JPS63502191A - Copolymer composition containing narrow width MWD component and method for producing the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] name of invention Copolymer composition containing narrow width MWD component and method for producing the same Background of the invention 1. Cross-reference of related inventions The present invention is part of U.S. Patent Application No. 881.951, filed December 14, 1984. Application No. 1140.562 filed on December 16, 1985, which is a continuation application No. 881.951 is a continuation application filed under U.S. Patent No. 4.540, In the partial continuation application of No. 753 (hereinafter referred to as COZEνITH et al.) All of these disclosures are interrelated.

2. Field of invention The present invention relates to new copolymer products and new methods of making such products.

More particularly, the invention relates to two copolymers, in particular ethylene propylene copolymers ( EPM) or terpolymer (EPDM), relatively narrow molecular weight distribution (IVD) and a relatively wide Ml/D; Concerning a method for producing a mixture. The present invention further provides lubricating oil compositions and elastomer Concerning the use of such mixtures in agents.

For convenience, terms used repeatedly throughout this specification are defined as follows.

a, CD-to-CD refers to the compositional change between polymer chains with respect to ethylene content. child is the total copolymer sample obtained by removing equal weight fractions from both ends of the distribution. a certain copolymer sample required to give a certain weight percent of the The minimum deviation in terms of weight percent ethylene from the average ethylene composition (standard (similar to standard deviation). Deviations do not have to be symmetrical. For example, 1 5% CD - When displayed as only one number, it indicates the magnitude of the positive or negative deviation. Show how to listen. For example, suppose the standard deviation is 10% for a Gaussian composition. Then, 95.5% of the polymer will be in an average of 20% ethylene by weight. 95. The CD-to-CD of 5% by weight polymer is 20% by weight ethylene in such samples.

b, Within CD- is the composition change of the copolymer sample with respect to ethylene. it is , between two parts of a mono-copolymer chain, each part consisting of at least 5% by weight of the chain. It is expressed as the minimum difference in weight percent ethylene present in .

C0 molecular weight distribution (MWD) is a measurement of the molecular weight range within a given copolymer sample. It is fixed. It is the ratio of weight average molecular weight to number average molecular weight (My/Mn) and and the ratio of Z average molecular weight to weight average molecular weight (Hz/My). Characterized by: (Ni is the number of molecules in weight old) d, viscosity index (V, 1.) is the minimum viscosity decrease, and the temperature can be increased. This is the ability of lubricating oil. The larger this ability is, the more V,1. becomes higher.

Ethylene-propylene copolymers, especially elastomers, are important commercial products.

Ethylene-propylene copolymers are commercially available in two basic types. ethylene - Propylene copolymer (EPM) can be used with free radical generators such as organic peroxides. It is a saturated compound that requires vulcanization. Ethylene-propylene terpolymer (E PDM) contains a dihydric acid that provides sufficient unsaturation to enable vulcanization with sulfur. Lopentagene, 1,4-hexadiene, or ethylidene norbornene, etc. Contains small amounts of non-military diolefins. At least two monomers, e.g. For example, such polymers containing EPM and EPD) are collectively referred to as copolymers.

EPM and EPDM have outstanding weathering resistance, good heat aging properties, and high It has the ability to mix with fillers and plasticizers, making it suitable for automotive and industrial machinery. This makes it a low-cost compound that is particularly useful for mechanical applications. Typical automotive applications are , tire side walls, internal tubes, radiator and heater hoses, vacuum tubes, plows. Improved viscosity index (V, 1.) of gaps, sponge door seals, and lubricant compositions It is a drug. Typical uses for mechanical products include industrial and horticultural equipment. Hoses, molded and extruded sponge parts, gaskets and seals, and conveyors -Belt cover. These copolymers are used in adhesives, appliance parts, hoses and Also found for use in gaskets, wire and cable insulation, and plastic mixtures. I can put it out.

The effectiveness of peroxide vulcanization is composition dependent. Kozewith et al., column 2, 31- As pointed out in line 40, the "chemical" crosslinks per peroxide molecule are: increases as ethylene levels rise, and ethylene content also increases rheological properties. Crystallinity, which affects quality and processability and is present at very high ethylene contents, It may impede workability.

As described in more detail in column 2, lines 40-49 of Kozewith et al. The milling action of EPM or EPDM copolymers fundamentally changes with MWD; In addition, the dependence of viscosity on shear rate is one of the characteristics that is affected by changes in MWD. Ru.

Motor oil avoids significant friction losses, facilitates cold starts, and allows the engine to start automatically. In order to provide proper oil circulation, it should not be too viscous at low temperatures. On the other hand 1 ．． To avoid excessive engine wear and excessive oil consumption, do not overly dilute at operating temperature. Don't even worry about it. Use lubricants whose viscosity changes least with changes in temperature. is the most desirable.

A lubricating oil's ability to increase temperature with minimal viscosity reduction is determined by its viscosity index (V , 1. ). The larger this ability is, the more V,1. becomes higher.

EPDM or EPM polymer, or more generally, has a desired viscosity and Helps impart temperature properties to compositions, including lubricating oils. EPM or EPDM copolymer coalescence, i.e., more generally, ethylene-(C3-Cl8) alpha ole fin copolymer, 1. The composition of the lubricating oil used as a lubricant is well known. Ru. These additives are used to minimize viscosity changes that occur with temperature changes. It is used to modify lubricating oils to make them more effective. Moisturizers containing such polymer additives Lubricating oil inherently maintains its viscosity at high temperatures while at the same time reducing engine starting temperatures. Maintain the desired low viscosity flow rate at a low temperature.

Two important properties of these additives (as is well known, are not the only essential properties): ) are related to low temperature performance and shear stability. Low temperature performance is very low The shear stability is related to maintaining low viscosity at It is related to the collapse resistance of small mirrors.

As can be seen from the above, based on their respective characteristics, EPM and EPDM are It can be found in many different uses.

The properties of such copolymers that make them useful for certain special uses are, in turn, their It is known that it is determined by composition and structure. For example, EPM or EP The basic properties of DM copolymers are composition, composition distribution, sequence distribution, molecular weight, and molecular weight fraction. It is determined by factors such as cloth()lW[).

It is well known that the range of Ml/D is characterized by the ratio of various molecular weight averages. Ru. One such average is the ratio of weight average molecular weight to number average molecular weight (k/Tln ). The other one is heterogeneous within the molecule, uniform between molecules, and less than 2 1l Characterized as at least one of lv/Mn and less than 1,8 ΦHz/My Ethylene, which has a narrow MWD that is The copolymer with one other alpha olefin monomer is effective in lubricating oil odor. It has improved properties. Such copolymers are disclosed in U.S. Pat. No. 4, Kozewith et al. No. 540.753 and is related to the present invention. For convenience, Such a polymer is hereinafter referred to as a narrow MWD copolymer. M greater than or equal to 2 y/Mn, or at least one of power/My greater than or equal to 1.8 The MVD copolymer having the following properties is hereinafter referred to as a broad MVD copolymer. .

Generally, a combination of ethylene and at least one other alpha-olefin monomer The vulcanization rate and physical properties of the polymer improve as the MVD becomes narrower. Narrow width MV D polymers have better vulcanization and tensile properties than such polymers with wider MVD. It has excellent strength characteristics. However, the physical properties obtained by having a narrow MVD This advantage is offset by the much poorer processability of such materials. They can be extruded or When grinding or calendering is difficult, the properties fundamentally change with MWD. become Narrow width MWD copolymers crumble into pieces in a grinder, but wide width MWD copolymers The quality hardens under the conditions encountered in normal processing operations. used in processing equipment At shear rate, the viscosity of a wide MWD copolymer is the same as that of a narrow MWD copolymer of the same weight average molecular weight. substantially lower than that of D copolymer.

U.S. patent for Wenner (νE)INER) disclosed in the Kozewith et al. patent No. 3,681.306 provides ethylene/high We are focusing on methods for producing alpha-olefin copolymers. Suitable manufactured The copolymer is an ethylene/propylene/non-conjugated terpolymer; Dienes have only one polymerizable double bond. In a preferred method, one tubular tube reactor, then one pot reactor is used, but one tubular reactor is used for different reactors. It is also disclosed that the two stages can also be simulated by operating in response conditions. No. As is clear from column 2, lines 14-20, the disclosed method and number average molecular weight (My/Mn), as measured by the ratio of Produces a polymer with a wider MWD than that of the polymer. First (pipeline) reaction As disclosed in column 5, lines 54-57, the intermediate polymer produced from the vessel is about 1 in 2 llv/)in ratio of the final polymer produced. fv/Mn is 2.4-5.

