# US 2022/0033688 A1 · Adhesive compositions with polyesters comprising 2,2,4,4-tetraalkyl-1,3-cyclobutanediol and methods of making the same

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- Number: US 2022/0033688 A1
- Document ID: US20220033688A1
- Status: Published application
- Kind: A1
- Application number: 17/309,563
- Filed: 2019-12-06
- Published: 2022-02-03
- Earliest claimed: 2018-12-06
- Assignees: Eastman Chemical (China) Co., Ltd.
- Applicants: Eastman Chemical (China) Co., Ltd.
- Inventors: Liu Deng; Emmett Dudley Crawford; Wentao Li; John Thorton Maddox; Christopher Harlan Burk; Cheng Wei Zhu; Kujtim Bizati; Bing Yuan; Dayu Zhang; Tara Renee Cary; Thauming Kuo
- Web page: https://patentgrep.com/patent/US20220033688A1

## CPC

- C09J 175/06: from polyesters
- B32B 5/26: another layer {next to it} also being fibrous or filamentary {(relative arrangement of fibres or filaments of different layers B32B5/12)}
- B32B 7/12: using interposed adhesives or interposed materials with bonding properties
- B32B 9/025: {comprising leather}
- B32B 9/04: comprising such {particular} substance as the main or only constituent of a layer, {which is} next to another layer of {the same or of} a {different material (next to a glass layer B32B17/06; layered products with at least two ceramic layers composed mainly of ceramic B32B18/00)}
- B32B 9/041: {of metal}
- B32B 9/042: {of wood}
- B32B 9/045: {of synthetic resin}
- B32B 9/047: {made of fibres or filaments}
- B32B 15/08: of synthetic resin
- B32B 15/085: comprising polyolefins
- B32B 15/09: comprising polyesters
- B32B 15/10: of wood
- B32B 15/14: next to a fibrous or filamentary layer
- B32B 15/20: comprising aluminium or copper {(B32B15/016 and B32B15/017 take precedence)}
- B32B 21/08: of synthetic resin
- B32B 21/10: Next to a fibrous or filamentary layer
- B32B 21/13: all layers being exclusively wood
- B32B 21/14: comprising wood board or veneer
- B32B 27/08: of synthetic resin
- B32B 27/12: next to a fibrous or filamentary layer
- B32B 27/32: comprising polyolefins {(comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30)}
- B32B 27/36: comprising polyesters
- C08G 18/12: using two or more compounds having active hydrogen in the first polymerisation step
- C08G 18/307: {Atmospheric humidity}
- C08G 18/4216: {from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols}
- C08G 18/423: {containing cycloaliphatic groups}
- C08G 18/425: {the polyols containing one or two ether groups}
- C08G 18/73: acyclic
- C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate}
- C08G 18/7657: {containing two or more aromatic rings}
- C08G 18/792: {formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates}
- C08G 63/181: Acids containing aromatic rings
- C08G 63/199: Acids or hydroxy compounds containing cycloaliphatic rings
- C08G 63/672: Dicarboxylic acids and dihydroxy compounds
- C09J 7/35: Heat-activated
- C09J 175/08: from polyethers
- B32B 2307/732: Dimensional properties
- B32B 2419/00: Buildings or parts thereof
- B32B 2439/70: Food packaging
- B32B 2457/00: Electrical equipment
- B32B 2553/00: Packaging equipment or accessories not otherwise provided for
- B32B 2605/00: Vehicles
- C08G 2170/00: Compositions for adhesives
- C08G 2170/20: Compositions for hot melt adhesives
- C08G 2390/00: Containers
- C09J 2203/326: for bonding electronic components such as wafers, chips or semiconductors
- C09J 2203/354: for automotive applications
- C09J 2301/122: the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
- C09J 2301/304: the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
- C09J 2301/306: the adhesive being water-activatable
- C09J 2400/163: in the substrate
- C09J 2423/106: in the substrate
- C09J 2467/006: in the substrate
- C09J 2475/00: Presence of polyurethane
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

Adhesive compositions comprise a polyester polyol that includes residues of at least one 2, 2, 4, 4-tetraalkylcyclobutane-1, 3-diol, including, for example, 2, 2, 4, 4-tetramethylcyclobutane-1, 3-diol (TMCD). Adhesive compositions as described herein exhibit enhanced properties as compared to conventional adhesive compositions, and may be suitable for a wide variety of end use applications, including, flexible packaging, woodworking, automotive uses, and electronics.

