the range of 0.01 to about 5000 g/10 min (AS~
D1238E). By "homogeneous, random", it is meant that substantially all of the copolymer molecules ha:e substantially the same chemical composition althougn their molecular weight can vary, and that the copolymer has a ratio of weight percent adjacent acid to total weight percent carboxylic acid in the copolymer less than 0.44 (as determined in accordance with U.S. 4,248,990).
~O The copolyme-s of the present invention combine toughness, flexibility and chemical resistance with outstanding transparency, increased heat seal strength, improved hot tack strength, excellent extrusion coating properties and reduced microgel levels. One of the surprising attributes of ~he copolymers of the present invention is the outstanding transparency obtained at relatively low comonomer concentrations (i.e., <10 percent by wt.). At such low Goncentrations, the copolymers of the present invention exhibit transparency ordinarily achievable only at high acid concentrations or via the additional preparation step of acid-salt neutralization, e.g. as described in U.S. 3,264,272, U.S. 4,248,990, and U.S. 4,351,931.
C-31,56~ -6-Thus, these copolymers are extremely useful as high clarity blown films in such applications as fle~ible packaging where the additional advantages of exceptional draw-down, handleability, adhesiveness and prin.ability (without corona or other forms of pretreatment) as well as excellent processability are observed.
The interpolymers of this inve~tion can also be readily prepared with molecular weight distri~utions (determined by gel permeation chromatography, which may require esterification pretreatment) suitable for coating applications where improved draw rates, adhesion and heat seal strengths are observed.
The previous ethylene/carboxylic acid copoly-mers commonly known in the art normally exhibit poor blown film optical properties that preclude their widespread utilization in some packaging applications.
Therefore, the known art of acid-salt neutralization for the preparation of "ionomers" is sometimes e~ployed to confer substantial transparency to the acid copolymer.
However, ionomer preparation tends to compromise some of the bulk adhesiveness by "neutralizing" carboxyl or acid groups imparting the adhesion. Routinely, blown film converters, coaters and laminators must pretreat the ionomer product to regain adequate adhesion. Other disadvantages of the known route to transparent, adhesive film grade or coatir.g grade products is the fact that the ionomer is rheologically harder to process on conventional polyethylene extrusion equipment (i.e., ionomers draw high amperages and require additional extruder cooling) and is detrimentally moisture sensitive.
C-31,566 -7-~ 3 1~
The lack of transparency exhibited by co~er-cially known copolymers indicates that these products are characterized by comparatively broad molecular weight distributions and/or inadequate homogeneity.
Pieski and Sashihara (U.S. Patent 4,248,990) teach copolymer homogeneity as an attribute of single-phase synthesis. Therefore, to prepare the homogeneous (but non-random) copolymers of u.s. 4,248,9so, the position of the phase boundary (i.e., the transition from two-phase to single-phase reaction conditions) must be identified, and the reaction zone must be maintained in steady state at a reactor pressure of from 0 to about 500 psi above, and at a reactor temperature of from 0 to about 15C above, that transition point.
The improved homogeneity of the "single-phase"
products described in U~S. 4,248,990 is evidenced by lower levels of micro-gels or "grain" than comparable "two-phasel' products. However, these "single-phase"
products still possess a fair amount of grain due to their preparaticn at synthesis conditions in the close proximity of their respective phase boundaries. Such "single-phase" products will also show broader molecular weight distributions (than comparable "two-phase"
products) with a subse~uent decrease in transparency, and hence, require acid-salt neutralization to achieve the transparency needed for a variety of packaging applications. The broad molecular weight distributions sf these "single-phase" products, which are not offset by improved homogeneity, also result in a decrease in the maximum draw rate for film, filament, or coatings as compared to comparable two-phase products.
C-31,566 -8-~x~~
At synthesis temperatures and pressur~s a~ove the range specified by Pies~i and Sashihara, the resul-tant single-phase products are said to be random ~versus non~random) as indicated by lower ratios of percent adjacent acid to total weight percent carboxylic acid.
Such single-phase products (like those prepared at synthesis conditions in the specified range directly above the phase bou~dary) are assumed to possess increasingly broader molecular weight distributions as reactor temperature and pressures are progressi~lely increased.
With reference to Figure 1, which plots the MWW~MWn ratio vs. synthesis conditions, there is illus-trated a curve which reaches an apex that is labeled as the MWD boundary. Near the lower end of the curve corresponding to the lower end of the syn.hesis conditions, there is shown a phase boundary between two-phase conditions and single-phase conditions. The two-phase portion of the curve is labeled as 1. The non-random single-phase portion disclosed by Pieski and Sashihara (U.S. 4,248,990) is labeled as 2, and repre-sents the relative position of the curve (not drawn to scale) for copolymers made at 0-~00 psi above, and 0-15C above, the process conditions at which the phase boundary occurs. All the products made at syn~hesis conditions above the phase boundary are single-phase products. The part of th~ curve labeled as 3 represents the relative position of the curve between the non-random single-phase portion (2) and the ~D boundary which lies in the random single-phase portion. Beyond the MWD boundary there is a portion of the random single-phase curve labeled as 4 to represent products having a ratio falling approximately in the same range C-31,5~o -9-as portions 2 and 3, but which have unex~ected 'mproved properties. A curve portion 5 represents produ-ts having about the same ratios one would obtain at the two-phase conditions, but which are an appreciable improvement over the two-phase products. Still refer-ring to Figure 1, the product improvements foun~ on both sides of the MWD boundary, but substantially above the process conditions which give the non-rando.
products, are within the purview of the present invention, especially those products in portions 4 and 5 of the ratio curve.
In accordance with the present invention, homogeneous, random single-phase ethylene copolymers with significantly improved transparency, heat seal strength and hot tack strength, and with molecular weight distributions similar to two-phase products, are readily prepared well above the position of the phase boundary and above the range of non-randomness disclosed in U.S. 4,248,990. Analogous to the phase boundary, we have found that there exists a transition boundary from broad molecular weight distributions to narrow molecular weight distributions. Unlike the phase boundary, the molecular weight distribution (MWD) boundary is not identified by the dramatic changes in initiator demand (efficiency), or by the significant changes in reactor stirrer motor amperage that are well-known to those skil~ed in the art. However, this position can be conveniently identified at a given comonomer concen-tration by observing the discontinuity in molecular weight distribution at a constant product melt index and comonomer concentration as synthesis conditions are changed in a manner to pass through the molecular weight dlstribution (Mv~) boundary (Figure 1). Before C-31,560 -10-JJ~
reaching this molecular weight distribution (MWD) boundary, random single-phase products exhibit broader molecular weight distributions than comparable two-phase products and non-random single-phase products. However, as the MWD boundary is approached, the random single-phase products will exhibit homogeneity that, surprisingly, offsets their broad molecular weight distributions and permits significantly improved transparency, heat seal strengths and drawdown rates. When synthesis conditions are increased further and/or progressively above the MWD boundary, the respective molecular weight distribution correspondingly narrows, i.e., the ratio of MWw/~1Wn decreases. Therefore, it is possible to conven-iently prepare "single-phase" products with molecular weight distributions equivalent to "two-phase" products by employing the appropriate synthesis conditions and consequently obtain additional product property improvements. The random single-phase products that are prepared under synthesis conditions at which the MMD
boundary is approached, reached, or surpassed are further distinguished from the previously known non-rand~m single-phase products, and the random two-phase products, in that the products of the present invention, at equivalent comonomer concentrations and polymer concentration in the polymerization mixture, will posses a ratio of weight average mol. wt. to number average mol.
