EP2956490A1 - Produit de la réaction entre un polymère de propylène et une cire, copolymères greffés dérivés du polymère de polypropylène et de la cire, compositions d'adhésifs thermofusibles comprenant ceux-ci, et procédés d'utilisation et de fabrication associés - Google Patents

Produit de la réaction entre un polymère de propylène et une cire, copolymères greffés dérivés du polymère de polypropylène et de la cire, compositions d'adhésifs thermofusibles comprenant ceux-ci, et procédés d'utilisation et de fabrication associés

Info

Publication number
EP2956490A1
EP2956490A1 EP14710678.5A EP14710678A EP2956490A1 EP 2956490 A1 EP2956490 A1 EP 2956490A1 EP 14710678 A EP14710678 A EP 14710678A EP 2956490 A1 EP2956490 A1 EP 2956490A1
Authority
EP
European Patent Office
Prior art keywords
wax
hot melt
melt adhesive
adhesive composition
reaction product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14710678.5A
Other languages
German (de)
English (en)
Inventor
Kevin P. Davis
Ameara S. MANSOUR
Sharf U. Ahmed
Cheryl L. CHASE
Maynard R. LAWRENCE
Scott C. Schmidt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HB Fuller Co
Original Assignee
HB Fuller Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/768,859 external-priority patent/US9593235B2/en
Priority claimed from US13/768,887 external-priority patent/US9267060B2/en
Application filed by HB Fuller Co filed Critical HB Fuller Co
Publication of EP2956490A1 publication Critical patent/EP2956490A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives 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
    • C09J123/10—Homopolymers or copolymers of propene
    • C09J123/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives 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
    • C09J123/10—Homopolymers or copolymers of propene
    • C09J123/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene

