Modified resins and uses thereof

Patent metadata

Field	Value
Publication number	US-11262338-B2
Application number	US-202016989569-A
Country	US
Kind code	B2
Filing date	Aug 10, 2020
Priority date	Apr 3, 2017
Publication date	Mar 1, 2022
Grant date	Mar 1, 2022

Abstract

Modified thermoplastic hydrocarbon thermoplastic resins are provided, as well as methods of their manufacture and uses thereof in rubber compositions. The modified thermoplastic resins are modified by decreasing the relative quantity of the dimer, trimer, tetramer, and pentamer oligomers as compared to the corresponding unmodified thermoplastic resin polymers, resulting in a product that exhibits a greater shift in the glass transition temperature of the elastomer(s) used in tire formulations. This translates to better viscoelastic predictors of tire tread performance, such as wet grip and rolling resistance. The modified thermoplastic resins impart remarkable properties on various rubber compositions, such as tires, belts, hoses, brakes, and the like. Automobile tires incorporating the modified thermoplastic resins are shown to possess excellent results in balancing the properties of rolling resistance, tire wear, snow performance, and wet braking performance.

First claim

What is claimed is:

1. An adhesive composition, comprising:
about 10 to about 90 weight percent of at least one polymer,
about 5 to about 70 weight percent of at least one modified thermoplastic resin,
about 0 to about 60 weight percent of at least one thermoplastic tackifying resin,
about 0 to about 50 weight percent of at least one wax,
about 0 to about 60 weight percent of at least one oil or plasticizer,
about 0.5 to about 3 weight percent of at least one stabilizer, and
about 0 to about 70 weight percent of at least one filler,
wherein the composition is non-vulcanized,
wherein the at least one modified thermoplastic resin has a glass transition temperature (Tg) of between −50° C. and 160° C.,
wherein the at least one modified thermoplastic resin has a number average (Mn) molecular weight of less than 3,000 g/mol,
wherein the at least one modified thermoplastic resin has a z-average molecular weight (Mz) of less than 9,000 g/mol,
wherein the modified thermoplastic resin is a pure monomer thermoplastic (PMR) resin, a C5 thermoplastic resin, a thermoplastic C5/C9 resin, a hydrogenated or partially hydrogenated C5 resin and/or a hydrogenated or partially hydrogenated C5/C9 thermoplastic resin, a C9 thermoplastic resin, a hydrogenated or partially hydrogenated dicyclopentadiene (DCPD) thermoplastic resin, a hydrogenated or partially hydrogenated C9 thermoplastic resin, or a hydrogenated or partially hydrogenated PMR thermoplastic resin, or a mixture thereof,
wherein:
(a) when the modified thermoplastic resin is the PMR thermoplastic resin, then the value of Tg/Mz of the modified thermoplastic resin is greater than or equal to 0.14 K/(g/mol), and the percent of the modified thermoplastic resin having a molecular weight of less than 300 g/mol is less than or equal to 2.5, and the percent of the modified thermoplastic resin having a molecular weight of less than 600 g/mol is less than or equal to 19;
(b) when the modified thermoplastic resin is the C5 thermoplastic resin, then the percent of the modified thermoplastic resin having a molecular weight of less than 300 g/mol is less than 3, and/or the percent of the modified thermoplastic resin having a molecular weight of less than 600 g/mol is less than 17;
(c) when the modified thermoplastic resin is the C5/C9 thermoplastic resin, then the percent of the modified thermoplastic resin having a molecular weight of less than 300 g/mol is less than 3, and/or the percent of the modified thermoplastic resin having a molecular weight of less than 600 g/mol is less than 17;
(d) when the modified thermoplastic resin is the C9 thermoplastic resin, then the value of Tg/Mz of the modified thermoplastic resin is greater than 0.09 K/(g/mol), the percent of the modified thermoplastic resin having a molecular weight of less than 300 g/mol is less than 5, and the percent of the modified thermoplastic resin having a molecular weight of less than 600 g/mol is less than 25;
(e) when the modified thermoplastic resin is the hydrogenated or partially hydrogenated DCPD thermoplastic resin, then the value of Tg/Mz of the modified thermoplastic resin is greater than 0.25 K/(g/mol), and: (i) the percent modified thermoplastic resin having a molecular weight of less than 300 g/mol is less than 16, and/or (ii) the percent modified thermoplastic resin having a molecular weight of less than 600 g/mol is less than 55;
(f) when the modified thermoplastic resin is the hydrogenated or partially hydrogenated C5 thermoplastic resin and/or the hydrogenated or partially hydrogenated C5/C9 thermoplastic resin, then the percent modified thermoplastic resin having a molecular weight of less than 300 g/mol is less than 15, and/or the percent modified thermoplastic resin having a molecular weight of less than 600 g/mol is less than 45;
(g) the modified thermoplastic resin is the hydrogenated or partially hydrogenated C9 thermoplastic resin, then the value of Tg/Mz of the modified thermoplastic resin is greater than 0.19 K/(g/mol), the percent modified thermoplastic resin having a molecular weight of less than 300 g/mol is less than or equal to 10, and the percent modified thermoplastic resin having a molecular weight of less than 600 g/mol is less than 34; and
(h) when the modified thermoplastic resin is the hydrogenated or the partially hydrogenated PMR thermoplastic resin, and:
the value of Tg/Mz of the modified thermoplastic resin is greater than or equal to 0.30 K/(g/mol), then the percent modified thermoplastic resin having a molecular weight of less than 300 g/mol is less than 10, and/or the percent modified thermoplastic resin having a molecular weight of less than 600 g/mol is less than 45, or
the value of Tg/Mz of the modified thermoplastic resin is less than 0.30 K/(g/mol), then the percent modified thermoplastic resin having a molecular weight of less than 300 g/mol is less than 10, and/or the percent modified thermoplastic resin having a molecular weight of less than 600 g/mol is less than 30, and