wt. as defined by log( w ) = [Cl + (C2) (wt. fractlon comonomer)]x[C3 or C4]
MWn where MWW is the wt. ave. mol. wt., MWn is the no. ave. mol. wt., ~ ~ 7~
C1 is the intercept of the wt. fraction cc~onomer versus log ~ MWw ~ plot for a given comonomer ~ MW I
n ~max.
type, where ~ MWw ~ is the ratio of wt. ave.
n Jmax.
mol. wt. to no. ave. mol. wt. at the MwD
boundary for a given comonomer type, C2 is the slope of the wt. fraction comono~er versus log ~ MWw ~ plot for a given comonomer ~ MWn )max-type, C3 is a numerical value in the range of a~out O . 75 tG 1 . O, pr~ferably about O.85 to 2bout 1.0, and C4 is a numerical value in the range of about 1.0 to about 0.1, where C3 is employed at process conditions which produce products between the single-phase non-random range and the MWD boundary, and where C4 is employed at process conditions which produce products beyond the MWD boundary.
At the MWD boundary, both C3 and C4 are equal to unity.
Since product performance is intimately related to molecular weight distribution ~for example, narrow molecular weight distributions are generally requir~d for excellent copolymer transparency, and a relatively broad MWD is usually required for excellent extrusion coating properties), the ability to prepare a wide range of distinct distributions at a single product melt index allows the manufacture of products suitable for a wide range of film, coating, moldi~g and lami-nating applications.
C-31,56~ -12-7.;~5 Although the exact position of a ~ ~ boundary depends upon coMonomer concentration and a number of other variables, tests as above will demonstrate that the position is well above the corresponding phase boundary for the given comonomer concentration. For example, the MWD boundary occurs >2000 psi above, and >15 above, the phase boundary when producing an ethylenejacrylic acid copolymer containing nine percent acry7 ic acid by weight.
In addition to the ability to "tailor" the desired molecular weight distributions and achieve improved transparency and coating proper~ies, in accor-dance with the present invention, "single-phase"
products prepared just below, at, or above the ~D
boundary possess less microgels or grain than comparable "two-phase" products as well as less grain than the non-random, "single-phase" products prepared e.g. in U.S. 4,24~,990. In fact, at or above a corresponding MWD boundary, completely "grain-free" products can be readily prepared. This reduction in microgels or "grain" has an aesthetic appeal, and the presence of excessive amounts of grain can contribute to inadeguate heat seal and hot tack strengths, as well as promote delamination by compromising the adhesiveness. The improved heat seal ~nd hot tack strengths of these "single-phase" products is also an object of this invention.
The copolymers of the present invention can be conveniently prepared at reactor pressures from about 18,000 to about 50,000 psi and at reactor temper-atures from about 150 to about 350C so long as the phase boundary conditions are appreciably exceeded.
C-31,506 -13-~.
~ ~7,3 ~
The preferred reactor is a continuous autoclav~ witn a 1:1 to about a 16:1 L/D ratio. The reactor may consist of one or more reaction zone(s) by installing b-ffling systems common in the art; the reactor may be in series with one or more other reactors and the reactor may also be provided with one or more comonomer ent~y point(s) as described by British Patent 1,096,9-5.
Hence, when more than one reaction zone is employed, the reactor(s) can be maintained to provide an "intra-zone" and/or "interzone" constant environment or it isalso possible to operate in such a manner that a gradient of environments exists between and/or within the zones and/or reactors.
The products of this invention can be prepared with or without the use of solvents or hydrocar~ons as telogens and/or carriers for the comonomer(s) and/or initiator(s). These products are also useful as base resins for the preparation of ionic copolymers, known in the art as "Ionomers", wherefrom additional i~prove-ments in transparency, chemical resistance and hot tackstrength are readily obtained.
The gels that often characterize ethylene/car-boxylic acid interpolymers can be of many different shapes, varying sizes and of more than one origin. For instance, microgels or "grain" (i.e., very small and fine gels) are shown in accordznce with this disclosure to be an attribute of operating within and/or in the close proximity of a respective phase b~undary; large gels (i.e., gels >25~ in diameter) are usually an attribute or the result of thermal oxidation/degra-dation; however, microgels or "grain" can actually "seed" these larger gels.
~,~ J~37L~
In this disclosure, the following gel rating is used:
EAA GEL RATING*
Rating Criteria 0 No visible gels 1 Very few microgels
2 Some microgels
3 Some microgels, some large gels
4 Numerous microgels, some large gels Numerous microgels, numerous large gels 6 Severe gels (* Rating according to criteria b~ visuzl inspection of blown film samples.) The following examples are to illustrate embodiments of the present invention, but the invention is not limited to the embodiments illustrated.
EXAMPLE 1 (for comparison purposes) A 1.5 mil blown film was prepared frcm an ethylene/acrylic acid copolymer that contained 6.5 percent acrylic acid by weight and had a 2.5 g/lO min melt index (ASTM D1238E). The copolymer was prepared about 0-500 psi above and about 0-15C above its respec-tive phase boundary and the film exhibited excessive micro.gels or "grain", a Gardner clarity of 12 percent transmission, a 20 film gloss of 25 percent reflected light, a film ha2e of 5.5 percent sca~tered light, a heat seal strength, at a 310F sealing bar temperature, of 3.2 lbs/in width and a hot tack strength, at a 300F
sealing bar temperature, of 150 grams/inch.
C-31,566 -15-Conversely, a 6.5 percent acrylic aci~ (by wt.) copolymer having the same melt index was prepa-ed about 3500 to about 4500 psi above and about 16 to about 18C above its corresponding phase bounda~y. The resultant blown film of this product had a Gardrer clarity o~ 47 percent, a 20 gloss of 45 percent, film haze of 3.2 percent, negligible microgels or "grain", a 4.9 lbs/in heat seal strength at 310F and a 200 g/in hot tack at 300F. Both film samples ~ere fabricated into 1.5 mil film on an NRM 20/1, L,~D
extruder that was equipped with an air ring, mandrel, annular die, and a ta~e-off unit. Both fabrica~ions maintained 204C melt temperature with a 2.25:1 blow-up ratio.
Data for the above examples and for additional samples of ethylene/acrylic acid copolymers are shown in the following tables. Whereas Examples 1, 5, 8, 11 and 15 are examples o~ prior art used in making non-random copolymers at 0-500 psi above, and 0-15C ~bove, the phase boundary, the remaining examples illustrate various embodiments of the present invention, all of which were produced at a temperature above the phase boundary temperature.