U.S. Pat. No. 3,380,978 to RYAN et al. Discloses a method for producing homopolymers and copolymers prepared from alpha olefins are doing. The patented method uses a short hold-up tubular reactor in the first stage. to produce a high molecular weight fraction with a broad molecular weight distribution, and then the resulting polymer and the remaining reaction mixture are sent directly to the second stage. At this stage, longer holds Forming narrow molecular weight distribution fractions using AP's constant environment autoclave reactor . It is noted that wider MVD polymers are produced in tubular reactors. moreover, No MWD or molecular weight values are given.

FINDLAY U.S. Patent No. 3,035,040 Those who manufacture olefin polymers and copolymers from monomers such as carbon and propylene. Discloses the law.

First, in the dilute phase of the steam-line flow reaction zone, at least a portion of the monomer is dissolved in the presence of a catalyst. Polymerizes with parts. The partially polymerized mixture is further polymerized in the stirring zone to substantially The polymerization reaction is completed. The first reaction zone may be an extension tube. The second reaction zone is A stirred tank type reaction zone, preferably a series of stirred reactors. unreacted olef Stir the polymer product and remove the zone effluent while recirculating the resin and diluent into the tube zone. It can be recovered from MvD or molecule between polymers produced in two reactors No difference in quantity is disclosed.

GRO3, U.S. Pat. No. 3,884,993, uses a separate reactor to By producing a molecular weight fraction and a high molecular weight fraction in parallel and mixing the products. Discloses a method for manufacturing EPM and EPD rubber consisting of EPM and EPD. What does this mean for MWD? Accordingly, it is an object of the present invention to provide new and improved polymer products and The purpose of the present invention is to provide a mixture of ethylene alpha olefin copolymers.

According to the invention: (a) My/Mn less than 2 and Mz/My less than 1.8 (1) at least a first copolymer having one; (b) a second copolymer having My/Mn greater than or equal to 2; An ethylene alpha olefin copolymer is provided.

Its composition will vary depending on the anticipated use of the product. Can include coalescence.

Therefore, more weight percent of the first copolymer and less weight percent The composition may alternatively be formed from a second copolymer of Formed by a weight percent of a second copolymer and a lesser weight percent of a first copolymer You may do so.

The first copolymer is preferably formed of monomers having from 3 to 18 carbon atoms. tyrene alpha olefin copolymers, most preferably such alpha olefin copolymers. The olefin monomer has 3 to 6 carbon atoms. Further, the first copolymer is preferably a first copolymer. 1 copolymer, 95% of the copolymer chains are less than 15% by weight, preferably less than 13%, most preferably less than 13% by weight. Preferably, the ethylene composition differs from its average frffi percent ethylene composition by no more than 10%. It seems to have a tyrene composition.

Further, in the composition of the present invention, preferably 95% of the copolymer chains of the first copolymer are , differs from its average weight percent ethylene composition by no more than 15 weight percent. tyrene composition, and at least essentially each copolymer chain of the first copolymer two parts, each part being at least about 5 percent by weight of the chain; contains at least about 5 weight percent ethylene in the composition, preferably at least about 10 weight percent (-cent ethylene, most preferably at least about 20 weight percent ethylene) Only chiren is different from each other.

The first copolymer is an ethylene alpha olefin copolymer. According to the present invention Preferably, the first copolymer is an ethylene propylene copolymer or an ethylene acetate copolymer. most preferably, the first copolymer is an ethyl olefin terpolymer. It is a lene propylene terpolymer.

Ethylene propylene terpolymer is ethylidene norbornene, 4-hexane Diene, dicyclopentadiene, bi, nylnorbornene, and methylene norbo a non-conjugated die most preferably selected from the group consisting of lunene, and mixtures thereof; It may consist of

Alternatively, the first copolymer may consist of a termonomer having a functional group.

In this case, the functional groups are hydroxy, carbonyl, amino, pyridyl, amido, i and mixtures thereof.

In yet another method, the first copolymer is an olefinic chlorosilane, an olefinic hydrocarbon halides, and mixtures thereof. May consist of nomer.

The first and second copolymers are copolymers of essentially the same monomers of the type described above. is preferable.

In accordance with the present invention, the compositions of the present invention are effective for improving the viscosity index of lubricating oils and lubricating oil compositions. It can be used in lubricating oil compositions consisting of amounts of copolymer compositions. The copolymer composition is , is preferably present in an amount of 0.1 to 5 weight percent of the total lubricating oil composition.

In an auxiliary method, the composition of the present invention can be prepared in such a way that the lubricating oil concentrate is 5 to 50% by weight of the lubricating oil. can be added to the concentrate to consist of a copolymer composition of

Furthermore, the compositions of the present invention provide improved processability along with good vulcanizability. the Therefore, the composition can be advantageously vulcanized.

Moreover, the present invention provides for less of Mv/Mn of less than 2 and MzlHv of less than 1.8. a first copolymer having both one and Mv/1lln greater than or equal to 2; an ethylene alpha olefin comprising forming a mixture of a second copolymer having A method of making a fin copolymer composition is contemplated.

The first copolymer is preferably prepared in a carefully controlled manner carried out in a tubular or batch reactor. Must be formed under controlled conditions. Conversely, a continuous flow stirring tank It cannot be carried out unless it is impossible to form the first copolymer in the reactor. stomach.

Therefore, in one embodiment of the invention, all copolymer chain members of the first copolymer are generation of essentially one catalytic species in a manner and under conditions sufficient to cause both reactions to occur simultaneously. From an essentially transfer agent-free reaction mixture consisting of a catalyst to The method is carried out by forming the first copolymer in a reactor.

The first copolymer is prepared using a catalyst with a lifetime longer than the residence time in the tubular reactor. It may also be formed in a non-mixing reactor. In such cases, some of the chains growing in the first reactor are It is then reacted with additional monomer and optionally a chain transfer agent in a stirred tank reactor to produce a second Experience the copolymer.

In yet another embodiment, a continuous flow stirred tank reactor operated in parallel with the tubular reactor. In a reactor, the second copolymer is separately formed and then the first and second copolymers are mixed.

Alternatively, the first copolymer may be formed in a tubular reactor operating in parallel with the tubular reactor forming the first copolymer. After separately forming the two copolymers, the first and second copolymers are mixed. This embodiment In this case, the second copolymer is heated in a tubular reactor, but the second copolymer has a relatively wide section. Formed under conditions that give a molecular weight distribution.

In yet another embodiment, a relatively broad) IVD to form the second copolymer is Under the conditions given, the catalyst and optionally additional monomers are The second copolymer may also be formed by injection in one direction.

or at least one direction along the tubular reactor to form the second copolymer. the second by injecting the transfer agent and optionally additional catalyst and monomer in the Copolymers may also be formed.

Chain transfer agents according to the invention include oxygen, diethylzinc, diethylaluminum chloride, and and mixtures thereof.

According to yet another method of forming the first and second copolymers in a tubular reactor, first ゛, forming a tubular reactor from the reaction mixture using the catalyst employed to form the second copolymer. A second copolymer is formed in a reactor. Next, the employed to form the first copolymer the catalyst from at least one direction along the tubular reactor along with the additional monomer of Renlu; inject. Then, the unreacted monomer is reacted with optionally added monomer. A first copolymer is formed.

In yet another possible embodiment, the second copolymer has a longer onset time than the first copolymer. is started in a tubular reactor while the first copolymer is forming. this In embodiments, the tubular reactor is only unmixed for the first copolymer; , the second copolymer is formed in a tubular reactor over a period of time, or the second copolymer is formed in a tubular reactor. A part of the first copolymer obtained is transferred from the reactor outlet to a tubular reactor in which a second copolymer is formed. It may also be formed in a tubular reactor by recirculating it to some point along the .

The two copolymers were catalyzed by a catalyst with a lifetime shorter than the residence time in the tubular reactor. In a mediated reaction, the first copolymer is formed in a tubular reactor and a catalyst reactivator and and optionally additional monomers downstream of the inlet of the tubular reactor to form a second copolymer. It may also be formed continuously in a tubular reactor.

According to yet another embodiment, the second copolymer is provided at a point where the downstream polymerization conditions are along the tubular reactor, which acts to form a second copolymer with a wide MWD. formed by further charging the reaction mixture at at least one point .

As previously pointed out, the first copolymer operates under conditions that provide the desired narrow MWD. It may also be formed in a batch reactor.

Therefore, the first copolymer is responsible for the growth of all copolymer chains of the first copolymer. transfer agent-free reaction consisting essentially of one catalytic species in a manner and under conditions sufficient to It can be formed from a reaction mixture in an unmixed batch reactor.

The first copolymer may be formed in an unmixed batch reactor. Then, the first copolymer is mixed with a wide MWD copolymer formed in a continuous flow stirred tank reactor.

