KR20070118088A - Viscosity index improver for lubricant compositions - Google Patents

Abstract

A lubricant composition comprises a base oil and a viscosity modifier including an ethylene/alpha-olefm interpolymer. The ethylene/alpha-olefm interpolymer is a block copolymer having at least a hard block and at least a soft block. The soft block comprises a higher amount of comonomers than the hard block. The block copolymer has a number of unique characteristics disclosed here. Such block copolymers offer the possibility of improved low temperature performance and flexibility in formulating motor oil, gear lubricants and greases, etc.

Description

Viscosity Index Improver for Lubricant Compositions

The present invention relates to a lubricant composition comprising a viscosity index improver comprising an ethylene / α-olefin interpolymer and a base oil and a process for preparing the lubricant composition.

In developed countries, including the US and European countries, annual economic losses associated with friction and wear are estimated at about 2-7% of GDP. In 1999, a report by the US Department of Energy indicated that US $ 12 billion was saved annually by introducing various measures to reduce friction and wear in automobiles and transmission systems in the United States. One such means involves the application of lubricant compositions in automotive and industrial equipment.

Modern lubricant compositions are widely used in various fields such as automotive oils, transmission fluids, gear oils, power steering fluids, shock absorber fluids, brake fluids, hydraulic fluids, and greases. The lubricant composition can be used to (1) control friction between moving part surfaces, (2) reduce wear of moving parts, (3) reduce corrosion of moving part surfaces, especially metal surfaces, (4) mechanical impact braking of gears, and (5) It may have various functions such as forming a seal on the wall of the engine cylinder. Each lubricant composition contains a base oil and, upon application, includes additives or modifiers such as viscosity index improvers, pour point depressants, dispersants, cleaners, antiwear agents, antioxidants, friction modifiers, rust inhibitors, corrosion inhibitors, demulsifiers and It may contain a combination of antifoaming agents.

Viscosity indices are generally used as units of viscosity change rate of a fluid with temperature. This temperature dependency is common to all fluids, including base oils. In general, the higher the viscosity index, the smaller the relative change in viscosity with temperature. Viscosity index (VI) improvers or viscosity modifiers are used to reduce the temperature dependence of the viscosity of the lubricant composition so that the lubricant composition can be used over a wide temperature range. In other words, the VI improver prevents the lubricant composition from becoming too dilute at high temperatures, eg hot summer temperatures, and too viscous at low temperatures, eg cold winter temperatures. Some known VI improvers include polymethacrylates, olefin copolymers such as ethylene-propylene copolymers and ethylene-propylene diene-modified copolymers (EPDM), and styrene-ethylene / butylene-styrene copolymers (SEBS Hydrogenated styrenic block copolymers such as

Hydrogenated styrenic block copolymers generally provide good thickening efficiency and good low temperature performance. However, these hydrogenated styrenic block copolymers are relatively expensive and have a limited shelf life due to low shear stability.

Olefin copolymers, such as amorphous ethylene-propylene copolymers, provide good low temperature performance but can provide poor thickening efficiency at high temperatures. The comonomer units of the olefin copolymer can be distributed in a tapered manner. In general, tapered olefin copolymers, such as tapered ethylene-propylene copolymers, are excellent thickeners, have improved low temperature performance, and avoid interaction with undesired base oils.

While many VI improvers for formulating lubricant compositions are available on the market, new VI improvers for lubricant compositions with improved properties and flexibility are always needed.

<Overview of invention>

This need is met by various aspects of the present invention.

The lubricant composition provided herein comprises (i) a base oil, and (ii) an ethylene / α-olefin interpolymer, wherein the ethylene / α-olefin interpolymer

(a) Mw / Mn is from about 1.7 to about 3.5 and has at least one melting point (Tm) (degrees Celsius), and density (d) (g / cm ³ ), wherein the values of Tm and d correspond to the relationship do or,

Tm> -2002.9 + 4538.5 (d)-2422.2 (d) ²

(b) the amount of delta (ΔT) (degrees C) defined by the heat of fusion (ΔH) (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak, with Mw / Mn of about 1.7 to about 3.5; Characterized in that the value of ΔT and ΔH has the following relationship,

ΔT> -0.1299 (ΔH) + 62.81 when ΔH is greater than 0 and less than or equal to 130 J / g

ΔT ≥ 48 ° C when ΔH is greater than 130 J / g

(Where the CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the cumulative polymer has an identifiable CRYSTAF peak, the CRYSTAF temperature is 30 ° C.),

(c) characterized by a 300% strain and an elastic recovery rate (Re) (%) measured in a compression molded film of an ethylene / α-olefin interpolymer, having a density (d) (g / cm ³ ) When the ethylene / α-olefin interpolymers substantially contain no crosslinked phase, the values of Re and d satisfy the following relationship,

Re> 1481-1629 (d)

(d) having a molecular fraction eluted at 40 ° C. to 130 ° C. when fractionated using TREF, wherein the fraction is less than the comonomer mole content of the comparative random ethylene interpolymer fraction eluted at the same temperature range as the comonomer molar content; Or a comonomer molar content of at least% (wherein the comparative random ethylene interpolymer has the same comonomer as the ethylene / α-olefin interpolymer and is less than 10% of the ethylene / α-olefin interpolymer Melt index, density, and comonomer molar content (based on total polymer)),

(e) having a storage modulus at 25 ° C. (G ′ (25 ° C.)) and a storage modulus at 100 ° C. (G ′ (100 ° C.)), wherein G ′ (25 ° C.) vs. G ′ (100 ° C.) The ratio of is in the range of about 1: 1 to about 9: 1. The ethylene / α-olefin interpolymers may have one or any combination of the above properties.

In one embodiment, the ethylene / α-olefin interpolymer has a Mw / Mn of about 1.7 to about 3.5, has one or more melting points (Tm) (degrees C), and a density (d) (g / cm ³ ), The numerical values of Tm and d correspond to the following relations.

Tm ≥ 858.91-1825.3 (d) + 1112.8 (d) ²

In another embodiment, the ethylene / α-olefin interpolymers are characterized by 300% strain and elastic recovery in one cycle (Re) (%) as measured by compression molded films of ethylene / α-olefin interpolymers, (d) The values of Re and d satisfy the following relationship when (g / cm ³ ) and the ethylene / α-olefin interpolymers are substantially free of crosslinked phase: Re> 1481-1629 (d) , Re> 1491-1629 (d), Re> 1501-1629 (d), or Re> 1511- 1629 (d).

In one embodiment, the ethylene / α-olefin interpolymers have a block index of at least 0.5 and up to about 1 and a molecular weight distribution (Mw / Mn), eluted at 40 ° C. to 130 ° C. when fractionated using (a) TREF. At least one fraction characterized by greater than about 1.3, or (b) an average block index greater than 0 and up to about 1.0, and a molecular weight distribution (Mw / Mn) greater than about 1.3.

In another embodiment, the ethylene / α-olefin interpolymers have molecular fractions that elute at 40 ° C. to 130 ° C. when fractionated using TREF, and the fractions of the comparative random ethylene interpolymer fractions that elute at the same temperature range. Wherein the comparative random ethylene interpolymer has the same comonomer as the ethylene / α-olefin interpolymer and has the same comonomer as the ethylene / α-olefin interpolymer. Melt index, density, and comonomer molar content (based on total polymer) within 10%.

In one embodiment, the ethylene / α-olefin interpolymer is a random block copolymer comprising one or more hard blocks and one or more soft blocks. In addition, the random block copolymer may comprise a plurality of hard blocks and a plurality of soft blocks, and the hard blocks and soft blocks may be randomly distributed within the polymer chain.

In another embodiment, the ethylene / α-olefin interpolymer has a storage modulus at 25 ° C. (G ′ (25 ° C.)), and a storage modulus at 100 ° C. (G ′ (100 ° C.)), wherein G ′ (25 ° C.) to G ′ (100 ° C.) is in the range of about 1: 1 to about 9: 1.

In one embodiment, the α-olefins used in the ethylene / α-olefin interpolymers are styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene , 1,5-hexadiene, or a combination thereof.

In another embodiment, the melt index of the ethylene / α-olefin interpolymers measured according to ASTM D-1238, Condition 190 ° C./2.16 kg, is from about 0.1 to about 2000 g / 10 minutes, from about 2 to about 1500 g / 10 Minutes, about 2 to about 1000 g / 10 minutes, or about 2 to about 500 g / 10 minutes.

In one embodiment, the lubricant composition comprises a base oil selected from the group consisting of base raw materials of API groups I, II, III, IV and V and combinations thereof. In one embodiment, the base oil is a natural oil, a synthetic oil or a combination thereof.

The lubricant composition may further comprise one or more additives such as detergents, dispersants, friction modifiers, pour point depressants, demulsifiers, antifoams, corrosion inhibitors, antiwear agents, antioxidants, rust inhibitors, thickeners or combinations thereof. .

In one embodiment, the lubricant composition is automotive oil, transmission fluid, gear oil, power steering fluid, shock absorber fluid, brake fluid, hydraulic fluid or grease. Automotive oils may further comprise pour point depressants, cleaners, dispersants, antiwear agents, antioxidants, friction modifiers, rust inhibitors or combinations thereof.

In another embodiment, the lubricant composition is a transmission fluid. The transmission fluid may further comprise friction modifiers, cleaners, dispersants, antioxidants, antiwear agents, extreme pressure agents, pour point depressants, antifoams, corrosion inhibitors or combinations thereof.

In one embodiment, the lubricant composition is a gear oil. Gear oils may further comprise antiwear agents, extreme pressure agents, rust inhibitors or combinations thereof.

In another embodiment, the lubricant composition is grease. The grease may further comprise thickeners, complexing agents, antioxidants, antiwear agents, extreme pressure agents, antifoaming agents, corrosion inhibitors or mixtures thereof.

The present invention also provides a process for preparing a lubricant composition comprising blending the base oil with the ethylene / α-olefin interpolymers described above and elsewhere herein.

Additional aspects of the invention and features and characteristics of various embodiments of the invention will be apparent from the following description.

Figure 1 shows the melting point / density relationship of the polymer of the present invention (denoted as diamond) compared to conventional random copolymers (shown as circles) and Ziegler-Natta copolymers (denoted as triangles).

2 shows a plot of delta DSC-CRYSTAF as a function of DSC melt enthalpy for various polymers. Diamonds represent random ethylene / octene copolymers, squares represent Polymer Examples 1-4, triangles represent Polymer Examples 5-9, and circles represent Polymer Examples 10-19. The symbol "X" represents Polymer Examples A ^* to F ^* .

Figure 3 shows the density of elastic recovery for non-oriented films made from the inventive interpolymers (represented by squares and circles) and conventional copolymers (Dow AFFINITY® polymers, represented by triangles). Effect. Squares represent ethylene / butene copolymers of the present invention, and circles represent ethylene / octene copolymers of the present invention.

4 is a plot of the octene content of the TREF fractionated ethylene / 1-octene copolymer fraction versus the TREF elution temperature of the polymer fraction of Example 5 (shown as circles) and comparative polymers E and F (shown with the symbol “X”). to be. Diamonds represent conventional random ethylene / octene copolymers.

FIG. 5 is a plot of the octene content of TREF fractionated ethylene / 1-octene copolymer fractions versus TREF elution temperatures of the polymer fractions of Example 5 (Curve 1) and Comparative Example F (Curve 2). Squares represent polymer Example F ^* and triangles represent Example 5.

FIG. 6 shows two ethylene / inventions of the invention prepared using comparative ethylene / 1-octene copolymer (curve 2) and ethylene / propylene copolymer (curve 3) and different amounts of chain shuttling agent. It is a graph of the natural log of storage modulus as a function of temperature for 1-octene block copolymer (curve 1).

FIG. 7 shows a plot of TMA (1 mm) versus flexural modulus for some polymers of the present invention (represented with diamonds) compared to some known polymers. Triangles Dow beosi pie (Dow VERSIFY) represents a polymer ^®, W represents various random ethylene / styrene copolymer, squares represent various Dow Affinity ^® polymer.

General definition

"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The general term "polymer" encompasses the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer".

"Interpolymer" means a polymer prepared by polymerizing two or more different types of monomers. The general term "interpolymer" refers to the term "copolymer" (commonly used to refer to a polymer made from two different monomers) and the term "terpolymer" (a polymer made from three different types of monomers) Commonly used). Interpolymers also encompass polymers made by polymerizing four or more monomers.

The term “ethylene / α-olefin interpolymer” generally refers to a polymer comprising ethylene and an α-olefin having at least 3 carbon atoms. Preferably, ethylene comprises most of the mole fraction of the total polymer, ie ethylene comprises at least about 50 mol% of the total polymer. More preferably, ethylene comprises at least about 60 mol%, at least about 70 mol%, or at least about 80 mol%, with the substantial remainder of the entire polymer being preferably an α-olefin having 3 or more carbon atoms. It consists of more than one species of other comonomers. For many ethylene / octene copolymers, preferred compositions have an ethylene content of greater than about 80 mol% of the total polymer and an octene content of about 10 to about 15 mol%, preferably about 15 to about 20 mol% of the total polymer. Include. In some embodiments, the ethylene / α-olefin interpolymers do not include those produced in low yield or in small amounts or as a byproduct of a chemical process. The ethylene / α-olefin interpolymers may be blended with one or more polymers, but the ethylene / α-olefin interpolymers as prepared are substantially pure and often constitute a major component of the reaction product of the polymerization process.

Ethylene / α-olefin interpolymers comprise ethylene and one or more copolymerizable α-olefin comonomers in polymerized form and feature multiple blocks or segments having two or more polymerized monomer units that differ in chemical or physical properties. It is done. In other words, the ethylene / α-olefin interpolymers are block interpolymers, preferably multiblock interpolymers or copolymers. The terms "interpolymer" and "copolymer" are used interchangeably herein. In some embodiments, the multiblock copolymer can be represented by the formula:

(AB) _n

Wherein n is an integer greater than or equal to 1, preferably greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or more "A" represents a hard block or segment and "B" represents a soft block or segment. Preferably, A and B are connected in a substantially linear manner rather than in a substantially branched or substantially star form. In other embodiments, A blocks and B blocks are randomly distributed along the polymer chain. In other words, the block copolymers typically do not have the following structure.

 AAA-AA-BBB-BB

In another embodiment, the block copolymers usually do not have a third type of block comprising different comonomers. In another embodiment, block A and block B each have monomers or comonomers distributed substantially randomly within the block. In other words, block A and block B both do not include two or more sub-segments (or sub-blocks) having separate compositions, such as tip segments having compositions that are substantially different from the remaining blocks.

Multiblock polymers typically include varying amounts of "hard" and "soft" segments. A "hard" segment refers to a block of polymerized units in which ethylene is present in an amount greater than about 95 weight percent, preferably greater than about 98 weight percent, based on the weight of the polymer. In other words, the comonomer content (monomer content other than ethylene) in the hard segment is less than about 5% by weight, preferably less than about 2% by weight, based on the weight of the polymer. In some embodiments, the hard segments are all or substantially all composed of ethylene. In contrast, “soft” segments have a comonomer content (monomer content other than ethylene) of greater than about 5 weight percent, preferably greater than about 8 weight percent, greater than about 10 weight percent, or about 15 weight percent based on the weight of the polymer. Blocks of excess polymerized units are shown. In some embodiments, the comonomer content in the soft segment is greater than about 20 weight percent, greater than about 25 weight percent, greater than about 30 weight percent, greater than about 35 weight percent, greater than about 40 weight percent, greater than about 45 weight percent, about 50 Greater than or equal to about 60 weight percent.

The soft segment is often from about 1% to about 99% by weight of the total weight of the block interpolymer in the block interpolymer, preferably from about 5% to about 95%, about 10% by weight to the total weight of the block interpolymer From about 90 wt%, about 15 wt% to about 85 wt%, about 20 wt% to about 80 wt%, about 25 wt% to about 75 wt%, about 30 wt% to about 70 wt%, about 35 wt% About 65%, about 40% to about 60%, or about 45% to about 55% by weight. In contrast, hard segments may exist within a similar range. Soft segment weight percentages and hard segment weight percentages can be calculated based on data obtained from DSC or NMR. These methods and calculations are filed on March 15, 2006, under the name of "ethylene / α-olefin block interpolymers", in the name of Colin LP Shan, Lonnie Hazlitt, et al. And the entirety of the specification, assigned to Dow Global Technologies Inc., incorporated herein by reference and simultaneously filed (Inserted if known), agent case number 385063-999558.

The term "crystalline", when used, refers to a polymer having a primary transition temperature or crystal melting point (Tm), measured by differential scanning calorimetry (DSC) or equivalent technique. This term may be used interchangeably with the term "semicrystalline". The term “amorphous” refers to a polymer having no crystalline melting point measured by differential scanning calorimetry (DSC) or equivalent technique.