C-31,560 -16-~ ~ lJ~ 7 L~
TABLE I
EXAMPLE EXA~LE EXAML--~E EXAMPLE
Percent Acry1ic Acid +0.25 6~5a 6 5a 6.5b 6.5b Melt Index g/10 min ~0.25 2.5 2.5 2.5 2.5 MWw/MWn (GPC)~ 7.9 10.2 10.2 9.01 Synthesis Pressure Abov2 Phase Bounda~y (psi~ 0-500 3500-4500 3500-4500 7500-8500 Blown Film Properties Gardner Clarity, % 10.9 47.1 72.1 69.4 Transmission 20 Film Gloss, % 22.5 45.1 110.5 126.6 Reflected Percent Haze, ~c 5.42 3.2 1.59 1.08 Scattered Gel Rating 4 0 0 0 Heat Seal Strength @ 310F, lb/in 3.0 4.9 Hot Tack Strength @ 300F g/in 150 200 - - - -a Blown Film Fabrication: 204C, 2.25 BUR, 1.5 mil thickness, NRM extruder b Blown Film Fabrication: 218C, 3.06 BUR, l.S mil thic~ness, N~M extruder * GPC refers to gel permeation chromatography for determining molecuIar wt. distri~ution.
C-31,~6~ -17-~ r ~ IJ3 ~ ~ 5 T ~ LE II
EXA*~LE EXAMPLE E~E-~-Percent Acrylic Acid +0.3 9.0 9.0 9.0 Melt Index g/lO min +0.25 3.0 3.0 3.0 MWw/~n (GPC) 6.6 8.5 9.5 Synthesis Pressure Above Phase Boundary (psi) 0-500 2000-3000 3500-'500 Blown Film Propertiesa Gardner Clarity, %
Transmission 13.3 24.1 48.1 20 Film Gloss, %
Reflected 32.4 41.6 70.5 45 Film Gloss, %
Reflected 65.1 62.2 81.9 Percent Haze, X
Scattered 4.2 3.5 1.91 Gel Rating 5 3 2 Heat Seal Strength @ 310F, lb/in 3.2 5.4 >6.0 Hot Tack Strength @ 300F g/in 150 205 250 a Blown Film Fabrication Conditions: 204~C, 2.25 BU~, 1.5 mils (thickness), NRM Extruder C-31, 5~G - 1~ -~ ~3~ S
T~BLE III
EXA~PLE EXAMPLE EXAMPLE
8 9 lO
Percent Acrylic Acid +0.25 9.0 9.0 9.0 Melt Index g/10 min +0.25 3.0 3.0 3.0 w/MWn (GPC) 6.5 9.5 8.9 Synthesis Pres~ure Above M~D Boundary (psi) (4500^3500)~ 0-500 2800-3800 Synthesis Pressure Above Phase Boundary (psi) 0-500 3500-4500 6800-7800 Blown Film PropertiesC
Gardner Clarity, % 12.1 26.1 36.5 Transmission 20 Film Gloss, ~ 14.6 13.3 28.0 Reflected 45 Film Gloss, % 52.1 48.3 61.8 Reflected Percent Haze 6.47 7.55 5.1 Gel Rating 5 3 1.5 c Glcucester Fabrication Conditions: 2-1/2" Extruder, 20~C melt temp., 2.75 BUR, 1.5 mil thick film, * Co~notes 4500-3500 psi below MWD boundary.
C-31,566 -lg-~ 7 T ~ LE IV
EX~hMPLE EXA~LE EYAMPI F. EXA~IPLE
11 12 _ 13 14 Percent Acrylic Acid +0.25 6.5 6.5 6.5 6.5 Melt Index g/10 min +0.25 5.5 5.5 5.5 5.5 MWw/~n (GPC) 7.1 10.1 13.7 l0.2 Synthesis Pr~ssure Above Phase Boundary (psi) 0-500 3500-45C0 5500-6500 7500-8500 Synthesis Pressure Above M~ Boundary (psi) (6500-5500)'-(2500-~5G0)*
~500 1500-2500 Extrusion Coating Propertiesd Neck-in @ 440 fpm (inches) - - 1.75 1.63 1.87 Nip Speed (fpm) 200 520 530 992 Draw-down Speed (fp~) 730 1075 1250 ~1500 Minimum Coating (mils) 2.2 0.85 0.83 0.44 Gel Rating 5 2 1 0 ~eal Seal Strength, @ 310F, lb/in width 2.3 2.2 >3.9 >4.0 Hot Tack Strength, @ 300F, g/in width 250 340 700 75 A1 Adhesion, lb/in width 0.80 0.75 1.22 - -d Black Clawson Extrusion Coater (3-1/2" extruder, 30/l L/D); melt temperature 550F, scre~ speed 85 RPM, air gap 6 inches * CGnnotes psi below the MWD boundary C-31,566 -20-.f T ~ LE V
EXAMPLE EX~ ~ LE
Percent Acr~,~lic Acid +0.3 9.0 5.0 Melt Index g/10 min +0.25 12.0 12.0 MWw/~n (GPC) 6.5 9.2 Syn;hesis Pressure Above Phase Boundary (psi) 0-500 3500-4500 Synthesis Pressure below MWD Boundary (psi) (4500-3500)~~ ~500 Extrusion Coating Propertiesd Nip Speed (fpm) 875 1275 ~raw-dow~ Speed (fpm) 1300 >1500 Minimum Coating ~mils)O.'tO 0.35 Sealing Properties Heat Seal Strength @ 260F, lblin 4.5 >4.1 Hot Tack Strength @ 300F, g/in 350 8S0 d Black Clawson Extrusion Coater (3-l/2" extruder, 30/l L/D); melt temperature 550F, screw speed 85 RPM, air gap 6 inches * connotes psi below MWD boundary C-31,~6~ -21-
EXAMPLE 1 (for comparison purposes) A 1.5 mil blown film was prepared frcm an ethylene/acrylic acid copolymer that contained 6.5 percent acrylic acid by weight and had a 2.5 g/lO min melt index (ASTM D1238E). The copolymer was prepared about 0-500 psi above and about 0-15C above its respec-tive phase boundary and the film exhibited excessive micro.gels or "grain", a Gardner clarity of 12 percent transmission, a 20 film gloss of 25 percent reflected light, a film ha2e of 5.5 percent sca~tered light, a heat seal strength, at a 310F sealing bar temperature, of 3.2 lbs/in width and a hot tack strength, at a 300F
sealing bar temperature, of 150 grams/inch.
C-31,566 -15-Conversely, a 6.5 percent acrylic aci~ (by wt.) copolymer having the same melt index was prepa-ed about 3500 to about 4500 psi above and about 16 to about 18C above its corresponding phase bounda~y. The resultant blown film of this product had a Gardrer clarity o~ 47 percent, a 20 gloss of 45 percent, film haze of 3.2 percent, negligible microgels or "grain", a 4.9 lbs/in heat seal strength at 310F and a 200 g/in hot tack at 300F. Both film samples ~ere fabricated into 1.5 mil film on an NRM 20/1, L,~D
extruder that was equipped with an air ring, mandrel, annular die, and a ta~e-off unit. Both fabrica~ions maintained 204C melt temperature with a 2.25:1 blow-up ratio.
Data for the above examples and for additional samples of ethylene/acrylic acid copolymers are shown in the following tables. Whereas Examples 1, 5, 8, 11 and 15 are examples o~ prior art used in making non-random copolymers at 0-500 psi above, and 0-15C ~bove, the phase boundary, the remaining examples illustrate various embodiments of the present invention, all of which were produced at a temperature above the phase boundary temperature.
