WO2006102150A2 - Adhesive and marking compositions made from interpolymers of ethylene/alpha-olefins - Google Patents

Adhesive and marking compositions made from interpolymers of ethylene/alpha-olefins Download PDF

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Publication number
WO2006102150A2
WO2006102150A2 PCT/US2006/009852 US2006009852W WO2006102150A2 WO 2006102150 A2 WO2006102150 A2 WO 2006102150A2 US 2006009852 W US2006009852 W US 2006009852W WO 2006102150 A2 WO2006102150 A2 WO 2006102150A2
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WIPO (PCT)
Prior art keywords
composition
ethylene
percent
polymer
interpolymer
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PCT/US2006/009852
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English (en)
French (fr)
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WO2006102150A3 (en
Inventor
Teresa P. Karjala
Selim Yalvac
Charles F. Diehl
Yunwa Wilson Cheung
Cynthia L. Rickey
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Priority claimed from PCT/US2005/008917 external-priority patent/WO2005090427A2/en
Priority to BRPI0609841-0A priority Critical patent/BRPI0609841B1/pt
Priority to EP06738855.3A priority patent/EP1858945B1/en
Priority to JP2008502121A priority patent/JP5231987B2/ja
Priority to US11/908,950 priority patent/US7989543B2/en
Priority to CN2006800084157A priority patent/CN101291964B/zh
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to CA002601273A priority patent/CA2601273A1/en
Priority to MX2007011324A priority patent/MX2007011324A/es
Priority to KR1020077021049A priority patent/KR101413315B1/ko
Priority to AU2006227348A priority patent/AU2006227348A1/en
Publication of WO2006102150A2 publication Critical patent/WO2006102150A2/en
Publication of WO2006102150A3 publication Critical patent/WO2006102150A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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    • C08F2/00Processes of polymerisation
    • C08F2/38Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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    • C08F297/00Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
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    • C08F297/08Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C08F297/083Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
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    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
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    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04Homopolymers or copolymers of ethene
    • C09J123/08Copolymers of ethene
    • C09J123/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815Copolymers of ethene with aliphatic 1-olefins
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    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08F2410/00Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01Additive used together with the catalyst, excluding compounds containing Al or B
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    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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Definitions

  • compositions that contain a polymer, a tackifier and optionally at least a filler or a pigment may be used as thermoplastic marking compositions.
  • the polymer can be a silane-modified petroleum resin, an ethylene-vinyl acetate copolymer, an atactic polypropylene; a carboxy-modiified hydrocarbon resin, an ester-modified hydrocarbon resin, a polyolefin copolymer, or a combination thereof.
  • Figure 2 shows plots of delta DSC-CRYSTAF as a function of DSC Melt
  • Figure 8 shows plots of Storage Modulus (G') versus temperature for
  • Figure 11 shows a DSC second heating curve for Polymer Example 31c.
  • the polymers when produced in a continuous process, desirably possess PDI from 1.7 to 2.9, preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to 2.1.
  • the polymers When produced in a batch or semi-batch process, the polymers possess PDI from 1.0 to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to 1.8.
  • ⁇ T is equal to or greater than 48 0 C for ⁇ H greater than 130 J/g.
  • the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer (that is, the peak must represent at least 5 percent of the cumulative polymer), and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 3O 0 C, and ⁇ H is the numerical value of the heat of fusion in J/g. More preferably, the highest CRYSTAF peak contains at least 10 percent of the cumulative polymer.
  • Figure 4 graphically depicts an embodiment of the block interpolymers of ethylene and 1-octene where a plot of the comonomer content versus TREF elution temperature for several comparable ethylene/1 -octene interpolymers (random copolymers) are fit to a line representing (- 0.2013) T + 20.07 (solid line). The line for the equation (- 0.2013) T + 21.07 is depicted by a dotted line. Also depicted are the comonomer contents for fractions of several block ethylene/1 -octene interpolymers of the invention (multi-block copolymers).
  • every fraction has a DSC melting point of about 11O 0 C or higher. More preferably, said polymer fractions, having at least 1 mol percent comonomer, has a DSC melting point that corresponds to the equation:
  • the inventive block interpolymers have a molecular fraction which elutes between 4O 0 C and 13O 0 C, when fractionated using TREF increments, characterized in that every fraction that has an ATREF elution temperature between 40°C and less than about 76°C, has a melt enthalpy (heat of fusion) as measured by DSC, corresponding to the equation: Heat of fusion (J/gm) ⁇ (1.1312)(ATREF elution temperature in Celsius) + 22.97.
