US20170292047A1 - Hexene-1 Containing Amorphous Polyalphaolefins For Improved Hot Melt Adhesives - Google Patents
Hexene-1 Containing Amorphous Polyalphaolefins For Improved Hot Melt Adhesives Download PDFInfo
- Publication number
- US20170292047A1 US20170292047A1 US15/486,115 US201715486115A US2017292047A1 US 20170292047 A1 US20170292047 A1 US 20170292047A1 US 201715486115 A US201715486115 A US 201715486115A US 2017292047 A1 US2017292047 A1 US 2017292047A1
- Authority
- US
- United States
- Prior art keywords
- hot
- melt
- propylene
- melt formulation
- hexene
- 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.)
- Abandoned
Links
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 title abstract description 22
- 229920013640 amorphous poly alpha olefin Polymers 0.000 title abstract description 22
- 239000004831 Hot glue Substances 0.000 title abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 229920001897 terpolymer Polymers 0.000 claims abstract description 29
- 238000009472 formulation Methods 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 42
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 37
- 239000012943 hotmelt Substances 0.000 claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 239000010690 paraffinic oil Substances 0.000 claims 2
- 238000009835 boiling Methods 0.000 claims 1
- 229920001519 homopolymer Polymers 0.000 claims 1
- 150000001282 organosilanes Chemical class 0.000 claims 1
- 229920005604 random copolymer Polymers 0.000 claims 1
- XPVIQPQOGTVMSU-UHFFFAOYSA-N (4-acetamidophenyl)arsenic Chemical compound CC(=O)NC1=CC=C([As])C=C1 XPVIQPQOGTVMSU-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 43
- 239000003054 catalyst Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 16
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000000155 melt Substances 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000004711 α-olefin Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008685 targeting Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 2
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 description 2
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- CHBOSHOWERDCMH-UHFFFAOYSA-N 1-chloro-2,2-bis(4-chlorophenyl)ethane Chemical compound C=1C=C(Cl)C=CC=1C(CCl)C1=CC=C(Cl)C=C1 CHBOSHOWERDCMH-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012967 coordination catalyst Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013400 design of experiment Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003055 full factorial design Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920006728 mPE Polymers 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C09J2205/114—
-
- 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
- C09J2423/00—Presence of polyolefin
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or 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
- C09J2453/00—Presence of block copolymer
Definitions
- the present invention generally relates to formulations suitable for use as hot-melt adhesives and pressure-sensitive adhesives. More particularly, it relates to APAO-based adhesives.
- Amorphous poly-alpha-olefins are produced by the (co-) polymerization of ⁇ -olefins, e.g. propylene or 1-butene with Ziegler-Natta catalysts.
- the (co-) polymers have an amorphous structure which makes them useful for the production of hot melt adhesives (HMAs).
- U.S. Pat. No. 5,302,675, “High Tensile Strength Amorphous 1-Butene/Propylene Copolymers,” describes a process for the production of propylene/1-butene copolymers comprising: reacting propylene and 1-butene monomers in the presence of a catalyst system comprising: (a) a solid supported catalyst component may be prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.1 to about 8:1.0; (b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al-
- U.S. Pat. Nos. 5,681,913, 5,637,665, and 5,714,554 each entitled “High Tensile Strength Amorphous 1-Butene/Propylene and Ethylene/Propylene Copolymers,” describe amorphous propylene/1-butene and ethylene/propylene copolymers having increased tensile properties produced by the process comprising: reacting propylene and 1-butene monomers or ethylene and propylene monomers in the presence of a catalyst system comprising: (a) a solid supported catalyst component is prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum tri-halide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetra-halide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:
- U.S. Pat. No. 6,586,543, “Process for the Preparation of Substantially Amorphous Poly-Alpha-Olefins,” describes a process for preparing a substantially amorphous poly- ⁇ -olefin, which includes: a) preforming a solid catalyst and, optionally, a first amount of a trialkylaluminum cocatalyst, by contacting the catalyst and optionally the cocatalyst with at least one selected from the group including oxygen and a compound which includes active oxygen, to form a preformed catalyst, wherein the solid catalyst includes magnesium, aluminum and titanium, and wherein said trialkylaluminum cocatalyst includes 1 to 9 carbon atoms in each alkyl group; b) contacting the preformed catalyst with a second amount of the cocatalyst, wherein a molar ratio of trialkylaluminum to the titanium ranges from 40:1 to 700:1, to form a catalyst mixture; c) polymerizing, in the
- U.S. Pat. No. 4,847,340 “Novel propylene polymerization process,” describes a process for the production of substantially amorphous copolymers consisting essentially of ethylene and propylene which comprises reacting from about 70 to about 96.5 wt. % propylene and from about 3.5 to about 30 wt. % ethylene at a temperature between about 130° F. and about 175° F.
- said higher 1-olefin is at least two members of the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.
- U.S. Pat. No. 4,826,939 “Highly amorphous olefin terpolymer”, describes an amorphous, pressure-sensitive terpolymer comprising repeating units from about 0.1 to about 10 percent by weight ethylene, from about 30 to about 78 percent by weight propylene, and from 20 to 70 percent by weight 1-hexene, the terpolymer having a ring-and-ball softening point of from about 75° C. to about 120° C., a melt viscosity of from about 100 to about 100,000 cps at 190° C., no DSC melting point, and a 180° peel strength of at least about 1.2 pounds/inch.
- Also described is a process for producing an amorphous, pressure-sensitive terpolymer having no DSC melting point comprising continuously polymerizing a mixture of from about 0.1 to about 10 percent by weight ethylene, from about 30 to about 78 percent by weight propylene, and from about 20 to about 70 percent by weight 1-hexene, in the presence of a catalyst comprising an anionic coordination catalyst and in a solvent medium, at a temperature of from about 140° C. to about 250° C. and at a pressure of about 100 to about 5,000 pounds per square inch gauge.
- Propylene-co-hexene-1 copolymers optionally containing 1-butene monomer to form propylene-co-hexene-1-co-butene-1 terpolymers, are made using a supported Ziegler-Natta catalyst either with or without an in-reactor added organosilicon external donor.
- Copolymers and terpolymers according to the invention may be used in the formulation of improved-performance APAO-based hot melt adhesives.