## Claims

### Claim 1

A hot melt adhesive composition, said adhesive composition comprising:
an isocyanate-terminated polyurethane prepolymer comprising residues of (i) at least one polyester polyol comprising a diol component having residues of 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) and (ii) at least one isocyanate,
wherein said adhesive composition has a solids content of at least 95 percent, based on the total weight of the composition.

### Claim 2 (depends on 1)

The adhesive composition of claim 1, wherein said polyester polyol has a glass transition temperature (Tg) of 0 to 100° C., a hydroxyl number of 5 to 200 mg KOH/g, an acid number of 0 to 10 mg KOH/g, and a number average molecular weight of 500 to 10,000 g/mole.

### Claim 3 (depends on 1)

The adhesive composition of claim 1, wherein said adhesive composition is a two-part adhesive composition.

### Claim 4 (depends on 1)

The adhesive composition of claim 1, wherein said adhesive composition is a one-part, moisture curable adhesive composition.

### Claim 5 (depends on 1)

The adhesive composition of claim 1, wherein said diol component of said polyester polyol comprise residues of at least one diol selected from the group consisting of 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,3-propanediol, 1,2-propanediol, ethylene glycol, diethylene glycol, pentanediol, dodecandiol, and 1,6-hexanediol.

### Claim 6 (depends on 1)

The adhesive composition of claim 1, wherein said polyester polyol comprises an acid component having residues of at least one dicarboxyl monomer selected from the group consisting of isophthalic acid or esters thereof, terephthalic acid or esters thereof, phthalic acid or esters thereof, phthalic anhydride, 1,4-cyclohexane-dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecanedioic acid, sebacic acid, azelaic acid, maleic acid or anhydride, fumaric acid, succinic anhydride, succinic acid, adipic acid, dimer acid, hydrogenated dimer acid, 2,6-naphthalenedicarboxylic acid, glutaric acid, and itaconic acid.

### Claim 7 (depends on 1)

The adhesive composition of claim 1, wherein said polyester polyol comprises residues of at least one diol selected from the group consisting of 1,4-cyclohexanedimethanol, 1,4-butanediol, 1,3-propanediol, diethylene glycol, and 1,6-hexanediol, pentanediol, dodecandiol, and combinations thereof.

### Claim 8 (depends on 1)

The adhesive composition of claim 1, wherein said diol component of said polyester polyol comprises residues of at least one diol selected from the group consisting of diethylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, and combinations thereof, and wherein said at least one diol is present in an amount of at least 3 mole percent, based on the total moles of said diol component and/or wherein said polyester polyol comprises an acid component having residues of at least one dicarboxyl monomer selected from the group consisting of 1,4-cyclohexanedicarboxylic acid, adipic acid, isophthalic acid, hexahydrophthalic anhydride, and combinations thereof.

### Claim 9 (depends on 1)

The adhesive composition of claim 1, wherein said polyester polyol has a Tg of from 10 to 100° C., a hydroxyl number of not more than 50 mg KOH/g, a number average molecular weight of 500 to 10,000, and a hydroxyl functionality of less than 2.1.

### Claim 10 (depends on 1)

The adhesive composition of claim 1, wherein said polyester polyol comprises an acid component having 5 to 100 mole percent of residues of a dicarboxyl monomer selected from the group consisting of 1,4-cyclohexanedicarboxylic acid, adipic acid, isophthalic acid, and hexahydrophthalic anhydride, based on the total moles of said acid component, and wherein said diol component further comprises 5 to 95 mole percent of residues of said at least one diol monomer is selected from the group consisting of 1,4-cyclohexanedimethanol, neopentyl glycol, and combinations thereof, based on the total moles of said diol component, wherein said polyester polyol has a hydroxyl number of 5 to 60 mg KOH/g and a glass transition temperature of from about 20 to about 70° C.