Definitions

  • the invention relates to reacting propylene polymer and wax in the presence of a free radical initiator.
  • Hot melt adhesive compositions are used in a variety of applications that require bonding two substrates together including, e.g., packaging applications (e.g., corrugated board and cardboard), nonwoven applications (e.g., disposable articles), bookbinding, and footwear manufacturing.
  • a hot melt adhesive composition is generally applied in a molten state and forms a bond as it cools and solidifies. It is important that adhesives used in packaging applications exhibit good bond strength over a wide temperature range and fast set times. It is often difficult to achieve a hot melt adhesive composition that exhibits good bonding properties at both low and high temperatures.
  • Hot melt adhesive compositions that are formulated with amorphous
  • polypropylene polymers are useful in a variety of applications. Many amorphous polypropylene polymers exhibit a long open time, are quite tacky immediately after solidifying from a molten state, and remain tacky for an undesirable period of time after solidifying. These properties are undesirable for applications that require short open times and non-tacky properties after solidification.
  • the invention features a propylene-wax copolymer that includes the reaction product of components that include a first polymer that includes at least one of polypropylene homopolymer and polypropylene-alpha-olefin copolymer, a first wax that includes at least one of polyethylene wax and Fischer Tropsch wax, and a free radical initiator, and that are free of an unsaturated compound that includes at least one functional group and having a molecular weight no greater than 1000 g/mole, the reaction product having a polydispersity index of no greater than 5 and a viscosity of no greater than 12,000 centipoise at 177 °C.
  • the invention features a propylene-wax copolymer that includes the reaction product of components that include a first polymer that includes at least one of polypropylene homopolymer and polypropylene-alpha-olefm copolymer, a first wax that includes polyethylene wax, and a free radical initiator, the reaction product having a number average molecular weight greater than 5000 g/mole, a polydispersity index no greater than 5, and a viscosity of no greater than 12,000 centipoise at 177 °C.
  • the components further include an unsaturated compound that includes at least one functional group.
  • the unsaturated compound includes at least one of maleic acid, maleic anhydride, and fumaric acid.
  • the invention features a propylene-wax copolymer that includes the reaction product of components that include a first polymer having a polydispersity index of no greater than 5 and including at least one of polypropylene homopolymer and polypropylene-alpha-olefin copolymer, a first wax that includes at least one of
  • the invention features a method of making a graft copolymer, the method including blending a first polymer and a first wax in the presence of a free radical initiator for a period of time and under sufficient conditions to achieve a reaction product having a polydispersity index of no greater than 5, the first polymer including at least one of polypropylene homopolymer and polypropylene-alpha-olefin copolymer, and the first wax including polyethylene wax.
  • the invention features a method of making a graft copolymer includes blending a first polymer and a first wax in the presence of a free radical initiator and in the absence of an unsaturated compound that includes at least one functional group and has a molecular weight no greater than 1000 g/mole for a period of time and under sufficient conditions to achieve a reaction product having a polydispersity index of no greater than 5, the first polymer including at least one of polypropylene homopolymer and polypropylene-alpha-olefin copolymer, and the first wax including at least one of polyethylene wax and Fischer Tropsch wax,
  • the invention features a hot melt adhesive composition that includes a propyl ene-wax copolymer described herein.
  • hot melt adhesive composition further includes at least one of a tackifying agent, a plasticizer, and a wax.
  • the invention features a hot melt adhesive composition that includes a) a reaction product of components that include a first polymer that includes at least one of polypropylene homopolymer and polypropylene-alpha-olefin copolymer, a first wax that includes at least one of polyethylene wax and Fischer Tropsch wax, a free radical initiator, and that are free of an unsaturated compound that includes at least one functional group and having a molecular weight no greater than 1000 g/mole, the reaction product having a number average molecular weight greater than 5000 g/mole, a polydispersity index of no greater than 5, and a viscosity of no greater than 32,000 centipoise at 177 °C, and b) a tackifying agent.
  • a reaction product of components that include a first polymer that includes at least one of polypropylene homopolymer and polypropylene-alpha-olefin copolymer, a first wax that includes at least one of polyethylene wax and Fischer
  • the hot melt adhesive composition further includes a second wax.
  • the first polymer has a polydispersity index of less than 5. In some embodiments, first polymer has a polydispersity index of less than 4.5. In other embodiments, the reaction product has a polydispersity index of no greater than 4.5. In another embodiment, the reaction product has a polydispersity index of no greater than 4.
  • the first polymer includes a polypropylene homopolymer.
  • the first wax is a non-functionalized wax.
  • the first wax includes polyethylene wax and Fischer Tropsch wax.
  • the second wax includes at least one of polyethylene wax, polypropylene wax, Fischer Tropsch wax, paraffin, and functionalized wax.
  • the second wax includes at least one of maleated polypropylene wax and maleated polyethylene wax.
  • the first polymer includes polypropylene homopolymer and the first wax includes polyethylene. In another embodiment, the first polymer includes polypropylene homopolymer and the first wax includes a Fischer Tropsch wax.
  • the hot melt adhesive compositions described herein include from about 30 % by weight to about 80 % by weight of the reaction product, from about 1 % by weight to about 40 % by weight of the tackifying agent, and from about 1 % by weight to about 35 % by weight of the second wax. In another embodiment, the hot melt 5 adhesive compositions described herein include from about 35 % by weight to about 70 % by weight of the reaction product, and from about 5 % by weight to about 35 % by weight of the tackifying agent.
  • die hot melt adhesive composition exhibits a fiber tearing bond at -29 °C and at 60 °C. In other embodiments, the hot melt adhesive composition ] 0 exhibits at least about 50 % fiber tear at -29 °C and at 60 °C. In one embodiment, the hot melt adhesive composition exhibits at least 80 % fiber tear at 71 °C.
  • the hot melt adhesive composition exhibits an initial Gardner color of no greater than 3.
  • the hot melt adhesive composition exhibits a change in ] 5 viscosity of no greater than 10 % after aging for 96 hours at 177 °C.
  • the hot melt adhesive composition is free of gelling after aging for 96 hours at 177 °C.
  • the composition exhibits a set time of no greater than 10 seconds. In another embodiment, the composition exhibits a set time of no greater than 5 0 seconds.
  • the composition exhibits an energy to break of at least 0.15 Joules. In one embodiment, the composition exhibits a strain at break of at least about 100 %. In other embodiments, the composition exhibits an energy to break of at least 0.15 Joules and a strain at break of at least 100 %. In another embodiment, the composition5 exhibits a heat stress resistance of at least 60 °C. In one embodiment, the composition exhibits an energy to break of at least 0.15 Joules and a heat stress resistance of at least 60 °C.
  • the composition exhibits an energy to break of at least 0.15 Joules and a strain at break of at least 100 %, and further includes a second wax0 selected from the group consisting of polyethylene wax, polypropylene wax, Fischer
  • the composition exhibits an energy to break of at least 0.15 Joules and a heat stress resistance of at least 60 °C, and further includes a second wax selec ted from the group consisting of polyethylene wax, polypropylene wax, Fischer Tropsch wax, paraffin, maleated polypropylene wax, and maleated polyethylene wax.
  • the composition exhibits a tensile strength of at least 1.38
  • composition includes at least 10 % by weight tackifying agent and exhibits at least about 75 % fiber tear at -29°C.
  • the reaction products disclosed herein include the reaction product of the first polymer, the first wax, the free radical initiator, and an unsaturated compound that includes at least one functional group.
  • the unsaturated compound includes at least one of inaleic acid, maleic anhydride, and fumaric acid.
  • reaction products disclosed herein include the reaction product of the first polymer, the first wax, the first wax being a non-functionalized wax, the free radical initiator, and a second wax, the second wax being a functionalized wax.
  • the hot melt adhesive compositions described herein further include a nucleating agent.
  • the invention features an article that includes a first substrate, a hot melt adhesive composition disclosed herein, and a second substrate bonded to the first substrate through the hot melt adhesive composition.
  • the first substrate includes cardboard.
  • the invention features a method of using the hot melt adhesive compositions disclosed herein, the method including contacting a first substrate that includes fibers with a hot melt adhesive composition disclosed herein, and bonding a second substrate that includes fibers to the first substrate through the hot melt adhesive composition such that the hot melt adhesive composition fonns a fiber tearing bond to the first substrate in no greater than 10 seconds.
  • the hot melt adhesive composition exhibits a fiber tearing bond to the first substrate in no greater than 5 seconds.