The term "multiblock copolymer" or "segmented copolymer" is preferably a polymer comprising at least two chemically distinct regions or segments (referred to as "blocks") connected in a linear manner, ie pendant or grafted manner. Rather, it refers to a polymer comprising chemically differentiated units that are linked end to end with respect to polymerized ethylene-based functional groups. In a preferred embodiment, the block comprises the amount or type of comonomer incorporated therein, the density, the amount of crystallinity, the microcrystalline size attributable to the polymer of this composition, the type or degree of tacticity (isotactic or synthetizing) Different amounts, homogeneity, or any other chemical or physical property of branching, including diotactic), regio-regular or site-irregularity, long chain branching or hyper-branching. Multiblock copolymers are characterized by the distribution of specific polydispersity indices (PDI or Mw / Mn), block length distribution and / or block number distribution due to specific copolymer preparation methods. More specifically, when produced in a continuous process, the polymer preferably has a PDI of 1.7 to 2.9, preferably 1.8 to 2.5, more preferably 1.8 to 2.2 and most preferably 1.8 to 2.1. When produced in a batch or semi-batch process, the polymer has a PDI of 1.0 to 2.9, preferably 1.3 to 2.5, more preferably 1.4 to 2.0 and most preferably 1.4 to 1.8.

In the following description, all values disclosed herein are approximations whether or not the term "about" or "approximately" is used in this regard. They may vary by 1%, 2%, 5%, or sometimes 10-20%. When a numerical range having a lower limit (R ^L ) and an upper limit (R ^U ) is disclosed, any numerical value included in the range is specifically disclosed. Specifically, the following numerical values within the range are specifically disclosed: R = R ^L + k * (R ^U -R ^L ) where k is a variable ranging from 1% to 100% in 1% increments, ie k Is 1%, 2%, 3%, 4%, 5%, ..., 50%, 51%, 52%, ..., 95%, 96%, 97%, 98%, 99% or 100% being). In addition, any numerical range defined by two R values as defined above is also specifically disclosed.

The lubricant composition disclosed herein

(a) a base oil, and

(b) an ethylene / α-olefin interpolymer, wherein the ethylene / α-olefin interpolymer has a Mw / Mn of about 1.7 to about 3.5,

(i) has at least one melting point (Tm) (degrees Celsius), and density (d) (g / cm ³ ), wherein the numerical value of the variable corresponds to

Tm> -2002.9 + 4538.5 (d)-2422.2 (d) ²

(ii) a heat of fusion (ΔH) (J / g), and a delta amount (ΔT) (degrees Celsius), defined as the difference between the highest DSC peak minus the highest CRYSTAF peak, wherein the values of ΔT and ΔH are Have

ΔT> -0.1299 (ΔH) + 62.81 if ΔH is greater than 0 and less than or equal to 130 J / g

ΔT = 48 ° C when ΔH is greater than 130 J / g

Wherein the CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the cumulative polymer has an identifiable CRYSTAF peak, the CRYSTAF temperature is 30 ° C. The ethylene / α-olefin interpolymers are characterized by additional properties discussed below.

The ethylene / α-olefin interpolymers disclosed herein act as VI improvers in lubricant compositions. The ethylene / α-olefin interpolymers control the distribution of comonomer units and the crystallinity of the ethylene / α-olefin interpolymers to provide flexibility in the formulation of the desired lubricant composition.

Ethylene / α-olefin Interpolymers

The ethylene / α-olefin interpolymers (also referred to as “interpolymers of the present invention” or “polymers of the present invention”) used in embodiments of the present invention may comprise a plurality of blocks or two or more polymerized polymers having different chemical or physical properties. In a polymerized form (block interpolymer) characterized by a plurality of blocks or segments of monomeric units, preferably in a multiblock copolymer, ethylene and at least one copolymerizable α-olefin comonomer are included. The ethylene / α-olefin interpolymers are characterized by one or more of the aspects described below.

In one aspect, the ethylene / α-olefin interpolymers used in embodiments of the present invention have an Mw / Mn of about 1.7 to about 3.5, and at least one melting point (Tm) (degrees C) and density (d) (g / cm ³ ), the numerical values of these variables correspond to the relation

Tm> -2002.9 + 4538.5 (d)-2422.2 (d) ² ,

Preferably Tm ≧ −6288.1 + 13141 (d) -6720.3 (d) ² ,

More preferably Tm> 858.91-1825.3 (d) + 1112.8 (d) ² .

This melting point / density relationship is shown in FIG. 1. Unlike typical random copolymers of ethylene / α-olefins, which have a lower melting point with decreasing density, the interpolymers of the present invention (denoted as diamonds), especially when the density is from about 0.87 g / cc to about 0.95 g / cc It shows a melting point that is substantially independent of density. For example, the melting point of such polymers range from about 110 ° C. to about 130 ° C. when the density ranges from 0.875 g / cc to about 0.945 g / cc. In some embodiments, the melting point of such polymers range from about 115 ° C. to about 125 ° C. when the density ranges from 0.875 g / cc to about 0.945 g / cc.

In another aspect, the ethylene / α-olefin interpolymers comprise ethylene and one or more α-olefins in polymerized form, wherein the temperature of the maximum differential scanning calorimetry (“DSC”) peak—the highest crystallization analysis fractionation (“CRYSTAF ΔT (degrees Celsius), defined as the temperature of the peak, and the heat of fusion ΔH (J / g), wherein ΔT and ΔH are the following relations for ΔH of 130 J / g or less: To satisfy.

ΔT> -0.1299 (ΔH) + 62.81,

Preferably ΔT ≧ −0.1299 (ΔH) +64.38,

More preferably ΔT ≧ −0.1299 (ΔH) +65.95.

In addition, when (DELTA) H exceeds 130 J / g, (DELTA) T is 48 degreeC or more. CRYSTAF peaks are measured using at least 5% of the cumulative polymer (ie, peaks must represent at least 5% of the cumulative polymer), and if less than 5% of the polymers have an identifiable CRYSTAF peak, the CRYSTAF temperature is 30 ° C. And ΔH are numerical values of heat of fusion (J / g). More preferably, the highest CRYSTAF peak contains at least 10% of the cumulative polymer. 2 shows the data plotted for the polymers of the invention as well as the comparative examples. The integral peak area and peak temperature are calculated with a computerized drawing program provided by the instrument manufacturer. The diagonal line shown for the random ethylene octene comparison polymer corresponds to the equation ΔT = −0.1299 (ΔH) +62.81.

In another aspect, the ethylene / α-olefin interpolymers have molecular fractions that elute at 40 ° C. to 130 ° C. when fractionated using temperature eluting fractionation (“TREF”), the fractions having a comonomer molar content, Characterized by being higher than the molar comonomer content of the comparative random ethylene interpolymer fraction eluting in the same temperature range, preferably at least 5% higher, more preferably at least 10% higher, wherein the comparative random ethylene interpolymer Contains the same comonomer (s) as the blocked interpolymer and the melt index, density and comonomer molar content (based on total polymer) are within 10% of that for the block interpolymer. Preferably, the Mw / Mn of the comparative interpolymers is also within 10% of the Mw / Mn of the block interpolymers and / or the total comonomer content of the comparative interpolymers is within 10% by weight of the block interpolymers. .

In another aspect, the ethylene / α-olefin interpolymers are characterized by 300% strain and elastic recovery in one cycle (Re) (%) measured on compression molded films of ethylene / α-olefin interpolymers, Having a density (d) (g / cm ³ ), wherein the values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymers do not substantially comprise a crosslinked phase.

Re> 1481-1629 (d);

Preferably Re ≧ 1491-1629 (d);

More preferably Re ≧ 1501-1629 (d);

Even more preferably Re ≧ 1511-1629 (d).

3 shows the effect of density on elastic recovery for non-oriented films made from certain interpolymers and conventional random copolymers of the present invention. At the same density, the inventive interpolymers have substantially higher elastic recovery.

In some embodiments, the ethylene / α-olefin interpolymer has a tensile strength of greater than 10 MPa, preferably of at least 11 MPa, more preferably of at least 13 MPa, and / or of 11 cm / min crosshead It has a breaking elongation of at least 600%, more preferably at least 700%, very preferably at least 800% and most very preferably at least 900% at the separation rate.

In another embodiment, the ethylene / α-olefin interpolymer has (1) a storage modulus ratio G ′ (25 ° C.) / G ′ (100 ° C.) of 1 to 50, preferably 1 to 20, more preferably 1 To 10 and / or; (2) 70 ° C. Compression set is less than 80%, preferably less than 70%, especially less than 60%, less than 50%, or less than 40% to 0%.

In another embodiment, the ethylene / α-olefin interpolymer has a 70 ° C. compression set of less than 80%, less than 70%, less than 60%, or less than 50%. Preferably, the 70 ° C. compression set of the interpolymer is less than 40%, less than 30%, less than 20% and can be reduced to about 0%.

In some embodiments, the ethylene / α-olefin interpolymer has a heat of fusion less than 85 J / g, and / or 100 lb / ft ² (4800 Pa) or less, preferably 50 lb / ft ² (2400 Pa) or less , In particular, has a pellet blocking strength of less than 5 lb / ft ² (240 Pa) and also as low as 0 lb / ft ² (0 Pa).

In other embodiments, the ethylene / α-olefin interpolymers comprise at least 50 mol% ethylene in polymerized form and have a 70 ° C. compression set of less than 80%, preferably less than 70%, or less than 60%, most Preferably it is less than 40-50% and decreases to near 0%.

In some embodiments, the multiblock copolymer has a PDI fitting that fits the Schultz-Flory distribution rather than the Poisson distribution. The copolymer has both a polydisperse block distribution and a polydisperse block size distribution, and is also characterized by having the most possible block length distribution. Preferred multiblock copolymers are copolymers containing four or more blocks or segments, including terminal blocks. More preferably, the copolymer comprises 5, 10 or 20 or more blocks or segments, including end blocks.

Comonomer content can be measured using any suitable technique, with techniques based on nuclear magnetic resonance ("NMR") spectroscopy preferred. In addition, in the case of polymers or blends of polymers having a relatively wide TREF curve, first the TREF is used to fractionate the polymers into fractions each having an elution temperature range of 10 ° C. or less. That is, each eluted fraction has a collection temperature window of 10 ° C. or less. By using this technique, the block interpolymers have one or more fractions having a higher comonomer molar content than the corresponding fractions of the comparative interpolymers.

In another aspect, the polymer of the present invention preferably comprises a plurality of blocks comprising two or more polymerized monomer units, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form and differing in chemical or physical properties ( That is, olefin interpolymers (blocked interpolymers) characterized by two or more blocks) or segments, most preferably multiblock copolymers, which block elution (individual fractions) which elute at 40 ° C. to 130 ° C. Collected and / or not isolated) peaks (not molecular fractions only), which peaks have comonomer content predicted by infrared spectroscopy at development using full width at half maximum (FWHM) area calculations, and average comonomer moles Average satin of comparative random ethylene interpolymer peaks at the same elution temperature with content developed using full width at half maximum (FWHM) area calculation Higher than the body molar content, preferably at least 5% higher, more preferably at least 10% higher, wherein the comparative random ethylene interpolymer has the same comonomer (s) as the blocked interpolymer and melts The index, density and comonomer molar content (based on total polymer) are within 10% for block interpolymers. Preferably, the Mw / Mn of the comparative interpolymer is also within 10% of the Mw / Mn of the blocked interpolymer and / or the total comonomer content of the comparative interpolymer is within 10% by weight of the block interpolymer. to be. The full width at half maximum (FWHM) calculation is based on the ratio of methyl to methylene reaction area [CH ₃ / CH ₂ ] from the ATREF infrared detector, where the highest (maximum) peak is identified from the baseline and thus the FWHM area is determined. In the distribution measured using the ATREF peak, the FWHM area is defined as the area under the curve between T ₁ and T ₂ , where T ₁ and T ₂ are horizontal lines to the baseline after dividing the ATREF peak height by 2 (ATREF Traversing the left and right sides of the curve) to determine the left and right sides of the ATREF peak. A calibration curve for comonomer content is obtained by plotting the FWHM area ratio of comonomer content from NMR to TREF peak using a random ethylene / α-olefin copolymer. In this infrared method, a calibration curve is obtained for the same comonomer type of interest. The comonomer content of the TREF peak of the polymers of the present invention can be measured with reference to such calibration curves using the FWHM methyl: methylene area ratio [CH ₃ / CH ₂ ] of its TREF peak.

Comonomer content can be measured using any suitable technique, with techniques based on nuclear magnetic resonance (NMR) spectroscopy preferred. Using this technique, the blocked interpolymers have a higher comonomer molar content than the corresponding comparative interpolymers.

Preferably, in the interpolymers of ethylene and 1-octene, the block interpolymers have a comonomer content of the TREF fraction eluting at 40 ° C. to 130 ° C. of at least (-0.2013) T + 20.07, more preferably (- Greater than or equal to 0.2013) T + 21.07 (where T is the value of the peak elution temperature of the compared TREF fraction, measured in ° C.).

FIG. 4 graphically illustrates embodiments of block interpolymers of ethylene and 1-octene and plots of comonomer content versus TREF elution temperature for various comparative ethylene / 1-octene interpolymers (random copolymers). (-0.2013) fitted to the line (solid line) representing T + 20.07. The line of Equation (-0.2013) T + 21.07 is shown as a dotted line. In addition, the comonomer content for the fractions of some block ethylene / 1-octene interpolymers (multiblock copolymers) of the present invention are shown. All block interpolymer fractions had significantly higher 1-octene content compared to the line at equivalent elution temperatures. These results are characteristic of the interpolymers of the present invention, which are believed to be due to the presence of differentiated blocks in the polymer chain having both crystalline and amorphous properties.

FIG. 5 graphically illustrates the TREF curve and comonomer content for the polymer fractions of Example 5 and Comparative Example F, discussed below. The peaks eluting at 40 ° C. to 130 ° C., preferably 60 ° C. to 95 ° C., for the two polymers were separated into three parts, each part eluting over a temperature range of less than 10 ° C. The actual data of Example 5 is shown in triangles. One skilled in the art can use different comonomers for comparison, using a line matching the TREF values obtained from comparative interpolymers of random copolymers prepared using the same monomers, preferably metallocenes or other homogeneous catalyst compositions. It will be appreciated that appropriate calibration curves can be constructed for the interpolymers it contains. The interpolymers of the present invention are characterized by a comonomer molar content that is greater than, preferably at least 5% and more preferably at least 10% greater than the value measured from the calibration curve at the same TREF elution temperature.

In addition to the foregoing aspects and properties described herein, the polymers of the present invention may be characterized as having one or more additional features. In one aspect, the polymer of the invention preferably comprises a plurality of blocks or segments comprising two or more polymerized monomer units, preferably in polymerized form, comprising ethylene and one or more copolymerizable comonomers in different chemical or physical properties. Olefin interpolymers (blocked interpolymers), most preferably multiblock copolymers, characterized in that the block interpolymers have molecular fractions that elute at 40 ° C. to 130 ° C. when fractionated using TREF increments. The silver comonomer molar content is higher than the comonomer molar content of the comparative random ethylene interpolymer fraction eluting in the same temperature range, preferably at least 5% higher, more preferably 10%, 15%, 20% or 25 At least% high, wherein the comparative random ethylene interpolymer is the same as the blocked interpolymer It has comonomer (s) and is preferably the same comonomer (s) and the melt index, density and comonomer molar content (based on total polymer) are within 10% of blocked interpolymers. Preferably, the Mw / Mn of the comparative interpolymer is also within 10% of the Mw / Mn of the blocked interpolymer, and / or 10% by weight for the interpolymer with the total comonomer content of the comparative interpolymer Within.

Preferably, the interpolymers, in particular, have a total polymer density of from about 0.855 to about 0.935 g / cm ³ , more particularly of polymers of at least one α-olefin with ethylene having more than about 1 mol% comonomer Interpolymers, wherein the blocked interpolymers have a comonomer content of the TREF fraction eluting at 40 ° C. to 130 ° C. of at least (−0.1356) T + 13.89, more preferably at least (−0.1356) T + 14.93, Most preferably greater than or equal to (-0.2013) T + 21.07, where T is the value of the highest ATREF elution temperature measured in degrees Celsius of the TREF fraction being compared.

Preferably, for interpolymers of ethylene and one or more alpha-olefins, in particular for the interpolymers having an overall polymer density of about 0.855 to about 0.935 g / cm ³ , more particularly greater than about 1 mol% In the case of the polymer having a comonomer, the blocked interpolymer has a comonomer content of the TREF fraction eluting at 40 ° C. to 130 ° C. that is at least (-0.2013) T + 20.07, more preferably (-0.2013) T + 21.07 (Where T is the value of the highest ATREF elution temperature of the compared TREF fraction, measured in ° C.).