- each of the comonomers adds a unique set of properties to the APAO, which may be enhanced, or changed, by the addition of an external organosilicon donor.
- APAO copolymers and terpolymers may add unique properties when used as components in hot melt adhesive formulations such as those used preferentially in pressure-sensitive adhesives and also in such applications as in personal hygiene products (e.g. diapers, feminine hygiene, elastic attachment, etc.), in assembly, construction, lamination, footwear and other applications that require such properties as permanent tackiness, controllable open time, low-temperature flexibility, good temperature resistance and other such desirable properties.
- An HMA according to the present invention may be made up of a propylene-co-hexene-1 copolymer APAO with a hexene-1 content of about 10 wt. %, more preferably, about 25 wt. %, much more preferably with about 30 wt. % and most preferably with about 50 wt. % by weight but it may contain up to 90 wt. %.
- This copolymer may be utilized in an unformulated form, that is, as-obtained from the reactor APAO.
- the subject of this invention bonds strongly, forming a destructive bond to the primary substrate.
- PSA's Pressure sensitive applications
- This copolymer exhibits this type of PSA properties.
- types of pressure sensitive adhesives may be considered for removable applications such as removable tapes and labels.
- the addition of another monomer component such as butene-1 results in a propylene-co-hexene-1-co-butene-1 terpolymer APAO with an even broader envelope of PSA- and other HMA-properties and performance.
- the terpolymer may have a butene-1 content of up to 40 wt.
- % preferably have about 5 to 25 wt. % and most preferably 5 to 10 wt. % by weight.
- a so-called external donor of the organosilicon class such as for example cyclohexylmethyldimethoxysilane (CMDMS), or phenyltriethoxysilane (PES)
- CDMS cyclohexylmethyldimethoxysilane
- PES phenyltriethoxysilane
- Co-adjuvants may form a part of the subject HMA, such as tackifiers, preferably the type considered compatible with APAO polymers.
- tackifiers are of the partially and fully hydrogenated C5, hydrogenated C5-C9, and hydrogenated DCPD-type resins but may be any other tackifier which, by its chemical nature, is compatible with the APAO terpolymer.
- Yet other components may be polyethylene, maleic anhydride grafted polyethylene, Fischer-Tropsch paraffinic waxes and metallocene waxes. These, as well as other similar compatible waxes, have the effect of controlling the melt viscosity and also controlling the rate of set of the HMA.
- liquid plasticizers such as mineral, paraffinic or naphthenic oils
- liquid plasticizers such as mineral, paraffinic or naphthenic oils
- components such as anti-oxidants and UV stabilizers may be added as co-adjuvants.
- Other compatible polymers which may be included in the formulation of the subject HMA include, for example, hydrogenated styrene block copolymers of the SEBS and SEPS type and polyethylenes such as LLDPE of melt indices (MIs) of typically more than 500 dg/min.
- mPEs metallocene polyethylenes
- metallocene polypropylenes mPP
- mPP Metallocene polypropylenes
- Both the propylene-co-hexene-1 copolymer and propylene-co-butene-1-co-hexene-1 terpolymer may be made according to the teachings of U.S. Pat. No. 4,847,340, whereby they are made at a temperature between about 130° F. and about 175° F. and at a reactor pressure sufficient to maintain propylene in the liquid phase (in the absence of any added solvent), and in the presence of from about 0.7 to about 3.0 mol % hydrogen based on the monomer feed.
- the hydrogen concentration present during the manufacture of the subject copolymers and terpolymers may be adjusted so that their melt viscosity, measured at 375° F., is less than 3500 cps, preferably less than 3000 cps.
- propylene-hexene-1 and propylene-co-hexene-1-cobutene-1 APAOs made in the presence of the externally added organosilicon when used either unformulated or, alternatively, properly formulated with the above-named co-adjuvants, at concentrations of 0 to up to 25 wt. % of tackifier(s), or between 0 to about 15 wt. % of the above-mentioned wax(es), or between 0 and 25 wt. % of the above mentioned oil(s), will result in hot melt adhesives with enhanced properties for use in pressure-sensitive adhesives, and also in personal hygiene products (e.g. diapers, feminine hygiene, elastic attachment, etc.), in assembly, and other such applications.
- personal hygiene products e.g. diapers, feminine hygiene, elastic attachment, etc.
- the above-named co-adjuvants may interact with the long polymeric chains of the propylene-co-hexene-1 and propylene-co-hexene-1-butene-1 APAOs made in the presence of the externally added organosilicon in such a way as to result in an HMA with a lower, yet desirable, melt viscosity which results in better wetting and penetration of various substrates, porous, or non-porous, resulting in a higher degree of adhesive bonding. Also, the interaction of the multiple components results in a higher, yet controllable, tackiness for such applications which demand a certain degree of tackiness and pressure sensitive adhesiveness. Other interactions will become obvious to the user.
- a hot-melt adhesive according to the invention may comprise: a) an APAO copolymer or terpolymer, preferably made in the presence of an externally added donor; b) a tackifier; and optionally, c) a wax component of the type(s) described above and d) a liquid plasticizer such as mineral oil or a naphthenic oil.
- dicyclopentyldimethoxy silane DDMS or D-Donor, CAS No. 126990-35-0
- diisopropyldimethoxy silane DPMS or P-Donor, CAS No. 18230-61-0
- DDMS or D-Donor CAS No. 126990-35-0
- DPMS or P-Donor CAS No. 18230-61-0
- Yet other less-common silane-based donors may also be used for the reactions in the subject matter.
- the polymerization reactions were carried out in an Autoclave EngineersTM 1-L autoclave typically at 70° C. and for one hour. Before running a reaction, the autoclave was cleaned of any residual polymer from any previous reaction using an organic solvent such as heptane to assure a clean reactor. The agitator/mixer assembly was placed on top of the autoclave which was then tightened securely. The autoclave was then heated, or baked, at 150° C., under a dry nitrogen atmosphere for about one hour, and then the autoclave was cooled to about 40° C., still under a nitrogen blanket. The temperature was controlled with a Julabo GmbH temperature control unit. A more detailed description of the polymerization process is described for example in U.S. Pat. Nos.