  • the invention features a hot melt adhesive composition that includes a reaction product of components that include a first polymer that includes at least one of polypropylene homopolymer and polypropylene-alpha -olefin copolymer, a first wax that includes at least one of polyethylene wax, Fischer Tropsch wax, and paraffin wax, and a free radical initiator, the reaction product having a viscosity at 177 °C that is less than the viscosity of a blend of the components of the reaction product other than the free radical initiator, the reaction product having a number average molecular weight greater than 5000 g/mole, a polydispersity index of no greater than 5, and a viscosity of no greater than 12,000 centipoise at 177 °C.
  • a reaction product of components that include a first polymer that includes at least one of polypropylene homopolymer and polypropylene-alpha -olefin copolymer, a first wax that includes at least one of polyethylene wax
  • the reaction product has a viscosity at 177 °C that is at least 20 % less than the viscosity at 1.77 °C of the blend of the components of the reaction product other than the free radical initiator.
  • the hot melt adhesive composition further includes a tackifying agent.
  • the invention features a hot melt adhesive composition that includes a reaction product of a first polymer that includes at least one of polypropylene homopolymer and polypropylene-alpha-olefm copolymer, a first non-functionaiized wax that includes at least one of polyethylene wax, Fischer Tropsch wax, and paraffin wax, and a free radical initiator, and a tackifying agent, the reaction product exhibiting a viscosity of no greater than 12,000 centipoise at 177 °C, and the hot melt adhesive composition exhibiting at least one of an energy to break of at least 0.15 Joules, a tensile strength of at least 3.28 MPa, and a heat stress resistance of at least 65 °C.
  • the invention features a hot melt adhesive composition that includes the reaction product of components that include a first polymer having a polydispersity index of no greater than 5 and including at least one of polypropylene homopolymer and polypropylene-alpha-olefm copolymer, a first wax that includes at least one of polyethylene wax, Fischer Tropsch wax, and paraffin wax, a free radical initiator, and being free of an unsaturated compound that includes at least one functional group and that has a molecular weight no greater than 1000 g/mole, the reaction product exhibiting a viscosity of no greater than 12,000 centipoise at 177 °C.
  • a hot melt adhesive composition that includes the reaction product of components that include a first polymer having a polydispersity index of no greater than 5 and including at least one of polypropylene homopolymer and polypropylene-alpha-olefm copolymer, a first wax that includes at least one of polyethylene wax, Fischer Tropsch wax, and paraffin wax
  • the invention features a hot melt adhesive composition that includes the reaction product of a first polymer that includes at least one of polypropylene homopolymer and polypropylene-alpha-olefm copolymer, a first wax that includes polyethylene wax, and a free radical initiator, the reaction product having a number average molecular weight greater than 5000 g/mole, a polydispersity index no greater than 5, and a viscosity of no greater than 12,000 centipoise at 177 °C.
  • the hot melt adhesive exhibits good bond strength over a wide temperature range and good adhesion to packaging materials.
  • wax means a polymer having crystallinity and a weight average molecular weight (Mw) less than 20,000 g/mole.
  • non-functionalized wax refers to a wax that is free of polar functional groups.
  • the hot melt adhesive composition includes a reaction product of a propylene polymer, a wax, and a free radical initiator.
  • the hot melt adhesive composition exhibits a viscosity of no greater than about 5,000 centipoise (cP), no greater than about 4,000 cP, no greater than about 3,500 cP, no greater than about 3,000 cP, no greater than about 2,500 cP, or even no greater than about 2,000 cP, at 177 °C.
  • the hot melt adhesive composition preferably forms a fiber tearing bond at -29 °C and at 60 °C, and preferably exhibits at least about 40 %, at least about 50 %, at least about 75 %, at least about 80 %, at least about 90 %, or even at least 100 % fiber tear at -29 °C and at 60 °C, at 65 °C, at 71 °C, at 75 °C, or even at 77 °C.
  • the hot melt adhesive composition also exhibits a set time of no greater than 1 seconds, no greater than 10 seconds, no greater than 8.5 seconds, no greater than 7 seconds, or even no greater than 5 seconds.
  • the hot melt adhesive composition preferably exhibits at least one of a strain at break of at least 10 %, at least about 50 %, at least about 75 %, at least about 100 %, or at least even about 120 %, a tensile strength of at least 1.38 megapascals (MPa) (200 pounds per square inch (psi)), at least about 1.72 MPa (250 psi), at least about 2.07 MPa (300 psi), at least about 2.41 MPa (350 psi), at least about 2.76 MPa (400 psi), at least about 3.26 MPa (475 psi), at least about 3.45 MPa (500 psi) at least 4.14 MPa (600 psi) or even at least 4.48 MPa (650 psi), and an energy to break of at least 0.15 Joules (J), at least about 0.20 J, of at least about 0.25 J, or even at least about 0.40 J.
  • MPa megapascals
  • J energy to break
  • the hot melt adhesive composition also preferably exhibits a heat stress resistance of at least 55 °C, at least 60 °C, at least 65 °C, or even at least 70 °C.
  • the hot melt adhesive composition also preferably exhibits an initial Gardner color of no greater than 5, no greater than 4, or even no greater than 3, a Gardner color of no greater than 1 1 or even no greater than 7 after aging for 96 hours at 177 °C, or even a change in Gardner color of no greater than 9, of no greater than 7, or even of no greater than 5 after aging for 96 hours at 177 °C.
  • the hot melt adhesive composition preferably is free of gelling after aging for 96 hours at 177 °C and preferably exhibits a change in viscosity of no greater than about 20 % or even no greater than about 10 % after aging for 96 hours at 177 °C.
  • the reaction product is derived from a propylene polymer that is at least one of a polypropylene homopolymer and a propylene-alpha-olefin copolymer, a first wax that is at least one of polyethylene wax, Fischer Tropsch wax, and paraffin wax, and a free radical initiator.
  • the reaction product includes a copolymer that includes units of the propylene polymer and units of the first wax, and optionally at least one of the propylene polymer and the first wax.
  • the reaction product preferably has a polydispersity index (Mw/Mn) of no greater than 5.5, no greater than about 5.0, no greater than about 4.5, no greater than about 4.0, or even no greater than about 3, and a viscosity of no greater than about 12,000 cP, no greater than about 10,000 cP, no greater than about 5000 cP, no greater than about 4000 cP, no greater than about 3500 cP, no greater than about 3000 cP, or even no greater than about 2500 cP, at 177 °C.
  • Mw/Mn polydispersity index
  • Useful reaction products exhibit a number average molecular weight (Mn) of at least 5000 grams/mole (g/mole), at least about 5500 g/mole, at least about 6000 g/mole or even at least about 6500 g/mole.
  • Mn number average molecular weight
  • the reaction product can exhibit a viscosity that is less than the viscosity of a blend of the components from which the reaction product is derived (other than the free radical initiator).
  • the reaction product can exhibit a viscosity that is at least 10 %, at least about 20 %, at least about 30 %, at least about 40 %, at least about 60 %, at least about 70 %, or even at least about 80 % less than the viscosity of the blend from which the reaction product is derived.
  • the reaction product can exhibit at least one of the properties of the hot melt adhesive composition.
  • the reaction product can be formulated with other components to exhibit at least one of the properties of the hot melt adhesive composition.
  • the reaction product preferably is present in the hot melt adhesive composition in an amount of about 100 % by weight, at least 30 % by weight, at least about 35 % by weight, at least about 40 % by weight, no greater than 99 % by weight, no greater than about 90 % by weight, from about 30 % by weight to about 80 % by weight, from about 35 % by weight to about 70 % by weight, or even from about 40 % by weight to about 60 % by weight.
  • Useful propylene polymers from which the reaction product can be derived have a polydispersity index (Mw/Mn) of no greater than about 5, no greater than about 4.5, no greater than about 4, or even no greater than about 3.
  • the propylene polymer preferably exhibits a viscosity of no greater than 20,000 cP, no greater than 1 ,000 cP, or even no greater than 10,000 cP, at 190 °C.
  • Useful propylene polymers include, e.g., polypropylene homopolymers, copolymers (i.e., copolymers, terpolymers, and higher order polymers) of propylene and at least one alpha-olefin co-monomer, and combinations thereof.
  • Useful propylene copolymers are derived from propylene and at least one alpha-olefin co-monomer (e.g., alpha-olefin monomers having at least two carbon atoms, at least four carbon atoms, and combinations of such monomers).
  • Useful alpha-olefin monomers include, e.g., ethylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-pentene- l , 3-methyl pentene-l ,3,5,5-trimethyl-hexene- l , 5-ethyl-l -nonene, and combinations thereof.
  • Suitable alpha-olefin co-monomers include mono-alpha olefins (i.e., one unsaturated double bond) and higher order olefins (e.g., a di-olefin, e.g., 1 ,9-decadiene).
  • suitable propyl ene-alpha-olefin copolymers include propylene-ethylene, propylene-butene, propylene-hexane, propylene-octene, and combinations thereof.
  • the propylene polymer preferably includes at least 50 mole %, at least abotit 60 mole %, at least about 70 mole %, at least about 80 mole %, at least about 90 mole %, at least about 95 mole %, or even from about 50 mole % to about 100 mole % propylene.
  • the propylene polymer optionally includes at least 2 mole %, at least about 5 mole %, at least about 10 mole %, at least about 20 mole %, at least about 30 mole %, no greater than about 50 mole %, or even from about 20 mole % to about 50 mole % of at least one alpha-olefm co-monomer.