C-31,560 -16-~ ~ lJ~ 7 L~
TABLE I
EXAMPLE EXA~LE EXAML--~E EXAMPLE
Percent Acry1ic Acid +0.25 6~5a 6 5a 6.5b 6.5b Melt Index g/10 min ~0.25 2.5 2.5 2.5 2.5 MWw/MWn (GPC)~ 7.9 10.2 10.2 9.01 Synthesis Pressure Abov2 Phase Bounda~y (psi~ 0-500 3500-4500 3500-4500 7500-8500 Blown Film Properties Gardner Clarity, % 10.9 47.1 72.1 69.4 Transmission 20 Film Gloss, % 22.5 45.1 110.5 126.6 Reflected Percent Haze, ~c 5.42 3.2 1.59 1.08 Scattered Gel Rating 4 0 0 0 Heat Seal Strength @ 310F, lb/in 3.0 4.9 Hot Tack Strength @ 300F g/in 150 200 - - - -a Blown Film Fabrication: 204C, 2.25 BUR, 1.5 mil thickness, NRM extruder b Blown Film Fabrication: 218C, 3.06 BUR, l.S mil thic~ness, N~M extruder * GPC refers to gel permeation chromatography for determining molecuIar wt. distri~ution.
C-31,~6~ -17-~ r ~ IJ3 ~ ~ 5 T ~ LE II
EXA*~LE EXAMPLE E~E-~-Percent Acrylic Acid +0.3 9.0 9.0 9.0 Melt Index g/lO min +0.25 3.0 3.0 3.0 MWw/~n (GPC) 6.6 8.5 9.5 Synthesis Pressure Above Phase Boundary (psi) 0-500 2000-3000 3500-'500 Blown Film Propertiesa Gardner Clarity, %
Transmission 13.3 24.1 48.1 20 Film Gloss, %
Reflected 32.4 41.6 70.5 45 Film Gloss, %
Reflected 65.1 62.2 81.9 Percent Haze, X
Scattered 4.2 3.5 1.91 Gel Rating 5 3 2 Heat Seal Strength @ 310F, lb/in 3.2 5.4 >6.0 Hot Tack Strength @ 300F g/in 150 205 250 a Blown Film Fabrication Conditions: 204~C, 2.25 BU~, 1.5 mils (thickness), NRM Extruder C-31, 5~G - 1~ -~ ~3~ S
T~BLE III
EXA~PLE EXAMPLE EXAMPLE
8 9 lO
Percent Acrylic Acid +0.25 9.0 9.0 9.0 Melt Index g/10 min +0.25 3.0 3.0 3.0 w/MWn (GPC) 6.5 9.5 8.9 Synthesis Pres~ure Above M~D Boundary (psi) (4500^3500)~ 0-500 2800-3800 Synthesis Pressure Above Phase Boundary (psi) 0-500 3500-4500 6800-7800 Blown Film PropertiesC
Gardner Clarity, % 12.1 26.1 36.5 Transmission 20 Film Gloss, ~ 14.6 13.3 28.0 Reflected 45 Film Gloss, % 52.1 48.3 61.8 Reflected Percent Haze 6.47 7.55 5.1 Gel Rating 5 3 1.5 c Glcucester Fabrication Conditions: 2-1/2" Extruder, 20~C melt temp., 2.75 BUR, 1.5 mil thick film, * Co~notes 4500-3500 psi below MWD boundary.
C-31,566 -lg-~ 7 T ~ LE IV
EX~hMPLE EXA~LE EYAMPI F. EXA~IPLE
11 12 _ 13 14 Percent Acrylic Acid +0.25 6.5 6.5 6.5 6.5 Melt Index g/10 min +0.25 5.5 5.5 5.5 5.5 MWw/~n (GPC) 7.1 10.1 13.7 l0.2 Synthesis Pr~ssure Above Phase Boundary (psi) 0-500 3500-45C0 5500-6500 7500-8500 Synthesis Pressure Above M~ Boundary (psi) (6500-5500)'-(2500-~5G0)*
~500 1500-2500 Extrusion Coating Propertiesd Neck-in @ 440 fpm (inches) - - 1.75 1.63 1.87 Nip Speed (fpm) 200 520 530 992 Draw-down Speed (fp~) 730 1075 1250 ~1500 Minimum Coating (mils) 2.2 0.85 0.83 0.44 Gel Rating 5 2 1 0 ~eal Seal Strength, @ 310F, lb/in width 2.3 2.2 >3.9 >4.0 Hot Tack Strength, @ 300F, g/in width 250 340 700 75 A1 Adhesion, lb/in width 0.80 0.75 1.22 - -d Black Clawson Extrusion Coater (3-1/2" extruder, 30/l L/D); melt temperature 550F, scre~ speed 85 RPM, air gap 6 inches * CGnnotes psi below the MWD boundary C-31,566 -20-.f T ~ LE V
EXAMPLE EX~ ~ LE
Percent Acr~,~lic Acid +0.3 9.0 5.0 Melt Index g/10 min +0.25 12.0 12.0 MWw/~n (GPC) 6.5 9.2 Syn;hesis Pressure Above Phase Boundary (psi) 0-500 3500-4500 Synthesis Pressure below MWD Boundary (psi) (4500-3500)~~ ~500 Extrusion Coating Propertiesd Nip Speed (fpm) 875 1275 ~raw-dow~ Speed (fpm) 1300 >1500 Minimum Coating ~mils)O.'tO 0.35 Sealing Properties Heat Seal Strength @ 260F, lblin 4.5 >4.1 Hot Tack Strength @ 300F, g/in 350 8S0 d Black Clawson Extrusion Coater (3-l/2" extruder, 30/l L/D); melt temperature 550F, screw speed 85 RPM, air gap 6 inches * connotes psi below MWD boundary C-31,~6~ -21-
Claims (93)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing homogeneous, random inter-polymers comprising about 99% to about 65% by weight of ethylene monomer and about 1% to about 35% by weight of at least one olefinically-unsaturated comonomer selected from the group com-prising unsaturated carboxylic acids, alkyl acrylates, alkyl methacrylates and vinyl esters, said process comprising inter-polymerizing the monomers in a substantially constant environment, under steady state conditions, in a single-phase reaction mixture, under the influence of a free-radical initiator, and in a well-stirred autoclave reactor operated in a continuous manner as the monomers are fed into the reactor and the reaction mixture is withdrawn, said process being characterized by the use of synthesis conditions of temperature and pres-sure which are elevated to a level high enough above the phase boundary between two-phase and single-phase operation such that the molecular weight distribution (MWD) boundary is approached, reached, or surpassed, the said molecular weight distribution boundary being the highest ratio of weight average molecular weight/number average molecular weight obtainable in single-phase operation, said elevated pressure being greater than 2000 psi above, and said elevated temperature being greater than 15°C
above, the synthesis conditions required at the phase boundary for a given mixture of ethylene and comonomer, thereby producing an interpolymer having less gels, microgels and/or grain.
above, the synthesis conditions required at the phase boundary for a given mixture of ethylene and comonomer, thereby producing an interpolymer having less gels, microgels and/or grain.