Alternatively, the second copolymer is produced in a separate batch from the batch reactor forming the first copolymer. The first and second copolymers may be formed separately in a reactor and then mixed.

In another possible embodiment, the second copolymer has a longer starting time than the first copolymer. The process is started in a batch reactor while forming the first copolymer.

In this embodiment, the batch reactor is only unmixed for the first copolymer; The second copolymer is released during a period of time, at least during a period where reactor conditions are not immiscible. will be started.

According to yet another embodiment, the second copolymer is mixed with the first copolymer in a batch reactor. the selected catalyst to form the second copolymer during a period that partially overlaps with the initiation of reaction from the reaction mixture.

In yet another method, a portion of the first copolymer, regardless of how it is formed, e.g. , cross-linking by nodulating a part of the chain by cross-linking with a conjugate of the polymer chain. combine to form a second copolymer. Nodulation is a U.S. patent application filed on December 26, 1985. National patent application No. H1,950 and its partial continuation patent application, patent attorney case reference number P5067. Another method is to build the reactor in random conditions. Periodically change the feed rate or catalyst concentration to drive the formation of the second copolymer. and then operating at constant feed and catalyst conditions to form a first copolymer. to form a broad MWD copolymer in a no-mixing tubular reactor. Then the first and Mix the second copolymer.

In a most preferred embodiment, the copolymer composition of the first and second copolymers is as follows: Can be formed into: ■, catalyst, ethylene, and at least one other alpha From the first anti-core temperature compound consisting of olefin monomers'! Forms #1 copolymer, This includes: a) at least one unmixed reactor; b) essentially one active catalyst species; and C) using at least one reaction mixture essentially free of transfer agent; d) a method and method sufficient to initiate essentially all of the copolymer chain growth simultaneously; comprising carrying out the polymerization of a first copolymer under conditions, wherein the first copolymer chain is and (1) reacting the second reaction mixture, which is dispersed in the first reaction mixture; forming a second copolymer having ¥4v/)rn greater than or equal to 2; A copolymer composition is prepared by mixing IJI41 and a second copolymer.

As mentioned above, a preferred method of forming the first copolymer is carried out in a tubular or batch reactor. However, the various alternatives described above can be used.

The present invention also provides a composition comprising a vulcanized ethylene alpha olefin copolymer, To them a) At least one of My/Mn less than 2 and Mz/My less than 1.8 a first copolymer having a My/14n of greater than or equal to 2; and a second copolymer having a My/14n of greater than or equal to 2. forming a mixture with a coalesce; and b) vulcanizing such a mixture; Also contemplated is a method of making a vulcanized ethylene alpha olefin composition comprising:

In a more preferred method, the invention comprises: 1. Catalyst, ethylene, and at least one other alpha olefin monomer forming a first copolymer from a first anti-core temperature polymer comprising a) at least is also one non-mixing reactor, b) with essentially one active catalyst species C) using at least one reaction mixture essentially free of transfer agent; d) a method and method sufficient to initiate growth of essentially all copolymer chains simultaneously; the first copolymer chain under conditions of dispersed within the first anti-core temperature compound; ■ reacting the second reaction mixture to have iv/)tn greater than or equal to 2; A second copolymer is produced, and the first and second copolymers are further mixed to form a copolymer assembly. form the formation of ■ Vulcanized copolymer of the first and second copolymers by vulcanizing the copolymer composition Intended as a method of manufacturing the composition.

The composition of the present invention contains two or more of either or both of the first and second copolymers. But that's fine. Similarly, two or more of one or both of the first and second copolymers may also be It can be manufactured by the method described in

DESCRIPTION OF THE PREFERRED EMBODIMENTS Since the present invention is considered to be most preferable in relation to EPM and EPDM copolymers, , BP)! and/or will be explained in detail in relation to EPDM.゛ Narrow width MvD copolymers according to the present invention can be used in tubular applications under carefully controlled conditions. Alternatively, it is suitable to produce in a batch reactor.

As pointed out in Kozewith et al., column 7, lines 4-36, the tubular reactor is When the monomer is supplied only at the pipe inlet, ethylene is preferentially polymerized. the As a result, as shown in the diagram below, the ethylene concentration gradually decreases and the propylene concentration increases. A copolymer silver having a high degree of strength is obtained.

The resulting chain is intramolecularly heterogeneous.

As shown in column 7, lines 37-48, narrow Uniformity when using more than two monomers in the production of wide and broad MvD copolymers As mentioned above, the characteristics related to intramolecular composition dispersion are called intra-CD, Characteristics related to intermolecular composition dispersion are called 1D intermolecular properties.

Preferred copolymers of the narrow MvD copolymers of the present invention include ethylene and at least one copolymer. of other alpha olefins. Such alpha olefins contain carbon If there are numbers 3 to 18, such as propylene, butene-11 pentene-1, etc. Conceivable. Considering the economic aspect, alpha olefins having 3 to 6 carbon atoms are preferred. It is. The most preferred narrow width MVD copolymers are ethylene and propylene. or ethylene, propylene and diene.

As is well known in the industry, ethylene and high alpha olefins such as propylene Copolymers of often contain polymerizable monomers. These other monomers Representative examples include non-conjugated dienes such as the following non-limiting examples: a, L, 4-hexane; diene, linear acyclic diene such as 1,6-octadiene, b, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,8-octa diene, 3,7-dimethyl-1,7-octadiene, and dihydromircene and branched acyclic dienes, such as mixed isomers of dihydroonemen, c, 1,4-cyclohexadiene, l, 5-cyclododecadiene, and l , monocyclic alicyclic dienes such as 5-cyclododecadiene, d, tetrahydroindene, methyltetrahydroindene, dicyclopentadi Polycyclic alicyclic solvents such as diene, bicyclo-(2,2,l)-hebuta-2,5-diene, etc. Fused and bridged ring diene, 5-methylene-2-norbornene (MN13) 5-e Thylidene-2-norbornene (END) 5-(4-cyclopentenyl)-2- alkenyl such as norbornene, 5-cyclohexylidene-2-norpornel; alkylidene, cyclopentenyl, and cycloalkylidene norbornene.

Among dienes, dienes having at least one double bond in the deformed ring are preferred. Yes. The most preferred diene is 5-ethylidene-2-norbornene (ENB). Ru. The amount of diene (by weight) in the copolymer is about θ% to 20%, preferably 0%. ~15%. The most preferred range is θ% to lO%.

As already shown, the most suitable narrow width HνD copolymer dipolymer is ethylene. ethylene-propylene, or ethylene-propylene-diene. In either case , the average ethylene content of the copolymer is only about 10% by weight.

A preferred minimum value is about 25%. A more preferred minimum value is about 30%. maximum ethi The len content can be as high as about 90% in heavy ffi bases. The preferred maximum value is about 85%, with the most Preferably it is about 80%.

The molecular weight of narrow MWD copolymers can vary widely. The weight average molecular weight is It is thought to be around 2,000 sh.

A preferred minimum value is approximately 10.000. The most preferred minimum value is approximately 20,000. Ru. The maximum weight average molecular weight may be as high as about 12,000,000. suitable The maximum value is approximately 1.000.000.

The most preferred maximum value is approximately 750.000.

The molecular weight distribution (MVD) of the narrow MVD copolymer has a My/Mn ratio of less than 2 and a ．． characterized by at least one of the following: 1ltz/)4v ratio of less than 8 very narrow. When related to EPM and EPDM, The copolymer has better physical properties. Especially applicable to oil additives When the My/Mn of the preferred copolymer is less than about 1°6 and less than about 1.4 is most preferable. A preferred Mz/My is less than about 1.5 and less than about 1.3. Most preferred.

The narrow MVD copolymer □ comprises a catalyst, ethylene and at least one additional alpha - produced by polymerization of a reaction mixture consisting of olefin monomers. solution polymerization It is preferable to do so.

In carrying out such solution polymerization, it is necessary to prepare an existing reaction mixture for the purpose. Any known solvent can be used. For example, suitable solvents include alicyclic hydrocarbon solvents such as formula, cycloaliphatic and aromatic hydrocarbon solvents, or such It is a halogenated solvent. Suitable solvents include C12 or less linear or branched Branched saturated hydrocarbons, C5-C9 saturated alicyclic or aromatic hydrocarbons, or 0 It is a 2-C6 halogenated hydrocarbon.

Most preferred are straight or branched chain hydrocarbons of 01□ or less, especially hexane. solvent Non-limiting illustrative examples of are butane, pentane, hexane, heptane, cyclopenkune , cyclohexane, cyclohebutane, methylcyclobencune, methylcyclohexane San, isooctane, benzene, toluene, xylene, chloroform, chlorobenzene dichloroethane, tetrachloroethylene, dichloroethane, and trichloroethane. Ru.