  • Useful propylene polymers include metallocene-catalyzed propylene polymers.
  • Suitable propylene polymers are commercially available under a variety of trade designations including, e.g., the L-MODU series of trade designations from Idemitsu Kosan Co., Ltd (Japan) including, e.g., L-MODU S400, S600, and S901 , the
  • VISTAMAXX series of trade designations from ExxonMobil Chemical Company ⁇ Houston, Texas including, e.g., VISTAMAXX 6202 and 2330
  • the LICOCENE series of trade designations from Clariant Int' l Ltd. (Muttenz. Switzerland) including, e.g., LICOCENE PP 1602 TP and PP 2602 TP.
  • the reaction product preferably is formed from at least at least 60 % by weight, at least 70 % by weight, at least 80 % by weight, from about 70 % by weight to about 99 % by weight, from about 80 % by weight to about 95 % by weight, or even from about 85 % by weight to about 95% by weight propylene polymer.
  • Useful waxes from which the reaction product can be derived include, e.g., polyethylene waxes (e.g., polyethylene homopolymers), Fischer Tropsch waxes, paraffin waxes, and combinations thereof, alone or in further combination with polypropylene wax.
  • the wax preferably is non-functionalized.
  • Useful polyethylene waxes are commercially available under a variety of trade designations including, e.g., the EPOLENE series of trade designations from Westlake Chemical Corporation (Houston, Texas) including, e.g., EPOLENE N-21 and N-14 polyethylene waxes, the BARECO series of trade designations from Baker Hughes Inc. ⁇ Sugar Land, Texas) including, e.g., BARECO C4040 polyethylene wax, and the AC series of trade designations from Honeywell Int'l Inc. (Morristown, New Jersey) including, e.g., A-C 8 and A-C 9 polyethylene waxes.
  • Fischer Tropsch waxes are commercially available under a variety of trade designations including, e.g., the BARECO series of trade designations from Baker Hughes Inc. (Sugar Land, Texas) including, e.g., BARECO PX-] 00 and PX-105 Fischer Tropsch waxes, the SHELLWAX series of trade designations from Shell Malaysia Ltd. (Kuala Lumpur, Malaysia) including, e.g., SHELLWAX SX100 and SX105 Fischer Tropsch waxes, the VESTOWAX series of trade designations from Evonik Industries AG
  • paraffin waxes are available under a variety of trade designations including, e.g., PARVAN 1580 and 3520 paraffin waxes from ExxonMobil Chemical Company (Houston, Texas).
  • Useful polypropylene waxes are commercially available under a variety of trade designations including, e.g., EPOLENE N15 from Westlake Chemical Corporation (Houston, Texas), HONEYWELL AC 1089 from Honeywell Int'l Inc. (Morristown, New Jersey) , and LICOCENE 6102 from Clariant Int'l Ltd. (Muttenz, Switzerland).
  • the reaction product preferably is formed from about 1 % by weight to about 40 % by weight, from about 3 % by weight to about 30 % by weight, from about 5 % by weight to about 25 % by weight, or even from about 7 % by weight to about 15 % by weight wax.
  • Useful free-radical initiators include, e.g., peroxide-type compounds, azo-type compounds, and mixtures thereof.
  • suitable peroxide-type compounds include diacyl peroxides, peroxy esters, peroxy ketals, di-alkyl peroxides, and hydroperoxides, specifically hydrogen peroxide, benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, cumene hydroperoxide, t-butylhydroperoxide, t-butyl peroxy acetate, 2,2-di(t-butyl peroxy) butane di-allyl peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy) hexane, cumyl peroxide, di-t-amyl peroxide, and combinations thereof.
  • Suitable 2,5-dimethyl-2,5-di(t-butyl peroxy) hexanes
  • Suitable azo-type compounds include azobisisobutyronitrile (AIBN), 2,2'-azobis ( ⁇ , ⁇ '-dimethyleneisobutyramide) dihydochloride (one example of which is commercially available under the VA-044 trade designation from Wako Chemical Co.), 2,2'-azobis(2,4-dimethyl valeronitrile) (one example of which is commercially available under the V-65 trade designation from Wako Chemical Co.), VAZO 64 2,2- azobis(isobutyronitrile) and VAZO 67 2,2'-azobis(2-methylbutyronitrile) both of which are commercially available from du Pont de Nemours and Company (Wilmington, Delaware), l,l '-azobis ( 1 -cyclohexane carbonitrile), acid-functional azo-type initiators e.g., 4,4' ⁇ azobis (4-cyanopentanoic acid), and combinations thereof.
  • AIBN azobisisobutyronitrile
  • the reaction product preferably is formed from about 0.005 % by weight to about 10 % by weight, from about 0.1 % by weight to about 5 % by weight, or even from about 0.2 % by weight to about 2 % by weight free-radical initiator based on the weight of the propylene polymer.
  • the blend from which the reaction product is derived can be free of an unsaturated compound that includes at least one functional group (i.e.. a functional unsaturated compound) and that has a molecular weight greater than 1000 g/mole.
  • the reaction product optionally is derived from an unsaturated compound, a functional unsaturated compound, and combinations thereof.
  • Useful functional groups include, e.g., acids, anhydrides, esters, hydroxyl, amides, epoxy, and combinations thereof.
  • Useful functional unsaturated compounds include, e.g., unsaturated acids, polyacids,
  • suitable unsaturated acids include acrylic acid and methacrylic acid.
  • suitable unsaturated polyacids and unsaturated polyanhydrides include dicarboxylic acids and tricarboxylic acids including, e.g., acids and anhydrides of aliphatic dicarboxylic acids (e.g. maleic acid, maleic anhydride, and fumaric acid), and combinations thereof.
  • the reaction product can be derived from 0 % by weight to no greater than about 7 % by weight, no greater than about 0.01 % by weight, no greater than 0.001 % by weight, from about 0.1 % by weight to about 3 % by weight, or even from about 0.1 % by weight to about 2 % by weight of a functional unsaturated compound, where the % by weight is based on the weight of the reaction product.
  • the reaction product preferably is prepared by combining the propylene polymer, wax, and free radical initiator (and any optional components) to form a reaction mixture and reacting the same at an elevated temperature (e.g., from about 150 °C to about 250 °C, or even from about 175 °C to about 225 °C) under a blanket of inert gas (e.g., nitrogen).
  • an elevated temperature e.g., from about 150 °C to about 250 °C, or even from about 175 °C to about 225 °C
  • inert gas e.g., nitrogen
  • the peroxide or agent is dispersed in the reaction mixture and the temperature of the process is at least as high as the melting point of the polymer.
  • the temperature preferably is sufficiently far above the melting point to obtain reasonably good agitation of the polymer.
  • Useful processing temperatures include from about 100 °C to about 250 °C, from about 150 °C to about 220 °C, or even from about 170 °C to about 190 °C.
  • the temperature of the process preferably is initially from about 10 °C to about 100 °C above the softening point of the polymer or polymer mixture to be treated.
  • the reaction time may vary from less than a minute to several hours depending on the temperature used and the half-life of the free radical initiator being used.
  • the process can be carried out using any suitable method including, e.g., continuous processes, semi-continuous processes, and batch processes.
  • Suitable continuous processes include, e.g., processes that use extruders (e.g., single screw, twin screw, disk screw, reciprocating single screw, and pin barrel single screw) and processes that use tandem extrusion techniques.
  • Suitable batch processes include, e.g., processes that utilize reaction vessels.
  • Suitable reaction vessels include those made from glass or metal.
  • the reactions may be conducted in glass flasks, glass lined reactors, steel autoclaves, extmders, Brabender plastographs, and Banbury mixers.
  • the reactions may be conducted in the presence of air or under inert gases such as nitrogen.
  • an inert solvent such as benzene.
  • a vacuum is applied to remove impurities and volatile byproducts of the reaction process.
  • the hot melt adhesive composition optionally includes a tackifying agent.
  • Tackifying agents suitable for tise in the adhesive composition preferably have Ring and Ball softening point of less than about 160 °C, less than about 150 °C, or even less than about 1.40 °C.
  • Suitable classes of tackifying agents include, e.g., aromatic, aliphatic and cycloaliphatic hydrocarbon resins, mixed aromatic and aliphatic modified hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, and hydrogenated versions thereof; terpenes, modified teipenes and hydrogenated versions thereof; natural rosins, modified rosins, rosin esters, and hydrogenated versions thereof; low molecular weight polylactic acid; and combinations thereof.
  • Examples of useful natural and modified rosins include gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin.
  • Examples of useful rosin esters include e.g., glycerol esters of pale wood rosin, glycerol esters of hydrogenated rosin, glycerol esters of polymerized rosin, pentaeiythritol esters of natural and modified rosins including pentaeiythritol esters of pale wood rosin, pentaeiythritol esters of hydrogenated rosin, pentaeiythritol esters of tall oil rosin, phenolic-modified pentaeiythritol esters of rosin, and combinations thereof.
  • polyterpene resins examples include polyteipene resins having a softening point- as determined by ASTM method E28-58T, of from about 10 °C to about 160 °C, hydrogenated polyteipene resins, and copolymers and terpolymers of natural teipenes (e.g. styrene-terpene, alpha-methyl styrene-teipene and vinyl toluene-terpene), and
  • useful aliphatic and cycloaliphatic petroleum hydrocarbon resins include aliphatic and cycloaliphatic petroleum hydrocarbon resins having Ring and Ball softening points of from about 10 °C to 160 °C, the hydrogenated derivatives thereof, and combinations thereof.
  • Suitable aliphatic and cycloaliphatic petroleum hydrocarbon resins include, e.g., branched, unbranched, and cyclic C5 resins, C9 resins, and CIO resins.