2. A process for producing homogeneous, random, inter-polymers of ethylene and lesser amounts by weight of olefinically-unsaturated organic monomers in a substantially constant environ-ment, under substantially steady state conditions, in a single-phase reaction mixture, under the influence of a free-radical initiator, and in a well-stirred reactor operated in a continuous manner as monomers are fed into the reactor and reaction mixture is withdrawn, said process being characterized by the use of synthesis conditions of temperature and pres-sure which are elevated to a level high enough above the phase boundary between two-phase and single-phase operation such that the molecular weight distribution boundary is approached, reached or surpassed, the said molecular weight distribution boundary being the highest ratio of weight average molecular weight/number average molecular weight obtainable in single-phase operation.
3. A process for producing homogeneous, random inter-polymers comprising about 99% to about 65% by weight of ethylene monomer and about 1% to about 35% by weight of at least one olefinically-unsaturated comonomer selected from the group com-prising unsaturated carboxylic acids, alkyl acrylates, alkyl meth-acrylates and vinyl esters, said process comprising interpoly-merizing the monomers in a substantially constant environment, under steady state conditions, in a single-phase reaction mixture, under the influence of a free-radical initiator, and in a well-stirred autoclave reactor operated in a continuous manner as the monomers are fed into the reactor and the reaction mixture is withdrawn, said process being characterized by the use of synthesis conditions of temperature and pres-sure which are elevated to a level high enough above the phase boundary between two-phase and single-phase operation such that the molecular weight distribution (MWD) boundary is reached, or surpassed, the said molecular weight distribution boundary being the highest ratio of weight average molecular weight/number average molecular weight obtainable in single-phase operation, said elevated pressure being greater than 2000 psi above, and said elevated temperature being greater than 15°C above, the synthesis conditions required at the phase boundary for a given mixture of ethylene and comonomer, thereby producing an interpolymer having less gels, microgels and/or grain.
4. The process of Claim 3 wherein the olefinically-unsaturated comonomer comprises acrylic acid or methacrylic acid.
5. The process of Claim 3 wherein the olefinically-unsaturated comonomer is acrylic acid.
6. The process of Claim 3 wherein the olefinically-unsaturated comonomer is methacrylic acid.
7. The process of Claim 3 wherein the so-produced interpolymers comprise from about 99% to about 88% by weight of ethylene units in the polymer chain, the remaining percentage comprising acrylic acid units.
8. The process of Claim 3 wherein the so-produced inter-polymers comprise from about 99% to about 88% by weight of ethylene units in the polymer chain.
9. The process of Claim 3 wherein the synthesis conditions comprise an elevated temperature which is in the range of about 150°C to about 350°C and an elevated pressure which is in the range of about 18,000 to about 50,000 psi, wherein said pressure is at least about 2000 psi above, and said temperature is at least 15°C above, the minimum amount needed to produce a single-phase reaction mixture and wherein the elevated temperature and elevated pressure are sufficient to sub-stantially exceed the temperature and pressure at which the mole-cular weight distribution boundary of the so-produced interpolymer is reached.
10. A process for producing substantially homogeneous, random interpolymers comprising about 99% to about 65% by weight of ethylene monomer with about 1% to about 35% by weight of at least one copolymerizable olefinically-unsaturated comonomer se-lected from the group comprising an unsaturated carboxylic acid, alkyl acrylates, alkyl methacrylates and vinyl esters, said pro-cess comprising interpolymerizing the monomers in a well-stirred autoclave reactor operated in a continuous manner at steady state conditions using a free-radical polymerization initiator under substantially constant conditions of temperature, pressure, and flow rates, wherein the conditions of temperature and pressure re-quired to produce operation at the phase boundary are exceeded, respectively, by using a temperature of at least 15°C above that at the phase boundary and a pressure of more than 2000 psi above that at the phase boundary, whereby the molecular weight distribution (MWD) boundary is reached or surpassed, thereby producing an interpolymer having less gels, microgels and/or grain.
11. The process of Claim 10 wherein the copolymerizable olefinically-unsaturated comonomer is an unsaturated carboxylic acid.
12. The process of Claim 10 wherein the copolymerizable olefinically-unsaturated comonomer is acrylic acid or methacrylic acid.
13. The process of Claim 10 wherein the copolymerizable olefinically-unsaturated comonomer is acrylic acid.
14. The process of Claim 10 wherein the interpolymer com-prises at least about 88% by weight of ethylene groups.
15. A random, homogeneous, single-phase interpolymer product comprising about 65% to about 99% by weight of ethylene monomer, the remaining percentage comprising at least one olefinically-unsaturated comonomer selected from the group comprising unsatu-rated carboxylic acids, alkyl acrylates, alkyl methacrylates and vinyl esters, said interpolymer being further characterized as having a weight average molecular weight/number average molecular weight ratio as defined by the formula where MWw is the weight average molecular weight;
MWn is the number average molecular weight;
C1 is the intercept of the wt. fraction comonomer versus plot for a given comonomer, where is the ratio of weight average molecular weight to number average molecular weight at the MWD boundary for a given comonomer;
C2 is the slope of the wt. fraction comonomer versus plot for a given comonomer;
C4 is a numerical value in the range of about 1.0 to about 0.1, representing conditions at, and beyond, the MWD
boundary with C4 being equal to unity at the MWD boundary;
said interpolymer being further characterized as having a ratio of weight percent adjacent comonomer unit to total weight percent comonomer in the polymer of less than 0.44 and as having less gels, microgels and/or grain.
MWn is the number average molecular weight;
C1 is the intercept of the wt. fraction comonomer versus plot for a given comonomer, where is the ratio of weight average molecular weight to number average molecular weight at the MWD boundary for a given comonomer;
C2 is the slope of the wt. fraction comonomer versus plot for a given comonomer;
C4 is a numerical value in the range of about 1.0 to about 0.1, representing conditions at, and beyond, the MWD
boundary with C4 being equal to unity at the MWD boundary;
said interpolymer being further characterized as having a ratio of weight percent adjacent comonomer unit to total weight percent comonomer in the polymer of less than 0.44 and as having less gels, microgels and/or grain.
16. The interpolymer of Claim 15 wherein the ethylene mo-nomer comprises about 88% to about 99% by weight of the polymer.
17. The interpolymer of Claim 15 wherein the ethylene mo-nomer comprises about 88% to about 99% by weight of the polymer and the comonomer comprises acrylic acid.