The composition of the narrow and wide MvD copolymers of the present invention is determined not only along the length of the chain. Can be changed between chains.

As noted, it is preferred to minimize the amount of silver content change measured from CD to CD.

CD- is more fully explained in column 7, lines 49-64 of Kozewith et al. This part of the patent is It is determined by methods using solvent composition, as described in more detail.

Between the CDs of the copolymer, 95% by weight of the copolymer chains are copolymer average weight percent. Such a material has an ethylene composition that differs by 15% by weight or less from the ethylene composition. It is something. A preferred CD-distance is about 13% or less, most preferably about 10% or less. .

Also, within the CD of the narrow MWD copolymer, each portion contains at least 5 weight percent In an individual intramolecular unconstrained chain of chains, at least two parts of the chain are at least as close in composition to each other. Preferably, the two also differ by 5 weight percent ethylene. C In D-, at least two portions of the copolymer chains are at least 10 weight percent ethyethyl. Only Len can be different. At least 40ffi amount par Not only centethylene but also differences of at least 20 weight percent are in accordance with the present invention. considered to be a thing.

For the narrow MvD copolymer, the CD-inside is determined by first determining the CD-space as described above. After that, the polymer chain is decomposed into two halves along its contour, and the CD-distance of both halves is then determined. established by experimental methods. The difference between the two results is shown in column 8 of Kozewith et al. , line 33 to column 9, line 31, as fully shown in the example, It depends.

Determination of polymer fractions that are intramolecularly heterogeneous in polymer mixtures combined from several sources In order to determine the Must. These two parts are subsequently destroyed and which are uneven It is fractionated to find out.

The characteristics of the required fragments and the required fractionation method are cosewied.

The ethylene content of narrow MVD copolymers is given in column 1O of Kozewith et al., lines 39-54. ASTM tests and proton and carbon It can be measured by element-13 nuclear magnetic resonance.

Molecular weight and molecular weight distribution can be measured by chromatographic methods. , the numerical analysis is according to Kozewith et al. 10g, line 55 to line 11 & I 8. Performed by computer as detailed.

The polymerization method for producing narrow width MWD copolymers must be carried out as follows. do not have: a. the catalyst system produces essentially one active catalyst species; The b0 reactive core contains essentially no chain transfer agent, and the C1 polymer chains are essentially free. in batch reactors and simultaneously in tubular reactors. starts at the same point along the length of the tube.

Narrow MWD copolymers can be produced in unmixed reactor systems; The mechanism is substantially similar between parts of the reaction mixture containing polymer chains initiated at different times. No mixing occurs. As disclosed in Kozewith et al. In this method, all polymer chains are initiated at the reactor inlet and chain movement is substantially controlled down the tube. Essentially one active catalyst species selecting polymerization conditions that do not occur along the length A tubular reactor is used that has a catalytic mechanism that provides .

A single continuous flow stirred tank reactor (CFST) as disclosed in Kozewith et al. R) is a narrow MVD copolymerization process to mix polymer chains initiated at different times. Not suitable for body manufacturing. However, if all of the catalyst supplied to the first reactor is used Three or more stirred tanks in series have shown a performance almost similar to that of a tubular reactor. is well known. Therefore, such a continuous tank is considered according to the invention. considered to belong to the term "tubular" as used herein.

Another suitable reactor is a batch reactor, preferably equipped with sufficient agitation; A catalyst, a solvent, and a monomer are added thereto at the start of polymerization. , then the reactants The feed remains to polymerize for a sufficient time to produce the desired product. There is. For economic reasons, tubular reactors are preferable to batch reactors for carrying out the process of the invention. is preferable.

Also, the temperature of the narrow MvD reaction mixture must be kept within certain limits. anti The temperature at the reactor inlet is adjusted to ensure complete and rapid chain initiation at the beginning of the polymerization reaction. must be high enough to The time it takes for the reaction mixture to set at high temperatures is undesirable. It must be short enough to minimize the amount of chain transfer and catalyst deactivation reactions.

Narrow-width MVD reaction mixtures, as described in detail by the patents of Kozewis et al. Temperature control is achieved by using pre-cooled feed and operating the reactor adiabatic. maintained. Alternatives to pre-cooling the feed are detailed in the Kozewith et al. patent. Heat exchangers such as those described can be used. Continuous batch reactor or or multiple stirring at about -50°C to 150°C. The exit temperature of the reaction mixture is approximately 200 It is expected to be ℃. A preferred maximum outlet temperature is about 70°C. Most suitable maximum value is approximately 50°C.

Narrow Width) Best Copolymer at the Reactor Outlet Suitable for the Process for Preparing IvD Copolymers Narrow constraints such as concentration, reaction mixture flow rate, and reaction mixture residence time in non-mixed reactors The reaction parameters for the method for producing the copolymer (width Ml) are as described by Huzewith et al. It is described in more detail in the 17th column, line 51 to the 18th column, line 23.

Briefly describing these parameters, the most suitable maximum at the reactor outlet is The polymer concentration is L5 weight 8 to 0 weight diluent, the preferred minimum is 2 weight to 0 weight The most preferred minimum value is at least 3% diluent by weight. Retention The preferred minimum value for the time is approximately 10 seconds, the most preferred minimum value is approximately 15 seconds, and the maximum value is about 3.600 seconds, but the preferred maximum value is about 1800 seconds, and the most preferred maximum value is is approximately 900 seconds. The flow rate is low enough to allow good mixing of the reactants in the radial direction and It must be high enough to minimize mixing.

Additional solvent and reactants can be added along the length of a tubular reactor or in a batch reactor. may be added during the polymerization.

In the process of making narrow MWD copolymers, the polymer chains are all initiated at the same time. is required. In addition to the disclosed reactor architecture, other devices may benefit from the present disclosure. You can also use things. Furthermore, two or more reactors can be used in parallel or in multiple ways to produce monomers. It can also be used continuously while supplying

Therefore, the method for producing a narrow MvD copolymer according to the present invention is as follows: (a) in at least one unmixed reactor; (b) producing essentially one active catalyst species; Using a catalyst system that (C) at least one reaction mixture essentially free of transfer agent; (d) methods and conditions sufficient to cause growth of essentially all chains to occur simultaneously; And it will be done.

Any of the method means disclosed in the Kozewith et al. patent is also disclosed therein. Narrow MvD copolymers were prepared using the reaction composition, parameters, additives, and equipment that were It can be used for manufacturing. The l1lv/Mn value of this copolymer is 2.0 Less than 1.2 to 1.5 sh.

As detailed in column 13, line 64 to column 14, line 25, , the catalyst used in the process for producing narrow HvD copolymers is preferably present in the reaction mixture. It must be such that it yields qualitatively one active catalyst species. Kozewith et al. Forming only narrow MVD polymers, as discussed in more detail in this part of If desired, as much as 35% by weight of the total copolymer is produced, but preferably 35% of the copolymer is produced. Additional active catalyst species may be present to produce less than 10 wt. Therefore , when forming only narrow MvD polymers, the one active species is the total polymer produced. It must provide at least 65% of the polymer, or preferably at least 90%. stomach.

Methods for measuring the activity of catalytic species and for characterizing catalytic species are given in column 14 of Kozewith et al. , discussed in lines 14-25.

The catalyst system used in carrying out the method for producing narrow width MVD copolymers is The typical catalyst is (a) Transition metals, i.e. periodic table 1-B, m-B, IVB, VB, VIB, ■B, and compounds of group ■ metals, and (b), periodic table 1-A, I Organometallic compounds of Group I-A, II-B and III-A metals.

Preferred catalyst systems for carrying out the process according to the invention have a vanadium valence of Comprising 3 to 5 hydrocarbon-soluble vanadium compounds and organoaluminium compounds. However, the catalytic system produces essentially one active catalytic species as described above. To be. At least one of the selected vanadium compound/organoaluminum pair is , must also contain a valence bonded halogen.

The formula for vanadium compounds useful in carrying out the process according to the invention is as follows: It becomes like this: V l (, (llR)3□ (1) In the formula, x-0 to 3, R-hydrocarbon group; VCJ4゜ VO(AcAc)2 (in the formula, AcAc-acetylacetonate); V(AcA c)3; VOCJ (AcAc)3. , (2) (in the formula, x-1 or 2): VCJ3, nB and mixtures thereof, however, nm2-3, B-tetrahydride V such as lofuran, 2-methyl-tetrahydrofuran, and dimethylpyridine It is a Lewis base that can form hydrocarbon soluble complexes with CJ23.