In another aspect, the polymer of the invention preferably comprises a plurality of blocks comprising two or more polymerized monomer units, preferably in polymerized form, comprising ethylene and one or more copolymerizable comonomers in different chemical or physical properties, or Olefin interpolymers (blocked interpolymers) characterized by segments, most preferably multiblock copolymers, said block interpolymers having molecular fractions which elute at 40 ° C. to 130 ° C. when fractionated using TREF increments, All fractions having a comonomer content of at least about 6 mol% have a melting point above about 100 ° C. For fractions having a comonomer content of about 3 mol% to about 6 mol%, all fractions have a DSC melting point of about 110 ° C. or greater. More preferably, the polymer fraction having at least 1 mol% comonomer has a DSC melting point corresponding to the following formula.

Tm ≥ (-5.5926) (mol% of comonomer in the fraction) + 135.90

In another aspect, the polymer of the invention preferably comprises a plurality of blocks comprising two or more polymerized monomer units, preferably in polymerized form, comprising ethylene and one or more copolymerizable comonomers in different chemical or physical properties, or Olefin interpolymers (blocked interpolymers) characterized by segments, most preferably multiblock copolymers, said block interpolymers having molecular fractions which elute at 40 ° C. to 130 ° C. when fractionated using TREF increments, All fractions having an ATREF elution temperature above about 76 ° C. are characterized by having a melting enthalpy (heat of fusion) corresponding to the following equation as determined by DSC.

Heat of fusion (J / g) ≤ (3.1718) (ATREF elution temperature (Celsius))-136.58

The block interpolymers of the present invention have molecular fractions that elute at 40 ° C. to 130 ° C. when fractionated using TREF increments, and all fractions having ATREF elution temperatures of 40 ° C. to less than about 76 ° C. It is characterized by having a melting enthalpy (heat of fusion) corresponding to the equation.

Heat of fusion (J / g) ≤ (1.1312) (ATREF elution temperature (Celsius)) + 22.97

By infrared detector ATREF  peak Comonomer  Measurement of composition

The comonomer composition of the TREF peak can be measured using an IR4 infrared detector available from Polymer Char (Valencia, Spain) ( http://www.polymerchar.com/ ).

The "composition mode" of the detector is equipped with a measuring sensor (CH ₂ ) and a composition sensor (CH ₃ ) (fixed narrow band infrared filter in the region of 2800 to 3000 cm ^-1 ). The measurement sensor detects methylene (CH ₂ ) carbon on the polymer, which is directly related to the polymer concentration in solution, and the composition sensor detects the methyl (CH ₃ ) group of the polymer. The mathematical ratio of the composition signal (CH ₃ ) divided by the measurement signal (CH ₂ ) is sensitive to the comonomer content of the polymer in the measured solution and its response is corrected by known ethylene alpha-olefin copolymer standards.

The detector, when used with an ATREF instrument, provides both the concentration (CH ₂ ) and composition (CH ₃ ) signal response of the polymer eluted during the TREF process. Polymer specific correction can be obtained by measuring the area ratio of CH ₃ to CH ₂ to the polymer by known comonomer content (preferably determined by NMR). The comonomer content of the ATREF peak of the polymer can be predicted by applying a baseline correction of the area ratio for the individual CH ₃ and CH ₂ reactions (ie, area ratio CH ₃ / CH ₂ to comonomer content).

The area of the peak can be calculated using the full width at half maximum (FWHM) calculation after integrating the individual signal responses from the TREF chromatogram using the appropriate baseline. The full width at half maximum is based on the ratio of methyl to methylene reaction area [CH ₃ / CH ₂ ] from the ATREF infrared detector, where the highest (maximum) peak is identified from the baseline and thus the FWHM area is determined. In the distribution measured using the ATREF peak, the FWHM area is defined as the area under the curve between T ₁ and T ₂ , where T ₁ and T ₂ are horizontal lines to the baseline after dividing the ATREF peak height by 2 (ATREF Traversing the left and right sides of the curve) to determine the left and right sides of the ATREF peak.

The application of infrared spectroscopy to determine the comonomer content of polymers in this ATREF-infrared method is in principle similar to that of the GPC / FTIR system as described in the following references: Markovich, Ronald P .; Hazlitt, Lonnie G .; Smith, Linley; "Development of gel-permeation chromatography-Fourier transform infrared spectroscopy for characterization of ethylene-based polyolefin copolymers", Polymeric Materials Science and Engineering (1991), 65, 98-100 .; And Deslauriers, P. J .; Rohlfing, D. C .; Shieh, E. T .; "Quantifying short chain branching microstructures in ethylene-1-olefin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTIR)", Polymer (2002), 43, 59-170.] Introduced for reference).

In other embodiments, the ethylene / a-olefin interpolymers of the invention are characterized by an average block index (ABI) of greater than 0 and up to about 1.0, and a molecular weight distribution (Mw / Mn) of greater than about 1.3. The average block index (ABI) is the weight average of the block index (“BI”) of each polymer fraction obtained in the preparative TREF at 20 ° C. to 110 ° C. in 5 ° C. increments.

Wherein BI _i is the block index for the i-th fraction of the ethylene / α-olefin interpolymers of the invention obtained in the preparative TREF and w _i is the weight percent of the i-th fraction.

For each polymer fraction, BI is defined by one of the following two equations, both of which give the same BI value.

Wherein T _X is the ATREF elution temperature (preferably expressed in Kelvin) for the i-th fraction, and P _X is the ethylene mole fraction for the i-th fraction, which can be measured by NMR or IR as above. P _AB is the ethylene mole fraction of the total ethylene / α-olefin interpolymer (before fractionation), which can also be measured by NMR or IR. T _A and P _A are the ATREF elution temperature and ethylene mole fraction for pure “hard segments” (referring to the crystalline segments of the interpolymer). If the measured value for the "hard segment" is not valid, the T _A and P _A values as the first approximation are set to the values for the high density polyethylene homopolymer. In the calculations performed herein, T _A is 372 ° K and P _A is 1 _.

T _AB is the ATREF elution temperature for random copolymers of the same composition having an ethylene mole fraction of P _AB . T _AB can be calculated from the following equation.

Ln P _AB = α / T _AB + β

Wherein α and β are two constants that can be determined by correction using a number of known random ethylene copolymers. It should be noted that α and β may vary from instrument to instrument. In addition, it is necessary to obtain an appropriate calibration curve by the polymer composition of interest within the similar molecular weight range for the fraction. There is a slight molecular weight effect. If the calibration curve is obtained from similar molecular weight ranges, this effect is essentially negligible. In some embodiments, the random ethylene copolymer satisfies the following relationship.

Ln P = -237.83 / T _ATREF + 0.639

T _XO is the ATREF temperature for a random copolymer of the same composition with an ethylene mole fraction of P _X. T _XO can be calculated from LnP _X = α / T _XO + β. Conversely, P _XO is the ethylene mole fraction for random copolymers of the same composition with an ATREF temperature of T _X , which can be calculated from Ln P _XO = α / T _X + β.

Once the block index (BI) for each preparative TREF fraction is obtained, the weight average block index (ABI) for the entire polymer can be calculated. In some embodiments, ABI is greater than zero but less than about 0.3, or from about 0.1 to about 0.3. In other embodiments, ABI is greater than about 0.3 and up to about 1.0. Preferably, the ABI should range from about 0.4 to about 0.7, about 0.5 to about 0.7, or about 0.6 to about 0.9. In some embodiments, ABI ranges from about 0.3 to about 0.9, about 0.3 to about 0.8, or about 0.3 to about 0.7, about 0.3 to about 0.6, about 0.3 to about 0.5, or about 0.3 to about 0.4. In other embodiments, ABI ranges from about 0.4 to about 1.0, about 0.5 to about 1.0, or about 0.6 to about 1.0, about 0.7 to about 1.0, about 0.8 to about 1.0, or about 0.9 to about 1.0.

Another feature of the ethylene / α-olefin interpolymers of the present invention is that the ethylene / α-olefin interpolymers of the present invention can be obtained by preparative TREFs, with a block index of greater than about 0.1 and up to about 1.0 and a molecular weight distribution ( One or more polymer fractions with Mw / Mn) greater than about 1.3. In some embodiments, the polymer fraction has a block index greater than about 0.6 and up to about 1.0, greater than about 0.7 and up to about 1.0, greater than about 0.8 and up to about 1.0, or greater than about 0.9 and up to about 1.0. In other embodiments, the polymer fraction has a block index greater than about 0.1 and up to about 1.0, greater than about 0.2 and up to about 1.0, greater than about 0.3 and up to about 1.0, greater than about 0.4 and up to about 1.0, or greater than about 0.4 and up to about 1.0. In yet another embodiment, the polymer fraction has a block index greater than about 0.1 and up to about 0.5, greater than about 0.2 and up to about 0.5, greater than about 0.3 and up to about 0.5, or greater than about 0.4 and up to about 0.5. In another embodiment, the polymer fraction has a block index greater than about 0.2 and up to about 0.9, greater than about 0.3 and up to about 0.8, greater than about 0.4 and up to about 0.7, or greater than about 0.5 and up to about 0.6.

For the copolymer of ethylene and an α-olefin, the polymer of the present invention is preferably (1) 1.3 or more, more preferably 1.5 or more, 1.7 or more, or 2.0 or more, most preferably 2.6 or more, maximum 5.0 or less, More preferably a PDI of at most 3.5, in particular at most 2.7; (2) heat of fusion of up to 80 J / g; (3) an ethylene content of at least 50% by weight; (4) has a glass transition temperature (Tg) of less than -25 ° C, more preferably less than -30 ° C, and / or (5) one and also a single Tm.

In addition, the polymers of the present invention have a storage modulus (G ′) at a temperature of 100 ° C. of which log (G ′) is at least 400 kPa, preferably at least 1.0 MPa, alone or in combination with any other properties. Can be. In addition, the polymers of the present invention have a relatively uniform storage modulus as a function of temperature in the range of 0 to 100 ° C. (shown in FIG. 6), which is a property of the block copolymer, which is characterized in that at least one of olefin copolymers, in particular ethylene, for C _{3 -8} aliphatic copolymers of α- olefin is unknown up to now. (In this context, the term "relatively uniform" means that the log G '(Pa) is reduced to less than one digit range at 50 to 100 ° C, preferably 0 to 100 ° C.)

The interpolymers of the present invention may be further characterized by a thermomechanical analysis penetration depth of 1 mm and a flexural modulus of 3 kpsi (20 MPa) to 13 kpsi (90 MPa) at temperatures above 90 ° C. Alternatively, the inventive interpolymers can have a thermomechanical analysis penetration depth of 1 mm and a flexural modulus of at least 3 kpsi (20 MPa) at temperatures of 104 ° C. or higher. They can be characterized as having a wear resistance (or volume loss) of less than 90 mm ³ . 7 shows the TMA (1 mm) for the flexural modulus of the polymers of the present invention compared to other known polymers. The polymers of the present invention have a significantly better flexibility-heat resistance balance than other polymers.

In addition, the ethylene / α-olefin interpolymers may be used in an amount of 0.01 to 2000 g / 10 minutes, preferably 0.01 to 1000 g / 10 minutes, more preferably 0.01 to 500 g / 10 minutes, especially 0.01 to 100 g / 10 minutes. May have a melt index (I ₂ ). In certain embodiments, the ethylene / α-olefin interpolymer has 0.01 to 10 g / 10 minutes, 0.5 to 50 g / 10 minutes, 1 to 30 g / 10 minutes, 1 to 6 g / 10 minutes, or 0.3 to 10 g Melt index (I ₂ ) of 10 minutes. In certain embodiments, the melt index of the ethylene / α-olefin polymer is 1 g / 10 minutes, 3 g / 10 minutes or 5 g / 10 minutes.

The polymer has a molecular weight (Mw) of 1,000 g / mol to 5,000,000 g / mol, preferably 1000 g / mol to 1,000,000, more preferably 10,000 g / mol to 500,000 g / mol, in particular 10,000 g / mol to 300,000 g / mol ) The density of the polymer of the present invention may be 0.80 to 0.99 g / cm ³ , preferably 0.85 g / cm ³ to 0.97 g / cm ³ for ethylene containing polymers. In certain embodiments, the density of the ethylene / α-olefin polymer is in the range of 0.860 to 0.925 g / cm ³ or 0.867 to 0.910 g / cm ³ .

Methods of making polymers are disclosed in the following patent applications: US Provisional Application No. 60 / 553,906, filed March 17, 2004; 60 / 662,937, filed March 17, 2005; 60 / 662,939, filed March 17, 2005; 60/5662938, filed March 17, 2005; PCT Application No. PCT / US2005 / 008916, filed March 17, 2005; PCT Application No. PCT / US2005 / 008915, filed March 17, 2005; And PCT / US2005 / 008917, filed March 17, 2005, all of which are incorporated herein by reference in their entirety. For example, one such method involves the process of adding ethylene and optionally one or more addition polymerizable monomers other than ethylene under addition polymerization conditions,

(A) a first olefin polymerization catalyst having a high comonomer incorporation index,

(B) a second olefin polymerization catalyst having a comonomer incorporation index of less than 90%, preferably less than 50%, most preferably less than 5% of the comonomer incorporation index of catalyst (A), and

(C) mixtures or reaction products formed by combining chain transfer agents

It comprises contacting with a catalyst composition comprising a.

Representative catalysts and chain transfer agents are as follows.

Catalyst (A1) : [N- (2,6-di (1-methyl), prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429,024, and WO 04/24740, filed May 2, 2003. Ethyl) phenyl) amido) (2-isopropylphenyl) (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium dimethyl.

Catalyst (A2) : [N- (2,6-di (1-methyl), prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429,024, and WO 04/24740, filed May 2, 2003. Ethyl) phenyl) amido) (2-methylphenyl) (1,2-phenylene- (6-pyridin-2-diyl) methane)] hafnium dimethyl.

Catalyst (A3) : Bis [N, N '"-(2,4,6-tri (methylphenyl) amido) ethylenediamine] hafnium dibenzyl.

Catalyst (A4) : Bis ((2-oxoyl-3- (dibenzo-1H-pyrrol-1-yl) -5- (methyl) phenyl) substantially prepared according to the teachings of US-A-2004 / 0010103 2-phenoxymethyl) cyclohexane-1,2-diyl zirconium (IV) dibenzyl.

Catalyst (B1) : 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (1-methylethyl) imino) methyl) (2-oxoyl) zirconium dibenzyl .

Catalyst (B2): 1,2-bis- (3,5-di-t-butylphenylene) (1- (N- (2-methylcyclohexyl) -imino) methyl) (2-oxoyl) zirconium Dibenzyl.

Catalyst ( C1 ) : (t-butylamido) dimethyl (3-N-pyrrolyl-1,2,3,3a, 7a-η-inden-1-yl substantially prepared according to the teachings of US Pat. No. 6,268,444 Silantitanium dimethyl.

Catalyst ( C2 ) : (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 7a-η- substantially prepared according to the teachings of US-A-2003 / 004286 Inden-1-yl) silanetitanium dimethyl.

Catalyst ( C3 ) : (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 8a-η- substantially prepared according to the teachings of US-A-2003 / 004286 s-indasen-1-yl) silanetitanium dimethyl.

Catalyst ( D1 ) : Bis (dimethyldisiloxane) (inden-1-yl) zirconium dichloride available from Sigma-Aldrich.

Transfer agent : The transfer agent used was diethylzinc, di (i-butyl) zinc, di (n-hexyl) zinc, triethylaluminum, trioctylaluminum, triethylgallium, i-butylaluminum bis (dimethyl (t-butyl) Siloxane), i-butylaluminum bis (di (trimethylsilyl) amide), n-octylaluminum di (pyridine-2-methoxide), bis (n-octadecyl) i-butylaluminum, i-butylaluminum bis (di (n-pentyl) amide), n-octyl aluminum bis (2,6-di-t-butylphenoxide), n-octyl aluminum di (ethyl (1-naphthyl) amide), ethylaluminum bis (t-butyl Dimethylsiloxide), ethylaluminum di (bis (trimethylsilyl) amide), ethylaluminum bis (2,3,6,7-dibenzo-1-azacycloheptanamide), n-octylaluminum bis (2,3, 6,7-dibenzo-1-azacycloheptanamide), n-octylaluminum bis (dimethyl (t-butyl) siloxide, ethylzinc (2,6-diphenylphenoxide) and ethylzinc (t-butoxide ).