  • Useful tackifying agents are commercially available under a variety of trade designations including, e.g., the ESCOREZ series of trade designations from ExxonMobil Chemical Company (Houston, Texas) including, e.g., ESCOREZ 5400, ESCOREZ 5415, ESCOREZ 5600, ESCOREZ 5615, and ESCOREZ 5690, the EASTOTAC series of trade designations from Eastman Chemical (Kingsport, Temiessee) including, e.g., EASTOTAC H-100R, EASTOTAC H-100L, EASTOTAC H130W, and EASTOTAC H142, the WINGTACK series of trade designations from Cray Valley HSC (Exton, Pennsylvania) including, e.g., WINGTACK 86, WINGTACK EXTRA, and WINGTACK 95, the PICCOTAC series of trade designations from Eastman Chemical Company (Kingsport, Tennessee) including, e.g., PICCOTAC 8095, the
  • the adhesive composition preferably includes no greater than about 50 % by weight, no greater than about 40 % by weight, no greater than about 30 % by weight, no greater than about 20 % by weight, no greater than about 10 % by weight, no greater than about 5 % by weight, at least about I % by weight, at least about 15 % by weight, at least about 20 % by weight, from about 1 % by weight to about 40 % by weight, from about 5 % by weight to about 35 % by weight, or even from about 10 % by weight to about 35 % by weight tackifymg agent.
  • the hot melt adhesive composition optionally includes a variety of additional components including, e.g., wax, antioxidants, stabilizers, additional polymers, plasticizers, oil (e.g., aliphatic napthenic oil, white oil, and combinations thereof), adhesion promoters, ultraviolet light stabilizers, rheology modifiers, biocides, corrosion inhibitors, dehydrators, colorants (e.g., pigments and dyes), fillers, surfactants, flame retardants, nucleating agents, and combinations thereof.
  • additional components including, e.g., wax, antioxidants, stabilizers, additional polymers, plasticizers, oil (e.g., aliphatic napthenic oil, white oil, and combinations thereof), adhesion promoters, ultraviolet light stabilizers, rheology modifiers, biocides, corrosion inhibitors, dehydrators, colorants (e.g., pigments and dyes), fillers, surfactants, flame retardants, nucleating agents, and combinations thereof.
  • wax e.g.
  • Classes of useful waxes include, e.g., functionalized waxes, non-functionalized waxes, and mixtures thereof.
  • Useful functionalized waxes include, e.g., functionalized polyethylene wax (e.g., maleated polyethylene wax and oxidized polyethylene wax), functionalized polypropylene wax (e.g., maleated polypropylene wax and oxidized polypropylene wax), polar waxes, functionalized stearamide waxes (e.g.,
  • hydroxystearamide N-(2-hydroxy ethyl)- 12-hydroxystearamide, N. '-ethylene bis 12- hydroxy stearamide, and 12-hydroxy stearic acid N,N ethyiene-bis stearamide
  • Useful non-functionalized waxes include, e.g., Fischer Tropsch waxes, polyolefm waxes (e.g., polypropylene waxes and polyethylene waxes), stearamide waxes, benzoate ester waxes, animal waxes, vegetable waxes, paraffin waxes,
  • microcrystalline waxes microcrystalline waxes, metallocene waxes, glycerin monostearate, sorbitan monostearate, and combinations thereof.
  • Useful commercially available functionalized waxes include, e.g., A-C 597P and A-C 596P maleated polypropylene wax, which are available from Honeywell international Inc.
  • Useful commercially available non-functionalized waxes include the waxes set forth above in the discussion of waxes from which the reaction product is derived.
  • the additional wax when present in the hot melt adhesive composition, is preferably present in an amount of at least 0.2 % by weight, at least 2 % by weight, at least about 5 % by weight, at least about 10 % by weight, no greater than about 35 % by weight, no greater than about 30 % by weight, no greater than about 25 % by weight, from about 5 % by weight to about 25 % by weight, or even from about 5 % by weight to about 20 % by weight.
  • Useful antioxidants include, e.g., pentaerythritol tetrakis[3,(3,5-di ⁇ tert ⁇ butyl-4- hydroxyphenyl)propionate], 2,2'-methylene bis(4-methyl-6-tert-butylphenol), phosphites including, e.g., tris-(p-nonylphenyl)-phosphite (TNPPJ and bis(2,4-di-tert- butylphenyl) 4,4 '-dipheny lene-diphosphonite, di -stearyl-3 , 3 '-thio d ipropio nate (DS TDP ) , and combinations thereof.
  • TNPPJ tris-(p-nonylphenyl)-phosphite
  • DS TDP 3 '-thio d ipropio nate
  • Useful antioxidants are commercially available under a variety of trade designations including, e.g., the IRGANOX series of trade designations including, e.g., IRGANOX 1010, IRGANOX 565, and IRGANOX 1076 hindered phenolic antioxidants and IRGAFOS 168 phosphite antioxidant, all of which are available from BASF Corporation (Florham Park, New Jersey), and ETHYL 702 4,4'-methylene bis(2,6- di-tert-butylphenol).
  • the adhesive composition preferably includes from about 0.1 % by weight to about 2 % by weight antioxidant.
  • Useful additional polymers include, e.g., homopolymers, copolymers, and terpolymers, thermoplastic polymers including, e.g., polyolefms (e.g., polyethylene, polypropylene, metallocene-catalyzed polyolefins, and combinations thereof), elastomers including, e.g., elastomeric block copolymers (e.g., styrene-butadiene-styrene, styrene- isoprene-styrene, styrene-ethylene/butene-styrene, styrene-ethylene/propylene-styrene, metallocene-based elastomeric block copolymers, and combinations thereof), and functionalized versions thereof, and combinations thereof.
  • suitable commercially available polymers include, e.g., EPOLENE C-15 branched polyethylene, and EPOLENE C-10 branched
  • the optional polymer when present in the hot melt adhesive composition, is preferably present in an amount no greater than about 10 % by weight, no greater than about 5 % by weight, no greater than about 3 % by weight, or even from about 1 % by weight to about 4 % by weight.
  • nucleating agents include, e.g., polymeric nucleating agents, minerals, amides, aromatic organic compounds, phosphate ester salts, organic salts and
  • nucleating agents examples include polypropylene, polypropylene wax, polyethylene, polyethylene wax, polystyrene, poly(vinylcyclohexane), stearamides, anthraquinones, fatty acid amides, adipic acid, benzoic acid, benzoic acid salts, phosphate ester salts, sorbitols, kaolin, talc and combinations thereof.
  • the nucleating agent preferably increases the set speed of at least one of the reaction product and the adhesive composition.
  • Suitable nucleating agents are commercially available under a variety of trade designations including, e.g., N-15 polypropylene wax from Westlake Chemical Coiporation (Houston, Texas), and HYPERFORM HPN-68L disodium cis-endo-bicyclo (2.2.1 ) heptane-2-3-dicarboxylate from Milliken Chemical (Spartanburg, South Carolina).
  • the reaction product can be applied on or incorporated in a variety of articles including, e.g., films (e.g., polyolefin films (e.g., polyethylene and polypropylene), polyester film, metalized polymer film, multi-layer film, and combinations thereof), fibers, substrates made from fibers (e.g., virgin fibers, recycled fibers, synthetic polymer fibers (e.g., nylon, rayon, polyesters, acrylics, polypropylenes, polyethylene, polyvinyl chloride, polyurethane), cellulose fibers (e.g., natural cellulose fibers such as wood pulp), natural fibers (e.g., cotton, silk and wool), and glass fibers, and combinations thereof), release liners, porous substrates, cellulose substrates, sheets (e.g., paper, and fiber sheets), paper products, woven and nonwoven webs (e.g., webs made from fibers (e.g., yarn, thread, filaments, microfibers, blown fibers, and spun fibers)
  • the hot melt adhesive composition is useful for bonding a variety of substrates including, e.g., cardboard, coated cardboard, paperboard, fiber board, virgin and recycled kraft, high and low density kraft, chipboard, treated and coated kraft and chipboard, and corrugated versions of the same, clay coated chipboard carton stock, composites, leather, polymer film (e.g., polyolefin films (e.g., polyethylene and polypropylene),
  • substrates including, e.g., cardboard, coated cardboard, paperboard, fiber board, virgin and recycled kraft, high and low density kraft, chipboard, treated and coated kraft and chipboard, and corrugated versions of the same, clay coated chipboard carton stock, composites, leather, polymer film (e.g., polyolefin films (e.g., polyethylene and polypropylene),
  • polyvinylidene chloride films ethylene vinyl acetate films, polyester films, metalized polymer film, multi-layer film, and combinations thereof
  • fibers and substrates made from fibers (e.g., virgin fibers, recycled fibers, synthetic polymer fibers, cellulose fibers, and combinations thereof), release liners, porous substrates (e.g., woven webs, nonwoven webs, and perforated films), cellulose substrates, sheets (e.g., paper, and fiber sheets), paper products, tape backings, and combinations thereof.
  • Useful composites include, e.g., chipboard laminated to metal foil (e.g., aluminum foil), which optionally can be laminated to at least one layer of polymer film, chipboard bonded to film, Kraft bonded to film (e.g., polyethylene film), and combinations thereof.
  • metal foil e.g., aluminum foil
  • polymer film e.g., chipboard bonded to film
  • Kraft bonded to film e.g., polyethylene film
  • the hot melt adhesive composition is useful in bonding a first substrate to a second substrate in a variety of applications and constructions including, e.g., packaging, bags, boxes, cartons, cases, trays, multi-wall bags, articles that include attachments (e.g., straws attached to drink boxes), ream wrap, cigarettes (e.g., plug wrap), filters (e.g., pleated filters and filter frames), bookbinding, footwear, disposable absorbent articles (e.g., disposable diapers, sanitary napkins, medical dressings (e.g., wound care products), bandages, surgical pads, drapes, gowns, and meat-packing products), paper products including, e.g., paper towels (e.g., multiple use towels), toilet paper, facial tissue, wipes, tissues, towels (e.g., paper towels), sheets, mattress covers, and components of absorbent articles including, e.g., an absorbent element, absorbent cores, impermeable layers (e.g., backsheets), tissue (e.g., wrapping