In formula 1 above, R is preferably ethyl (Et)phenyl, isopropyl, butyl propyl, n-butyl, 1-butyl, hexyl, cyclohexyl, octyl , 01-am aliphatic, cycloaliphatic, or aromatic hydrocarbon radicals such as naphthyl represents. Non-limiting illustrative examples of compounds of formula (1) are VOCl3, VOCI! , 2 (OBi) (Bu-butyl), and VO (OC2H5) 3. These are vanadyl halides, alkoxy halides, and alkoxides. most A suitable vanadium compound is VCI;! 4, VOC (l a and vOCI2 2 (OR) Theal.

As mentioned above, the cocatalyst is preferably an organoaluminium compound. this The chemical formula of these compounds is as follows: Al2 R3, l (OR') R2, Al2 R2C1゜R2Aρ-0-A I R2, i l? ’　Reρ, AlR211Af12R3Cj23, AρRC ρ2, and mixtures thereof In the formula, R and R' are not related to the vanadium compound formula.

The preferred organic aluminum compound is Al2R3Cρ3, and the most preferred organic aluminum compound is Al2R3Cρ3. Et3C cocatalyst is ethylaluminum sesquichloride (EASC)-i2Et3C It is J2 a.

The catalyst system used for the production of narrow width MVD copolymers is VCI4 and Al2R. a C9x (preferably R is ethyl), the first of Kozewith et al. As further detailed in column 5, lines 37-54, the aluminum/vanadium The molar ratio should be at least 2, with a preferred minimum of about 4 and a maximum of about 25. A preferred maximum value is about 17, and a most preferred maximum value is about 15.

Chain transfer with aluminum alkyl or propylene occurs along the length of the reactor. It is possible to select the catalyst system and set the reactor temperature, as it rarely happens. Wear.

Essentially all chain growth must begin near the catalyst feed point. E.A. Catalytic systems containing SC can meet these requirements.

The catalyst composition was premixed as detailed in the Kozewith et al. patent. However, it is preferable to ripen it before introducing it into the reactor. The preferred minimum aging period is approximately It is 0.1 second. More preferably this period is about 0.5 seconds, most preferably about 1 second. Ru. The maximum aging period is about 200 seconds or more preferably about 100 seconds. most preferred Suitably, this period is about 50 seconds.

Premixing can be carried out at temperatures below 40°C. More preferably, the premix is 25 It is carried out at a temperature below 15°C, most preferably below 15°C.

There are no limitations to the known methods of making broad MVD copolymers. This method A variety of catalyst systems and polymerization conditions can be used to obtain polymers with quantities and molecular weights of It can be implemented as follows. The same unit disclosed in the preparation of narrow width MWI) copolymers Broad MVD copolymers can be made using polymers, solvents, and catalysts.

Reaction parameters may be varied to form broader MWDs of this copolymer. stomach. Such reaction parameters that can be varied include the temperature of the reactor body; Alternatively, the reactor inlet and the hydrogen gas as disclosed in the Kozewith et al. Chain transfer agents such as diethylzinc may be added to the process to broaden the MwD.

Extending the MWD by catalyst deactivation, as disclosed in the patent of Kozewith et al. Good too.

Furthermore, diethyl aluminum chloride (DBAC) is added to the reaction to widen M’[). You can also

Broad MVD copolymers can be prepared in tubular reactors or stirred tanks. stirring tank The reactor may be a continuous flow stirred tank reactor (CFSTR).

According to one novel method for producing the products of the present invention, narrow width MVD copolymers are produced. The first reactor operated at the conditions selected to It can be operated in parallel with a second reactor operated to produce the copolymer. Ru. The second tubular reactor may be separate from the first reactor or may be of the same It may be extended as long as it meets the conditions.

If the second reactor is a continuous flow stirred reactor, typical operating conditions include a temperature of 2O -7 (1°C residence time is 5 to SO min. The concentration of the exit polymer from this reactor is , 2 weight/lOO weight diluent to 20 weight/100 weight diluent. is preferable. Any of the previously disclosed catalyst systems forms a second polymer. It can be used in a second reactor for this purpose. Selection of catalyst composition for use in continuous flow stirred reactors It is well known in the art that this affects the MwD of the polymer produced. catalyst If selected appropriately, it is possible to produce a second polymer with a Tlv/'Mn of 2 to 100. can.

Lubricating oils according to the invention contain an effective amount of the polymer of the invention as a major amount of viscosity index improver. It consists of a basic raw material lubricating oil (lubricating oil) of lubricating viscosity containing a mixture of substances. In addition, polymer mixtures The compounds can also be combined into oil additive concentrate compositions.

The polymer mixture of the present invention can be used as a viscosity index improver or viscosity modifier for lubricating oils. It is used in amounts varying widely from o, ooi to 50/wt%. special oil or The most suitable proportions for a concentrate will depend on the nature of the oil or concentrate and its particular use. evening. The composition is preferably present in an amount of 0.1-5% of the total lubricating oil composition. lubricant concentrate When used in products, the composition is present in an amount of 5 to 50% of the total amount. Kozewith et al. Polymer mixtures are typically used in combination, as disclosed in column 20, lines 41-61. The lubricating oil has a viscosity of approximately 2 to 40 centistokes at 99°C (ASTM D-445 ), but contains hydrocarbon mineral oil and approximately 25% by weight of dibasic acids, monobasic acids, and polyglycerides. Synthesis of complex esters derived from liqueurs, dibasic acids and alcohols, etc. Lubricating oil basestocks consisting of lubricating oils may also be suitable.

Such lubricating oils and oil additive concentrate compositions contain the necessary components to provide their normal attendant functions. Such additives may contain amounts of conventional additives, such as those described by Kozewith et al. As disclosed in more detail in column 20, line 62 to column 22, line 8, Free dispersants, metal or excess based metal detergents, dihydrocarbyl dithiophosphates Zinc, anti-wear additives, antioxidants, flow reducers, rust inhibitors, fuel economy or wear antifriction additives, additional suitable conventional viscosity index improvers and viscosity modifiers, and There is a detergent.

Regarding the method for producing the narrow width Ml/D copolymer of the present invention, a catalyst system can be used. Combinations of vanadium and aluminum compounds or polymers containing high levels of dienes It is well known that scales undergo branching and gelation during polymerization. To prevent this from happening In addition, ammonia, tetrahydrofuran, pyridine, tributylamine, tetrahydrofuran A Lewis base, such as dorothiophene, is added to the polymerization system using methods well known in the art. can be added to the mixture.

The mixture of the narrow MWD copolymer and the wide MWD#ffi polymer was first subjected to an unmixed tubular reaction. It is formed by preparing a narrow MWD copolymer in a vessel. In this method, narrow Conditions are sufficient to cause simultaneous growth of all copolymer chains in the width MWD copolymer. The reaction mixture utilized and used has a lifetime longer than its residence time in the reactor. Consists of a catalyst that generates qualitatively one catalytic species. Then, this narrow MwD copolymerization reacted with additional monomers in a stirred tank reactor to form a broad MWD copolymer. Form.

The mixture can also be used in the tubular reactor used for the preparation of 4WD copolymers (narrow width) and flat After preparing the broad MWD copolymer in a second tubular reactor operated in It can also be manufactured by combining.

The mixture of the two copolymers is produced in a narrow width) tubular reactor used to prepare the IVD copolymer. It can be prepared with The broad MWD copolymer of the mixture may contain a catalyst or transfer agent, - Alternatively, additional reaction mixture can be injected in at least one direction along the tubular reactor. It can be formed by

When the narrow MWD copolymer consists of ethylene-propylene conjugate chains, the mixture The broad MVD copolymer composition of the conjugate allows cross-linking with a conjugating agent to knot some of the chains. Thus, the stranded strands can be prepared and then mixed with the narrow MvD strands.

Another method of mixture formation is through catalysts suitable for the preparation of broad MWD copolymers. This copolymer was first prepared in a tubular reactor using inducing a reaction to form a narrow MWD copolymer suitable for manufacturing.

If the broad and narrow compositions occur “at the same time,” the reactor will be at the narrow MWD catalyst composition. It is unmixed. The imitation of a wide Ml+”D composition has a period comparable to that of the chain. and may overlap in some respects with narrow MWD copolymer mimicry. substantially are the parts of the reaction mixture containing polymer chains that are initiated at different times by the MWD catalyst. No mixing occurs between them.

A non-mixing tubular reactor used for the preparation of narrow MwD copolymers. wide MW by recirculating a portion of the reactor outlet to a point along the reactor. D copolymers can be prepared.