Preferably, the method includes using a plurality of catalysts that can not be interconversion of block copolymers, especially multi-block copolymer, preferably two or more monomers, more especially ethylene and a C _{3 -20} olefin or cycloolefin, and most specially it takes the form of a continuous solution process for the production of ethylene and C _{4 -20} linear multi-block of the α- olefin copolymer. That is, the catalyst is chemically different. Under continuous solution polymerization conditions, the process is ideally suited for the polymerization of monomer mixtures of high monomer conversion. Under these polymerization conditions, the transfer from the chain transfer agent to the catalyst is favored over the chain growth, so that multiblock copolymers, especially linear multiblock copolymers, are formed with high efficiency.

The interpolymers of the present invention can be differentiated from conventional random copolymers, physical blends of polymers and block copolymers prepared by sequential monomer addition, flow catalysts, anionic or cationic living polymerization techniques. In particular, compared to random copolymers having the same monomer and monomer content at equivalent crystallinity or modulus, the interpolymers of the present invention have better (higher) heat resistance (measured by melting point), higher TMA penetration temperature, higher high temperature. Tensile strength and / or higher hot torsional storage modulus (measured by dynamic mechanical analysis). Compared to random copolymers having the same monomers and monomer content, the interpolymers of the invention have lower compression set, lower stress relaxation, higher creep resistance, higher tear strength, higher blocking resistance, especially at elevated temperatures, Faster set-up due to higher crystallization (solidification) temperature, higher recovery rate (especially at elevated temperatures), better wear resistance, higher shrinkage, and better oil and filler tolerance.

The interpolymers of the present invention also exhibit specific crystallization and branching distribution relationships. That is, the interpolymers of the present invention are CRYSTAF as a function of heat of fusion, in particular compared to random copolymers or physical blends of polymers containing the same monomers and monomer concentrations, such as blends of high density polymers and low density copolymers at equivalent overall density and There is a relatively large difference between the highest peak temperatures measured using DSC. It is believed that this particular feature of the interpolymers of this invention is due to the unique comonomer distribution in the blocks in the polymer backbone. In particular, the interpolymers of the present invention may include alternating blocks (including homopolymer blocks) having different comonomer contents. The interpolymers of the present invention may comprise a distribution that is a Schultz-Florie distribution in the number and / or block size of polymer blocks having different densities or comonomer contents. In addition, the inventive interpolymers also have specific peak melting points and crystallization temperature profiles that are substantially independent of polymer density, modulus, and shape. In a preferred embodiment, the order of the microcrystals of the polymer exhibits characteristic spherulite and lamella, even distinguishable from random or block copolymers, even at PDI values of less than 1.7, or less than 1.5 and also less than 1.3.

In addition, the interpolymers of the present invention can be prepared using techniques that affect the degree or level of blocking. That is, the length and amount of comonomers of each polymer block and segment can be varied by controlling the ratio and type of catalyst and transfer agent as well as the polymerization temperature, and other polymerization parameters. A surprising advantage of this phenomenon is the discovery that as the degree of blocking increases, the optical properties, tear strength and high temperature recovery properties of the resulting polymers improve. In particular, as the average number of blocks in the polymer increases, the transparency, tear strength and high temperature recovery properties increase while the haze decreases. By selecting a combination of a catalyst and a transfer agent having the desired chain transfer capacity (high transfer rate at low chain termination), other forms of polymer termination are effectively suppressed. Thus, the polymerization of ethylene / α-olefin comonomer mixtures according to embodiments of the present invention results in very little β-hydride removal, even when present, and the resulting crystalline blocks have little or no long chain branching and are very or substantially Completely linear.

Polymers with highly crystalline chain ends can optionally be prepared in accordance with embodiments of the present invention. In elastomer applications, reducing the relative amount of polymer terminated by amorphous blocks reduces the effect of intermolecular dilution on crystalline regions. These results can be obtained by selecting chain transfer agents and catalysts having an appropriate reaction with hydrogen or other chain terminators. Specifically, catalysts that produce highly crystalline polymers (such as by the use of hydrogen, for example) in comparison to catalysts that produce polymer segments that are less crystalline (e.g., by large comonomer incorporation, site-error or atactic polymer formation). If more susceptible to chain termination, the highly crystalline polymer segment occupies the terminal portion of the polymer. Not only are the resulting end groups crystalline, but upon termination, a highly crystalline polymer forming catalyst site is available for resumption of polymer formation once again. Thus, the initially formed polymer is another highly crystalline polymer segment. Thus, both ends of the resulting multiblock copolymer are predominantly highly crystalline.

The ethylene / α-olefin interpolymers used in the embodiments of the present invention are preferably interpolymers of ethylene and at least one C ₃ -C ₂₀ α-olefin. Particular preference is given to copolymers of ethylene and C ₃ -C ₂₀ α-olefins. The interpolymers may further comprise C ₄ -C ₁₈ diolefins and / or alkenylbenzenes. Suitable unsaturated comonomers useful for polymerizing with ethylene include, for example, ethylenically unsaturated monomers, conjugated or nonconjugated dienes, polyenes, alkenylbenzenes and the like. Examples of such comonomers are C ₃ -C ₂₀ α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene , 1-nonene, 1-decene and the like. Particular preference is given to 1-butene and 1-octene. Other suitable monomers include styrene, halo- or alkyl-substituted styrenes, vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene and naphthenic components (eg cyclopentene, cyclohexene and Cyclooctene).

Although ethylene / α-olefin interpolymers are preferred polymers, other ethylene / olefin polymers may be used. Olefin as used herein refers to a group of unsaturated hydrocarbon-based compounds having at least one carbon-carbon double bond. Depending on the choice of catalyst, any olefin can be used in embodiments of the present invention. Preferably, suitable olefins are C ₃ -C ₂₀ aliphatic and aromatic compounds containing vinylic unsaturated groups, and cyclic compounds such as cyclobutene, cyclopentene, dicyclopentadiene and norbornene (positions 5 and 6) To norbornene substituted with a C ₁ -C ₂₀ hydrocarbyl or cyclohydrocarbyl group). Mixtures of the olefins as well as mixtures of C ₄ -C ₄₀ diolefin compounds with the olefins are included.

Examples of olefin monomers include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4 Vinylcyclohexene, vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene, C ₄ -C ₄₀ diene (1,3-butadiene, 1,3 -Pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene), other C ₄ -C ₄₀ α- Olefins and the like, but are not limited thereto. In certain embodiments, the α-olefin is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or a combination thereof. Any hydrocarbon potentially containing vinyl groups can be used in embodiments of the invention, but practical problems such as monomer availability, cost, and the ability to conveniently remove unreacted monomer from the resulting polymer as the molecular weight of the monomer becomes too high Can be even more problematic.

The polymerization process described herein is well suited for the preparation of olefin polymers comprising monovinylidene aromatic monomers including styrene, o-methyl styrene, p-methyl styrene, t-butyl styrene and the like. In particular, interpolymers comprising ethylene and styrene can be prepared according to the teachings herein. Optionally, copolymers comprising optionally C ₄ -C ₂₀ dienes, including ethylene, styrene and C ₃ -C ₂₀ alpha olefins with improved properties can be prepared.

Suitable nonconjugated diene monomers may be straight, branched or cyclic hydrocarbon dienes having 6 to 15 carbon atoms. Examples of suitable nonconjugated dienes include straight chain acyclic dienes such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes such as 5 -Methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyriene and dihydrooxyene, monocyclic alicyclic dienes such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene, and multicyclic alicyclic conjugated and bridged ring dienes such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo- ( 2,2,1) -hepta-2,5-diene; Alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornene, such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene Butene, 5-vinyl-2-norbornene and norbornadiene. Among the dienes typically used for EPDM preparation, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB ), 5-methylene-2-norbornene (MNB) and dicyclopentadiene (DCPD). Particularly preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of preferred polymers that may be prepared according to embodiments of the present invention are elastomeric interpolymers of ethylene, C ₃ -C ₂₀ α-olefins, in particular propylene, and optionally one or more diene monomers. Preferred α-olefins for use in this embodiment of the invention are represented by the formula CH ₂ = CHR ^{* wherein} R ^* is a linear or branched alkyl group having from 1 to 12 carbon atoms. Examples of suitable α-olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. Particularly preferred α-olefins are propylene. Propylene based polymers are generally referred to in the art as EP or EPDM polymers. Suitable dienes for use in preparing such polymers, especially multiblock EPDM type polymers, include conjugated or nonconjugated, straight or branched chain, cyclic or polycyclic dienes comprising 4 to 20 carbons. Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene and 5-butylidene-2-norbornene. Included. Particularly preferred dienes are 5-ethylidene-2-norbornene.

Diene-containing polymers contain alternating segments or blocks containing more or less amounts of dienes (including if not present) and α-olefins (including if not present), thereby reducing diene without subsequent loss of polymer properties. And the total amount of α-olefins can be reduced. That is, since dienes and α-olefin monomers are predominantly incorporated into one type of polymer block rather than uniformly or randomly incorporated throughout the polymer, they are used more effectively, and the crosslinking density of the polymer can then be better controlled. . Such crosslinkable elastomers and cured products have advantageous properties, including higher tensile strength and better elastic recovery.

In some embodiments, interpolymers of the invention prepared by two catalysts incorporating different amounts of comonomer have a weight ratio of the blocks formed thereby from 95: 5 to 5:95. The elastomeric polymer preferably has 20 to 90% ethylene content, 0.1 to 10% diene content and 10 to 80% α-olefin content, based on the total weight of the polymer. More preferably, the multiblock elastomeric polymer has an ethylene content of 60 to 90%, a diene content of 0.1 to 10% and an α-olefin content of 10 to 40% based on the total weight of the polymer. Preferred polymers have a weight average molecular weight (Mw) of 10,000 to about 2,500,000, preferably 20,000 to 500,000, more preferably 20,000 to 350,000, a polydispersity of less than 3.5, more preferably less than 3.0, and Mooney ) Is a high molecular weight polymer having a viscosity (ML (1 + 4) 125 ° C.) of 1 to 250. More preferably, such polymers have an ethylene content of 65 to 75%, a diene content of 0 to 6% and an α-olefin content of 20 to 35%.

Ethylene / α-olefin interpolymers can be functionalized by incorporating one or more functional groups into their polymer structure. Examples of functional groups may include, for example, ethylenically unsaturated monofunctional and difunctional carboxylic acids, ethylenically unsaturated monofunctional and difunctional carboxylic anhydrides, salts thereof and esters thereof. Such functional groups may be grafted onto ethylene / α-olefin interpolymers or copolymerized with ethylene and optionally further comonomers to form interpolymers of ethylene, functional comonomers and optionally other comonomer (s). Can be. Means for grafting functional groups onto polyethylene are described, for example, in US Pat. Nos. 4,762,890, 4,927,888 and 4,950,541, the disclosures of which are incorporated herein by reference in their entirety. One particularly useful group is maleic anhydride.

The amount of functional groups present in the functional interpolymer can vary. The functional group may typically be present in the copolymerized functionalized interpolymer in an amount of at least about 1.0 wt%, preferably at least about 5 wt%, more preferably at least about 7 wt%. The functional group will typically be present in the copolymerized functionalized interpolymer in an amount of less than about 40 wt%, preferably less than about 30 wt%, more preferably less than about 25 wt%.

The amount of ethylene / α-olefin interpolymers in the lubricant compositions disclosed herein is from about 0.01 to about 30 weight percent, from about 0.05 to about 20 weight percent, from about 0.1 to about 15 weight percent, from about 0.5 to based on the total amount of lubricant composition. About 10% by weight, or about 1% to about 5% by weight.

Foundation oil

Any base oil known to those skilled in the art can be used to prepare the lubricant composition. Suitable base oils for preparing lubricant compositions are described in Mortier et al., "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, Chapters 1 and 2 (1996). In general, the lubricant composition may comprise from about 70 to 99% by weight of the base oil based on the total weight of the lubricant composition. In some embodiments, the lubricant composition comprises about 80-98 weight percent of the base oil based on the total weight of the lubricant composition.

In some embodiments, the base oil is disclosed in American Petroleum Institute (API) Publication 1509, Fourteen Edition, December 1996 (ie, API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils), which is incorporated herein by reference. And any basic raw material of the specified groups I to V. The API guide defines basic raw materials as lubricant components that can be prepared using a variety of different methods. Group I, II and III basic raw materials are mineral oils each having a specific range of amount of saturates, sulfur content and viscosity index. Group IV base raw materials are polyalphaolefins (PAO). Group V base stocks include all other base stocks not included in Group I, II, III, or IV. In certain embodiments, the base oil comprises a combination of base stocks in Groups I-V.

In other embodiments, the base oil comprises natural oils, synthetic oils or combinations thereof. Non-limiting examples of suitable natural oils include animal oils (eg lard oil), vegetable oils (eg corn oil, castor oil, and peanut oil), oils derived from coal or shale, mineral oils (eg Liquid petroleum oils and solvent treated or acid treated mineral oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic type) and combinations thereof. Non-limiting examples of suitable synthetic lubricating oils include poly-alpha-olefins, alkylated aromatics, polybutenes, aliphatic diesters, polyol esters, polyalkylene glycols, phosphate esters, and combinations thereof.

In further embodiments, the base oil may be a polyolefin (eg, polybutylene, polypropylene, propylene isobutylene copolymer, polyhexene, polyoctene, polydecene, etc.); Alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di- (2-ethylhexyl) benzene, etc.); Polyphenyls (eg, biphenyls, terphenyls, alkylated polyphenyls, etc.); Alkylated diphenyl ethers; Alkylated diphenyl sulfides; And hydrocarbon oils such as derivatives, isomers, analogs, homologs and combinations thereof.

In a further embodiment, the base oil comprises a poly-alpha-olefin (PAO). In general, poly-alpha-olefins can be derived from alpha-olefins having about 2 to about 30, or about 4 to about 20, or about 6 to about 16 carbon atoms. Non-limiting examples of suitable poly-alpha-olefins include those derived from octene, decene, mixtures thereof, and the like. The viscosity of the poly-alpha-olefin may be about 2 to about 15 centistokes, or about 3 to about 12 centistokes, or about 4 to about 8 centistokes at 100 ° C. In some cases, poly-alpha-olefins may be used with other base oils, such as mineral oils.

In a further embodiment, the base oil comprises a polyalkylene glycol or polyalkylene glycol derivative wherein the terminal hydroxyl groups of the polyalkylene glycol can be modified by esterification, etherification, acetylation and the like. Non-limiting examples of suitable polyalkylene glycols include polyethylene glycol, polypropylene glycol, polyisopropylene glycol, and combinations thereof. Non-limiting examples of suitable polyalkylene glycol derivatives include ethers of polyalkylene glycol (eg, methyl ether of polyisopropylene glycol, diphenyl ether of polyethylene glycol, diethyl ether of polypropylene glycol, etc.), polyalkylene Mono- and polycarboxylic acid esters of glycols, and combinations thereof. In some cases, polyalkylene glycols or polyalkylene glycol derivatives may be used with other basic oils such as poly-alpha-olefins and mineral oils.

In a further embodiment, the base oil may comprise various alcohols (eg, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.) and dicarboxylic acids ( For example, phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl mal Random esters of lonic acid and the like). Non-limiting examples of such esters are dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate , Didecyl phthalate, diecosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and the like.

In a further embodiment, the base oil comprises a hydrocarbon prepared by a Fischer-Tropsch reaction. The Fischer-Tropsch reaction uses a Fischer-Tropsch catalyst to produce hydrocarbons from hydrogen and carbon monoxide containing gases. The hydrocarbon may require further processing in order to be useful as a base oil. For example, hydrocarbons can be dewaxed, hydroisomerized, and / or hydrocracked using methods known to those skilled in the art.

In further embodiments, the base oil comprises refined, crude, or refined oils. Crude oil is obtained directly from natural or synthetic sources without further purification. Non-limiting examples of crude oils include shale streams obtained directly from retort processing, petroleum oils obtained directly from primary distillation, and ester oils obtained directly from esterification reactions and used without further treatment. Refined oils are similar to crude oils except that they are further processed by one or more purification methods to improve one or more properties. Many such purification methods are known to those skilled in the art, such as solvent extraction, secondary distillation, acid or base extraction, filtration, permeation extraction, and the like. Refined oils are obtained by applying methods to the refined oils similar to those used to obtain refined oils. Such refined oils are also known as regenerated or reprocessed oils and are often further processed by methods that direct the removal of used additives and oil decomposition products.

additive

Optionally, the lubricant composition may further comprise one or more additives or modifiers (hereinafter referred to as "additives") that can impart or improve any desired properties of the lubricant composition. Any additive known to those skilled in the art can be used in the lubricant compositions disclosed herein. Some suitable additives are all described by Mortier et al., "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, (1996), and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications, "New York, Marcel Dekker (2003). In some embodiments, the additive may be selected from the group consisting of detergents, dispersants, friction modifiers, pour point depressants, demulsifiers, antifoams, corrosion inhibitors, antiwear agents, antioxidants, rust inhibitors, and combinations thereof. In general, the concentration of each additive in the lubricant composition in use may range from about 0.001 to about 20 weight percent, from about 0.01 to about 10 weight percent, or from about 0.1 to about 5 weight percent based on the total weight of the lubricant composition. .

