Modified resins and uses thereof

Patent metadata

Field	Value
Publication number	US-10837947-B2
Application number	US-201815944418-A
Country	US
Kind code	B2
Filing date	Apr 3, 2018
Priority date	Apr 3, 2017
Publication date	Nov 17, 2020
Grant date	Nov 17, 2020

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. A method of manufacturing a modified thermoplastic resin, which comprises:
polymerizing or co-polymerizing one or more of an unsaturated aliphatic monomer, terpenes, rosin acid, unsaturated cycloaromatic monomers, unsaturated cycloaliphatic monomers, unsaturated fatty acids, methacrylates, unsaturated aromatic monomers, vinyl aromatic monomers, and an unsaturated aliphatic/aromatic monomer mixture; and
selectively reducing the amount of oligomer in the modified thermoplastic resin,

wherein the modified thermoplastic resin:
has a glass transition temperature (Tg) of between −50° C. and 160° C.,
has a number average molecular (Mn) weight of less than 3,000 g/mol,
has a z-average molecular weight (Mz) of less than 9,000 g/mol,
comprises less than or equal to 55 wt % oligomers by gel permeation chromatography (GPC), or less than or equal to 38 wt % by high resolution thermogravimetric analysis (TGA), and

wherein oligomers consist of dimers, trimers, tetramer, pentamers, or a mixture thereof, of the one or more monomers.

2. The method of claim 1 , wherein selectively reducing the amount of oligomer in the modified thermoplastic resin comprises one or more steps of: membrane separation, selective precipitation, evaporation and distillation, and preparative gel permeation chromatography.

3. The method of claim 1 , wherein the modified thermoplastic resin is a modified pure monomer (PMR) thermoplastic resin, modified hydrogenated or partially hydrogenated pure monomer (PMR) thermoplastic resin, modified hydrogenated or partially hydrogenated C5 thermoplastic resin, modified hydrogenated or partially hydrogenated C5/C9 thermoplastic resin, modified hydrogenated or partially hydrogenated C9 thermoplastic resin, modified hydrogenated or partially hydrogenated dicyclopentadiene (DCPD) thermoplastic resin, modified C5 thermoplastic resin, modified C5/C9 thermoplastic resin, modified C9 thermoplastic resin, DCPD thermoplastic resin, modified terpene thermoplastic resin, modified indene-coumarone (IC) thermoplastic resin, or a mixture thereof.

4. The method of claim 1 , wherein:
(a) the glass transition temperature (Tg) is between −50° C. and 160° C.;
(b) the number average molecular weight is less than 1,000 g/mol; and/or
(c) the z-average molecular weight is less than 6,000 g/mol.

5. The method of claim 1 , wherein:
(a) the Tg is between 0° C. and 140° C.;
(b) the number average molecular weight is less than 850 g/mol; and/or
(c) the z-average molecular weight is less than 8,000 g/mol.

6. The method of claim 3 , wherein:
the high resolution TGA analysis is conducted using a thermal gravimetric analyzer calibrated by curie point of magnetic transition standards according to ASTM method E1582, procedure C; and/or wherein the high resolution TGA analysis is conducted using a TA Instruments Q500 thermal gravimetric analyzer with sensitivity set to 2.0 and resolution set to 3.0 by heating the modified thermoplastic resin in nitrogen with a scanning rate of 20 degrees per minute from ambient temperature to 625° C., and/or
the GPC analysis is conducted at 30° C. in tetrahydrofuran solvent at a flow rate of 1 ml/min with a GPC instrument comprising a refractive index detector, a highly cross-linked polystyrene-divinylbenzene gel column, and/or a column comprising polymer particles with a nominal particle size of 6 μm.

7. The method of claim 1 , wherein the modified thermoplastic resin has a glass transition temperature (Tg) of between −50° C. and 160° C.

8. The method of claim 1 , wherein the number average molecular weight (Mn) of the modified thermoplastic resin is less than or equal to 1,000 g/mol, and/or wherein the z-average molecular weight (Mz) is less than or equal to 9,000 g/mol.

9. A method of manufacturing a modified thermoplastic resin, which comprises:
polymerizing or co-polymerizing one or more of an unsaturated aliphatic monomer, terpenes, rosin acid, unsaturated cycloaromatic monomers, unsaturated cycloaliphatic monomers, unsaturated fatty acids, methacrylates, unsaturated aromatic monomers, vinyl aromatic monomers, and an unsaturated aliphatic/aromatic monomer mixture; and
selectively reducing the amount of oligomer in the modified thermoplastic resin,
wherein the modified thermoplastic resin possesses the properties of formula I:

S
=

(

T
g

M
z

)

⁢

/

⁡

[

Oligomer
×

(

1
-

T
10

T
max

)

]

I

wherein:
Tg is the glass transition temperature of the modified thermoplastic resin;
Mz is the z-average molecular weight of the modified thermoplastic resin;
Oligomer is the fraction of oligomer present in the modified thermoplastic resin as measured by high resolution thermal gravimetric analysis (TGA) or gel permeation chromatography (GPC);
T10 is the temperature at which the modified thermoplastic resin loses about 10% of its weight as measured by high resolution TGA;
Tmax is the temperature of the maximum first derivative value of the modified thermoplastic resin as measured by high resolution TGA;
S is greater than or equal to 2 and less than 50,000 when Oligomer is determined by GPC, or greater than or equal to 5 and less than 10,000 when Oligomer is determined by high resolution TGA; and
Wherein the value of Mz is less than or equal to 9,000 g/mol.

10. The method of claim 9 , wherein selectively reducing the amount of oligomer in the modified thermoplastic resin comprises one or more steps of: membrane separation, selective precipitation, evaporation and distillation, and preparative gel permeation chromatography.

11. The method of claim 9 , wherein the modified thermoplastic resin is a modified pure monomer (PMR) thermoplastic resin, modified hydrogenated or partially hydrogenated pure monomer (PMR) thermoplastic resin, modified hydrogenated or partially hydrogenated C5 thermoplastic resin, modified hydrogenated or partially hydrogenated C5/C9 thermoplastic resin, modified hydrogenated or partially hydrogenated C9 thermoplastic r

Assignees

• Eastman Chem Co

Inventors

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

Classifications

• B60C1/0016 Primary

  Compositions of the tread · CPC title

• C08G2261/724

  Hydrogenation · CPC title

• C09J153/02

  Vinyl aromatic monomers and conjugated dienes · CPC title

• C08G61/08

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C09J191/00

  Adhesives based on oils, fats or waxes; Adhesives based on derivatives thereof · CPC title