  • Tx is the preparative ATREF elution temperature for the ith fraction (preferably expressed in Kelvin)
  • Px is the ethylene mole fraction for the ith fraction, which can be measured by NMR or IR as described above.
  • P AB is the ethylene mole fraction of the whole ethylene/ ⁇ -olefm interpolymer (before fractionation), which also can be measured by NMR or IR.
  • TA and PA are the ATREF elution temperature and the ethylene mole fraction for pure "hard segments" (which refer to the crystalline segments of the interpolymer). As a first order approximation, the TA and PA values are set to those for high density polyethylene homopolymer, if the actual values for the "hard segments" are not available. For calculations performed herein, TA is 372°K, PA is 1.
  • the weight average block index, ABI for the whole polymer can be calculated.
  • 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, ABI should be in the range of from about 0.4 to about 0.7, from about 0.5 to about 0.7, or from about 0.6 to about 0.9.
  • 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 still other embodiments, 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.
  • the foregoing process takes the form of a continuous solution process for forming block copolymers, especially multi-block copolymers, preferably linear multi-block copolymers of two or more monomers, more especially ethylene and a C 3 . 20 olefin or cycloolefm, and most especially ethylene and a C 4 . 2 o ⁇ -olefin, using multiple catalysts that are incapable of interconversion. That is, the catalysts are chemically distinct.
  • the process is ideally suited for polymerization of mixtures of monomers at high monomer conversions. Under these polymerization conditions, shuttling from the chain shuttling agent to the catalyst becomes advantaged compared to chain growth, and multi-block copolymers, especially linear multi- block copolymers are formed in high efficiency.
  • shuttling agents and catalyst combinations having the desired chain transferring ability high rates of shuttling with low levels of chain termination
  • other forms of polymer termination are effectively suppressed. Accordingly, little if any ⁇ -hydride elimination is observed in the polymerization of ethylene/ ⁇ -olefin comonomer mixtures according to embodiments of the invention, and the resulting crystalline blocks are highly, or substantially completely, linear, possessing little or no long chain branching.
  • the ethylene/ ⁇ -olefin interpolymers can be functionalized by incorporating at least one functional group in its polymer structure.
  • exemplary functional groups may include, for example, ethylenically unsaturated mono- and di-functional carboxylic acids, ethylenically unsaturated mono- and di-functional carboxylic acid anhydrides, salts thereof and esters thereof.
  • Such functional groups may be grafted to an ethylene/ ⁇ -olefin interpolymer, or it may be copolymerized with ethylene and an optional additional comonomer to form an interpolymer of ethylene, the functional comonomer and optionally other comonomer(s).
  • the compositions disclosed herein can comprise a tackiiier or tackifying resin or tackifier resin.
  • the tackifier may modify the properties of the composition such as viscoelastic properties (e.g., tan delta), rheological properties (e.g., viscosity), tackiness (i.e., ability to stick), pressure sensitivity, and wetting property.
  • the tackifier is used to improve the tackiness of the composition.
  • the tackifier is used to reduce the viscosity of the composition.
  • the tackifier is used to render the composition a pressure-sensitive adhesive.
  • the Hildebrand solubility parameter for a copolymer may be calculated using a volume fraction weighting of the individual Hildebrand solubility parameters for each monomer comprising the copolymer, as described for binary copolymers in Barton A. F.
  • the cloud point is usually close to the melting point of the wax.
  • the lower the cloud point temperature the greater the compatibility.
  • the cloud point measurement is disclosed in "Adhesives and Coatings Manual” by National Distillers and Chemical Corporation (1983), which is incorporated herein by reference.
  • Non-limiting examples of batch methods include those methods using BRABENDER® mixing equipment (e.g., BRABENDER PREP CENTER®, available from C. W. Brabender Instruments, Inc., Southhackensack, NJ.) or BANBURY® internal mixing and roll milling (available from Farrel Company, Ansonia, Conn.) equipment.
  • Non-limiting examples of continuous methods include single screw extruding, twin screw extruding, disk extruding, reciprocating single screw extruding, and pin barrel single screw extruding.
  • An aqueous dispersion of the ethylene/ ⁇ -olefm interpolymer may also be used in the formulation of various compositions.
  • U.S. Patent No. 5,574,091, incorporated by reference herein in its entirety teaches the preparation of aqueous dispersions of olefin copolymers in the presence of a stabilizing and an emulsifying amount of a suitable surfactant, such as sulfate of an ethoxylated phenol, e.g., poly(oxy-l,2-ethanediyl) ⁇ -sulfo- ⁇ (nonylphonoxy) ammonium salt.