  • the hot melt adhesive composition is also useful in forming laminates of porous substrates and polymer films such as those used in the manufacture of disposable articles including, e.g., medical drapes, medical gowns, sheets, feminine hygiene articles, diapers. adult incontinence articles, absorbent pads (e.g., for animals (e.g., pet pads) and humans (e.g., bodies and corpses)), and combinations thereof.
  • disposable articles including, e.g., medical drapes, medical gowns, sheets, feminine hygiene articles, diapers. adult incontinence articles, absorbent pads (e.g., for animals (e.g., pet pads) and humans (e.g., bodies and corpses)), and combinations thereof.
  • the hot melt adhesive composition can be applied to a substrate in any useful form including, e.g., as fibers, as a coatmg (e.g., a continuous coatings and discontinuous coatings (e.g., random, pattern, and array)), as a bead, as a film (e.g., a continuous films and discontinuous films), and combinations thereof, using any suitable application method including, e.g., slot coating, spray coating (e.g., spiral spray, random spraying, and random fiberization (e.g., melt blowing)), foaming, extrusion (e.g., applying a bead, fine line extrusion, single screw extrusion, and twin screw extrusion), wheel application, noncontact coating, contacting coatmg, gravure, engraved roller, roll coating, transfer coating, screen printing, flexographic, and combinations thereof.
  • a coatmg e.g., a continuous coatings and discontinuous coatings (e.g., random, pattern, and array)
  • Test procedures used in the examples include the following. Ail ratios and percentages are by weight unless otherwise indicated. The procedures are conducted at room temperature (i.e., an ambient temperature of from about 20°C to about 25°C) unless otherwise specified.
  • Viscosity is determined in accordance with ASTM D-3236 entitled, ''Standard Test Method for Apparent Viscosity of Hot Melt Adhesives and Coating Materials, " (October 31 , 1988) using a Brookfield Thermosel Viscometer Model RVDV 2+ and an appropriate spindle. The results are reported in centipoise ('3 ⁇ 4P").
  • the percentage fiber tear is the percentage of fiber that covers the area of the adhesive after two substrates, which have been previously bonded together through the adhesive, are separated by force.
  • the percentage of fiber tear exhibited by an adhesive composition is determined as follows. A bead of the adhesive composition measuring 15.24 cm (6 inch) x 0.24 cm (3/32 inch) is applied to a first substrate of ROCKTENN 44 pound 87 % virgin liner board, using a ROCKTENN bond simulator at the specified application temperature.
  • the bead of adhesive is contacted with a second substrate of ROCKTENN 44 pound 87 % virgin liner board, which is pressed against the adhesive and the first substrate with a pressure of 0.21 MPa (30 pounds per square inch (psi)) for a period of 2 seconds.
  • the resulting constructions are then conditioned at room temperature for at least 4 hours and then conditioned at the specified test temperature for at least 12 hours.
  • the substrates of the construction are then separated from one another by pulling the two substrates apart from one another by hand.
  • the surface of the adhesive composition is observed and the percent of the surface area of the adhesive composition that is covered by fibers is determined and recorded. A minimum of five samples are prepared and tested for each hot melt adhesive composition. The results are reported in % fiber tear.
  • a bead of adhesive composition measuring 15.24 cm (6 inch) x 0.24 cm (3/32 inch) is applied to a first substrate of ROCKTENN 44 pound 87 % virgin liner board, using a ROCKTENN bond simulator at the specified application temperature. 0.2 seconds after the bead of adhesive is applied to the first substrate, the bead of adhesive is contacted with a second substrate of ROCKTENN 44 pound 87 % virgin liner board, which is pressed against the adhesive and the first substrate with a pressure of 0.21 Mpa (30 pounds per square inch (psi)) for a period of 0.2 seconds. A timer is started as the bead is applied to the first substrate. When the timer is at 3 seconds, the now formed bond is pulled apart.
  • Heat stress resistance is measured according to standard number IOPP T-3006 entitled, "Suggested Test Method for Determining the Heat Stress Resistance of Hot Melt Adhesives," using a starting temperature of 130 °F (54.4 °C) and five bonded samples per adhesive. The pass temperature for each adhesive, which is defined as the maximum temperature at which 80 % of the samples remain bonded, is the heat stress resistance and is reported in degrees Celsius (°C).
  • Tensile properties are determined using ASTM D638 modified by the film thickness and aging time. Films of each sample are created by using a draw down square, which is preheated at 350 °F ( 177 °C), with a cut out of 40 mils, which when cooled provides a sample film thickness of 25 mils. Each sample is heated to 350 D F ( 1 77 °C), poured onto a Teflon board, and quickly drawn down using the square. Once cooled, the thickness of each film is measured using a micrometer. The target film thickness is 25 mils +/- 5 mils, where 1 mil is equal to 0.001 inch. Tensile specimens are punched out of the film using a Type IV dog bone die.
  • the thickness of the film specimen is not to vary by greater than 1 mil along the gauge length of a given specimen.
  • Specimens are aged at room temperature for at least 12 hours prior to testing. The specimens are run on an I STRON 4502 at 23 °C, 50 % relative humidity, and 2 inch/min extension rate.
  • a calibrated 100 N INSTRON static load cell is used to quantify the force, and an INSTRON 2663-821 Advanced Video Extensometer, calibrated using a custom calibration bar, measures the change in the gage length.
  • BLUE HILL 2 software is used for data acquisition and analysis.
  • Strain at break is calculated according to the portion of ASTM D638 pertaining to "percent elongation at break,” and is reported in percent (%).
  • Maximum tensile strength is calculated according to the portion of ASTM D638 pertaining to "tensile strength,” and is reported in megapascals (MPa).
  • a 200 gram (g) sample of hot melt composition is placed in a 400 milliliter (ml) PYREX glass beaker and held at 350 °F (177 °C) for periods of 24 hours, 48 hours, 72 hours, 96 hours, and 200 hours. An aliquot is removed from the sample for testing at each of the aforementioned time periods.
  • a sample is conditioned according to the thermal conditioning procedure and then tested (in the molten state) to determine Gardner color by comparing the color of the sample against the Gardner Color Standards as set forth in ASTM D-l 544. The comparison is made using a Gardner Delta Comparator equipped with an Illuminator available from Pacific Scientific (Bethesda, Maryland). The result is reported as the number corresponding to the Gardner Color Standard.
  • Molecular weights (Mn, Mw, and Mz) are determined using a Polymer Labs PL- GPC 220 High Temperature Size Exclusion Chromatograph (HT-SEC) operating at 160 °C with 1 ,2,4-trichlorobenzene (TCB) as the mobile phase.
  • the system contains three PL- gel mixed B columns in series and is equipped with a Refractive Index (RI) detector.
  • the SEC operates at a flow rate of 1 .0 ml/min with an injection volume of 100 ⁇ . All HT- SEC samples are prepared with a concentration of 4.0 mg/ml.
  • Molecular weights are calculated from the Mark-Houwink relation using known polystyrene standards.
  • the polymer and wax are combined and heated to a temperature of from 175 °C to 180 °C with mixing.
  • a peroxide e.g., 92 % 2,5-dimethyl-2,5-di(tertbutylperoxy)hexane (United Initiator Incorporated, Elyria, Ohio), is then added, under nitrogen atmosphere, to the molten polymer and wax mixture in 4 or 5 portions over a period of from 30 minutes to 45 minutes with mixing. After addition of the peroxide, the mixture is further heated and stirred under nitrogen for another 45 minutes to 60 minutes. Vacuum is then applied by pulling a pressure of about 29 inches of mercury (Hg) for 30 minutes, and the reaction product is recovered.
  • Hg 29 inches of mercury
  • Control CI was L-MODU S400 polypropylene (Idemitsu Kosan Co., Ltd, Japan).
  • the reaction products of Examples 1-7 were prepared by combining 90 % by weight L-MODU S400 polypropylene (Idemitsu) and 10 % by weight wax of the type specified in Table 1 and heating the same to from 175 °C to 180 °C, with mixing, to achieve a molten liquid.
  • the molten liquid was then treated with 92 % 2,5-dimethyl-2,5- di(tertbutylperoxy)hexane (United Initiator Incorporated, Elyria, Ohio), in the amount specified (in % by weight) in Table 1 , under nitrogen atmosphere.
  • the reaction products of Examples 1-7 were tested according to the Viscosity Test Method at 177 °C, and the weight average molecular weight (Mw), number average molecular weight (Mn), and z average molecular weight (Mz) were determined according to the Method for Determining Molecular Weight.
  • the polydispersity index (PDI) was calculated by dividing Mw by Mn. The results are reported in Table 1 .
  • Control C2 was LICOCENE 2602 propylene- ethylene copolymer (Clariant Int'l Ltd., Muttenz, Switzerland).
  • the reaction products of Examples 8 and 9 were prepared by combining 90 % by weight LICOCENE 2602 propylene-ethylene copolymer and 10 % by weight wax of the type specified in Table 1 and heating the same to from 175 °C to 180 °C, with mixing, to achieve a molten liquid.
  • the molten liquid was then treated with 92 % 2,5-dimethyI-2.5- di(tertbutylperoxy)hexane (United Initiator Incoiporated), in the amount specified (in % by weight) in Table 1 , under nitrogen atmosphere.
  • Nl 1 EPOLENE Nl 1 polyethylene wax (Westlake Chemical Corporation, Houston, Texas)
  • N 14 EPOLENE 14 polyethylene wax (Wcstlake)
  • N21 EPOLENE N21 polyethylene wax (Westlake)
  • PX105 BARECO Fischer Tropsch wax (Baker Hughes Inc., Sugar Land, Texas)
  • reaction products C3, C4, and 10-18 were prepared according to the General Procedure for Preparing a Reaction Product with the exception that the components and the amounts thereof ⁇ in % by weight) used to form the reaction product were as set forth in Table 2 below.
  • the Mw, Mn, and Mz for C3 were determined to be 24200 g/mol, 4130 g/mol, and 51000 g/mol, respectively.