18. The interpolymer of Claim 15 wherein the comonomer is an olefinically-unsaturated carboxylic acid.
19. The interpolymer of Claim 15 wherein the comonomer is acrylic acid.
20. The interpolymer of Claim 15 wherein the comonomer is methacrylic acid.
21. The process of Claim 3 wherein the comonomer is an alkyl acrylate.
22. The process of Claim 3 wherein the comonomer is an alkyl methacrylate.
23. The process of Claim 3 wherein the comonomer is a vinyl ester.
24. The product of Claim 15 wherein the comonomer is an alkyl acrylate.
25. The product of Claim 15 wherein the comonomer is an alkyl methacrylate.
26. The product of Claim 15 wherein the comonomer is a vinyl ester.
27. A process for producing homogeneous, random inter-polymers comprising about 99% to about 65% by weight of ethylene monomer and about 1% to about 35% by weight of acrylic acid comonomer, said process comprising interpolymerizing the monomers in a substantially constant environment, under steady state con-ditions, in a single-phase reaction mixture, under the influence of a free-radical initiator, and in a well-stirred autoclave reactor operated in a continuous manner as the monomers are fed into the reactor and the reaction mixture is withdrawn, said pro-cess being characterized by the use of synthesis conditions of temperature and pressure which are elevated to a level high enough above the phase boundary between two-phase and single-phase operation such that the molecular weight distribution (MWD) boundary is reached, or surpassed, the said molecular weight distribution boundary being the highest ratio of weight average molecular weight/number average molecular weight obtainable in single-phase operation, said elevated pressure being greater than 2000 psi above, and said elevated temperature being greater than 15°C above, the synthesis conditions required at the phase boundary for a given mixture of ethylene and comonomer, thereby producing an interpolymer having less gels, microgels and/or grain.
28. The process of Claim 27 wherein the so-produced inter-polymers comprise from about 99% to about 88% by weight of ethylene units in the polymer chain.
29. The process of Claim 27 wherein the synthesis conditions comprise an elevated temperature which is in the range of about 150°C to about 350°C and an elevated pressure which is in the range of about 18.000 to about 50,000 psi, wherein said pressure is at least about 2000 psi above, and said temperature is at least 15°C above, the minimum amount needed to produce a single-phase reaction mixture and wherein elevated temperature and elevated pressure are sufficient to substantially exceed the temperature and pressure at which the molecular weight distribution boundary of the so-produced interpolymer is reached.
30. A process for producing substantially homogeneous, random interpolymers comprising about 99% to about 65% by weight of ethylene monomer with about 1% to about 35% by weight of acrylic acid comonomer, said process comprising interpolymerizing the monomers in a well-stirred autoclave reactor operated in a continuous manner at steady state conditions using a free-radical polymerization initiator under substantially constant conditions of temperature, pressure, and flow rates, wherein the conditions of temperature and pressure re-quired to produce operation at the phase boundary are exceeded, respectively, by using a temperature of at least 15°C above that at the phase boundary and a pressure of more than 2000 psi above that at the phase boundary, whereby the molecular weight distribution (MWD) boundary is reached or surpassed, thereby producing an interpolymer having less gels, microgels and/or grain.
31. The process of Claim 30 wherein the interpolymer com-prises at least about 88% by weight of ethylene groups.
32. A random, homogeneous, single-phase interpolymer product comprising about 65% to about 99% by weight of ethylene monomer, the remaining percentage comprising acrylic acid comonomer, said interpolymer being further characterized as having a weight average molecular weight/number average molecular weight ratio as defined by the formula where MWw is the weight average molecular weight;
MWn is the number average molecular weight;
C1 is the intercept of the wt. fraction comonomer versus plot for a given comonomer, where is the ratio of weight average molecular weight to number average molecular weight at the MWD boundary for the comonomer;
C2 is the slope of the wt. fraction comonomer versus plot for the comonomer, and C4 is a numerical value in the range of about 1.0 to about 0.1, representing conditions at, and beyond, the MWD
boundary, with C4 being equal to unity at the MWD boundary, said interpolymer being further characterized as having a ratio of weight percent adjacent comonomer unit to total weight percent comonomer in the polymer of less than 0.44, and as having less gels, microgels and/or grain.
MWn is the number average molecular weight;
C1 is the intercept of the wt. fraction comonomer versus plot for a given comonomer, where is the ratio of weight average molecular weight to number average molecular weight at the MWD boundary for the comonomer;
C2 is the slope of the wt. fraction comonomer versus plot for the comonomer, and C4 is a numerical value in the range of about 1.0 to about 0.1, representing conditions at, and beyond, the MWD
boundary, with C4 being equal to unity at the MWD boundary, said interpolymer being further characterized as having a ratio of weight percent adjacent comonomer unit to total weight percent comonomer in the polymer of less than 0.44, and as having less gels, microgels and/or grain.
33. The interpolymer of Claim 32 wherein the ethylene mo-nomer comprises about 88% to about 99% by weight of the polymer.
34. A process for producing homogeneous, random inter-polymers comprising about 99% to about 65% by weight of ethylene monomer and about 1% to about 35% by weight of methacrylic acid comonomer, said process comprising interpolymerizing the monomers in a substantially constant environment, under steady state con-ditions, in a single-phase reaction mixture, under the influence of a free-radical initiator, and in a well-stirred autoclave reactor operated in a continuous manner as the monomers are fed into the reactor and the reaction mixture is withdrawn, said pro-cess being characterized by the use of synthesis conditions of temperature and pres-sure which are elevated to a level high enough above the phase boundary between two-phase and single-phase operation such that the molecular weight distribution (MWD) boundary is reached, or surpassed, the said molecular weight distribution boundary being the highest ratio of weight average molecular weight/number average molecular weight obtainable in single-phase operation, said elevated pressure being greater that 2000 psi above, and said elevated temperature being greater than 15°C above, the synthesis conditions required at the phase boundary for a given mixture of ethylene and comonomer thereby producing an interpolymer having less gels, microgels and/or grain.
35. The process of Claim 34 wherein the so-produced inter-polymers comprise from about 99% to about 88% by weight of ethylene units in the polymer chain.
36. The process of Claim 34 wherein the synthesis conditions comprise an elevated temperature which is in the range of about 150°C to about 350°C and an elevated pressure which is in the range of about 18,000 to about 50,000 psi, wherein said pressure is at least about 2000 psi above, and said temperature is at least 15°C above, the minimum amount needed to produce a single-phase reaction mixture and wherein elevated temperature and elevated pressure are sufficient to substantially exceed the temperature and pressure at which the molecular weight distribution boundary of the so-produced interpolymer is reached.
37. A process for producing substantially homogeneous, random interpolymers comprising about 99% to about 65% by weight of ethylene monomer with about 1% to about 35% by weight of methacrylic acid comonomer, said process comprising inter-polymerizing the monomers in a well-stirred autoclave reactor operated in a continuous manner at steady state conditions using a free-radical polymerization initiator under substantially constant conditions of temperature, pressure, and flow rates, wherein the conditions of temperature and pressure re-quired to produce operation at the phase boundary are exceeded, respectively, by using a temperature of at least 15°C above that at the phase boundary and a pressure of more than 2000 psi above that at the phase boundary, whereby the molecular weight distribution (MWD) boundary is reached or surpassed, thereby producing an interpolymer having less gels, microgels and/or grain.
38. The process of Claim 37 wherein the interpolymer com-prises at least about 88% by weight of ethylene groups.
39. A random, homogeneous, single-phase interpolymer product comprising about 65% to about 99% by weight of ethylene monomer, the remaining percentage comprising methacrylic acid comonomer, said interpolymer being further characterized as having a weight average molecular weight/number average molecular weight ratio as defined by the formula where MWW is the weight average molecular weight;
MWn is the number average molecular weight;
C1 is the intercept of the wt. fraction comonomer versus plot for a given comonomer, where is the ratio of weight average molecular weight to number average molecular weight at the MWD boundary for the comonomer;
C2 is the slope of the wt. fraction comonomer versus plot for the given comonomer; and C4 is a numerical value in the range of about 1.0 to about 0.1, representing conditions at, and beyond, the MWD
boundary, with C4 being equal to unity at the MWD boundary;
said interpolymer being further characterized as having a ratio of weight percent adjacent comonomer unit to total weight percent comonomer in the polymer of less than 0.44, and as having less gels, microgels and/or grain.