Another method for preparing mixtures in a single unmixed tubular reactor is to prepare mixtures of narrow-width copolymers. During the preparation process the catalyst reactivator, and optionally additional monomers, are added to the reactor inlet stream. to form a broad MVD copolymer composition of the mixture.

A narrow MWD copolymer is a narrow MWD copolymer in which all copolymer chains in the narrow MVI copolymer have the same growth. can be prepared in an unmixed batch reactor using conditions sufficient to occur at times.

The mixture can also be prepared using a catalyst in a batch reactor and then the resulting narrow MWD copolymer Coalesces can also be formed by adding them to broad MvD polymers. Additionally, the mixture prepared a wider MWD copolymer in a batch reactor and then transferred it to the batch reactor. It can also be formed by mixing it with the first copolymer produced in a reactor.

Narrow and wide MWD copolymers essentially react with both catalysts to produce one catalyst species. and a second copolymerization mixture to produce a narrow MWD copolymer. formation simultaneously in a single batch reactor by introducing suitable catalysts for the formation of can do. .

The method of the present invention recovers an EPDM copolymer product from a mixture of effluents from a reactor. This is a detailed explanation.

Narrow width MW in a tubular reactor incorporating 318′ diameter tubes and operating with a residence time of 30 seconds. D Copolymer is produced. Hexane as solvent, vCρ4 as catalyst, cocatalyst Use M2Et2C (13). Hexane must be sieved with 4-person molecular sieves (unionized) before use. on carbide, Linde part, FA1116', Herrett) and silica gel (W , R. Brace Company, Davidson Chemical Department, PA-40020-4 Me. This process removes polar impurities that act as catalyst poisons. gaseous Ethylene and propylene are heated in a heat (270°C) Cub (Hersha) to remove oxygen. U Chemical Company, C019001/4' ball) and then to remove water. After molecular sieving treatment, non-conjugated diene and 5-ethylidene are extracted upstream of the reactor. - Combines with 2-norbornene (ENB) and hexane to provide sufficiently low temperatures.

Pass through a chiller to completely dissolve the monomer in hexane.

5.01. Dissolve 55.5 g of vanadium tetrachloride in purified n-hexane. Prepare a catalyst solution. The cocatalyst was 428 g of 5, (11, in purified hexane) ethylaluminum sesquichloride, consisting of M2Et2C(la.2 The two solutions are premixed at 10°C and aged for 8 seconds.

Typical feed rates and reaction conditions for the tubular reactor are shown in Table 1.

Table 1 Tube stirring Tank reactor supply temperature ('C) -10-10 Reactor outlet temperature ('C) 20 30 Counterreactor effluent Hexane (kg/hour) 60.3 1fi, 5 Ethylene (kg/hour) 0.6[ i 0.19 Propylene (kg/hour) 6.0 0.4ENB (kg/hour) 0.1 0.7, vanadium (ga/hour) 6.88 0.7 aluminum (g m1 hour) 51 2.4 Pre-catalyst mixing temperature ("C) 10 None Pre-catalyst mixing time (seconds) 8 Pre-mixing Total reactor residence time (min) 0.5 8 NH3 (grn1 hour) 10 H2 (gm/hr) 0 5X 10-2 These speeds are 145kg 7h’Qn -θO, (100 and Mn/Mn = L, S) Set it so that

The stirred tank contained VOCρ2(OEt)/DEAC catalyst with a residence time of 8 seconds. Operates at an isothermal temperature of 20°C, Mn is 80.000 and '\4v/Mn is equal to B and O. The polymer is produced at 0.33 kg/h. Polymer composition can be adjusted by adjusting the proportion of monomers. Set to desired level. Hydrogen is added to the reactor to adjust the molecular weight of the polymer.

Table 1 shows the feed rate and reaction conditions for the stirred tank reactor.

Mix the polymer solutions exiting the tube and stirred tank reactors and make the polymer by standard methods. to recover. The final product has Mn-Ei 2.800, My/Mn-2,57. do. Its physical properties are excellent and its workability is also good.

Example 2 In this example, a series of tubular reactors and A stirred tank reactor is operated to prepare a bimodal distribution.

Mixture of VCρ4 and EASC and DEAC (A!/V-8,5 and 3.5 respectively) A tubular reactor is operated under the same conditions as in Example 1 using the compound. Continuous flow stirring The tank was operated at 30°C and contained the effluent from the tube, additional ethylene and a small amount of molten liquid. The diene (ENB) dissolved in the medium is fed. Stirred tank, ethylene supply to reactor The feed rate is adjusted to give a polymerization rate of 0.41 kg/hr.

The tubular reactor has an actual measurement of Mn-83,000, My/\In-1,5, Hz/My A polymer having -1', 5 is produced. The final product is the polymer produced in the tank. For broad molecular weight MVD polymers. Low molecular weight composition is lacking in the mixture.

It has excellent physical properties and good workability.

Example 3 In this example, both MWD types are produced in tubular reactors. One reactor is a catalyst is operated without premixing to produce a broad MVD fraction.

The tubular reactor was operated under similar conditions as in Example 1, but in parallel with the second reactor. let A solvent and monomer cooled to -10°C are fed into the second reactor. VCJ2 4 and diethyl aluminum chloride are added in separate streams to the second reactor inlet. reaction The vessel is operated insulated with a residence time of 1 minute. The supply rate is 100. '000 Set to produce 0.33 kg/hour of polymer with iv/¥ln equal to 3. do. Polymer composition can be set to the desired level by adjusting the monomer proportions. Ru.

The polymer solution exiting the tube is mixed and the polymer is recovered using standard methods. The final product is Mn -64, OQQ, 'iv7\In = 2.0. Its physical properties are excellent It also has good workability.

The tubular reactor of Example 1 was used under the same conditions as Example 1, but with vOCI23 reacted. It is activated by adding it in a separate stream to the inlet of the reactor. This VOCj23 style has a wide MWD is added to produce a second polymer having After reaching steady state, the reaction effluent Demineralize, wash and remove the solvent. The obtained polymer has a multisensitivity-like MWD EPD It is M. Its physical properties are excellent and its workability is also good.

Example 5 In this example, to produce a multi-sensitivity distribution, the catalyst is injected downstream of the reactor inlet. Thus, a broad MWD copolymer component of the mixture is prepared.

VOCρ3/Et2MC flooding and additional By adding streams of ethylene, propylene and ethylidene norbornene to the reactor. The tubular reactor was otherwise operated in the same manner as in Example 1. The product opens at the reactor inlet. Narrow-width Ml/D mode and ■OCρ3/Et2 structure manufactured by CJ Contains a broad MVD polymer with several aspects.

Example 6 In this example, by appropriately adding a chain transfer agent, multiple embodiments of ethylene polymers were prepared. Prepare a pyrene ethylidene norbornenta polymer.

At a point corresponding to the 15 second residence time in the reactor, the model of ■Cρ4 flowing into the reactor inlet The procedure was carried out except that 1/4 of the amount of hydrogen gas was added to the reactor along with the additional monomer. The reactor is operated as in Example 1. The hydrogen is approximately Finish half 1. Start a new chain.

The product polymer of the reactor effluent has a narrow width M representing chains grown throughout the length of the reactor. It consists of a VD aspect and a broad HVD aspect consisting of chains formed as a result of hydrogenation. a Under such conditions, the wide MVD feature itself becomes a multiplex feature.

Example 7 In this example, catalyst injection at the reactor inlet to produce a wide width MVD polymer and narrow width Multimodal distribution is achieved by injection of a second catalyst downstream of the inlet to produce MWD polymers. Prepared in a tubular reactor. As a result of this method, the narrow width Mwo = is even worse than the MW bad mode. low (naru)

Tubular reactor replaces VCfi 4 with VOC flood 3) except without premixing the catalyst is operated at the feed rate of Example 1. This catalyst feed creates a wide MwD profile. 3 Additional supply corresponding to the total population supply in Example 1 at the location where the residence time is 0 seconds. Add. The reaction is allowed to proceed for an additional 30 seconds. The final product is wide and narrow) Consisting of a mixture of IVD polymers.

Example 8 In this example, a single vanadium component is used in conjunction with two aluminum alkyls, Narrow and wide MWD copolymers are produced.

VOCla is used in place of VCρ4 to form a premixed catalyst feed, and ■OCρ3 and except that an additional separate stream of Et2AICρ is entered into the reactor inlet without premixing. The tubular reactor is operated as in Example 1. Pre-mixed VOCj23/EI AeCf3i; L narrow width) IVD copolymer was produced, and VOCJ2a/Et2 AiICρ reacts in a reactor to form a catalyst to produce broad width) IWD copolymers. . The two copolymers were formed simultaneously in the reactor. In this example, a portion of the reactor effluent was The upstream port of the tubular reactor is recirculated to continue the growth of a portion of the chain, with a narrow width gw.