- the agitator was stopped, the temperature of the Julabo unit was reduced and the autoclave was slowly depressurized to remove any unreacted reactants. Due to the high productivity, in grams of polymer produced per gram of catalyst, no catalyst deactivation, other than exposure to the atmosphere, was required. Once decompressed, the top was removed and the polymer was harvested from the reactor. Other polymerization reaction temperatures as low as 40° C. and as high as 90° C. may also be used. Reaction times may range from 5 minutes to as long as three hours. The reactions were performed in the absence of any added organic solvent because the liquefied monomers a) serve to remove the high exothermal heat of polymerization reaction, and b) serve as the suspension medium for the formed polymeric products.
- the propylene monomer used was of very high purity, typically 99.99%+propylene with the remaining components being low-molecular-weight saturated hydrocarbons.
- This type of propylene is known in the trade as PGP or polymer grade propylene.
- Other propylene grades such as CGP, or chemical grade propylene, typically made up of at least 90+% propylene with the balance consisting of inert hydrogenated hydrocarbons may also be used.
- BB butane/butylene
- the butene-1 monomer used was high purity plant butene or it may be from what is called bottled, in small tanks, butene-1, with purities typically over 99+%.
- the hexene-1 used in the reactions was high purity (>97%) from vendors such as Sigma-Aldrich.
- TABLE 1 shows 22 polymerization reactions that were run varying the amounts of monomers, external donor (as represented by the F2/F3 ratio), or the alkyl aluminum-to-donor ratio, and the hydrogen pressure to control the melt viscosity or molecular weight of the produced polymers.
- Total reaction volume was targeted at 700 ml.
- the reaction variables were chosen using a full factorial design of experiment, DoE, generated by Minitab 15 DoE software which covered a broad spectrum of factors or reaction variables.
- the melt viscosity, MV was typically determined at 375° F. (190° C.), as per the ASTM D-3236 test method.
- the needle penetration, NP was determined at 72 to 75° F., as per the ASTM D-1321 test method, while the ring and ball softening point, RBSP, was determined as per ASTM E-28.
- the tensile strength, TS was determined as per ASTM D-638, and finally the shear adhesion failure temperature as per a modified TMHM-32 test.
- Example 2 The same procedure as described in Example 1 was followed targeting a F2/F3 of 200, but adding 375 ml of propylene, 75 ml of butene-1, 250 ml of hexene-1 and 90 psi of hydrogen. The reaction was started, allowed to proceed for an hour, then stopped, unreacted monomers were vented and a somewhat harder solid than that of Example 1 was recovered. The properties are presented in Table 2 and a RBT of about 1.5 to 2 cm would give this product PSA properties.
- Example 2 The same procedure as described in Example 1 was followed targeting a F2/F3 of 400, but adding 150 ml of propylene, 150 ml of butene-1, 400 ml of hexene-1 and 120 psi of hydrogen. The reaction was started, allowed to proceed for an hour, then stopped, unreacted monomers were vented and a somewhat harder solid than that of Example 1 was recovered. The properties are presented in Table 2 and a RBT of over 30 cm does not give it PSA properties.
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Abstract
Propylene-co-hexene-1-co-butene-1 terpolymers, made either with or without an in-reactor-added organosilicon external donor, are used in the formulation of improved-performance, APAO-based, hot melt adhesives. The addition of an external donor during the manufacture of hexene-1 based amorphous polyalpha-olefins (APAO's) results in products having enhanced physical and mechanical properties compared to similar adhesive products made without the addition of the external donor.
Description
- This application claims the benefit of U.S. Provisional Application No. 62/321,663, filed on Apr. 12, 2016, the contents of which are hereby incorporated by reference in their entirety.
- Not Applicable
- The present invention generally relates to formulations suitable for use as hot-melt adhesives and pressure-sensitive adhesives. More particularly, it relates to APAO-based adhesives.
- Amorphous poly-alpha-olefins (APAO) are produced by the (co-) polymerization of α-olefins, e.g. propylene or 1-butene with Ziegler-Natta catalysts. The (co-) polymers have an amorphous structure which makes them useful for the production of hot melt adhesives (HMAs).
- U.S. Pat. No. 5,302,675, “High Tensile Strength Amorphous 1-Butene/Propylene Copolymers,” describes a process for the production of propylene/1-butene copolymers comprising: reacting propylene and 1-butene monomers in the presence of a catalyst system comprising: (a) a solid supported catalyst component may be prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.1 to about 8:1.0; (b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al-to-Ti ratio may be between about 50:1 and about 500:1; (c) an alkoxy silane component of the formula Rn Si(OR′)4-n where n=1-3, R=aryl or alkyl and R′=C1-C3 alkyl in a sufficient quantity such that the molar ratio of organoaluminum co-catalyst to alkoxy silane is in the range from about 20:1 to about 45:1, said copolymer being characterized by a propylene content of 25 to 50 wt. %, a 1-butene content of 75 to 50 wt. % and a tensile strength of at least 300 psig.
- U.S. Pat. Nos. 5,681,913, 5,637,665, and 5,714,554 each entitled “High Tensile Strength Amorphous 1-Butene/Propylene and Ethylene/Propylene Copolymers,” describe amorphous propylene/1-butene and ethylene/propylene copolymers having increased tensile properties produced by the process comprising: reacting propylene and 1-butene monomers or ethylene and propylene monomers in the presence of a catalyst system comprising: (a) a solid supported catalyst component is prepared by the method comprising: (i) co-comminuting magnesium halide support base and aluminum tri-halide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor; and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetra-halide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.1 to about 8:1.0; (b) a trialkylaluminum co-catalyst, having from 1 to 9 carbon atoms in each alkyl group in an amount such that the Al-to-Ti ratio is between about 50:1 and about 500:1; and (c) an alkoxy silane component of the formula Rn Si(OR′)4-n where n=1-3, R=aryl or alkyl and R′=C1-C3 alkyl.