MWn is the number average molecular weight;
C1 is the intercept of the wt. fraction comonomer versus plot for a given comonomer, where is the ratio of weight average molecular weight to number average molecular weight at the MWD boundary for the comonomer;
C2 is the slope of the wt. fraction comonomer versus plot for the given comonomer; and C4 is a numerical value in the range of about 1.0 to about 0.1, representing conditions at, and beyond, the MWD
boundary, with C4 being equal to unity at the MWD boundary;
said interpolymer being further characterized as having a ratio of weight percent adjacent comonomer unit to total weight percent comonomer in the polymer of less than 0.44, and as having less gels, microgels and/or grain.
40. The interpolymer of Claim 39 wherein the ethylene mo-nomer comprises about 88% to about 99% by weight of the polymer.
41. A random interpolymer having a molecular weight suf-ficient to form a melt extruded film, comprising at least 65% by weight of ethylene, the remaining percentage comprising at least one .alpha.,.beta. -olefinically-unsaturated organic comonomer, wherein the microgel level is such that the interpolymer has a Gel Rating of 3 or less than 3.
42. The interpolymer of Claim 41 wherein the comonomer is selected from the group consisting of unsaturated carboxylic acids, alkyl acrylates, alkyl methacrylates and vinyl esters.
43. The interpolymer of Claim 41 wherein the comonomer is selected from the group consisting of acrylic and methacrylic acid.
44. The interpolymer of Claim 41, 42 or 43 having a Gel Rating of less than 2.
45. The interpolymer of Claim 41, 42 or 43 having a Gel Rating of less than 1.
46. The interpolymer of Claim 41 wherein the ethylene mo-nomer comprises about 88% to about 99% by weight of the polymer.
47. The interpolymer of Claim 41 wherein the ethylene mo-nomer comprises about 88% to about 99% by weight of the polymer and the comonomer comprises acrylic acid.
48. The interpolymer of Claim 41 wherein the comonomer is acrylic acid.
49. The interpolymer of Claim 41 wherein the comonomer is methacrylic acid.
50. The interpolymer of Claim 41 wherein the comonomer is an alkyl acrylate.
51. The interpolymer of Claim 41 wherein the comonomer is an alkyl methacrylate.
52. The interpolymer of Claim 41 wherein the comonomer is a vinyl ester.
53. The interpolymer of Claim 46, 47 or 48 having a Gel Rating of less than 2.
54. The interpolymer of Claim 49, 50 or 51 having a Gel Rating of less than 2.
55. The interpolymer of Claim 52 having a Gel Rating of less than 2.
56. The interpolymer of Claim 46, 47 or 48 having a Gel Rating of less than 1.
57. The interpolymer of Claim 49, 50 or 51 having a Gel Rating of less than 1.
58. The interpolymer of Claim 52 having a Gel Rating of less than 1.
59. A melt extruded film comprising a random homogeneous, single-phase interpolymer of at least 65% by weight of ethylene and 35% by weight or less of at least one .alpha.,.beta.-olefinically-unsaturated organic monomer, wherein the microgel level is such that said interpolymer has a Gel Rating of 3 or less than 3.
60. A film according to Claim 59 wherein the comonomer is selected from the group consisting of unsaturated carboxylic acids, alkyl acrylates, alkyl methacrylates and vinyl esters.
61. A film according to Claim 59 wherein the comonomer is selected from the group consisting of acrylic and methacrylic acid.
62. A film according to Claim 59, 60 or 61 wherein the interpolymer has a Gel Rating of less than 2.
63. A film according to Claim 59, 60 or 61 wherein the interpolymer has a Gel Rating of less than 1.
64. A film according to Claim 59 wherein in said inter-polymer the ethylene monomer comprise about 88% to about 99% by weight of the polymer.
65. A film according to Claim 59 wherein in said inter-polymer the ethylene monomer comprises about 88% to about 99% by weight of the polymer and the comonomer comprises acrylic acid.
66. A film according to Claim 59 wherein in said inter-polymer the comonomer is acrylic acid.
67. A film according to Claim 59 wherein in said inter-polymer the comonomer is methacrylic acid.
68. A film according to Claim 59 wherein in said inter-polymer the comonomer is an alkyl acrylate.
69. A film according to Claim 59 wherein in said inter-polymer the comonomer is an alkyl methacrylate.
70. A film according to claim 59 wherein in said inter-polymer the comonomer is a vinyl ester.
71. A film according to claim 64, 65 or 66 having a Gel Rating of less than 2.
72. A film according to claim 67, 68 or 69 having a Gel Rating of less than 2.
73. A film according to claim 70 having a Gel Rating of less than 2.
74. A film according to claim 64, 65 or 66 having a Gel Rating of less than 1.
75. A film according to claim 67, 68 or 69 having a Gel Rating of less than 1.
76. A film according to claim 70 having a Gel Rating of less than 1.
77. A film according to claim 59 wherein the film is a melt extruded coating.
78. A process for producing homogeneous, random inter-polymers of ethylene and lesser amounts by weight of olefinically-unsaturated organic monomers in a substantially constant environ-ment, under substantially steady state conditions, in a single-phase reaction mixture, under the influence of a free-radical initiator, and in a well stirred reactor operated in a continuous manner as monomers are fed into the reactor and reaction mixture is withdrawn, said process being characterized by the use of synthesis conditions of temperature and pres-sure which are elevated to a level high enough above the phase boundary between two-phase and single-phase operation such that the molecular weight distribution boundary is approached, but without the molecular weight distribution boundary being reached, or surpassed, the said molecular weight distribution boundary being the highest ratio of weight average molecular weight/number average molecular weight obtainable in single-phase operation.
79. The process of claim 78 wherein the olefinically-unsaturated organic monomers comprise at least one of acrylic acid, methacrylic acid, alkyl acrylates, alkyl methacrylates, and vinyl esters.
80. The process of claim 78 wherein the olefinically-unsaturated organic monomer comprises acrylic acid or methacrylic acid.
81. The process of claim 78 wherein the olefinically-unsaturated organic monomer is acrylic acid.
82. The process of Claim 78 wherein the olefinically-unsaturated organic monomer is methacrylic acid.
83. The process of Claim 78 wherein the so-produced inter-polymers comprise from about 99% to about 65% by weight of ethy-lene units in the polymer chain.
84. The process of Claim 78 wherein the so-produced inter-polymers comprise from about 99% to about 88% by weight of ethy-lene units in the polymer chain.
85. A process for producing substantially homogeneous, random interpolymers of ethylene with a lesser amount by weight of at least one copolymerizable olefinically-unsaturated comonomer, said process being performed in a well-stirred autoclave reactor operated in continuous manner at steady state conditions using a free-radical polymerization initiator under substantially constant conditions of temperature, pressure, and flow rates, wherein the conditions of temperature and pressure re-quired to produce operation at the phase boundary are exceeded, respectively, by using a temperature above that at the phase boundary and a pressure in a range of more than 500 up to 2,000 psi above that at the phase boundary.