Lubricant compositions disclosed herein may include detergents that preserve water-insoluble particles in colloidal suspensions and in some cases neutralize acids to control varnishes, ring zone deposits, and rust. Any detergent known to those skilled in the art can be used in the lubricant composition. Non-limiting examples of suitable detergents include metal sulfonates, phenates, salicylates, phosphonates, thiophosphonates, and combinations thereof. The metal can be any metal suitable for making sulfonate, phenate, salicylate or phosphonate cleaners. Non-limiting examples of suitable metals include alkali metals, alkaline metals and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li, and the like. The amount of detergent can vary from about 0.01 to about 10 weight percent, from about 0.05 to about 5 weight percent, or from about 0.1 to about 3 weight percent based on the total weight of the lubricant composition. Some suitable detergents are all described by Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 3, pages 75-85 (1996), and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter 4, pages 113-136 (2003).

The lubricant compositions disclosed herein can include dispersants that can preserve suspended particles in the colloidal state to prevent sludge, varnishes, and other deposits. Any dispersant known to those skilled in the art can be used in the lubricant composition. Non-limiting examples of suitable dispersants include succinimide, succinamide, benzylamine, succinic acid esters, succinic acid ester-amides, Mannich type dispersants, phosphorus containing dispersants, boron containing dispersants, and combinations thereof. The amount of dispersant may vary from about 0.01 to about 10 weight percent, from about 0.05 to about 7 weight percent, or from about 0.1 to about 4 weight percent based on the total weight of the lubricant composition. Some suitable dispersants are all described by Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 3, pages 86-90 (1996), and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter 5, pages 137-170 (2003).

The lubricant compositions disclosed herein can include friction modifiers that can lower friction between moving parts. Any friction modifier known to those skilled in the art can be used in the lubricant composition. Non-limiting examples of suitable friction modifiers include fatty acid carboxylic acids; Derivatives of fatty acid carboxylic acids (eg, esters, amides, metal salts, etc.); Mono-, di- or tri-alkyl substituted phosphoric acid or phosphonic acid; Derivatives of mono-, di- or tri-alkyl substituted phosphoric or phosphonic acids (eg, esters, amides, metal salts, etc.); Mono-, di- or tri-alkyl substituted amines; Mono-, di-alkyl substituted amides and combinations thereof. In some embodiments, the friction modifier is an aliphatic amine, ethoxylated aliphatic amine, aliphatic carboxylic acid amide, ethoxylated aliphatic ether amine, aliphatic carboxylic acid, glycerol ester, aliphatic carboxylic acid ester-amide, aliphatic imidazoline, aliphatic Selected from the group consisting of tertiary amines, said aliphatic or aliphatic groups contain at least about 8 carbon atoms to make suitably oil soluble compounds. In other embodiments, the friction modifier comprises aliphatic substituted succinimides formed by reacting ammonia or primary amines with aliphatic succinic acids or anhydrides. The amount of friction modifier may vary from about 0.01 to about 10 weight percent, from about 0.05 to about 5 weight percent, or from about 0.1 to about 3 weight percent based on the total weight of the lubricant composition. Some suitable friction modifiers are all referenced herein by Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 6, pages 183-187 (1996), and Leslie R Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapters 6 and 7, pages 171-222 (2003).

The lubricant composition disclosed herein may include a pour point depressant that can lower the pour point of the lubricant composition. Any pour point depressant known to those skilled in the art can be used in the lubricant composition. Non-limiting examples of suitable pour point depressants include polymethacrylates, polyacrylates, di (tetra-paraffin phenol) phthalates, condensates of tetra-paraffin phenols, condensates of naphthalene and chlorinated paraffins, and combinations thereof. In some embodiments, the pour point depressant comprises ethylene-vinyl acetate copolymers, condensates of chlorinated paraffins and phenols, polyalkyl styrenes, and the like. The amount of pour point depressant may vary from about 0.01 to about 10 weight percent, from about 0.05 to about 5 weight percent, or from about 0.1 to about 3 weight percent based on the total weight of the lubricant composition. Some suitable pour point depressants are all described by Mortier et al., "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, Chapter 6, pages 187-189 (1996), and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter 11, pages 329-354 (2003).

The lubricant composition disclosed herein may include a demulsifier that can promote oil-water separation in the lubricant composition exposed to water or steam. Any demulsifier known to those skilled in the art can be used in the lubricant composition. Non-limiting examples of suitable demulsifiers include anionic surfactants (eg, alkyl-naphthalene sulfonates, alkyl benzene sulfonates, etc.), nonionic alkylated alkylphenol resins, polymers of alkylene oxides (eg, polyethylene oxides, Polypropylene oxide, ethylene oxide, block copolymers of propylene oxide, and the like), esters of oil soluble acids, and combinations thereof. The amount of demulsifier may vary from about 0.01 to about 10 weight percent, from about 0.05 to about 5 weight percent, or from about 0.1 to about 3 weight percent based on the total weight of the lubricant composition. Some suitable demulsifiers are described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 6, pages 190-193 (1996).

The lubricant compositions disclosed herein can include antifoams that can disperse the foam in the oil. Any antifoaming agent known to those skilled in the art can be used in the lubricant composition. Non-limiting examples of suitable antifoams include silicone oils or polydimethylsiloxanes, fluorosilicones, alkylated aliphatic acids, polyethers (eg polyethylene glycols), branched polyvinyl ethers, polyacrylates, polyalkoxyamines and combinations thereof It includes. In some embodiments, the antifoaming agent comprises glycerol monostearate, polyglycol palmitate, trialkyl monothiophosphate, esters of sulfonated ricinoleic acid, benzoylacetone, methyl salicylate, glycerol monooleate, or glycerol dioleate do. The amount of antifoam may vary from about 0.01 to about 5 weight percent, from about 0.05 to about 3 weight percent, or from about 0.1 to about 1 weight percent based on the total weight of the lubricant composition. Some suitable antifoams are described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 6, pages 190-193 (1996).

The lubricant compositions disclosed herein can include corrosion inhibitors that can reduce corrosion. Any corrosion inhibitor known to those skilled in the art can be used in the lubricant composition. Non-limiting examples of suitable corrosion inhibitors include semiesters or amides of dodecylsuccinic acid, phosphate esters, thiophosphates, alkyl imidazolines, sarcosine and combinations thereof. The amount of corrosion inhibitor can vary from about 0.01 to about 5 weight percent, from about 0.05 to about 3 weight percent, from about 0.1 to about 1 weight percent, based on the total weight of the lubricant composition. Some suitable corrosion inhibitors are described in Mortier et al., “Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, Chapter 6, pages 193-196 (1996).

The lubricant compositions disclosed herein can include antiwear agents that can reduce friction and excessive wear. Any antiwear agent known to those skilled in the art can be used in the lubricant composition. Non-limiting examples of suitable antiwear agents include zinc dithiophosphate, metal (eg Pb, Sb, Mo, etc.) salts of dithiocarbamate, metals of dithiocarbamate (eg Zn, Pb, Sb, Mo, etc.) salts, metals of fatty acids (eg, Zn, Pb, Sb, etc.) salts, boron compounds, phosphate esters, phosphite esters, phosphate esters or amine salts of thiophosphoric esters, dicyclopentadiene and thiophosphoric acid Reaction products and combinations thereof. The amount of antiwear agent may vary from about 0.01 to about 5 weight percent, from about 0.05 to about 3 weight percent, or from about 0.1 to about 1 weight percent based on the total weight of the lubricant composition. Some suitable antiwear agents are described in Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter 8, pages 223-258 (2003).

The lubricant compositions disclosed herein can include extreme pressure (EP) agents that can prevent slippage of the metal surface from seizing under extreme pressure conditions. Any extreme pressure agent known to those skilled in the art can be used in the lubricant composition. In general, extreme pressure agents are compounds that can chemically bond with metal to form a surface film that prevents welding of asperity on the facing metal surface under high loadings. Non-limiting examples of suitable extreme pressure agents include sulfided animal or vegetable fats or oils, sulfided animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfided olefins, dihydrocarbyl polysulfides, Sulfurized Diels-Alder adducts, sulfided or co-sulfurized mixtures of sulfided dicyclopentadienes, fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty acids, fatty acid esters and alpha-olefins, sensory substitutions Of polydisulfide blends and polysulfide olefin products, phosphate esters or thiophosphate esters of dihydrocarbyl polysulfite, thia-aldehyde, thia-ketone, epithio compounds, sulfur containing acetal derivatives, terpenes and acyclic olefins Salts and combinations thereof. The amount of extreme pressure agent may vary from about 0.01 to about 5 weight percent, about 0.05 to about 3 weight percent, or about 0.1 to about 1 weight percent based on the total weight of the lubricant composition. Some suitable extreme pressure agents are described in Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter 8, pages 223-258 (2003).

The lubricant compositions disclosed herein can include antioxidants that can reduce or prevent oxidation of the base oil. Any antioxidant known to those skilled in the art can be used in the lubricant composition. Non-limiting examples of suitable antioxidants include amine based antioxidants (eg, alkyl diphenylamines, phenyl-α-naphthylamines, alkyl or aralkyl substituted phenyl-α-naphthylamines, alkylated p-phenylene diamines). , Tetramethyl-diaminodiphenylamine, etc.), phenolic antioxidants (for example, 2-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,4,6-tri tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 4,4'-methylenebis- (2,6-di-tert-butyl Phenol), 4,4'-thiobis (6-di-tert-butyl-o-cresol) and the like, sulfur based antioxidants (e.g., dilauryl-3,3'-thiodipropionate, Sulfurized phenolic antioxidants and the like), phosphorus based antioxidants (eg, phosphites and the like), zinc dithiophosphate, oil soluble copper compounds and combinations thereof. The amount of antioxidant can vary from about 0.01 to about 10 weight percent, from about 0.05 to about 5 percent, or from about 0.1 to about 3 percent, based on the total weight of the lubricant composition. Some suitable antioxidants are described in Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter 1, pages 1-28 (2003).

The lubricant compositions disclosed herein may include a rust inhibitor that can inhibit corrosion of the ferrous metal surface. Any rust inhibitor known to those skilled in the art can be used in the lubricant composition. Non-limiting examples of suitable rust inhibitors include oil soluble monocarboxylic acids (eg, 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, sertric acid, etc.) , Oil soluble polycarboxylic acids (e.g., those prepared from tall oil fatty acids, oleic acid, linoleic acid, etc.), alkenylsuccinic acids in which alkenyl groups contain at least 10 carbon atoms (e.g., tetrapropenyl succinic acid , Tetradecenyl succinic acid, hexadecenyl succinic acid, etc.); Long chain alpha, omega-dicarboxylic acids and combinations thereof having a molecular weight in the range of 600 to 3000 Daltons. The amount of rust inhibitor can vary from about 0.01 to about 10 weight percent, from about 0.05 to about 5%, or from about 0.1 to about 3%, based on the total weight of the lubricant composition.

The additive may be in the form of an additive concentrate having one or more additives. The additive concentrate may comprise a suitable diluent, most preferably a hydrocarbon oil of suitable viscosity. Such diluents can be selected from the group consisting of natural oils (eg mineral oils), synthetic oils and combinations thereof. Non-limiting examples of mineral oils include paraffin based oils, naphthenic based oils, asphalt based oils and combinations thereof. Non-limiting examples of synthetic base oils include polyolefin oils (particularly hydrogenated alpha-olefin oligomers), alkylated aromatics, polyalkylene oxides, aromatic ethers, and carboxylate esters (particularly diester oils) and combinations thereof. In some embodiments, the diluent is a light hydrocarbon oil that is natural or synthetic. In general, the viscosity of the diluent oil may be in the range of 13 to 35 centistokes at 40 ° C.

The lubricant compositions disclosed herein may be suitable for use as automotive oil (or engine oil or crankcase oil), transformer fluid, gear oil, power steering fluid, shock absorber fluid, brake fluid, hydraulic fluid, and / or grease.

In some embodiments, the lubricant composition disclosed herein is automotive oil. Such automotive oil compositions can be used to lubricate all major moving parts in any reciprocating internal combustion engine, reciprocating compressor and crankcase steam engine. In automotive applications, automotive oil compositions can also be used to cool hot engine parts, keep the engine free of rust and deposition, and seal rings and valves against leakage of combustion gases. Automotive oil compositions may include base oils and ethylene / α-olefin interpolymers. The automotive oil composition may further comprise one or more additives. In some embodiments, the automotive oil composition further comprises a pour point depressant, detergent, dispersant, antiwear, antioxidant, friction modifier, rust inhibitor, or a combination thereof.

In other embodiments, the lubricant compositions disclosed herein are gear oils for automotive or industrial applications. Gear oil compositions can be used to lubricate gears, rear axles, automotive transmissions, final drive shafts, agricultural accessories and construction equipment, gear housings and sealed chain drives. The gear oil composition may comprise a base oil and an ethylene / α-olefin interpolymer. The gear oil composition may further comprise one or more additives. In some embodiments, the gear oil composition further comprises an antiwear, extreme pressure, rust inhibitor, or combination thereof.

In a further embodiment, the lubricant composition disclosed herein is a transmission fluid. Transmission fluid compositions can be used to reduce transmission losses in automatic transmissions or manual transmissions. The transmission fluid composition may comprise a base oil and an ethylene / α-olefin interpolymer. The transmission fluid composition may further comprise one or more additives. In some embodiments, the transmission fluid composition further comprises a friction modifier, cleaner, dispersant, antioxidant, antiwear, extreme pressure, pour point depressant, antifoam, corrosion inhibitor, or combinations thereof.

In further embodiments, the lubricant compositions disclosed herein are greases used in various applications, for example, on the vertical axis, when extensive lubrication is required and oil is not retained. The grease composition may comprise a base oil, an ethylene / α-olefin interpolymer and a thickener. In some embodiments, the grease composition further comprises a complexing agent, antioxidant, antiwear, extreme pressure, antifoam, corrosion inhibitor, or mixtures thereof. In some embodiments, the thickener is a soap formed by reacting a fat, fatty acid, or ester with a metal hydroxide (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, zinc hydroxide, and the like). In general, the type of soap used depends on the desired grease properties. In other embodiments, the thickener may be a non-soap thickener selected from the group consisting of clay, silica gel, carbon black, various synthetic organic materials, and combinations thereof. In further embodiments, the thickener comprises a combination of soap and non-soap thickeners.

Process for preparing lubricant composition

The lubricant compositions disclosed herein may be prepared by any method for preparing lubricating oils known to those of ordinary skill in the art. In some embodiments, the base oil may be blended or mixed with the ethylene / α-olefin interpolymer and optionally one or more additives. Ethylene / α-olefin interpolymers and optional additives may be added to the base oil individually or simultaneously. In some embodiments, the ethylene / α-olefin interpolymers and any additives are added individually to the base oil in one or more additions, which additions may be in any order. In other embodiments, the ethylene / α-olefin interpolymer and the additive are added to the base oil simultaneously, optionally in the form of an additive concentrate. In some embodiments, the mixture is heated to a temperature of about 25 to about 200 ° C., about 50 to about 150 ° C. or about 75 to about 125 ° C. to dissolve the ethylene / α-olefin interpolymer or any solid additive in the base oil. Can help.

Any mixing or dispersing equipment known to those skilled in the art can be used for blending, mixing or dissolving the components. Blending, mixing or solubilizing may be performed on blenders, stirrers, dispersers, mixers (e.g. Ross dual planetary mixers and Collette planetary mixers), homogenizers (e.g. Gaulin homogenizers and Rannie homogenizers, mills (eg colloidal mills, ball mills and sand mills) or any other mixing or dispersing equipment known in the art.

Embodiments of the present invention provide a lubricant composition made from a base oil and an ethylene / α-olefin interpolymer. Preferably, the ethylene / α-olefin interpolymer is a multiblock copolymer comprising at least one soft block and at least one hard block.

The following examples are provided to illustrate embodiments of the invention and are not intended to limit the invention to the specific embodiments described. Unless otherwise stated, all parts and percentages are by weight. All figures are approximate. When provided with a numerical range, it should be understood that embodiments outside the stated range may also be included within the scope of the present invention. The specific details described in each example should not be considered as essential features of the invention.

Test method

In the following examples, the following analytical techniques were used.