- U.S. Pat. No. 6,586,543, “Process for the Preparation of Substantially Amorphous Poly-Alpha-Olefins,” describes a process for preparing a substantially amorphous poly-α-olefin, which includes: a) preforming a solid catalyst and, optionally, a first amount of a trialkylaluminum cocatalyst, by contacting the catalyst and optionally the cocatalyst with at least one selected from the group including oxygen and a compound which includes active oxygen, to form a preformed catalyst, wherein the solid catalyst includes magnesium, aluminum and titanium, and wherein said trialkylaluminum cocatalyst includes 1 to 9 carbon atoms in each alkyl group; b) contacting the preformed catalyst with a second amount of the cocatalyst, wherein a molar ratio of trialkylaluminum to the titanium ranges from 40:1 to 700:1, to form a catalyst mixture; c) polymerizing, in the liquid phase, with the catalyst mixture, an olefin or an olefin mixture at a temperature between 30° and 160° C., to produce the poly-α-olefin.
- U.S. Pat. No. 4,309,522, “Process for the production of extensively amorphous butene-1-propene-ethene terpolymers having a high softening point,” describes a process for preparing an extensively amorphous butene-1-propeneethene terpolymer having a high softening point that comprises low-pressure solution polymerizing butene-1, propene and ethene by contacting these monomers with a catalytically effective amount of a mixed catalyst of a thermally unstable crystalline TiCl3·0.30 to 0.35 AlCl3 and a trialkyl aluminum or dialkyl aluminum hydride, each having alkyl groups of 2-4 carbon atoms, the atomic ratio of Al:Ti being 0.8-4.0.
- U.S. Pat. No. 4,322,514, “Process for preparing a copolymer,” describes a process for preparing a non- or low-crystalline soft copolymer, characterized in that 50 to 98 mole % of propylene, 0.2 to 30 mole % of ethylene and 0.2 to 45 mole % of a straight-chained α-olefin having not less than four carbon atoms are copolymerized using a catalyst, said catalyst comprising (1) a solid substance containing magnesium and titanium and (2) an organometallic compound.
- U.S. Pat. No. 4,826,939, “Highly amorphous olefin terpolymer,” describes highly amorphous olefin terpolymers from propylene, 1-hexene, and ethylene in which the ethylene units are incorporated in the polymer chain in a highly random manner, and a process for producing such terpolymers.
- U.S. Pat. No. 4,847,340, “Novel propylene polymerization process,” describes a process for the production of substantially amorphous copolymers consisting essentially of ethylene and propylene which comprises reacting from about 70 to about 96.5 wt. % propylene and from about 3.5 to about 30 wt. % ethylene at a temperature between about 130° F. and about 175° F. and at a reactor pressure sufficient to maintain propylene in the liquid phase, in the presence of from about 0.7 to about 3.0 mol % hydrogen based on the monomer feed to the process and employing as catalyst a composition of: (a) a solid catalyst component produced by the method comprising: (i) co-comminuting magnesium halide support base and aluminum trihalide in a molar ratio from about 8:0.5 to about 8:3 in the absence of added electron donor and (ii) then co-comminuting the product of step (i) in the absence of added electron donor with sufficient titanium tetrahalide to provide a molar ratio of magnesium halide to titanium tetrahalide from about 8:0.4 to about 8:1.
- U.S. Pat. No. 3,954,697, “Poly(higher-1-olefin-co-propylene) copolymers as hot-melt, pressure-sensitive adhesives” describes a hot melt, pressure sensitive adhesive comprising an amorphous propylene/higher 1-olefin copolymer containing 40 to 60 mole percent higher 1-olefin having a melt viscosity range at 190° C. of 10,000 cp. to 75,000 cp., a density of 0.85 to 0.86 grs/cc, a glass transition temperature of −30° to −45° C., and having no melting point measurable by Differential Scanning Calorimetry, wherein said higher 1-olefin is a member of the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.
- U.S. Pat. No. 4,072,812, “Poly(higher-1-olefin/propylene) copolymers as hot-melt pressure-sensitive adhesives”, describes a hot melt, pressure sensitive adhesive comprising an amorphous propylene/higher 1-olefin copolymer containing 40 to 60 mole percent higher 1-olefin having a melt viscosity range at 190° C. of 10,000 cps. to 75,000 cps., a density of 0.85 to 0.86 grs/cc, a glass transition temperature of −30° to −45° C., and having no melting point measurable by Differential Scanning Calorimetry, wherein said higher 1-olefin is at least two members of the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.
- U.S. Pat. No. 4,169,116, “Blends of substantially amorphous olefin copolymers and compatible tackifying resins useful as hot-melt, pressure-sensitive adhesives”, describes an adhesive composition capable of being used as a hot-melt, pressure-sensitive adhesive comprising a blend of (1) about 95 to 50 weight percent of a substantially amorphous olefin copolymer containing at least one C3 to C5 linear alpha-olefin and 40 to 60 mole percent of at least one higher alpha-olefin of 6 to 10 carbon atoms, said copolymer having a melt viscosity of >76,000 to 1,000,000 centipoise at 190° C., and (2) 5 to 50 weight percent of at least one compatible tackifying resin.
- U.S. Pat. No. 4,210,570, “Blends of substantially amorphous olefin copolymers, compatible tackifying resins and plasticizing oils useful as hot melt, pressure-sensitive adhesives”, describes an adhesive composition capable of being used as a hot-melt, pressure-sensitive adhesive comprising a blend of (1) about 98 to 25 weight percent of a substantially amorphous or semicrystalline olefin copolymer containing at least one C3 to C5 linear alpha-olefin and 15 to 60 mole percent of at least one higher linear alpha-olefin of 6 to 10 carbon atoms, said copolymer having a melt viscosity of 5,000 to 1,000,000 centipoise at 190° C., (2) 1 to 60 weight percent of at least one compatible tackifying resin, and (3) 1 to 25 weight percent plasticizing oil.
- U.S. Pat. No. 4,288,358, “Blends of propylene/1-butene or 1-pentene/higher .alpha.-olefin copolymers, compatible tackifying resins and plasticizing oils useful as hot-melt, pressure-sensitive adhesives,” describes an adhesive composition capable of being used as a hot-melt, pressure-sensitive adhesive comprising a blend of (1) about 98 to 25 weight percent of an olefin copolymer containing 10-65 mole % propylene, 15-75 mole % of either 1-butene or 1-pentene and 3 to 14 mole percent of at least one higher linear alpha-olefin of 6 to 10 carbon atoms, said copolymer having a melt viscosity of 10,000 to 1,000,000 centipoise at 190° C., (2) 1 to 60 weight percent of at least one compatible tackifying resin, and (3) 1 to 25 weight percent plasticizing oil.