  • the Mw, Mn, and Mz for C4 were determined to be 21 ,800 g/mol, 4300 g/mol, and 45,000 g/mol, respectively.
  • the polydispersity index of C3 and C4 was determined to be 5.87 and 5.07, respectively.
  • REXTAC 2765 propylene butene copolymer (Rextac LLC, Odessa, Texas)
  • AC 1783 A-C-X 1783 maleated linear low density polyethylene wax having an acid number of 4.5, a saponification value of 6.2, a viscosity at 140°C of 60 centipoise, a penetration value of 0.5 drum, a Mw of 8,650, a Mn of 1 ,700, a Mz of 1 8,000, and a Mw/Mn of 5.08 (Honeywell International Inc., Morristown, New Jersey).
  • EPOLENE N21 polyethylene wax
  • DHBP 92 % 2,5-dimethyl-2,5-di(tertbutylperoxy)hexane (United Initiator Incorporated, Elyria, Ohio)
  • PAR VAN 1580 paraffin wax (Exxon Mobil Chemical Company, Houston, Texas)
  • Hot melt adhesive compositions were prepared by mixing, at 177 °C for approximately 20 minutes, the components in the amounts (in % by weight) set forth in Table 3.
  • the row heading "Reaction Product” refers to the reaction products of Controls C3 and C4 and Examples 10-16 from Table 2.
  • the hot melt adhesive compositions of Controls C5-C7 and Examples 19-27 were tested according to the Viscosity test method at 177 °C, the Fiber Tear test method at test temperatures -28.9 °C, -17.8 °C, 4.4 °C, 60 °C, 65.6 Q C, and 71.1 °C, and the Heat Stress Resistance test method, and for Energy to Break, Strain at Break, and Tensile Strength according to the Tensile test method,. The results are set forth below in Table 3.
  • EASTOTAC H130W Eastman Chemical (Kingsport, Tennessee)
  • EPOLENE N2 ⁇ polyethylene wax
  • EPOLENE 15 polyethylene wax
  • A-C596P maleated polypropylene wax (Honeywell International Inc., Morristown, New Jersey)
  • A-C5 7P maleated polypropylene wax (Honeywell International)
  • IRGANOX 1010 antioxidant (BASF Coiporation, Fiorham Park, New Jersey)
  • PE LICOCENE 2602 propylene-ethylene copolymer
  • EPOLENE N21 polyethylcne wax
  • EPOLENE N14 polyethylene wax
  • EPOLENE N 15 polyethylene wax
  • a propylene-wax copolymer comprising a reaction product of components comprising a first polymer comprising polypropylene homopolymer, polypropylene-alpha- olefin copolymer, or a combination thereof, a first wax comprising polyethylene wax, Fischer Tropsch wax, or a combination thereof, and a free radical initiator, and that is free of an unsaturated compound that includes at least one functional group and has a molecular weight no greater than 1000 g/mole, the reaction product having a number average molecular weight greater than 5000 g/niole, a polydispersity index of no greater than 5, and a viscosity of no greater than 12,000 centipoise at 177 °C.
  • a propylene-wax copolymer comprising a reaction product of components comprising a first polymer that includes polypropylene homopolymer. polypropylene - alpha-olefin copolymer, or a combination thereof, a first wax comprising polyethylene wax, and a free radical initiator, the reaction product having a number average molecular weight greater than 5000 g/mole, a polydispersity index no greater than 5, and a viscosity of no greater than 12,000 centipoise at 177 °C.
  • a propylene-wax copolymer comprising the reaction product of components comprising a first polymer having a polydispersity index of no greater than 5 and including polypropylene homopolymer, polypropylene-alpha-olefm copolymer, or a combination thereof, a first wax comprising polyethylene wax, Fischer Tropsch wax, paraffin wax, or a combination thereof, a free radical initiator, and being free of an unsaturated compound comprising at least one functional group and having a molecular weight no greater than 1000 g/mole, the reaction product exhibiting a viscosity of no greater than 12,000 centipoise at 77 °C.
  • composition comprising the copolymer of any of paragraphs 1-5.
  • a hot melt adhesive composition comprising the copolymer of any of paragraphs 1 -5. 8. The hot melt adhesive composition of paragraph 7, wherein the hot melt adhesive composition exhibits an initial Gardner color of no greater than 3.
  • thermoplastic adhesive composition of any of paragraphs 7-8 further comprising tackifying agent, plasticizer, wax, or a combination thereof.
  • thermoplastic adhesive composition of any of paragraphs 7- 10, wherein the composition exhibits an energy to break of at least 0.15 Joules and a strain at break of at least 100 %.
  • thermoplastic adhesive composition of any of paragraphs 7-10, wherein the composition exhibits an energy to break of at least 0.15 Joules and a heat stress resistance of at least 60 °C.
  • compositions exhibits an energy to break of at least 0.1 Joules and a strain at break of at least 100 %, and further comprises a second wax selected from the group consisting of polyethylene wax, polypropylene wax, Fischer Tropsch wax, paraffin, maleated polypropylene wax, and maleated polyethylene wax.
  • the hot melt adhesive composition of any of paragraphs 7-10 wherein the composition exhibits an energy to break of at least 0.15 Joules and a heat stress resistance of at least 60 °C, and further comprises a second wax selected from the group consisting of polyethylene wax, polypropylene wax, Fischer Tropsch wax, paraffin, maleated polypropylene wax, and maleated polyethylene wax.
  • a second wax selected from the group consisting of polyethylene wax, polypropylene wax, Fischer Tropsch wax, paraffin, maleated polypropylene wax, and maleated polyethylene wax.
  • a method of making a graft copolymer comprising:
  • the first polymer comprising polypropylene homopolymer, polypropylene- alpha-olefin copolymer, or a combination thereof
  • the first wax comprising polyethylene wax
  • a method of making a graft copolymer comprising:
  • the first polymer comprising polypropylene homopolymer, polypropylene- alpha-olefin copolymer, or a combination thereof
  • the first wax comprising polyethylene wax, paraffin wax, Fischer Tropsch wax, or a combination thereof.
  • a propylene-wax copolymer comprising:
  • a first polymer comprising polypropylene homopolymer, polypropylene-alpha-olefm copolymer, or a combination thereof
  • a first wax comprising polyethylene wax, Fischer Tropsch wax, or a combination thereof
  • reaction product having a viscosity at 177 °C that is less than the viscosity of a blend of the components of the reaction product other than the free radical initiator
  • reaction product having a number average molecular weight greater than 5000 g/mole, a polydispersity index of no greater than 5, and a viscosity of no greater than 12,000 centipoise at 177 °C.
  • thermoplastic adhesive composition of any of paragraphs 7-20 further comprising a tackifying agent.
  • the hot melt adhesive composition of paragraph 29 further comprising a second wax.
  • thermoplastic adhesive composition of any of paragraphs 7-20, 29, and 30, wherein the components further comprise a second wax.
  • Tropsch wax paraffin, functionalized wax, or a combination thereof.
  • thermoplastic adhesive composition of any of paragraphs 7-20 and 29-35, wherein the first polymer comprises polypropylene homopolymer and the first wax comprises polyethylene.
  • thermoplastic adhesive composition of any of paragraphs 7-20 and 29-35, wherem the first polymer comprises polypropylene homopolymer and the first wax comprises a Fischer Tropsch wax.
  • reaction product from about 30 % by weight to about 80 % by weight of the reaction product
  • the hot melt adhesive composition of any of paragraphs 29-41 comprising: from about 35 % by weight to about 70 % by weight of the reaction product;
  • thermoplastic adhesive composition of any of paragraphs 7-20 and 29-44, wherein the composition exhibits at least about 50 % fiber tear at -29 °C and at 60 °C.
  • thermoplastic adhesive composition of any of paragraphs 7-20 and 29-48, wherein the composition exhibits a change in viscosity of no greater than 10 % after aging for 96 hours at 177 °C.
  • thermoplastic adhesive composition of any of paragraphs 7-20 and 29-50, wherein the composition exhibits a set time of no greater than 10 seconds.
  • thermoplastic adhesive composition of any of paragraphs 29-52, wherein the composition comprises at least 10 % by weight tackifying agent and exhibits at least about 75 % fiber tear at -29 °C.
  • the hot melt adliesive composition forming a fiber tearing bond to the first substrate in no greater than 10 seconds.
  • a hot melt adhesive composition comprising:
  • a first polymer comprising polypropylene homopolymer, polypropylene-alpha-olefin copolymer, or a combination thereof
  • a first wax comprising polyethylene wax, Fischer Tropsch wax, or a combination thereof
  • reaction product having a viscosity at 177 °C that is less than the viscosity of a blend of the components of the reaction product other than the free radical initiator;
  • reaction product having a number average molecular weight greater than 5000 g/mole, a polydispersity index of no greater than 5, and a viscosity of no greater than 12,000 centipoise at 177 °C.
  • a hot melt adhesive composition comprising:
  • reaction product of a first polymer comprising polypropylene homopolymer, polypropylene-alpha-olefin copolymer, or a combination thereof
  • a first non-fimctionalized wax comprising polyethylene wax, Fischer Tropsch wax, paraffin wax, or a combination thereof, and
  • reaction product exhibiting a viscosity of no greater than 12,000 centipoise at 377 °C;
  • the hot melt adhesive composition exhibiting an energy to break of at least 0.15 Joules, a tensile strength of at least 3.28 MPa, a heat stress resistance of at least 65 °C, or a combination thereof.
  • a hot melt adhesive composition comprising:
  • a first wax comprising polyethylene wax, Fischer Tropsch wax, paraffin wax, or a combination thereof
  • reaction product exhibiting a viscosity of no greater than 12,000 centipoise at 177 °C;
  • a hot melt adhesive composition comprising:
  • a first polymer comprising polypropylene homopolymer, polypropylene-alpha-olefin copolymer, or a combination thereof
  • a first wax comprising polyethylene wax
  • reaction product having a number average molecular weight greater than 5000 g/mole, a polydispersity index no greater than 5. and a viscosity of no greater than 12,000 centipoise at 177 °C;