For samples 1-4 and A-C GPC  Way

Using an automated liquid-handling robot equipped with a heated needle set at 160 ° C., sufficient 1,2,4-trichlorobenzene stabilized by 300 ppm Ionol was added to each dried polymer sample by 30 A final concentration of mg / mL was obtained. A small glass stir bar was placed in each tube and the sample was heated to 160 ° C. for 2 hours in a heated rotary shaker rotating at 250 rpm. The polymer concentrate was then diluted to 1 mg / ml using an automated liquid-handling robot and a heated needle set at 160 ° C.

Molecular weight data for each sample was measured using the Symyx Rapid GPC system. Three Plgels placed in series as a mobile phase with helium purged 1,2-dichlorobenzene stabilized with 300 ppm ionol using a Gilson 350 pump set at a flow rate of 2.0 ml / min. Pumped through a 10 micrometer (μm) Mix-B 300 mm × 7.5 mm column and heated to 160 ° C. The Polymer Labs ELS 1000 Detector was set to an evaporator set at 250 ° C., a nebulizer set at 165 ° C., and nitrogen set at 1.8 SLM at a pressure of 60 to 80 psi (400 to 600 kPa) N ₂ . Used with flow rate. The polymer samples were heated to 160 ° C. and each sample was injected into a 250 μl loop using a liquid-handling robot and heated needle. A series of polymer sample analyzes and duplicate injections using two switched loops were used. Sample data was collected and analyzed using Symyx Epoch ™ software. Peaks were manually integrated and molecular weight information was recorded uncorrected against the polystyrene standard calibration curve.

Standard CRYSTAF  Way

Branching distribution was measured by crystallization analysis fractionation (CRYSTAF) using a CRYSTAF 200 unit commercially available from Polymer Char (Valencia, Spain). The sample was dissolved in 1,2,4-trichlorobenzene at 160 ° C. for 1 hour (0.66 mg / mL) and stabilized at 95 ° C. for 45 minutes. Sampling temperatures ranged from 95 to 30 ° C. at a cooling rate of 0.2 ° C./min. The polymer solution concentration was measured using an infrared detector. The cumulative soluble concentration was measured when the polymer crystallized with decreasing temperature. Analytical derivatives of the cumulative profile reflect the short chain branching distribution of the polymer.

CRYSTAF peak temperature and area were confirmed by the peak analysis module included in the CRYSTAF software (version 2001.b, Polymer Char, Valencia, Spain). The CRYSTAF peak identification routine confirmed the area between the peak temperature as the maximum in the dW / dT curve, and the maximum amount of bend on each side of the peak identified in the derivative curve. To calculate the CRYSTAF curve, a preferred processing parameter is to perform parameter planarization above the temperature limit of 0.1 and below the temperature limit of 0.3 with a temperature limit of 70 ° C.

DSC  Standard method (except samples 1-4 and A-C)

The results of the differential scanning calorimetry were measured using a TAI model Q1000 DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge gas flow of 50 ml / min was used. The sample was pressed into a thin film and melted in a press at about 175 ° C. and then air cooled to room temperature (25 ° C.). Subsequently, 3-10 mg of material was cut into 6 mm diameter disks, accurately weighed, placed in a lightweight aluminum pan (about 50 mg) and then crimped off. The thermal behavior of the samples was investigated with the following temperature profiles. The sample was rapidly heated to 180 ° C. and kept isothermal for 3 minutes to remove any previous thermal history. The sample was then cooled to −40 ° C. at a cooling rate of 10 ° C./min and held at −40 ° C. for 3 minutes. The sample was then heated to 150 ° C. at a heating rate of 10 ° C./min. Cooling and second heating curves were recorded.

The DSC melt peak was measured as the maximum of heat flow rate (W / g) with respect to the linear baseline shown between −30 ° C. and the melting end point. The heat of fusion was measured as the area under the melting curve between −30 ° C. and the melting end point using a linear baseline.

GPC  Method (except Samples 1-4 and A-C)

The gel permeation chromatography system consisted of Polymer Laboratories Model PL-210 or Polymer Laboratories Model PL-220 instruments. The column and carousel compartments were operated at 140 ° C. Three Polymer Laboratories 10-micron Mixed-B columns were used. The solvent was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). Samples were prepared by gently stirring at 160 ° C. for 2 hours. The injection volume used was 100 microliters and the flow rate was 1.0 ml / min.

Calibration of the set of GPC columns was carried out using 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in six “cocktail” mixtures separated by at least 10 between individual molecular weights. Was performed. Standards were purchased from Polymer Laboratories, Shropshire, UK. Polystyrene standards were prepared in 0.025 grams in 50 milliliters of solvent for molecular weights greater than 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standard was dissolved at 80 ° C. with gentle stirring for 30 minutes. The narrow standard mixture was run first and then in decreasing order from the highest molecular weight component to minimize degradation. Equation: _Polyethylene standard peak molecular weight was converted to polyethylene molecular weight using M _polyethylene = 0.431 (M _polystyrene ) (Williams and Ward, J. Poym. Sci., Polym. Let., 6, 621 (1968)). Listed).

Polyethylene equivalent molecular weights were calculated using Viscotek TriSEC software version 3.0.

Compression set

Compression set was measured according to ASTM D 395. Samples were prepared by laminating circular discs of diameter 25.4 mm with a thickness of 3.2 mm, 2.0 mm and 0.25 mm until the total thickness reached 12.7 mm. The discs were cut from 12.7 cm x 12.7 cm compression molded plaques formed by hot press under the following conditions. A pressure of 0 at 190 ° C. for 3 minutes followed by 86 MPa at 190 ° C. for 2 minutes, followed by cooling water at 86 MPa for cooling in the press.

density

Samples for density measurement were prepared according to ASTM D 1928. Measurements were made within 1 hour of sample compression using ASTM D792, Method B.

curve/ secant Modulus /Save Modulus

Samples were compression molded using ASTM D 1928. Flexural and 2% secant modulus were measured according to ASTM D-790. Storage modulus was measured according to ASTM D 5026-01 or equivalent technique.

Optical properties

A 0.4 mm thick film was compression molded using a hot press (Carver model # 4095-4PR1001R). The pellet was placed between polytetrafluoroethylene sheets and heated at 190 ° C. for 3 minutes at 55 psi (380 kPa) then 3 minutes at 1.3 MPa and then 3 minutes at 2.6 MPa. The film was then cooled in a press by flowing cooling water at 1.3 MPa for 1 minute. Compression molded films were used for optical measurements, tensile behavior, recovery and stress relaxation rates.

Transparency was measured using BYK Gardner Haze-gard as specified in ASTM D 1746.

45 ° gloss was measured using BYK Gardner Glossmeter Microgloss 45 ° as specified in ASTM D-2457.

Internal haze was measured using a BYK Gardner Haze-Guard based on ASTM D 1003 Procedure A. Mineral oil was applied to the film surface to remove surface scratches.

Mechanical properties-tensile, Hysteresis ( Hysteresis ) And Tear

The stress-strain behavior at uniaxial tension was measured using ASTM D 1708 microtensile test specimens. Samples were stretched by Instron at 500C / min at 21 ° C. Tensile strength and elongation at break were recorded from the average of five test pieces.

100% and 300% hysteresis was measured from cyclic loading for 100% and 300% strain using ASTM D 1708 microtensile test specimens by an Instron ™ instrument. Samples were loaded and unloaded at 21 ° C. at 267% / min for 3 cycles. Circulation experiments were performed at 300% and 80 ° C using an environmental chamber. In the 80 ° C. experiment, the samples were equilibrated for 45 minutes at the test temperature before testing. In a 21 ° C., 300% strain cycling experiment, shrinkage stress at 150% strain from the first unloading cycle was recorded. The percent recovery in all experiments was calculated from the first unloading cycle using the strain at which loading returned to baseline. Recovery rate (%) is defined as follows.

Where ε _f is the strain obtained for cyclic loading and ε _s is the strain at which the loading returns to the baseline during the first unloading cycle.

Stress relief was measured at 50% strain and 12 hours at 37 ° C. using an Instron ™ instrument equipped with an environmental chamber. The gauge geometry was 76 mm x 25 mm x 0.4 mm. After equilibrating at 37 ° C. for 45 minutes in an environmental chamber, the sample was stretched to 50% strain at 333% / min. The stress was recorded as a function of time for 12 hours. The stress relaxation rate (%) was calculated after 12 hours using the following equation.

In the formula, L ₀ is loading at 50% strain at 0 hours and L ₁₂ is loading at 50% strain after 12 hours.

Tensile notched tear experiments were performed on samples with a density of 0.88 g / cc or less using an Instron ™ instrument. The geometry consisted of a 76 mm x 13 mm x 0.4 mm gauge region with a 2 mm notch cut into the sample at half the test piece length. The sample was stretched at 21 ° C. to 508 mm / min until the sample broke. Tear energy was calculated as the area under the stress-elongation curve up to strain at maximum loading. The average of three or more test pieces was recorded.

TMA

Thermomechanical analysis (penetration temperature) was performed on compression molded discs of 30 mm diameter x 3.3 mm thickness which were then air quenched at 180 ° C. and 10 MPa molding pressure for 5 minutes. The instrument used was TMA 7 (trademark available from Perkin-Elmer). In the test, a probe with a radius of 1.5 mm (P / N N519-0416) was applied to the surface of the sample disc with a force of 1 N. The temperature was raised from 25 ° C. to 5 ° C./min. Probe penetration distance was measured as a function of temperature. The experiment was terminated when the probe had penetrated 1 mm into the sample.

DMA

Dynamic mechanical analysis (DMA) was performed on compression molded discs that were formed in a hot press for 5 minutes at 180 ° C. and 10 MPa pressure and then water cooled to 90 ° C./min in the press. The test was performed using an ARES controlled strain rheometer (TA instrument) equipped with a double cantilever fixture for torsion testing.

1.5 mm plaques were pressed and cut into bars measuring 32 x 12 mm. Samples were clamped both ends between fixtures at 10 mm intervals (grip spacing (ΔL)) and a subsequent temperature step (5 ° C. per step) from −100 ° C. to 200 ° C. was performed. At each temperature, the torsional modulus (G ′) was measured at each frequency of 10 rad / s, and the strain amplitude was maintained between 0.1% and 4% to ensure that the torque was sufficient and the measurement was maintained in a linear manner.

An initial static force of 10 g was maintained (automatic tension mode) to prevent sagging in the sample when thermal expansion occurred. As a result, the grip spacing (ΔL) increased with temperature, especially at temperatures above the melting or softening point of the polymer sample. The test was stopped at the maximum temperature or when the gap between the fixtures reached 65 mm.

Melt index

Melt index or I ₂ was measured according to ASTM D 1238, Condition 190 ° C./2.16 kg. In addition, the melt index or I ₁₀ was measured according to ASTM D 1238, condition 190 ° C./10 kg.

ATREF

US Pat. No. 4,798,081 and Wilde, L .; Ryle, T. R .; Knobeloch, D. C .; Peat, I. R .; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20, 441-455 (1982), performed analytical temperature rising elution fractionation (ATREF) analysis. The composition to be analyzed was dissolved in trichlorobenzene and crystallized in a column containing an inert support (stainless steel shot) by slowly decreasing the temperature to 20 ° C. at a cooling rate of 0.1 ° C./min. The column was equipped with an infrared detector. The crystallized polymer sample was then eluted from the column by slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 ° C. to 120 ° C. at a rate of 1.5 ° C./min to obtain an ATREF chromatogram curve.

¹³ C NMR  analysis

Samples were prepared by adding approximately 3 g of 50/50 mixture of tetrachloroethane-d ² / orthodichlorobenzene to 0.4 g of sample in a 10 mm NMR tube. The sample was dissolved and homogenized by heating the tube and its contents to 150 ° C. Data was collected using a JEOL Eclipse ™ 400 MHz spectrometer or Varian Unity Plus ™ 400 MHz spectrometer, corresponding to a ¹³ C resonance frequency of 100.5 MHz. Data was acquired using 4000 transients per data file with a 6 second pulse repetition delay. To obtain the minimum signal-to-noise for quantitative analysis, multiple data files were added together. At a minimum file size of 32K data points, the spectral width was 25,000 Hz. Samples were analyzed at 130 ° C. in a 10 mm wide band probe. Randall's triad method (Randall, JC; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989)), which is incorporated herein by reference in its entirety. Comonomer incorporation was measured.

TREF Polymer fractionation by

Large scale TREF fractionation was performed by dissolving 15-20 g of polymer at 160 ° C. for 4 hours and dissolving in 2 liters of 1,2,4-trichlorobenzene (TCB). Polymer solutions were prepared from 30 to 40 mesh (600 to 425 μm) spherical industrial glass beads (available from Potters Industries, Brownwood HC 30 Box 20, 76801, USA) and diameter 0.028 "(0.7) mm) packing with a 60:40 (v: v) mixture of cut steel short (available from Pellets, Inc., Industrial Drive 63, North Towanda, NY, USA 14120). Was added with 15 psig (100 kPa) of nitrogen on a 3 inch by 4 foot (7.6 cm x 12 cm) steel column, which was deposited into a thermally controlled oil jacket and initially set at 160 ° C. The column was first cooled rapidly to 125 ° C. and then slowly cooled to 0.04 ° C./min to 20 ° C. and held for 1 h.The temperature was increased to 0.167 ° C./min and fresh TCB was introduced at about 65 ml / min.

Approximately 2000 ml portions of the eluate from the preparative TREF column were collected in 16 zones of heated fraction collector. The polymer was concentrated in each fraction using a rotary evaporator until about 50-100 ml of polymer solution remained. After leaving the concentrate overnight, excess methanol was added, filtered and rinsed (approximately 300-500 ml of methanol, including the final rinse). The filtration step was carried out in a three position vacuum assisted filtration zone using a 5.0 μm polytetrafluoroethylene coated filter paper (available from Osmonics Inc., Cat # Z50WP04750). The filtered fractions were dried overnight in a vacuum oven at 60 ° C., weighed on an analytical balance and then further tested.

Melt strength

Melt strength (MS) was measured using a capillary rheometer equipped with a 20: 1 die with a diameter of 2.1 mm and an inlet angle of approximately 45 degrees. After equilibrating the sample at 190 ° C. for 10 minutes, the piston was run at a speed of 1 inch / minute (2.54 cm / minute). Standard test temperature was 190 ° C. Samples were uniaxially stretched with a set of acceleration nips located 100 mm below the die with an acceleration of 2.4 mm / sec ² . The required tensile force was recorded as a function of the winding speed of the nip rolls. The maximum tensile force achieved during the test is defined as the melt strength. When the polymer melt exhibits stretching resonance, the tensile force before the start of the stretching resonance is taken as the melt strength. Melt strength was reported in centinewtons (“cN”).

catalyst

When the term “overnight” is used, it refers to a time of approximately 16 to 18 hours, the term “room temperature” refers to a temperature of 20 to 25 ° C., and the term “mixed alkanes” is the trade name Isopar from ExxonMobil Chemical Company. (Isopar) refers to a commercially available mixture of C _{6 -9} aliphatic hydrocarbons, available as E ^®. If a compound name does not match its structural representation herein, the structural representation is governed. The synthesis of all metal complexes and the preparation of all screening experiments were carried out in a dry nitrogen atmosphere using dry box technology. All solvents used were HPLC grade and they were used after drying.

MMAO refers to modified methylalumoxane, triisobutylaluminum modified methylalumoxane, commercially available from Akzo-Noble Corporation.

Preparation of the catalyst (B1) was carried out as follows.

a) (1- Methylethyl ) (2-hydroxy-3,5- Di (t-butyl) phenyl ) Methylimine  Produce

3,5-di-t-butylsalicylaldehyde (3.00 g) was added to 10 mL of isopropylamine. The solution rapidly turned bright yellow. After stirring for 3 hours at ambient temperature, the volatiles were removed under vacuum to yield a light yellow crystalline solid (yield 97%).

b) 1,2- Vis -(3,5-di-t- Butylphenylene ) (1- (N- (1- Methylethyl ) Imino ) methyl )(2- Oxoyl Zirconium Dibenzyl  Produce

A solution of (1-methylethyl) (2-hydroxy-3,5-di (t-butyl) phenyl) imine (605 mg, 2.2 mmol) in 5 mL toluene was added Zr (CH ₂ Ph) ₄ in 50 mL toluene. (500 mg, 1.1 mmol) was added slowly to the solution. The resulting dark yellow solution was stirred for 30 minutes. Removal of solvent under reduced pressure gave the desired product as a reddish brown solid.