wherein molecular weight of the modified thermoplastic resin is determined by gel permeation chromatography (GPC) with polystyrene standards.

2. The composition of claim 1 , wherein the composition exhibits:
a glass transition temperature (Tg) as measured by differential scanning calorimetry (DSC) of a 50:50 wt % blend that is at least 1° C. closer to a predicted Fox Tg as compared with a Tg of a composition comprising an unmodified standard resin of an identical type having ring and ball softening point within 3° C. of the modified thermoplastic resins and determined under identical test conditions;
a VOC and/or FOG value as measured per VDA 278, or mineral oil saturated hydrocarbon (MOSH) and/or mineral oil aromatic hydrocarbon (MOAH) value, that is lower than a VOC, FOG, MOSH, and/or MOAH value exhibited by an equivalent composition comprising a corresponding unmodified thermoplastic resin having ring and ball softening point within 3° C. of the modified thermoplastic resin;
less surface staining of areas near or in contact with the composition as compared with an equivalent composition comprising a corresponding unmodified thermoplastic resin having ring and ball softening point within 3° C. of the modified thermoplastic resin;
a lower Brookfield viscosity at 160° C. as compared with an equivalent composition comprising a corresponding unmodified thermoplastic resin having ring and ball softening point within 3° C. of the modified thermoplastic resin;
a greater percent fiber tear at −7° C. on corrugated cardboard as compared with an equivalent composition comprising a corresponding unmodified thermoplastic resin having ring and ball softening point within 3° C. of the modified thermoplastic resin; and/or
a longer hold time on corrugated cardboard at 70° C. measured by JAI-7C as compared with an equivalent composition comprising a corresponding unmodified thermoplastic resin having ring and ball softening point within 3° C. of the modified thermoplastic resin.

3. The composition of claim 1 , which comprises:
about 40 to about 90 weight percent of the at least one polymer,
about 10 to about 60 weight percent of the at least one modified thermoplastic resin,
about 0 to about 50 weight percent of the at least one thermoplastic tackifying resin,
about 0 to about 30 weight percent of the at least one wax, and
about 0 to about 20 weight percent of the at least one oil or plasticizer.

4. The composition of claim 1 , which comprises about 60 to about 90 weight percent of the at least one polymer, and wherein the composition forms a film with 10 percent lower haze measured by ASTM D1003 method A, or lower water vapor transmission rate (WVTR) measured by ASTM F1249, than an equivalent composition comprising a corresponding unmodified thermoplastic resin having a similar ring and ball softening poin

Assignees

• Eastman Chem Co

Inventors

• Arigo Mark
• Carvagno Terri Roxanne
• De Hullu Jacobus Gillis
• Finger Sebastian
• Hirschlag Hubert
• Klomp Janine
• Muvundamina Mutombo Joseph
• Peters Fabian
• Recker Carla
• Robertson Christopher George
• Versluijs Peter

Classifications

• C08L45/00

  Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers (of cyclic anhydrides or imides C08L35/00; of cyclic esters of polyfunctional acids C08L31/00) · CPC title

• C08L23/26

  modified by chemical after-treatment (saponified copolymers C08L23/0861; unsaturated acid salts C08L23/0876) · CPC title

• C08L23/20 Primary

  having four to nine carbon atoms · CPC title

• C08L23/08

  Copolymers of ethene (C08L23/16 takes precedence) · CPC title

• C08L15/00

  Compositions of rubber derivatives (C08L11/00, C08L13/00 take precedence) · CPC title