86. The process of Claim 85 wherein the copolymerizable olefinically-unsaturated comonomer is an unsaturated carboxylic acid.
87. The process of Claim 85 wherein the copolymerizable olefinically-unsaturated comonomer is acrylic acid or methacrylic acid.
88. The process of Claim 85 wherein the copolymerizable olefinically-unsaturated comonomer is acrylic acid.
89. The process of Claim 85 wherein the interpolymer com-prises at least about 65% by weight of ethylene groups.
90. A random, homogeneous, single-phase interpolymer product comprising at least about 65% by weight of ethylene, the remaining percentage comprising at least one olefinically-unsaturated organic comonomer, said interpolymer being further characterized as having a weight average molecular weight/number average molecular weight ratio as defined by the formula where MWW is the weight average molecular weight;
MWn is the number average molecular weight;
C1 is the intercept of the wt. fraction comonomer versus plot for a given comonomer, where is the ratio of weight average molecular weight to number average molecular weight at the MWD boundary for a given comonomer;
C2 is the slope of the wt. fraction comonomer versus plot for a given comonomer;
C3 is a numerical value in the range of about 0.75 to less than 1.0, and where C3 is employed at process conditions which produce products between the single-phase non-random range and the MWD boundary.
MWn is the number average molecular weight;
C1 is the intercept of the wt. fraction comonomer versus plot for a given comonomer, where is the ratio of weight average molecular weight to number average molecular weight at the MWD boundary for a given comonomer;
C2 is the slope of the wt. fraction comonomer versus plot for a given comonomer;
C3 is a numerical value in the range of about 0.75 to less than 1.0, and where C3 is employed at process conditions which produce products between the single-phase non-random range and the MWD boundary.
91. The interpolymer of Claim 90 wherein the comonomer is an olefinically-unsaturated carboxylic acid.
92. The interpolymer of Claim 90 wherein the comonomer is acrylic acid.
93. The interpolymer of Claim 90 wherein the comonomer is methacrylic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US504,032 | 1983-06-13 | ||
| US06/504,032 US4599392A (en) | 1983-06-13 | 1983-06-13 | Interpolymers of ethylene and unsaturated carboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1273745A true CA1273745A (en) | 1990-09-04 |
Family
ID=24004586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000456439A Expired - Fee Related CA1273745A (en) | 1983-06-13 | 1984-06-13 | Interpolymers of ethylene and unsaturated carboxylic acids |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4599392A (en) |
| EP (2) | EP0146620B2 (en) |
| JP (4) | JPS60501563A (en) |
| AU (1) | AU557828B2 (en) |
| CA (1) | CA1273745A (en) |
| DE (2) | DE3486025T3 (en) |
| WO (1) | WO1984004926A1 (en) |
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Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4351931A (en) * | 1961-06-26 | 1982-09-28 | E. I. Du Pont De Nemours And Company | Polyethylene copolymers |
| US3520861A (en) * | 1968-12-26 | 1970-07-21 | Dow Chemical Co | Copolymers of ethylene |
| US3988509A (en) * | 1971-05-14 | 1976-10-26 | E. I. Du Pont De Nemours And Company | Reduced melt index, low gel content ethylene copolymers and process for preparation thereof |
| CA998789A (en) * | 1971-05-14 | 1976-10-19 | E.I. Du Pont De Nemours And Company | Low gel content ethylene polymer/wax blends and process for preparation thereof |
| JPS5221329B2 (en) * | 1971-08-18 | 1977-06-09 | ||
| JPS50127987A (en) * | 1974-03-29 | 1975-10-08 | ||
| DE2524274B2 (en) * | 1975-05-31 | 1980-03-13 | Basf Ag, 6700 Ludwigshafen | Process for the production of copolymers of ethylene |
| DE2617411B2 (en) * | 1976-04-21 | 1980-07-17 | Basf Ag, 6700 Ludwigshafen | Process for the production of copolymerization of ethylene |
| US4248990A (en) * | 1979-04-05 | 1981-02-03 | E. I. Du Pont De Nemours & Company | Nonrandom copolymers of ethylene and unsaturated acid |
| US4252924A (en) * | 1979-04-05 | 1981-02-24 | E. I. Du Pont De Nemours And Company | Continuous process for the preparation of nonrandom ethylene/acid copolymer |
| US4599392A (en) * | 1983-06-13 | 1986-07-08 | The Dow Chemical Company | Interpolymers of ethylene and unsaturated carboxylic acids |
| JPH0315923A (en) * | 1989-06-13 | 1991-01-24 | Nec Corp | Graphic input device |
-
1983
- 1983-06-13 US US06/504,032 patent/US4599392A/en not_active Expired - Lifetime
-
1984
- 1984-06-12 EP EP84902562A patent/EP0146620B2/en not_active Expired - Lifetime
- 1984-06-12 DE DE3486025T patent/DE3486025T3/en not_active Expired - Lifetime
- 1984-06-12 JP JP59502507A patent/JPS60501563A/en active Granted
- 1984-06-12 DE DE198484902562T patent/DE146620T1/en active Pending
- 1984-06-12 WO PCT/US1984/000914 patent/WO1984004926A1/en active IP Right Grant
- 1984-06-12 AU AU30656/84A patent/AU557828B2/en not_active Expired
- 1984-06-12 EP EP19880120911 patent/EP0318058A3/en not_active Withdrawn
- 1984-06-13 CA CA000456439A patent/CA1273745A/en not_active Expired - Fee Related
-
1989
- 1989-04-18 JP JP1096563A patent/JPH0712636B2/en not_active Expired - Lifetime
-
1990
- 1990-03-22 JP JP2069877A patent/JPH0786129B2/en not_active Expired - Lifetime
-
1992
- 1992-07-28 JP JP4241126A patent/JPH08847B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3486025D1 (en) | 1993-02-11 |
| EP0146620B1 (en) | 1992-12-30 |
| AU557828B2 (en) | 1987-01-08 |
| JPH08847B2 (en) | 1996-01-10 |
| EP0318058A3 (en) | 1991-05-15 |
| EP0318058A2 (en) | 1989-05-31 |
| EP0146620B2 (en) | 2006-04-05 |
| JPH02103115A (en) | 1990-04-16 |
| EP0146620A1 (en) | 1985-07-03 |
| JPH03170510A (en) | 1991-07-24 |
| DE3486025T2 (en) | 1993-04-29 |
| JPS60501563A (en) | 1985-09-19 |
| JPH0315923B2 (en) | 1991-03-04 |
| WO1984004926A1 (en) | 1984-12-20 |
| DE3486025T3 (en) | 2007-04-12 |
| JPH05310846A (en) | 1993-11-22 |
| DE146620T1 (en) | 1988-05-19 |
| JPH0786129B2 (en) | 1995-09-20 |
| US4599392A (en) | 1986-07-08 |
| JPH0712636B2 (en) | 1995-02-15 |
| EP0146620A4 (en) | 1985-09-26 |
| AU3065684A (en) | 1985-01-04 |
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