  • a suitable surfactant such as sulfate of an ethoxylated phenol, e.g., poly(oxy-l,2-ethanediyl) ⁇ -sulfo- ⁇ (nonylphonoxy) ammonium salt.
  • thermoplastic marking compositions are advantageous in that they may be readily designed to be applied by the various techniques used in the industry. For instance, it is now possible to develop a single formulation, which may be usefully applied by extrusion, screed, or spray techniques.
  • the thermoplastic marking compositions will preferably exhibit an adhesion, as measured in accordance with the techniques set forth in Example Two of U.S. Patent No. 6,552,110, of at least 1.0 N/mm 2 , preferably at least 1.2 N/mm 2 , more preferably at least 1.3 N/mm , and most preferably at least 1.5 N/mm .
  • U.S. Patent No. 6,552,110 is incorporated herein by reference.
  • thermoplastic marking compositions further exhibit good low temperature abrasion resistance.
  • the subject formulations exhibit improved low temperature flexibility and low temperature adhesion, and exhibit improved smoke and low odor properties at high temperatures.
  • the subject formulations exhibit a broad potential range of application temperatures, particularly at temperatures of from 150 °C to 250 0 C, which makes them suitable for application by different means. For instance, the ability of the compositions to be applied at lower application temperatures, that is, temperatures of about 150 to 170 °C, makes them suitable for application by extrusion coating -techniques; -while the ability of the compositions to be applied at higher application temperatures, that is, temperatures of 200 0 C to 250 °C makes them suitable for application by spray coating techniques.
  • the order of addition is mixed alkanes solvent (4 ml), ethylene, 1-octene comonomer (1 ml), cocatalyst 1 or cocatalyst 1/MMAO mixture, shuttling agent, and catalyst or catalyst mixture.
  • the reagents are premixed in a small vial immediately prior to addition to the reactor.
  • a reagent is omitted in an experiment, the above order of addition is otherwise maintained. Polymerizations are conducted for approximately 1-2 minutes, until predetermined ethylene consumptions are reached. After quenching with CO, the reactors are cooled and the glass tubes are unloaded.
  • the DSC curve for Comparative Example C* shows a 125.3°C melting point (Tm) with a heat of fusion of 143.0 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 81.8 0 C with a peak area of 34.7 percent as well as a lower crystalline peak at 52.4 °C.
  • the separation between the two peaks is consistent with the presence of a high crystalline and a low crystalline polymer.
  • the difference between the DSC Tm and the Tcrystaf is 43.5°C.
  • the DSC curve for the polymer of Comparative Example F* shows a peak with a 124.8 0 C melting point (Tm) with a heat of fusion of 90.4 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 77.6°C with a peak area of 19.5 percent. The separation between the two peaks is consistent with the presence of both a high crystalline and a low crystalline polymer.
  • the delta between the DSC Tm and the Tcrystaf is 47.2°C.
  • Table 5 shows results for mechanical properties for the new polymers as well as for various comparison polymers at ambient temperatures. It may be seen that the inventive polymers have very good abrasion resistance when tested according to ISO 4649, generally showing a volume loss of less than about 90 mm 3 , preferably less than about 80 mm 3 , and especially less than about 50 mm 3 . In this test, higher numbers indicate higher volume loss and consequently lower abrasion resistance.
  • Table 5 also shows that the polymers of the invention have better retractive stress at 150 percent strain (demonstrated by higher retractive stress values) than some of the comparative samples.
  • Comparative Examples F*, G* and H* have retractive stress value at 150 percent strain of 400 kPa or less, while the inventive polymers have retractive stress values at 150 percent strain of 500 kPa (Ex. 11) to as high as about 1100 kPa (Ex. 17).
  • Polymers having higher than 150 percent retractive stress values would be quite useful for elastic applications, such as elastic fibers and fabrics, especially nonwoven fabrics. Other applications include diaper, hygiene, and medical garment waistband applications, such as tabs and elastic bands.
  • LPE is a homogeneously branched substantially linear polyethylene as described by Lai et al. in U.S. Pat. Nos. 5,272,236, 5,278,272, 5,665,800 and
  • 12540N is high density polyethylene from The Dow Chemical Company, Midland, MI.
  • KRATON® 1652 is a SEBS copolymer obtained from Kraton Polymers, Houston, TX.