Preparation of the catalyst (B2) was carried out as follows.

a) (1- (2- Methylcyclohexyl ) Ethyl) (2- Oxoyl -3,5- Di (t-butyl) phenyl Production of immigration

2-methylcyclohexylamine (8.44 mL, 64.0 mmol) was dissolved in methanol (90 mL) and di-t-butylsalicylaldehyde (10.00 g, 42.67 mmol) was added. The reaction mixture was stirred for 3 hours and then cooled to -25 ° C for 12 hours. The resulting yellow solid precipitate was collected by filtration, washed with cold methanol (2 × 15 mL) and then dried under reduced pressure. 11.17 g of a yellow solid were obtained. ¹ H NMR was consistent with the desired product as an isomer mixture.

b) Vis -(1- (2- Methylcyclohexyl ) Ethyl) (2- Oxoyl -3,5- Di (t-butyl) phenyl ) Imino )zirconium Dibenzyl  Produce

Zr in 600 mL toluene with a solution of (1- (2-methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-butyl) phenyl) imine (7.63 g, 23.2 mmol) in 200 mL toluene To the solution of (CH ₂ Ph) ₄ (5.28 g, 11.6 mmol) was added slowly. The resulting dark yellow solution was stirred at 25 ° C. for 1 hour. The solution was further diluted with 680 mL toluene to give a solution with a concentration of 0.00783 M.

Cocatalyst 1: Long chain trialkylamines (Armeen ™ M2HT, Akzo-Nobel, Inc.) substantially as disclosed in US Pat. No. 5,919,983, Example 2. Available from)), methyldi (C _14-18 alkyl) ammonium salt of tetrakis (pentafluorophenyl) borate (hereafter aluminum borate), prepared by reacting HCl and Li [B (C ₆ F ₅ ) ₄ ] ) Mixture.

Co-catalyst 2: U.S. Patent No. 6,395,671 prepared according to Example 16, bis (tris (pentafluorophenyl) - aluminate only) -2-undecyl-mixing of the microporous Jolly DE C _{14 -18-alkyl} dimethyl ammonium salts.

Transfer agent : The transfer agent used was diethylzinc (DEZ, SA1), di (i-butyl) zinc (SA2), di (n-hexyl) zinc (SA3), triethylaluminum (TEA, SA4), trioctylaluminum ( SA5), triethylgallium (SA6), i-butylaluminum bis (dimethyl (t-butyl) siloxane) (SA7), i-butylaluminum bis (di (trimethylsilyl) amide) (SA8), n-octylaluminum di (Pyridine-2-methoxide) (SA9), bis (n-octadecyl) i-butylaluminum (SA10), i-butylaluminum bis (di (n-pentyl) amide) (SA11), n-octylaluminum bis (2,6-di-t-butylphenoxide) (SA12), n-octylaluminum di (ethyl (1-naphthyl) amide) (SA13), ethylaluminum bis (t-butyldimethylsiloxide) (SA14) , Ethylaluminum di (bis (trimethylsilyl) amide) (SA15), ethylaluminum bis (2,3,6,7-dibenzo-1-azacycloheptanamide) (SA16), n-octylaluminum bis (2, 3,6,7-dibenzo-1-azacycloheptanamide) (SA17), n-octylaluminum bis (dimethyl (t-butyl) Include hydroxide (SA18), ethyl zinc (2,6-diphenyl-phenoxide) (SA19), and zinc acetate (t- butoxide) (SA20).

Example  1 to 4, Comparative example  A to C

General high throughput parallel polymerization conditions

The polymerization is carried out using a high throughput parallel polymerization reactor (PPR) available from Simyx Technologies, Inc., and is substantially US Pat. No. 6,248,540, 6,030,917, 6,362,309. Work was performed in accordance with US Pat. No. 6,306,658 and 6,316,663. Ethylene copolymerization was carried out at 130 ° C. and 200 psi (1.4 MPa) with the required ethylene using 1.2 equivalents of cocatalyst 1 (1.1 equivalents when MMAO was present) based on the total catalyst used. A series of polymerizations was performed in a parallel pressure reactor (PPR) containing 48 individual reactor cells in a 6 × 8 array equipped with pre-weighed glass tubes. The working volume in each reactor cell was 6000 μl. Each cell was stirred by a separate stirring paddle and temperature and pressure controlled. Monomer gas and quench gas were plumbed directly into the PPR unit and controlled by an automatic valve. Liquid reagent was robotically added to each reactor cell by syringe, and the reservoir solvent was mixed alkanes. The order of addition was mixed alkane solvent (4 ml), ethylene, 1-octene comonomer (1 ml), cocatalyst 1 or cocatalyst 1 / MMAO mixture, transfer agent, and catalyst or catalyst mixture. When using a mixture of cocatalyst 1 and MMAO or a mixture of two catalysts, the premix was premixed in small vials just prior to adding the reagents to the reactor. If reagents were omitted from the experiment, the order of addition was maintained in a different way. The polymerization was carried out for approximately 1 to 2 minutes until the desired ethylene consumption was reached. After quenching with CO, the reactor was cooled and the glass tube was unloaded. The tube was transferred to a centrifuge / vacuum drying unit and dried at 60 ° C. for 12 hours. The tube containing the dried polymer was weighed and the net yield of the polymer was obtained from the difference between this weight and the container weight. The results are shown in Table 1. In Table 1 and elsewhere herein, the comparative compound is indicated by an asterisk (*).

Examples 1 to 4 show the products of a very narrow MWD, in particular monomodal copolymers, and also a broad molecular weight distribution of bimodal in the absence of DEZ (mixture of separately prepared polymers) when DEZ is present The synthesis of the linear block copolymers according to the invention, as evidenced by the formation of, is indicated. Due to the fact that catalyst (A1) is known to introduce more octenes compared to catalyst (B1), different blocks or segments of the resulting copolymers according to embodiments of the present invention are based on branching or density It is distinguishable.

It is found that the polymers prepared according to the invention have a relatively narrow polydispersity (Mw / Mn) and higher block-copolymer content (trimers, tetramers or more) compared to polymers prepared in the absence of transfer agents. Can be.

Further characterization data for the polymers in Table 1 were determined with reference to the figures. More specifically, the DSC and ATREF results are shown below.

The DSC curve for the polymer of Example 1 showed a heat of fusion of 158.1 J / g and a melting point (Tm) of 115.7 ° C. The corresponding CRYSTAF curve shows the tallest peak at 34.5 ° C. and a peak area of 52.9%. The difference between the DSC Tm and the Tcrystaf was 81.2 ° C.

The DSC curve for the polymer of Example 2 showed a peak with a heat of fusion of 214.0 J / g and a melting point (Tm) of 109.7 ° C. The corresponding CRYSTAF curve shows the tallest peak at 46.2 ° C. and a peak area of 57.0%. The difference between the DSC Tm and the Tcrystaf was 63.5 ° C.

The DSC curve for the polymer of Example 3 showed a peak with a heat of fusion of 160.1 J / g and a melting point (Tm) of 120.7 ° C. The corresponding CRYSTAF curve shows the tallest peak at 66.1 ° C. and a peak area of 71.8%. The difference between the DSC Tm and the Tcrystaf was 54.6 ° C.

The DSC curve for the polymer of Example 4 showed a peak with a heat of fusion of 170.7 J / g and a melting point (Tm) of 104.5 ° C. The corresponding CRYSTAF curve shows the tallest peak at 30 ° C. and a peak area of 18.2%. The difference between the DSC Tm and the Tcrystaf was 74.5 ° C.

The DSC curve for Comparative Example A showed a heat of fusion of 86.7 J / g and a melting point (Tm) of 90.0 ° C. The corresponding CRYSTAF curve shows the tallest peak at 48.5 ° C. and the peak area of 29.4%. Both of these values were consistent with low density resins. The difference between the DSC Tm and the Tcrystaf was 41.8 ° C.

The DSC curve for Comparative Example B showed a heat of fusion of 237.0 J / g and a melting point (Tm) of 129.8 ° C. The corresponding CRYSTAF curve shows the tallest peak at 82.4 ° C. and the peak area of 83.7%. Both of these values were consistent with high density resins. The difference between the DSC Tm and the Tcrystaf was 47.4 ° C.

The DSC curve for Comparative Example C showed a heat of fusion of 143.0 J / g and a melting point (Tm) of 125.3 ° C. The corresponding CRYSTAF curve shows the highest peak at 81.8 ° C. and the peak area of 34.7% as well as the lower crystal peak at 52.4 ° C. The spacing between the two peaks was consistent with the presence of high and low crystalline polymers. The difference between DSC Tm and Tcrystaf was 43.5 ° C.

Example  5 to 19, Comparative example  D to F, continuous solution polymerization, catalyst A1 / B2 + DEZ

Continuous solution polymerization was carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkane solvent (Isopar ™ E available from ExxonMobil Chemical Company), 2.70 lbs / hr (1.22 kg / hr) of ethylene, 1-octene and hydrogen (if used) were loaded with an internal thermocouple and temperature control jacket It was fed to a fitted 3.8 L reactor. Solvent feed to the reactor was measured by a mass flow controller. A variable speed diaphragm pump was used to control the solvent flow rate and pressure into the reactor. On pump discharge, side flow was taken to provide flush flow for the catalyst and cocatalyst 1 injection line and reactor stirrer. These flows were measured by a Micro-Motion mass flow meter and controlled by a control valve or by manual adjustment of the needle valve. The remaining solvent was combined with 1-octene, ethylene and hydrogen (if used) and fed to the reactor. If necessary, a mass flow controller was used to deliver hydrogen to the reactor. The temperature of the solvent / monomer solution was adjusted using a heat exchanger and then introduced into the reactor. The stream was introduced at the bottom of the reactor. The catalyst component solution was metered, combined with the catalyst flush solvent and introduced into the bottom of the reactor using a pump and a mass flow meter. The reactor was liquid-full at 500 psig (3.45 MPa) with vigorous stirring. Product was removed through the outlet line at the top of the reactor. All outlet lines from the reactor were vapor traced and insulated. A small amount of water was added to the outlet line with any stabilizer or other additives and the polymerization was stopped by passing the mixture through a static mixer. The product stream was then heated through a heat exchanger and then devolatilized. The polymer product was recovered by extrusion using a devolatilization extruder and a water cooled pelletizer. Process details and results are listed in Table 2. Selected polymer properties are listed in Table 3.

The resulting polymer was tested by DSC and ATREF as in the above examples. The results were as follows.

The DSC curve for the polymer of Example 5 showed a peak with a heat of fusion of 60.0 J / g and a melting point (Tm) of 119.6 ° C. The corresponding CRYSTAF curve shows the tallest peak at 47.6 ° C. and a peak area of 59.5%. The delta between the DSC Tm and the Tcrystaf was 72.0 ° C.

The DSC curve for the polymer of Example 6 showed a peak with a heat of fusion of 60.4 J / g and a melting point (Tm) of 115.2 ° C. The corresponding CRYSTAF curve shows the tallest peak at 44.2 ° C. and the peak area of 62.7%. The delta between the DSC Tm and the Tcrystaf was 71.0 ° C.

The DSC curve for the polymer of Example 7 showed a peak with a heat of fusion of 69.1 J / g and a melting point of 121.3 ° C. The corresponding CRYSTAF curve shows the tallest peak at 49.2 ° C. and the peak area of 29.4%. The delta between the DSC Tm and the Tcrystaf was 72.1 ° C.

The DSC curve for the polymer of Example 8 showed a peak with a heat of fusion of 67.9 J / g and a melting point (Tm) of 123.5 ° C. The corresponding CRYSTAF curve shows the tallest peak at 80.1 ° C. and the peak area of 12.7%. The delta between the DSC Tm and the Tcrystaf was 43.4 ° C.

The DSC curve for the polymer of Example 9 showed a peak with a heat of fusion of 73.5 J / g and a melting point (Tm) of 124.6 ° C. The corresponding CRYSTAF curve shows the tallest peak at 80.8 ° C. and the peak area of 16.0%. The delta between the DSC Tm and the Tcrystaf was 43.8 ° C.

The DSC curve for the polymer of Example 10 showed a peak with a heat of fusion of 60.7 J / g and a melting point (Tm) of 115.6 ° C. The corresponding CRYSTAF curve shows the tallest peak at 40.9 ° C. and a peak area of 52.4%. The delta between the DSC Tm and the Tcrystaf was 74.7 ° C.

The DSC curve for the polymer of Example 11 showed a peak with a heat of fusion of 70.4 J / g and a melting point (Tm) of 113.6 ° C. The corresponding CRYSTAF curve shows the tallest peak at 39.6 ° C. and the peak area of 25.2%. The delta between the DSC Tm and the Tcrystaf was 74.1 ° C.

The DSC curve for the polymer of Example 12 showed a peak with a heat of fusion of 48.9 J / g and a melting point (Tm) of 113.2 ° C. The corresponding CRYSTAF curve did not show a peak above 30 ° C. (Thus, Tcrystaf was set to 30 ° C. for further calculation.) The delta between the DSC Tm and Tcrystaf was 83.2 ° C.

The DSC curve for the polymer of Example 13 showed a peak with a heat of fusion of 49.4 J / g and a melting point (Tm) of 114.4 ° C. The corresponding CRYSTAF curve shows the tallest peak at 33.8 ° C. and the peak area of 7.7%. The delta between the DSC Tm and the Tcrystaf was 84.4 ° C.

The DSC curve for the polymer of Example 14 showed a peak with a heat of fusion of 127.9 J / g and a melting point (Tm) of 120.8 ° C. The corresponding CRYSTAF curve shows the tallest peak at 72.9 ° C. and a peak area of 92.2%. The delta between the DSC Tm and the Tcrystaf was 47.9 ° C.

The DSC curve for the polymer of Example 15 showed a peak with a heat of fusion of 36.2 J / g and a melting point (Tm) of 114.3 ° C. The corresponding CRYSTAF curve shows the tallest peak at 32.3 ° C. and the peak area of 9.8%. The delta between the DSC Tm and the Tcrystaf was 82.0 ° C.

The DSC curve for the polymer of Example 16 showed a peak with a heat of fusion of 44.9 J / g and a melting point (Tm) of 116.6 ° C. The corresponding CRYSTAF curve shows the tallest peak at 48.0 ° C. and a peak area of 65.0%. The delta between the DSC Tm and the Tcrystaf was 68.6 ° C.

The DSC curve for the polymer of Example 17 showed a peak with a heat of fusion of 47.0 J / g and a melting point (Tm) of 116.0 ° C. The corresponding CRYSTAF curve shows the tallest peak at 43.1 ° C. and a peak area of 56.8%. The delta between the DSC Tm and the Tcrystaf was 72.9 ° C.

The DSC curve for the polymer of Example 18 showed a peak with a heat of fusion of 141.8 J / g and a melting point (Tm) of 120.5 ° C. The corresponding CRYSTAF curve shows the tallest peak at 70.0 ° C. and the peak area of 94.0%. The delta between the DSC Tm and the Tcrystaf was 50.5 ° C.

The DSC curve for the polymer of Example 19 showed a peak with a heat of fusion of 174.8 J / g and a melting point (Tm) of 124.8 ° C. The corresponding CRYSTAF curve shows the tallest peak at 79.9 ° C. and a peak area of 87.9%. The delta between the DSC Tm and the Tcrystaf was 45.0 ° C.

The DSC curve for the polymer of Comparative Example D showed a peak with a heat of fusion of 31.6 J / g and a melting point (Tm) of 37.3 ° C. The corresponding CRYSTAF curve did not show a peak above 30 ° C. Both of these values were consistent with low density resins. The delta between the DSC Tm and the Tcrystaf was 7.3 ° C.

The DSC curve for the polymer of Comparative Example E showed a peak with a heat of fusion of 179.3 J / g and a melting point (Tm) of 124.0 ° C. The corresponding CRYSTAF curve shows the tallest peak at 79.3 ° C. and a peak area of 94.6%. Both of these values were consistent with high density resins. The delta between the DSC Tm and the Tcrystaf was 44.6 ° C.

The DSC curve for Comparative Example F showed a peak with a heat of fusion of 90.4 J / g and a melting point (Tm) of 124.8 ° C. The corresponding CRYSTAF curve shows the tallest peak at 77.6 ° C. and the peak area of 19.5%. The spacing between the two peaks was consistent with the presence of both high and low crystalline polymers. The delta between the DSC Tm and the Tcrystaf was 47.2 ° C.

Physical property testing

Polymer samples are evaluated for physical properties such as TMA temperature test, pellet block strength, hot recovery rate, hot compressive strain, and high temperature resistance exhibited by the storage modulus ratio (G '(25 ° C) / G' (100 ° C)). It was. Several commercial polymers were included in the test. Comparative Example G ^* was a substantially linear ethylene / 1-octene copolymer (Affinity® available from The Dow Chemical Company), and Comparative Example H ^* was a substantially linear ethylene / 1-octene elastomer copolymer (The Dow Affinity® EG8100 available from Chemical Company, Comparative Example I was a substantially linear ethylene / 1-octene copolymer (Affinity® PL1840 available from The Dow Chemical Company), and Comparative Example J was hydrogenated styrene / Butadiene / styrene triblock copolymer (KRATON ™ G1652 available from KRATON Polymers) and Comparative Example K was a thermoplastic vulcanizate (TPV, polyolefin blend with crosslinked elastomer dispersed) . The results are shown in Table 4.