In addition to the embodiments, wide MWD embodiments are manufactured.

A portion of the effluent representing 20% of the total volume was transferred for 20% of the initial residence time, i.e. The tubular reactor was operated as in Example 1, except for recirculation downstream from the inlet to the 6 s point. let

Some of the polymer chains in the recycled stream continue to grow to high molecular weights and also undergo chain transfer reactions. Thus some low molecular weight polymers are also formed. Therefore, regarding the recirculation flow, The resulting polymer consists of both high and low molecular weight embodiments. Therefore, M.W. D is wide.

Example 1O In the present invention, catalyst reactivation is performed to gradually reactivate a part of the dead catalyst. Addition of a curing agent to form new chains that grow at different times, resulting in wide MV Form a D copolymer.

Except extending the residence time to 180 seconds to produce narrow width MVD copolymers. The tubular reactor is operated as in Example 1. Most of the active catalytic sites are at this time Finished at the end of the point. At points along the reactor corresponding to a residence time of 180 seconds, the buffer Initial feed by adding 1 mole of butyl perchlorocrotonate per mole of sodium Additional ethylene corresponding to 50% of the volume is also added. Let the reaction proceed for an additional 3 minutes to produce a wide MWD embodiment.

Example 11 In this example, ethylene equivalent to 50% of the amount added to the inlet was dissolved in hexane. except for further injections at points along the length corresponding to a dwell time of 30 seconds. The tubular reactor is operated as in Example 1. At this point, the concentration of unreacted propylene is is high and the temperature is 50 °C due to the conditions chosen for the adiabatic operation of the reactor. . The combination of temperature and propylene concentration results in a large amount of chain transfer and termination downstream of the inlet. occurs. Therefore, the additive polymer formed has a broad MWD. After total residence time 60 seconds The product obtained is a mixture of narrow and wide MVD copolymers.

Example 12 In this example, the feed to the tubular reactor was changed periodically to produce products with different molecular weights. Manufacture. The effluents are mixed to form a mixture of narrow and wide MWD copolymers. Manufacture.

Example 1 is modified as follows and the tubular reactor is operated in the same manner. Retains effluent Collect in the mixing tank at a time of 800 seconds. The tubular reactor was operated for 10 minutes with constant catalyst feed. at which point the catalyst feed was increased linearly to 0.2 of the initial ratio for 20 minutes. to lower the target. Then, the supply is suddenly returned to its original rate and the cycle repeats. one During periods of constant supply, a narrow width MvD feature is formed. The period of variable supply is the original narrow width Mv The worst case is to produce a molecular weight that gradually changes to about 5 times the value of 5. these products Upon mixing, narrow and wide versions of the product are obtained.

Although this invention discusses particular methods, materials, and embodiments, this invention discloses without being limited to the particulars specified, but extending to all matters within the scope of the claims. It is understood that

Proceedings October 7, 1986 2 Name of the invention Copolymer composition containing narrow width MWD component and method for producing the same 3 Person making correction Relationship to the incident: Patent applicant Name: Exxon Research and Engineering Company 4 agents Address: 1-11-28 Nagatacho, Chiyoda-ku, Tokyo, Showa, month, day 6 Target of correction Column for the representative of the patent applicant in the document pursuant to Article 184-5, Paragraph 1 of the Patent Act, Thailand Translation of the specification and claims, international search report

Claims (1)