- U.S. Pat. No. 4,826,939, “Highly amorphous olefin terpolymer”, describes an amorphous, pressure-sensitive terpolymer comprising repeating units from about 0.1 to about 10 percent by weight ethylene, from about 30 to about 78 percent by weight propylene, and from 20 to 70 percent by weight 1-hexene, the terpolymer having a ring-and-ball softening point of from about 75° C. to about 120° C., a melt viscosity of from about 100 to about 100,000 cps at 190° C., no DSC melting point, and a 180° peel strength of at least about 1.2 pounds/inch. Also described is a process for producing an amorphous, pressure-sensitive terpolymer having no DSC melting point comprising continuously polymerizing a mixture of from about 0.1 to about 10 percent by weight ethylene, from about 30 to about 78 percent by weight propylene, and from about 20 to about 70 percent by weight 1-hexene, in the presence of a catalyst comprising an anionic coordination catalyst and in a solvent medium, at a temperature of from about 140° C. to about 250° C. and at a pressure of about 100 to about 5,000 pounds per square inch gauge.
- The contents of each of the above-listed patents is hereby incorporated by reference in its entirety.
- Propylene-co-hexene-1 copolymers, optionally containing 1-butene monomer to form propylene-co-hexene-1-co-butene-1 terpolymers, are made using a supported Ziegler-Natta catalyst either with or without an in-reactor added organosilicon external donor.
- Copolymers and terpolymers according to the invention may be used in the formulation of improved-performance APAO-based hot melt adhesives.
- Due to the compositional nature of propylene-co-hexene-1 copolymer APAOs, and optionally propylene-co-hexene-1-co-butene-1 terpolymers, each of the comonomers adds a unique set of properties to the APAO, which may be enhanced, or changed, by the addition of an external organosilicon donor.
- The use of these APAO copolymers and terpolymers, may add unique properties when used as components in hot melt adhesive formulations such as those used preferentially in pressure-sensitive adhesives and also in such applications as in personal hygiene products (e.g. diapers, feminine hygiene, elastic attachment, etc.), in assembly, construction, lamination, footwear and other applications that require such properties as permanent tackiness, controllable open time, low-temperature flexibility, good temperature resistance and other such desirable properties.
- An HMA according to the present invention may be made up of a propylene-co-hexene-1 copolymer APAO with a hexene-1 content of about 10 wt. %, more preferably, about 25 wt. %, much more preferably with about 30 wt. % and most preferably with about 50 wt. % by weight but it may contain up to 90 wt. %. This copolymer may be utilized in an unformulated form, that is, as-obtained from the reactor APAO. When applied, or coated, as a hot melt, or cast from an organic solvent solution, onto a substrate typically such as stock paper or a plastic film or any other porous or non-porous substrate (the primary substrate) by any of the commercially known and used coating methods, the subject of this invention bonds strongly, forming a destructive bond to the primary substrate.
- Pressure sensitive applications (PSA's) require good adhesion to a variety of substrates, but such adhesion should be reversible and no adhesive should be transferred to the surface or secondary substrate or substrates onto which the primary substrate coated with the HMA subject of this invention, may be applied. This copolymer exhibits this type of PSA properties. Such types of pressure sensitive adhesives may be considered for removable applications such as removable tapes and labels. The addition of another monomer component such as butene-1, results in a propylene-co-hexene-1-co-butene-1 terpolymer APAO with an even broader envelope of PSA- and other HMA-properties and performance. The terpolymer may have a butene-1 content of up to 40 wt. %; however, it should preferably have about 5 to 25 wt. % and most preferably 5 to 10 wt. % by weight. Moreover, the addition of a so-called external donor of the organosilicon class, such as for example cyclohexylmethyldimethoxysilane (CMDMS), or phenyltriethoxysilane (PES), imparts certain unique characteristics to the physical and mechanical properties of the copolymer and also to the terpolymer, properties that reflect favorably in the final performance of the hot melt adhesive containing it.
- Co-adjuvants may form a part of the subject HMA, such as tackifiers, preferably the type considered compatible with APAO polymers. Such tackifiers are of the partially and fully hydrogenated C5, hydrogenated C5-C9, and hydrogenated DCPD-type resins but may be any other tackifier which, by its chemical nature, is compatible with the APAO terpolymer. Yet other components may be polyethylene, maleic anhydride grafted polyethylene, Fischer-Tropsch paraffinic waxes and metallocene waxes. These, as well as other similar compatible waxes, have the effect of controlling the melt viscosity and also controlling the rate of set of the HMA. Also, so-called liquid plasticizers such as mineral, paraffinic or naphthenic oils, may be used in the terpolymer-based formulation to add such properties as melt viscosity control, tackiness and controllable open time. Also, components such as anti-oxidants and UV stabilizers may be added as co-adjuvants. Other compatible polymers which may be included in the formulation of the subject HMA include, for example, hydrogenated styrene block copolymers of the SEBS and SEPS type and polyethylenes such as LLDPE of melt indices (MIs) of typically more than 500 dg/min. Also used, preferably as the minor component, may be the so-called metallocene polyethylenes which are known in the art as mPEs and whose composition consists of ethylene copolymerized with such alpha-olefins as 1-butene or 1-hexene or 1-octene. Metallocene polypropylenes (mPP), of the appropriate molecular weight so as to be compatible with the subject APAO terpolymer, may also be added as a minor component.
- Both the propylene-co-hexene-1 copolymer and propylene-co-butene-1-co-hexene-1 terpolymer may be made according to the teachings of U.S. Pat. No. 4,847,340, whereby they are made at a temperature between about 130° F. and about 175° F. and at a reactor pressure sufficient to maintain propylene in the liquid phase (in the absence of any added solvent), and in the presence of from about 0.7 to about 3.0 mol % hydrogen based on the monomer feed. The hydrogen concentration present during the manufacture of the subject copolymers and terpolymers may be adjusted so that their melt viscosity, measured at 375° F., is less than 3500 cps, preferably less than 3000 cps.