In Table 4, Comparative Example F (which is a physical blend of two polymers resulting from co-polymerization with Catalysts A1 and B1) has a 1 mm penetration temperature of about 70 ° C., while Examples 5-9 are 100 ° C. Had a penetration temperature of at least 1 mm. In addition, Examples 10-19 all had a 1 mm penetration temperature above 85 ° C., mostly with 1 mm TMA temperatures above 90 ° C. or even above 100 ° C. This shows that the new polymers have better dimensional stability at higher temperatures compared to the physical blends. Comparative Example J (commercial SEBS) had a good 1 mm TMA temperature of about 107 ° C., but had a very poor (high temperature 70 ° C.) compression set of about 100%, which also recovers 300% strain at high temperature (80 ° C.). Recovery failed (sample failure). Thus, the polymers exemplified had a unique combination of properties that could not be obtained even with some commercially available high performance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio (G ′ (25 ° C.) / G ′ (100 ° C.)) of 6 or less for the polymers of the present invention, while the physical blend (Comparative Example F) The storage modulus ratio is 9 and similar density random ethylene / octene copolymers (Comparative Example G) show that the storage modulus ratio 89 is as large as the single-digit range. The storage modulus ratio of the polymer is preferably as close to 1 as possible. Such polymers are relatively unaffected by temperature, and articles made from such polymers can be usefully used over a wide temperature range. This low storage modulus ratio and temperature independence feature is particularly useful in elastomer applications such as in pressure sensitive adhesive formulations.

The data in Table 4 also demonstrates that the polymers according to the invention have improved pellet blocking strength. In particular, Example 5 has a pelletized block strength of 0 MPa, which means free flow under test conditions compared to Comparative Examples F and G, which show significant blocking. Blocking strength is important because bulk transport of polymers with large blocking strength can result in cohesion or adhesion of the product with storage or dropping, resulting in poor handling.

The high temperature (70 ° C.) compression set of the polymers of the present invention is generally good, meaning that it is generally less than about 80%, preferably less than about 70%, in particular less than about 60%. In contrast, Comparative Examples F, G, H and J all had a 70 ° C. compression set of 100% (maximum possible, indicating no recovery). Good high temperature compression set (low values) is particularly necessary for applications such as gaskets, window profiles, o-rings, and the like.

Table 5 shows the results for the mechanical properties at ambient temperatures of the various polymers as well as the new polymers. It can be seen that the polymers of the invention have very good wear resistance when tested according to ISO 4649, which generally exhibits a volume loss of less than about 90 mm ³ , preferably less than about 80 mm ³ , in particular less than about 50 mm ^3. have. In this test, high values indicate high volume loss, and consequently low wear resistance.

As shown in Table 5, the tear strength measured by the tensile notch tear strength of the polymer of the present invention was generally 1000 mJ or more. The tear strength of the polymers of the invention can be as high as 3000 mJ, even as high as 5000 mJ. Comparative polymers generally had a tear strength of 750 mJ or less.

Table 5 also shows that the inventive polymers are better (represented by higher shrinkage stress values) at 150% strain compared to some comparative samples. Comparative Examples F, G and H have a shrinkage stress value of 400 kPa or less at 150% strain, whereas the polymer of the present invention has a shrinkage stress value of 500 kPa (Example 11) to about 1100 kPa at 150% strain (Example 17). Polymers with higher 150% shrinkage stress values will be very useful for elastic applications such as elastic fibers and fabrics, especially nonwovens. Other uses include diapers, hygiene and medical garment waistband articles such as tabs and elastic bands.

Table 5 also shows that the polymers of the present invention have an improved (lower) stress relaxation rate (at 50% strain) compared to Comparative Example G, for example. Low stress relaxation rate means that the polymer has a better effect in applications such as diapers and other garments where long term retention of elasticity at body temperature is desired.

Optical testing

The optical properties reported in Table 6 are based on compression molded films that are not substantially oriented. The optical properties of the polymer can vary over a wide range due to microcrystalline size changes resulting from changes in the amount of chain transfer agent used in the polymerization.

Extraction of Multiblock Copolymers

Extraction studies for the polymers of Examples 5, 7 and Comparative Example E were performed. In this experiment, polymer samples were weighed into a glass frit extraction thimble and placed in a Kumagawa type extractor. The extractor with sample was purged with nitrogen and a 50 mL round bottom flask was charged with 350 mL of diethyl ether. The flask was then fixed to the extractor. The ether was heated with stirring. The time at which the ether began to condense into the thimble was recorded and the extraction was run under nitrogen for 24 hours. At this time, heating was stopped and the solution was cooled. Any ether remaining in the extractor was returned to the flask. The ether in the flask was evaporated in vacuo at ambient temperature and the resulting solids were nitrogen purged dried. Any residue was transferred to a weighed bottle using hexane continuous wash. The combined hexane washes were then evaporated by further nitrogen purge and the residue was dried at 40 ° C. under vacuum overnight. Any ether remaining in the extractor was nitrogen purged dried.

Then, a second transparent round bottom flask filled with 35 mL of hexane was connected to the extractor. Hexane was stirred and heated to reflux and held at reflux for 24 hours after hexane was first observed to condense into the thimble. The heating was then stopped and the flask was cooled. Any hexane remaining in the extractor was transferred back to the flask. Hexane was removed by evaporation under vacuum at ambient temperature and any residue remaining in the flask was transferred to a weighed bottle using hexane continuous wash. Hexane in the flask was evaporated by nitrogen purge and the residue was vacuum dried at 40 ° C. overnight.

The polymer sample remaining in the thimble after extraction was transferred from the thimble to a weighed bottle and vacuum dried overnight at 40 ° C. The results are shown in Table 7.

Additional polymers Example  19 A to F, continuous solution polymerization, catalyst A1 / B2 + DEZ

Continuous solution polymerization was carried out in a computer controlled sufficiently mixed reactor. Purified mixed alkane solvent (Isopar ™ E available from ExxonMobil Chemical Company), ethylene, 1-octene, and hydrogen (if used) were combined and fed to a 27 gallon reactor. The feed to the reactor was measured with a mass flow controller. The temperature of the feed stream was controlled using a glycol cold heat exchanger prior to introduction into the reactor. The catalyst component solution was metered using a pump and a weight flow meter. The reactor was fully run at approximately 550 psig pressure. When leaving the reactor, water and additives were injected into the polymer solution. Water hydrolyzed the catalyst and terminated the polymerization reaction. The reactor solution was then heated in the production of two stage devolatilization. The solvent and unreacted monomers were removed during the devolatilization process. The polymer melt was injected into a die for cutting underwater pellets.

The description and results of the method are included in Table 8. Selected polymer properties are provided in Table 9.

Examples 20-23 -Ethylene / α-olefin Interpolymers

Polymer Examples 20-23 were prepared under reaction conditions substantially similar to the reaction conditions for Polymer Examples 1-19. One skilled in the art will know how to process the processing conditions, for example shuttle agent ratio, hydrogen flow, monomer concentration, etc., to produce the target polymer of the desired properties using the processing conditions already described in the instant application. The properties of the polymers of Examples 20-23 are shown in Tables 10A and 10B.

General Procedure for the Preparation of Lubricant Compositions

Examples 24-27 and Comparative Examples L-W are lubricant compositions having the formulations and treatment conditions shown in Tables 11A, 11B, and 11C below. Each lubricant composition comprises the same base oil, ie exon FN1365 100LP5, but different polymers or VI improvers. The ratio of base oil to polymer is 99: 1 by weight for all lubricant compositions.

Testing of Lubricant Compositions

The kinematic viscosity, shear stability, shear stability index and viscosity loss were tested for the lubricant compositions, i.e. Examples 24 to 27 prepared above. The results are listed in Tables 12A, 12B and 12C below. Kinematic viscosity and shear stability at 40 ° C. and 100 ° C. were measured according to ASTM D445, incorporated herein by reference. Shear stability index was measured according to ASTM D6022, incorporated herein by reference. Viscosity loss was measured according to ASTM D6278, incorporated herein by reference.

As described above, embodiments of the present invention provide various lubricant compositions based on the disclosed ethylene / α-olefin interpolymers as viscosity modifiers for all types of oils and lubricants. These include automotive oils, transmission fluids, gear oils and the like. Such novel polymers may also be used in other hydrocarbons such as natural and synthetic diesel fuels, hydraulic fluids and petroleum derived products, synthetic oils and other oils, including natural oils. Ethylene / α-olefin interpolymers can provide properties with similar benefits such as styrene block copolymers such as Kraton®. These ethylene / α-olefin interpolymers can be used in thickening automotive oils. They offer the possibility of improved low temperature performance and good flexibility in the formulation of automotive oils, gear lubricants and greases. By controlling the block distribution of these polymers, low temperature performance can be optimized and unwanted oil and wax interactions can be avoided. By controlling the degree of crystallinity, the polymer produced form can be varied from pellet to package. Additional advantages and features will be apparent to those skilled in the art.

Although the present invention has been described with respect to a limited number of embodiments, certain features of one embodiment should not be applied to other embodiments of the invention as well. There is no single embodiment that is representative of all aspects of the invention. In some embodiments, a composition or method may comprise many of the compounds or steps mentioned herein. In other embodiments, the compositions or methods do not comprise or substantially comprise any compound or step listed herein. There are variations and modifications from the described embodiments. Finally, any numerical value disclosed herein should be intended to mean an approximation, regardless of whether the term “about” or “approximately” is used in describing the numerical value. It is intended that the appended claims cover all such modifications and variations as fall within the scope of the present invention.

Claims (24)

(i) a base oil, and (ii) an ethylene / α-olefin interpolymer, wherein the ethylene / α-olefin interpolymer (a) Mw / Mn is from about 1.7 to about 3.5 and has at least one melting point (Tm) (degrees Celsius), and density (d) (g / cm ³ ), wherein the values of Tm and d correspond to the relationship do or, Tm> -2002.9 + 4538.5 (d)-2422.2 (d) ² (b) the amount of delta (ΔT) (degrees C) defined by the heat of fusion (ΔH) (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak, with Mw / Mn of about 1.7 to about 3.5; Characterized in that the value of ΔT and ΔH has the following relationship, ΔT> -0.1299 (ΔH) + 62.81 when ΔH is greater than 0 and less than or equal to 130 J / g ΔT ≥ 48 ° C when ΔH is greater than 130 J / g Wherein the CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the cumulative polymer has an identifiable CRYSTAF peak, the CRYSTAF temperature is 30 ° C. (c) characterized by a 300% strain and an elastic recovery rate (Re) (%) measured in a compression molded film of an ethylene / α-olefin interpolymer, having a density (d) (g / cm ³ ) When the ethylene / α-olefin interpolymers are substantially free of crosslinked phases, the values of Re and d satisfy the relationship Re> 1481-1629 (d) (d) comonomers having molecular fractions eluting at 40 ° C. to 130 ° C. when fractionated using TREF, wherein the fractions are at least 5% higher than the mole content of comonomers of comparative random ethylene interpolymer fractions eluting at the same temperature range Molar content (wherein the comparative random ethylene interpolymer has the same comonomer as the ethylene / α-olefin interpolymer, and has a melt index, density, within 10% of the ethylene / α-olefin interpolymer, And comonomer molar content (based on total polymer)), (e) having a storage modulus at 25 ° C. (G ′ (25 ° C.)), and a storage modulus at 100 ° C. (G ′ (100 ° C.)), wherein G ′ (25 ° C.) vs. G ′ (100 ° C.) And the ratio is in the range of about 1: 1 to about 9: 1. The method of claim 1 wherein the Mw / Mn of the ethylene / α-olefin interpolymer is about 1.7 to about 3.5, and has one or more melting points (Tm) (degrees C), and a density (d) (g / cm ³ ), Wherein the numerical values of Tm and d correspond to the following relations. Tm ≥ 858.91-1825.3 (d) + 1112.8 (d) ² The ethylene / a-olefin interpolymer of claim 1 wherein the Mw / Mn is from about 1.7 to about 3.5, defined by the heat of fusion (ΔH) (J / g), and the temperature difference between the highest DSC peak and the highest CRYSTAF peak. Delta T (degree Celsius), wherein the values of ΔH and ΔT have the following relationship (where CRYSTAF peak is determined using at least 5% of the cumulative polymer and is less than 5% of the cumulative polymer): Lubricant having a CRYSTAF peak, wherein the CRYSTAF temperature is 30 ° C. ΔT> -0.1299 (ΔH) + 62.81 if ΔH is greater than 0 and less than or equal to 130 J / g ΔT ≥ 48 ° C when ΔH is greater than 130 J / g The ethylene / α-olefin interpolymer is characterized by a 300% strain and an elastic recovery rate (Re) (%) in one cycle as measured by the compression molded film of the ethylene / α-olefin interpolymer, (d) A lubricant composition having (g / cm ³ ) and wherein the values of Re and d satisfy the following relationship when the ethylene / α-olefin interpolymers substantially contain no crosslinked phase. Re> 1481-1629 (d) The lubricant composition according to claim 1, wherein the values of Re and d satisfy the following relationship. Re> 1491-1629 (d) The lubricant composition according to claim 1, wherein the values of Re and d satisfy the following relationship. Re> 1501-1629 (d) The lubricant composition according to claim 1, wherein the values of Re and d satisfy the following relationship. Re> 1511-1629 (d) (i) a base oil, and (ii) an ethylene / α-olefin interpolymer, wherein the ethylene / α-olefin interpolymer (a) at least one molecule characterized by a block index of at least 0.5 and up to about 1 and a molecular weight distribution (Mw / Mn) of greater than about 1.3, eluting between 40 ° C and 130 ° C when fractionated using TREF Have fractions, (b) a lubricant composition having an average block index greater than 0 and less than or equal to about 1.0 and a molecular weight distribution (Mw / Mn) greater than about 1.3. The comparative random according to claim 1 or 8, wherein the ethylene / α-olefin interpolymer has molecular fractions that elute between 40 ° C and 130 ° C when fractionated using TREF, and the fractions are eluted at the same temperature range. Having a comonomer molar content of at least 5% higher than the comonomer mole content of the ethylene interpolymer fraction, wherein the comparative random ethylene interpolymer has the same comonomer (s) as the ethylene / α-olefin interpolymer and lubricant composition having a melt index, density and comonomer molar content (based on total polymer) within 10% of the α-olefin interpolymer. The ethylene / α-olefin interpolymers of claim 1 or 8 have a storage modulus at 25 ° C. (G ′ (25 ° C.)) and a storage modulus at 100 ° C. (G ′ (100 ° C.)). And wherein the ratio of G ′ (25 ° C.) to G ′ (100 ° C.) is in the range of about 1: 1 to about 9: 1. The method according to claim 1 or 8, wherein the α-olefin is styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1,5- A lubricating agent composition that is hexadiene, or a combination thereof. 9. The lubricant composition according to claim 1 or 8, wherein the base oil is selected from the group consisting of base stocks of API groups I, II, III, IV and V and combinations thereof. The lubricant composition according to claim 1 or 8, wherein the base oil is a natural oil, a synthetic oil or a combination thereof. 9. The lubricant composition of claim 1 or 8 further comprising at least one additive. The lubricant composition of claim 14 wherein the additive is a detergent, a dispersant, a friction modifier, a pour point depressant, a demulsifier, an antifoaming agent, a corrosion inhibitor, an antiwear agent, an antioxidant, a rust inhibitor, a thickener, or a combination thereof. The lubricant composition according to claim 1 or 8, which is an automobile oil, transmission fluid, gear oil, power steering fluid, shock absorber fluid, brake fluid, hydraulic fluid or grease. The lubricant composition according to claim 16, which is an automobile oil. 18. The lubricant composition of claim 17 wherein the automotive oil further comprises a pour point depressant, detergent, dispersant, antiwear, antioxidant, friction modifier, rust inhibitor, or a combination thereof. 17. The lubricant composition of claim 16 which is a transmission fluid. 20. The lubricant composition of claim 19 wherein the transmission fluid further comprises a friction modifier, cleaner, dispersant, antioxidant, antiwear, extreme pressure, pour point depressant, antifoam, corrosion inhibitor or combinations thereof. The lubricant composition of claim 16 which is a gear oil. 22. The lubricant composition of claim 21 wherein the gear oil further comprises an antiwear, extreme pressure, rust inhibitor, or combination thereof. 17. The lubricant composition of claim 16 which is grease. 24. The lubricant composition of claim 23, wherein the grease further comprises a thickener, complexing agent, antioxidant, antiwear, extreme pressure, antifoam, corrosion inhibitor or mixtures thereof.

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