[Claims] 1. (a) a first copolymer having at least one of Mw/Mn less than 2 and Mz/Mw less than 1.8; and (b) a first copolymer having a Mw/Mn greater than or equal to 2. An ethylene-alpha olefin copolymer composition comprising a second copolymer. 2. 2. The composition of claim 1, wherein the second copolymer has an Mz/Mw ratio greater than or equal to 1.8. 3. the first copolymer has a Mw/Mn of less than 2 and an Mz/Mw of less than 1.8 The composition according to claim 2. 4. A composition according to claim 1, comprising a greater weight percent of the first copolymer and a lesser weight percent of the second copolymer. 5. 2. The composition of claim 1, comprising a greater weight percent of the second copolymer and a lesser weight percent of the first copolymer. 6. The first copolymer is an ethylene polymer formed of a monomer having 3 to 18 carbon atoms. The composition according to claim 1, which is a Lupha olefin copolymer. 7. The first copolymer has an average weight percentage of 95% by weight of the copolymer chains of the first copolymer. 7. The composition of claim 6, wherein the composition has an ethylene composition that differs by no more than 15% by weight from the -cent ethylene composition. 8. 95 weight percent of the copolymer chains of the first copolymer are essentially each of the first copolymer has an ethylene composition that differs by no more than 15 weight percent from the chain ethylene composition, and each portion comprises at least about 5 weight percent of the chain. at least two portions of each copolymer chain are at least about 5 percent by weight in the composition. 7. Compositions according to claim 6, which differ from each other only in the amount of ethylene. 9. 2. The composition of claim 1, wherein the first copolymer is an ethylene-alpha olefin copolymer. 10. 10. The composition according to claim 9, wherein the first copolymer is an ethylene-propylene copolymer. 11. The first copolymer is an ethylene-alpha olefin terpolymer. The composition according to claim 9. 12. 12. The composition of claim 11, wherein the first copolymer is an ethylene-propylene terpolymer. 13. 13. The composition of claim 12, wherein the ethylene-propylene terpolymer further comprises a non-conjugated diene. 14. The non-conjugated diene is ethylidenenorbornene, 1,4-hexadiene, disilane, etc. 14. The composition of claim 13 selected from the group consisting of clopentadiene, vinylnorbornene, methylenenorbornene, and mixtures thereof. 15. 13. The composition according to claim 10, wherein the first copolymer comprises a functional group containing a termonomer. 16. 16. The composition of claim 15, wherein the functional group is selected from the group consisting of hydroxy, carboxy, amino, pyridino, amide, imide, and mixtures thereof. 17. Termonomer further converts into olefin chlorosilane and olefin hydrocarbon. containing a component selected from the group consisting of elementary halides, and mixtures thereof. The composition according to claim 10 or 12. 18. 2. The composition of claim 1, wherein the first and second copolymers are copolymers of essentially the same monomer. 19. A lubricating oil composition comprising a lubricating oil and an amount of the copolymer composition of claim 1 effective to improve the viscosity index of the lubricating oil composition. 20. 20. The lubricating oil composition of claim 19, wherein the copolymer composition is present in an amount of 1 to 5% by weight of the total lubricating oil composition. 21. A lubricating oil and 5 to 50% by weight of the copolymer composition according to claim 1. A lubricating oil composition concentrate consisting of: at least one of Mw/Mn less than 22.2 and Mz/Mw less than 1.8. forming a mixture of at least one first copolymer and at least one second copolymer having a Mw/Mn greater than or equal to 2; A method for producing an olefin copolymer composition. 23. from an essentially transfer agent-free reaction mixture consisting of a catalyst generating essentially one catalytic species in a mix-free tubular reactor; Methods and conditions sufficient to simultaneously initiate growth of all copolymer chains of coalescence. 23. The method of claim 22, comprising forming at least one first copolymer under conditions. 24. Forming at least one first copolymer in a mix-free tubular reactor using a catalyst with a lifetime longer than the residence time in the tubular reactor, and then further forming an additional polymer in a stirred tank reactor. claim 23, comprising reacting a portion of such at least one first copolymer with a copolymer and, optionally, a chain transfer agent to form a second copolymer. The method described in Section . 25. Separately forming at least one second copolymer and mixing such at least one first and second copolymer in a stirred tank reactor operating in parallel with the tubular reactor. 24. The method of claim 23, comprising: 26. a tube operating in parallel with the tubular reactor forming at least one first copolymer; 24. The method of claim 23, comprising separately forming a second copolymer in a reactor and mixing such at least one first and second copolymers. 27. Additionally, along the tubular reactor to form the at least one second copolymer, 24. The method of claim 23, comprising forming said at least one second copolymer by injecting a catalyst at at least one location. 28. Additionally, along the tubular reactor to form the at least one second copolymer, forming said at least one second copolymer by injecting a transfer agent, and optionally additional catalyst and monomer, in at least one position of said copolymer. The method described in Item 23 of the Scope of Claim. 29. forming at least one second copolymer from the reaction mixture in a tubular reactor using a catalyst employed to form the at least one second copolymer, leaving behind unreacted monomer; The catalyst employed to form at least one first copolymer is then The medium and optionally additional monomer are injected into such a tubular reactor, and the unreacted monomer and optionally added monomer are injected into such a tubular reactor. 23. The method of claim 22, comprising reacting the added monomers to form at least one first copolymer. 30. and simultaneously forming at least one second copolymer from the reaction mixture in a tubular reactor by catalyzing with a catalyst selected to form the at least one second copolymer. 24. The method of claim 23, comprising: 31. Furthermore, a portion of the at least one first copolymer formed in the tubular reactor is 24. The method of claim 23, comprising recycling from the reactor outlet to locations along the tubular reactor to form at least one second copolymer. 32. A reaction catalyzed by a catalyst having a lifetime shorter than the residence time in the tubular reactor, forming at least one first copolymer in the tubular reactor and containing a catalyst reactivator and a catalyst reactivator. and optionally additional monomers downstream of the inlet of the tubular reactor to form the at least one second copolymer. 33. Growth of all copolymer chains of at least one first copolymer from a transfer agent-free reaction mixture consisting of a catalyst generating essentially one catalyst species in a mix-free batch reactor. in a manner and under conditions sufficient to cause them to start at the same time. 23. The method of claim 22, comprising forming at least one first copolymer. 34. forming at least one first copolymer in a mix-free batch reactor; and then mixing at least one first copolymer and at least one second copolymer. 34. The method of claim 33, comprising: 35. forming said at least one second copolymer in a batch reactor operating separately from said batch reactor forming said at least one first copolymer; and A claim comprising mixing a first copolymer and a second copolymer. The method according to item 33. 36. The second copolymer has a longer onset time than the at least one first copolymer, and the method further comprises, after derivation of the first copolymer, at least one second copolymer. forming at least one second copolymer by inducing at least a portion of the copolymer; 34. The method of claim 33, comprising forming at least one second copolymer from the reaction mixture in a batch reactor with a catalyst selected to produce a second copolymer. 37. Additional reaction mixing is performed at at least one location along the tubular reactor such that the downstream polymerization conditions at at least one location are effective for the formation of at least one second copolymer. 24. The method of claim 23, comprising forming at least one second copolymer by injecting a copolymer. 38. at least one first copolymer comprises ethylene-propylene coupling agent chains, and the method includes nodulating some of the chains by crosslinking the coupling agent. 24. The method of claim 23, thus comprising forming at least one second copolymer. 39.1. catalyst, ethylene, and at least one other alpha olefin a) in at least one mix-free reactor; b) with essentially one active catalyst species; and c) using at least one reaction mixture that is essentially free of transfer agents; d) methods and conditions sufficient to cause growth of essentially all of the copolymer chains to occur simultaneously; in which the first copolymer chain is polymerized in a first reaction mixture. shall be dispersed within the object, and II. reacting the second reaction mixture to produce a second copolymer having a Mw/Mn greater than or equal to 2; and mixing the first and second copolymers to form a copolymer composition. producing a copolymer composition of a first and a second copolymer; Polymerization method to produce. 40. The first and/or second copolymer has a Mw/Mn of less than 2 and less than 1.8. 40. The method of claim 39, having at least one of Mz/Mw of: 41. Claim 39, wherein essentially one catalyst of step (b) comprises: a hydrocarbon soluble vanadium compound and an organoaluminum compound reacted to form essentially one active catalyst species. the method of. 42. 42. The method of claim 41, wherein the first reaction mixture consists of ethylene, propylene, and a nonconjugated diene, and the second reaction mixture consists of ethylene and at least one other alpha olefin. 43. The second reaction mixture consists of ethylene, propylene and a non-conjugated diene. Scope of Claim 42. The method according to item 42. 44. 44. A method according to any of claims 42 or 43, wherein the second reaction mixture comprises a chain transfer agent. 15. Chain transfer agents include hydrogen, diethylzinc, diethylaluminum chloride, and 45. The method of claim 44, wherein the method is selected from the group consisting of mixtures thereof. 46. 44. The method of any of claims 42 or 43, wherein the second reaction mixture further comprises a solvent and at least one catalyst. 47. At least one catalyst reacts with the reaction product of VOCl2(OEt) and AlEt2Cl. 47. The method of claim 46, wherein 48. After forming the first copolymer in a mix-free tubular reactor using a catalyst with a lifetime longer than the residence time in the tubular reactor, a portion of the first copolymer is transferred to a stirred tank. further reacting with the second reaction mixture in a tank reactor to form a second copolymer. 41. The method of claim 40, comprising: 49. Claim 40 comprising separately forming the second copolymer in a stirred tank reactor operating in parallel with the mix-free reactor and then mixing the first and second copolymers. Method described. 50. Claims comprising separately forming a second copolymer and mixing the first and second copolymers in a tubular reactor operating in parallel with the reactor forming the first copolymer. The method according to paragraph 40. 51. The reactor is a tubular reactor, and the method further includes forming a second copolymer. forming the second copolymer by injecting the catalyst and optionally additional monomer at at least one location along the tubular reactor to Method. 52. The reactor is a tubular reactor, and such a method can also accommodate a wider range of molecular weights. a second copolymerization process by injecting a transfer agent and optionally additional catalyst and monomer at at least one location along the tubular reactor to form a second copolymer of the fabric; 41. The method of claim 40, comprising forming a body. 53. the reactor is a tubular reactor, and the method comprises forming a second copolymer under conditions other than mix-free conditions, and comprising a catalyst employed to form the second copolymer; Leaving unreacted monomer from the second reactant mixture, then mix The catalyst employed to form the first copolymer under gas-free conditions, and optionally additional monomers, are injected into the tubular reactor, and the unreacted monomers and optionally added monomers are The method according to claim 40, which comprises reacting to form a first copolymer. Law. 54. The reactor is a tubular reactor and the second copolymer is longer at the start than the first copolymer. said reaction with a catalyst selected to form a second copolymer, at least partially overlapping, for a period of time that is longer than the initiation of the first copolymer. 41. The method of claim 40, comprising deriving the second copolymer from the second reaction mixture in a vessel. 55. The reactor is a tubular reactor, and the method further includes recycling a portion of the first copolymer formed in the tubular reactor to a point along the tubular reactor to form a second copolymer. 41. The method of claim 40, comprising: 56. Although the reactor is a tubular reactor and such a process forms the first copolymer leaving unreacted monomer in the reactor, the catalyst has a short lifetime due to its residence time in the reactor. 41. The method of claim 40, further comprising adding a catalyst reactivator and optionally an additional monomer downstream of the inlet to form a second copolymer. 57. 41. The method of claim 40, wherein the reactor is a batch reactor, and the method comprises forming the first copolymer from the first reaction mixture in the batch reactor. Law. 58. Claim 57 comprising forming a first copolymer in a mix-free batch reactor and then mixing the first copolymer with a second copolymer formed in a stirred tank reactor. The method described in. 59. forming a second copolymer separately and mixing the first and second copolymers in a batch reactor operating in parallel with the batch reactor forming the first copolymer. The method described in paragraph 57. 60. The second copolymer has a longer onset time than the first copolymer, and such a method further comprising inducing the second copolymer with a catalyst selected to form the second copolymer during a period that partially overlaps with the first copolymer. The method described in section. 61. The reactor is a tubular reactor, and the method includes at least one location along the tubular reactor where conditions downstream of the at least one location are effective for the formation of the second copolymer. forming a second copolymer by injecting an additional reaction mixture at 40. The method of claim 39, comprising: 62. The first copolymer comprises ethylene-propylene chains with a coupling agent, and the method forms a second copolymer by nodulating some of the chains by crosslinking the coupling agent. 54. The method of claim 53, comprising: 63. Cured ethylene-alpha olefin copolymer set according to claim 1 composition consisting of ingredients. 64. a) a first copolymer having at least one of Mw/Mn less than 2 and Mz/Mn less than 1.8 and a second copolymer having Mw/Mn greater than or equal to 2; b) curing the mixture; A method for producing a fur olefin copolymer composition. 65. I. catalyst, ethylene, and at least one other alpha olefin forming a first copolymer from a first reaction mixture of monomers, which is a) in at least one mix-free reactor, b) with essentially one active catalyst species, c) a) using at least one reaction mixture that is essentially free of transfer agents, and d) using methods and conditions sufficient to cause growth of essentially all of the copolymer chains to occur simultaneously. polymerization of a first copolymer, wherein the first copolymer chain is in a first reaction mixture. and II. reacting a second reaction mixture to have a Mw/Mn greater than or equal to 2; The first copolymer and the second copolymer are mixed to form a copolymer assembly. III. A method for producing a cured copolymer composition of first and second copolymers, comprising curing the copolymer composition. 66. The mix-free reactor is a tubular reactor, and the method includes forming a second copolymer in the tubular reactor by varying the monomer or catalyst concentration in the reaction mixture as a function of time; 40. The method of claim 39, comprising forming the first copolymer in a reactor.