  • WINGTACK® 95 is a tackifier from GoodYear Chemical, Beaumont, TX.
  • EASTOTAC® H142R is a tackifier from Eastman Company, Kingsport, Tennessee.
  • ESCOREZTM 5400 is a tackifier from ExxonMobil Chemical Company, Houston, TX.
  • ENGAGE® 8100 is a polyolefin elastomer obtained from The Dow Chemical Co., Midland, MI.
  • RT Shear Static shear at room temperature (RT) was tested using a 1 kg weight and a modified ASTM-D-4498, which is incorporated herein by reference. The static shear at room temperature test results are listed in Table 13 below.
  • the percent fiber tear test was conducted with a corrugated board stock according to a standard industry test.
  • the adhesive sample to be tested was heated to 177°C/350°F and was applied on the board stock cut into 1 x 3 inch (25 x 76 mm) rectangular sheets with the corrugated flutes running lengthwise.
  • the adhesive sample was applied, running lengthwise, as about a 5 mm (i.e., 0.2 inch) wide strip and could be drawn down with a spatula or hot melt applicator.
  • a second strip was applied within 2 seconds and held, with moderate pressure, for 5 seconds to laminate.
  • the samples contained 0.5 wt % IRGANOX® 11010, a hindered phenolic antioxidant from Ciba Specialty Chemicals, Tarrytown, NY.
  • the poly/nonwoven laminations were peeled apart using an I-Mass slip peel tester set at a peel rate if 12 inches/minute and the average force recorded over a 20 second time period. For each product 6 constructs were peeled and the average of the 6 averages recorded along with the standard deviation.
  • Initial peel means peeled at room temperature after equilibrating at room temperature for 24 hours.
  • Aged peel means aging the bonds at room temperature for 24 hours then 50 0 C for two weeks and then equilibrating at room temperature for 24 hours and then peeling.
  • the 37 0 C peel means conditioning the bonds for 24 hours at RT and then placing the constructs in a chamber set at 37 0 C for one hour and peeling them at 37 0 C.
  • Examples 81-83 all exhibited good viscosity, sprayability, pattern rating (10 being the highest) and good average and aged peels at 100 0 F as compared to Comparative Example AF and HL-8128, indicating that these materials would be good construction adhesives.
  • Example 83 also showed unexpected and favorable behavior in that the peel increased with aging at 100 0 F indicating that it may be more advantageous for use at both room temperature and higher temperatures such as 100 0 F.
  • Figure 10 is a DSC curve showing the melting behavior of Polymer Example 30.
  • Table 19 shows that the adhesive properties using two polymers with the same overall density but with different melting behavior as shown in Figures 11 and 12; with Polymer Example 31c having a broad melting curve with peaks at 108 0 C and 40 0 C and Polymer Example 3 Id having sharper melting behavior with a melting point at 117 0 C. Both samples, when formulated, showed good viscosity, indicating the ability to be applied at the application temperature of 300 0 F - 350 0 F and good loop tack, peel to various substrates and SAFT.

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AU2006227348A AU2006227348A1 (en) 2005-03-17 2006-03-15 Adhesive and marking compositions made from interpolymers of ethylene/alpha-olefins
MX2007011324A MX2007011324A (es) 2005-03-17 2006-03-15 Composiciones adhesivas y de marcado hechas a partir de interpolimeros de etileno/alfa-olefinas.
JP2008502121A JP5231987B2 (ja) 2005-03-17 2006-03-15 エチレン/α−オレフィン共重合体から製造される接着剤およびマーキング用組成物
US11/908,950 US7989543B2 (en) 2005-03-17 2006-03-15 Adhesive and marking compositions made from interpolymers of ethylene/α-olefins
CN2006800084157A CN101291964B (zh) 2005-03-17 2006-03-15 由乙烯/α-烯烃共聚体制造的粘结剂和标记组合物
BRPI0609841-0A BRPI0609841B1 (pt) 2005-03-17 2006-03-15 Composição de interpolímero de etileno/a-olefina e artigo
CA002601273A CA2601273A1 (en) 2005-03-17 2006-03-15 Adhesive and marking compositions made from interpolymers of ethylene/alpha-olefins
EP06738855.3A EP1858945B1 (en) 2005-03-17 2006-03-15 Adhesive and marking compositions made from interpolymers of ethylene/alpha-olefins
KR1020077021049A KR101413315B1 (ko) 2005-03-17 2006-03-15 에틸렌/알파-올레핀 혼성중합체로부터 제조된 접착제 및표지 조성물

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