- The use of the propylene-hexene-1 and propylene-co-hexene-1-cobutene-1 APAOs made in the presence of the externally added organosilicon when used either unformulated or, alternatively, properly formulated with the above-named co-adjuvants, at concentrations of 0 to up to 25 wt. % of tackifier(s), or between 0 to about 15 wt. % of the above-mentioned wax(es), or between 0 and 25 wt. % of the above mentioned oil(s), will result in hot melt adhesives with enhanced properties for use in pressure-sensitive adhesives, and also in personal hygiene products (e.g. diapers, feminine hygiene, elastic attachment, etc.), in assembly, and other such applications.
- The above-named co-adjuvants may interact with the long polymeric chains of the propylene-co-hexene-1 and propylene-co-hexene-1-butene-1 APAOs made in the presence of the externally added organosilicon in such a way as to result in an HMA with a lower, yet desirable, melt viscosity which results in better wetting and penetration of various substrates, porous, or non-porous, resulting in a higher degree of adhesive bonding. Also, the interaction of the multiple components results in a higher, yet controllable, tackiness for such applications which demand a certain degree of tackiness and pressure sensitive adhesiveness. Other interactions will become obvious to the user.
- A hot-melt adhesive according to the invention may comprise: a) an APAO copolymer or terpolymer, preferably made in the presence of an externally added donor; b) a tackifier; and optionally, c) a wax component of the type(s) described above and d) a liquid plasticizer such as mineral oil or a naphthenic oil.
- Several propylene-co-hexene-1 copolymerization and propylene-co-butene-1-co-hexene-1 terpolymerization reactions were carried out either in the absence or in the presence of an external donor. External donors such as phenyltriethoxysilane (PES or A-Donor, CAS No. 780-69-8) or cyclohexylmethyldimethoxysilane (CMDMS or C-Donor, CAS No. 17865-32-6) were used. Other silane-based external donors such as diphenyldimethoxysilane (B-Donor, CAS No. 6843-66-9), diisobutyldimethoxy silane (CAS No. 17980-32-4), dicyclopentyldimethoxy silane (DDMS or D-Donor, CAS No. 126990-35-0) and diisopropyldimethoxy silane (DPMS or P-Donor, CAS No. 18230-61-0) may also be used. Yet other less-common silane-based donors may also be used for the reactions in the subject matter.
- The polymerization reactions were carried out in an Autoclave Engineers™ 1-L autoclave typically at 70° C. and for one hour. Before running a reaction, the autoclave was cleaned of any residual polymer from any previous reaction using an organic solvent such as heptane to assure a clean reactor. The agitator/mixer assembly was placed on top of the autoclave which was then tightened securely. The autoclave was then heated, or baked, at 150° C., under a dry nitrogen atmosphere for about one hour, and then the autoclave was cooled to about 40° C., still under a nitrogen blanket. The temperature was controlled with a Julabo GmbH temperature control unit. A more detailed description of the polymerization process is described for example in U.S. Pat. Nos. 5,681,913, 5,637,665, 5,714,554 and/or 5,302,675. Once the reactor reached the set temperature, a mineral oil slurry of the catalyst, pre-contacted with the alkyl aluminum co-catalyst, TEA, was dosed into the reactor, followed by the monomers [propylene (CAS No. 115-07-1), butene-1 (CAS No. 106-98-9) and hexene-1 (CAS No. 592-41-6)], and by the hydrogen gas. The reaction was started by turning on the agitator and typically the reactions were quite exothermic but the Julabo unit was efficient in controlling the reaction temperature. The order of addition of the reactants may be varied to a certain extent, but the catalyst/cocatalyst mixture was always introduced first. After the prescribed reaction time, for example 1 hour, the agitator was stopped, the temperature of the Julabo unit was reduced and the autoclave was slowly depressurized to remove any unreacted reactants. Due to the high productivity, in grams of polymer produced per gram of catalyst, no catalyst deactivation, other than exposure to the atmosphere, was required. Once decompressed, the top was removed and the polymer was harvested from the reactor. Other polymerization reaction temperatures as low as 40° C. and as high as 90° C. may also be used. Reaction times may range from 5 minutes to as long as three hours. The reactions were performed in the absence of any added organic solvent because the liquefied monomers a) serve to remove the high exothermal heat of polymerization reaction, and b) serve as the suspension medium for the formed polymeric products.
- The propylene monomer used was of very high purity, typically 99.99%+propylene with the remaining components being low-molecular-weight saturated hydrocarbons. This type of propylene is known in the trade as PGP or polymer grade propylene. Other propylene grades such as CGP, or chemical grade propylene, typically made up of at least 90+% propylene with the balance consisting of inert hydrogenated hydrocarbons may also be used. RGP, or refinery grade propylene, wherein the propylene content is usually 65-75%, propane is 20-30%, with the balance butane/butylene (BB) and ethylene/ethane may also be used but it gives quite low polymer yields.
- The butene-1 monomer used was high purity plant butene or it may be from what is called bottled, in small tanks, butene-1, with purities typically over 99+%. The hexene-1 used in the reactions was high purity (>97%) from vendors such as Sigma-Aldrich.
- TABLE 1 shows 22 polymerization reactions that were run varying the amounts of monomers, external donor (as represented by the F2/F3 ratio), or the alkyl aluminum-to-donor ratio, and the hydrogen pressure to control the melt viscosity or molecular weight of the produced polymers. Total reaction volume was targeted at 700 ml. The reaction variables were chosen using a full factorial design of experiment, DoE, generated by Minitab 15 DoE software which covered a broad spectrum of factors or reaction variables.