Abstract

La présente invention concerne un produit de réaction et des compositions d'adhésifs thermofusibles comprenant ledit produit de réaction. Ledit produit de réaction comprend le produit de la réaction entre un premier polymère comprenant au moins un homopolymère polypropylène et un copolymère polypropylène-alpha-oléfine, une première cire comprenant au moins une cire parmi une cire de polyéthylène, une cire de Fischer Tropsch et une cire de paraffine, et un initiateur de radicaux libres et présente une viscosité inférieure à 12 000 centipoises à 177 °C.
EP14710678.5A 2013-02-15 2014-02-13 Produit de la réaction entre un polymère de propylène et une cire, copolymères greffés dérivés du polymère de polypropylène et de la cire, compositions d'adhésifs thermofusibles comprenant ceux-ci, et procédés d'utilisation et de fabrication associés Withdrawn EP2956490A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US13/768,859 US9593235B2 (en) 2013-02-15 2013-02-15 Reaction product of propylene polymer and wax, graft copolymers derived from polypropylene polymer and wax, hot melt adhesive compositions including the same, and methods of using and making the same
US13/768,887 US9267060B2 (en) 2013-02-15 2013-02-15 Reaction product of propylene polymer and wax, graft copolymers derived from polypropylene polymer and wax, hot melt adhesive compositions including the same, and methods of using and making the same
PCT/US2014/016184 WO2014127093A1 (fr) 2013-02-15 2014-02-13 Produit de la réaction entre un polymère de propylène et une cire, copolymères greffés dérivés du polymère de polypropylène et de la cire, compositions d'adhésifs thermofusibles comprenant ceux-ci, et procédés d'utilisation et de fabrication associés

Publications (1)

Publication Number Publication Date
EP2956490A1 true EP2956490A1 (fr) 2015-12-23

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EP14710678.5A Withdrawn EP2956490A1 (fr) 2013-02-15 2014-02-13 Produit de la réaction entre un polymère de propylène et une cire, copolymères greffés dérivés du polymère de polypropylène et de la cire, compositions d'adhésifs thermofusibles comprenant ceux-ci, et procédés d'utilisation et de fabrication associés

Country Status (5)

Country Link
EP (1) EP2956490A1 (fr)
CN (1) CN105008415A (fr)
BR (1) BR112015019715A2 (fr)
MX (1) MX2015010500A (fr)
WO (1) WO2014127093A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10308740B2 (en) 2014-02-07 2019-06-04 Eastman Chemical Company Amorphous propylene-ethylene copolymers
US10723824B2 (en) 2014-02-07 2020-07-28 Eastman Chemical Company Adhesives comprising amorphous propylene-ethylene copolymers
US11267916B2 (en) 2014-02-07 2022-03-08 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins
US10696765B2 (en) 2014-02-07 2020-06-30 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and propylene polymer
US10647795B2 (en) 2014-02-07 2020-05-12 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins
US9399686B2 (en) 2014-02-07 2016-07-26 Eastman Chemical Company Amorphous propylene-ethylene copolymers
MX2019011531A (es) 2017-03-30 2019-12-09 Rohm & Haas Composicion curable libre de formaldehido.
CN113866345A (zh) * 2021-09-30 2021-12-31 内蒙古伊泰煤基新材料研究院有限公司 一种马来酸酐接枝费托蜡的接枝率的测定方法

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EP1295926A1 (fr) * 2001-09-19 2003-03-26 ExxonMobil Chemical Patents Inc. Composants pour des compositions adhésives et procédé pour leur préparation
US8110623B2 (en) * 2006-09-27 2012-02-07 H.B. Fuller Company Hot melt pressure sensitive adhesive composition that includes vegetable wax and articles including the same
BR112013033143A2 (pt) * 2011-06-27 2017-01-24 Fuller H B Co composição adesiva termofundida modificada por iniciador de radical livre incluindo polietileno funcionalizado e polímero de propileno-alfa-olefina

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MX2015010500A (es) 2016-05-16
WO2014127093A1 (fr) 2014-08-21
BR112015019715A2 (pt) 2017-07-18
CN105008415A (zh) 2015-10-28

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