-
TABLE 1 Example C3=, ml C4=, ml C6=, ml H2, psi F2/F3 1 300 0 400 60 400 2 375 75 250 90 200 3 150 150 400 120 400 4 375 75 250 90 200 5 150 150 400 60 400 6 450 150 100 60 0 7 150 150 400 120 0 8 150 150 400 60 0 9 450 150 100 120 400 10 450 150 100 60 400 11 375 75 250 90 200 12 300 0 400 60 0 13 375 75 250 90 200 14 375 75 250 90 200 15 300 0 400 120 400 16 375 75 250 90 200 17 300 0 400 120 0 18 300 0 100 120 0 19 300 0 100 60 0 20 450 150 100 120 0 21 600 0 100 60 400 22 600 0 100 120 400 -
TABLE 2 Physical and mechanical characterization of the polymerization products. C4=, C6=, MV, NP, RBSP, OT, RBT, SAFT, Example % % cps dmm ° F. sec cm TS, psi ° F. 1 NA 49.2 1530 82 233 PSA 3 ± 1.6 Too Soft 110 ± 3 2 2.4 29.7 1248 42 253 PSA 1.8 ± 0.3 59 ± 3 149 ± 4 3 19.8 47.9 1147 TS TS PSA 2.0 ± 0.5 Too Soft <85 4 2.2 28.2 1150 39 254 100 3.0 ± 1.2 25 ± 1.4 149 ± 2 5 10.6 9.4 4738 166 131 PSA 1.9 ± 0.4 Too Soft <85 6 14.4 11.3 1855 31 254 150 24 ± 1.7 86 ± 3 184 ± 6 7 13.4 11.5 440 TS TS PSA 1.4 ± 0.2 Too Soft 83 ± 3 8 19.6 47.0 1500 ~187 TS PSA 1.2 ± 0.3 Too Soft 88 ± 3 9 10.4 10.2 1010 23 269 30 >30 183 ± 8 222 ± 12 10 12.4 9.8 4250 17 267 40 >30 323 ± 18 235 ± 6 11 4.4 26.9 718 42 254 100 16 ± 2.9 50 ± 2 154 ± 3 12 NA 57.2 1313 145 212 PSA 1.1 ± 0.3 Too Soft 176 ± 4 13 4.5 28.7 7275 36 259 240 2.3 ± 0.2 1.7 ± 0.1 158 ± 6 14 4.9 32.4 905 62 237 PSA 1.8 ± 0.8 29 ± 1 133 ± 4 15 NA 55.7 400 ~286 144 PSA 2.5 ± 1.1 Too Soft 87 ± 3 16 4.7 31.5 800 70 232 PSA 1.4 ± 0.2 19 ± 0.4 123 ± 3 17 NA 50.1 520 155 215 Too Soft 1.6 ± 0.4 Too Soft 110 ± 4 18 NA 14.5 845 13 278 10 >30 110 ± 9 245 ± 6 19 NA 13.0 13000 15 285 10 >30 495 ± 29 256 ± 8 20 13.6 11.5 750 36 251 100 >30 60 ± 3 188 ± 5 21 NA 11.2 20750 8 290 Too Thick >30 880 ± 70 275 ± 2 22 NA 13.5 980 13 280 10 >30 236 ± 18 254 ± 3 - The concentration of incorporated butene-1 in the polymers (C4=, %), as well as the concentration of hexene-1 (C6=, %), was obtained using a proprietary FTIR spectroscopic test method. The melt viscosity, MV, was typically determined at 375° F. (190° C.), as per the ASTM D-3236 test method. The needle penetration, NP, was determined at 72 to 75° F., as per the ASTM D-1321 test method, while the ring and ball softening point, RBSP, was determined as per ASTM E-28. The open time, OT, as per ASTM D-4497, and the rolling ball tack, RBT, as per a modified ASTM D-3121 test. The tensile strength, TS, was determined as per ASTM D-638, and finally the shear adhesion failure temperature as per a modified TMHM-32 test.
- An Autoclave Engineers™ 1-L autoclave, properly conditioned as described above, to which calculated amounts of catalyst, co-catalyst and external donor, e.g. PES (targeting a F2/F3 of 400) were added, was loaded with 300 ml of propylene and 400 ml of hexene-1 and with 60 psi of hydrogen overpressure. The reaction was started and after an hour, it was stopped, unreacted monomers were vented and a soft solid product was recovered. The properties are described in Table 2 and according to a test commonly used in the pressure sensitive industry, the RBT of about 2 to 4 cm would give this product PSA properties.
- The same procedure as described in Example 1 was followed targeting a F2/F3 of 200, but adding 375 ml of propylene, 75 ml of butene-1, 250 ml of hexene-1 and 90 psi of hydrogen. The reaction was started, allowed to proceed for an hour, then stopped, unreacted monomers were vented and a somewhat harder solid than that of Example 1 was recovered. The properties are presented in Table 2 and a RBT of about 1.5 to 2 cm would give this product PSA properties.
- The same procedure as described in Example 1 was followed targeting a F2/F3 of 400, but adding 150 ml of propylene, 150 ml of butene-1, 400 ml of hexene-1 and 120 psi of hydrogen. The reaction was started, allowed to proceed for an hour, then stopped, unreacted monomers were vented and a somewhat harder solid than that of Example 1 was recovered. The properties are presented in Table 2 and a RBT of over 30 cm does not give it PSA properties.
- The data presented in the above tables indicates that different polymer properties are obtained when using different reaction variables.
- The foregoing presents particular embodiments of a system embodying the principles of the invention. Those skilled in the art will be able to devise alternatives and variations which, even if not explicitly disclosed herein, embody those principles and are thus within the scope of the invention. Although particular embodiments of the present invention have been shown and described, they are not intended to limit what this patent covers. One skilled in the art will understand that various changes and modifications may be made without departing from the scope of the present invention as literally and equivalently covered by the following claims.
Claims (16)
1. A hot-melt formulation comprising:
a propylene-co-hexene-1-co-butene-1 terpolymer made using a supported Ziegler-Natta catalyst, at a process temperature between about 130° F. and about 175° F. and at a reactor pressure sufficient to maintain propylene in the liquid phase (in the absence of any added solvent) and the hydrogen concentration present during the manufacture of the subject terpolymers is adjusted so that their melt viscosity, measured at 190° C., is less than 3500 cps, preferably less than 3000 cps, optionally in the presence of an organo-silane external donor and optionally with,
a tackifier; and/or
a styrenic block copolymer; and/or
a high melt flow index metallocene or single-site catalyzed polyethylene; and/or
a high melt flow rate polypropylene, either a homopolymer or random copolymer, of varying degrees of crystallinity or isotacticity, functionalized or without any polar functionality; and/or
a wax component; and/or
a liquid plasticizer.
2. The hot-melt formulation of claim 1 wherein the copolymer is made in the presence of an externally-added organosilicon donor.
3. The hot-melt formulation of claim 8 wherein the terpolymer is made in the presence of an externally-added organosilicon donor.
4. The hot-melt formulation of claim 1 comprising a propylene-co-hexene-1 copolymer with a boiling heptane insolubility of less than 20 wt. %.
5. The hot-melt formulation of claim 1 comprising a propylene-co-hexene-1 copolymer manufactured in the absence of any added solvent
6. The hot-melt formulation of claim 1 wherein the liquid plasticizer comprises a naphthenic oil.
7. The hot-melt formulation of claim 8 wherein the liquid plasticizer comprises a naphthenic oil.
8. The hot-melt formulation of claim 1 wherein the liquid plasticizer comprises a paraffinic oil.
9. The hot-melt formulation of claim 8 wherein the liquid plasticizer comprises a paraffinic oil.
10. The hot-melt formulation of claim 1 wherein the wax component comprises a paraffinic wax.
11. The hot-melt formulation of claim 8 wherein the wax component comprises a paraffinic wax.
12. The hot-melt formulation of claim 1 wherein the wax component comprises a metallocene wax.
13. The hot-melt formulation of claim 2 wherein the wax component comprises a metallocene wax.
14. The hot-melt formulation of claim 1 wherein the terpolymer is made at a process temperature between about 130° F. and about 175° F. and at a reactor pressure sufficient to maintain propylene in the liquid phase (in the absence of any added solvent).
15. The hot-melt formulation of claim 1 wherein the hydrogen concentration present during the manufacture of the terpolymer is adjusted such that its melt viscosity, measured at 375° F., is less than 3500 cps.
16. The hot-melt formulation of claim 1 wherein the hydrogen concentration present during the manufacture of the terpolymer is adjusted such that its melt viscosity, measured at 375° F., is less than 3000 cps.
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US15/486,115 US20170292047A1 (en) | 2016-04-12 | 2017-04-12 | Hexene-1 Containing Amorphous Polyalphaolefins For Improved Hot Melt Adhesives |
US16/108,631 US10174228B2 (en) | 2016-04-12 | 2018-08-22 | Amorphous poly alpha olefins of low acid and organoleptic properties and a process for producing same |
US16/111,494 US10266731B2 (en) | 2016-04-12 | 2018-08-24 | Amorphous hexene-1 based polymeric hot melt adhesive |
US16/153,895 US10421886B2 (en) | 2016-04-12 | 2018-10-08 | Low molecular weight butene-1-co-hexene-1 amorphous poly alpha olefins for hot melt adhesives with enhanced properties |
US16/376,298 US20190233685A1 (en) | 2016-04-12 | 2019-04-05 | Method for making hexene-1 containing amorphous polyalphaolefins for improved hot melt adhesives |
US16/383,914 US10738222B2 (en) | 2016-04-12 | 2019-04-15 | Method for making hexene-1 containing amorphous poly alpha olefins for improved hot-melt adhesives |
US16/539,988 US10752815B2 (en) | 2016-04-12 | 2019-08-13 | Low molecular weight butene-1-co-hexene-1 amorphous poly alpha olefins for hot-melt adhesives with enhanced properties |
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US16/111,494 Continuation US10266731B2 (en) | 2016-04-12 | 2018-08-24 | Amorphous hexene-1 based polymeric hot melt adhesive |
US16/153,895 Continuation US10421886B2 (en) | 2016-04-12 | 2018-10-08 | Low molecular weight butene-1-co-hexene-1 amorphous poly alpha olefins for hot melt adhesives with enhanced properties |
US16/376,298 Continuation US20190233685A1 (en) | 2016-04-12 | 2019-04-05 | Method for making hexene-1 containing amorphous polyalphaolefins for improved hot melt adhesives |
US16/383,914 Continuation US10738222B2 (en) | 2016-04-12 | 2019-04-15 | Method for making hexene-1 containing amorphous poly alpha olefins for improved hot-melt adhesives |
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US16/111,494 Active US10266731B2 (en) | 2016-04-12 | 2018-08-24 | Amorphous hexene-1 based polymeric hot melt adhesive |
US16/153,895 Active US10421886B2 (en) | 2016-04-12 | 2018-10-08 | Low molecular weight butene-1-co-hexene-1 amorphous poly alpha olefins for hot melt adhesives with enhanced properties |
US16/376,298 Abandoned US20190233685A1 (en) | 2016-04-12 | 2019-04-05 | Method for making hexene-1 containing amorphous polyalphaolefins for improved hot melt adhesives |
US16/383,914 Active US10738222B2 (en) | 2016-04-12 | 2019-04-15 | Method for making hexene-1 containing amorphous poly alpha olefins for improved hot-melt adhesives |
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US16/111,494 Active US10266731B2 (en) | 2016-04-12 | 2018-08-24 | Amorphous hexene-1 based polymeric hot melt adhesive |
US16/153,895 Active US10421886B2 (en) | 2016-04-12 | 2018-10-08 | Low molecular weight butene-1-co-hexene-1 amorphous poly alpha olefins for hot melt adhesives with enhanced properties |
US16/376,298 Abandoned US20190233685A1 (en) | 2016-04-12 | 2019-04-05 | Method for making hexene-1 containing amorphous polyalphaolefins for improved hot melt adhesives |
US16/383,914 Active US10738222B2 (en) | 2016-04-12 | 2019-04-15 | Method for making hexene-1 containing amorphous poly alpha olefins for improved hot-melt adhesives |
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US10738222B2 (en) | 2020-08-11 |
US20190241774A1 (en) | 2019-08-08 |
US20190002742A1 (en) | 2019-01-03 |
US10266731B2 (en) | 2019-04-23 |
US10174228B2 (en) | 2019-01-08 |
US20190071592A1 (en) | 2019-03-07 |
US20190233685A1 (en) | 2019-08-01 |
US20180355228A1 (en) | 2018-12-13 |
US10421886B2 (en) | 2019-09-24 |
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