### Claim 11 (depends on 1)

The adhesive composition of claim 1, wherein said isocyanate is selected from the group consisting of 4,4′-MDI, and 2,4′-MDI, and combinations thereof.

### Claim 12

A hot melt adhesive composition, said adhesive composition comprising:
a polyurethane prepolymer comprising residues of (i) at least one polyester polyol comprising a diol component having residues of 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) and (ii) at least one isocyanate,
wherein at least one property of said adhesive selected from the group consisting of green strength, heat resistance, and hydrolytic stability is at least 5 percent higher than the same property exhibited by an identical adhesive composition formed with a polyurethane prepolymer having an identical composition as said polyurethane prepolymer, but having residues of a comparative polyester polyol instead of said polyester polyol, wherein said comparative polyester polyol has an acid component comprising 50 mole % terephthalic acid (TPA) and 50 mole % isophthalic acid (IPA) and a diol component comprising 52 mole % neopentyl glycol (NPG) and 48 mole % ethylene glycol with a hydroxyl number of 45 mg KOH/g, a glass transition temperature of 50° C., and a melt viscosity of 130° C. at 60 Pa·s, all other components being the same.

### Claim 13 (depends on 12)

The adhesive composition of claim 12, wherein said polyester polyol comprises an acid component having residues of at least one dicarboxyl monomer selected from the group consisting of isophthalic acid or esters thereof, terephthalic acid or esters thereof, phthalic acid or esters thereof, phthalic anhydride, 1,4-cyclohexane-dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecanedioic acid, sebacic acid, azelaic acid, maleic acid or anhydride, fumaric acid, succinic anhydride, succinic acid, adipic acid, dimer acid, hydrogenated dimer acid, 2,6-naphthalenedicarboxylic acid, glutaric acid, and itaconic acid, and combinations thereof and/or wherein said diol component further comprises residues of at least one diol selected from the group consisting of 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,3-propanediol, 1,2-propanediol, ethylene glycol, diethylene glycol, 1,6-hexanediol, pentanediol, dodecandiol, and combinations thereof.

### Claim 14 (depends on 12)

The adhesive composition of claim 12, wherein said diol component further comprises residues of at least one diol selected from the group consisting of diethylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, and combinations thereof, and wherein said at least one diol is present in an amount of at least 3 mole percent, based on the total moles of said diol component.

### Claim 15 (depends on 12)

The adhesive composition of claim 12, wherein said polyol has a Tg of 0 to 70° C., a hydroxyl number of 15 to 60 mg KOH/g, and a number average molecular weight of 2500 to 5500 Daltons.

### Claim 16 (depends on 15)

The adhesive composition of claim 15, wherein said polyester polyol has an acid component comprising 5 to 100 mole percent of residues of a dicarboxyl monomer selected from the group consisting of 1,4-cyclohexanedicarboxylic acid, adipic acid, isophthalic acid, and hexahydrophthalic anhydride, based on the total moles of said acid component, and wherein said diol component further comprises 5 to 95 mole percent of residues of said at least one diol monomer is selected from the group consisting of 1,4-cyclohexanedimethanol, neopentyl glycol, and combinations thereof, based on the total moles of said diol component, wherein said polyester polyol has a hydroxyl number of 5 to 60 mg KOH/g and a glass transition temperature of from about 20 to about 70° C. and wherein said isocyanate is selected from the group consisting of 4,4′-MDI, 2,4′-MDI, and combinations thereof.

### Claim 17

A method of using an adhesive composition, said method comprising:
(a) applying an adhesive composition to a first surface of a first substrate to form an adhesive layer, wherein said adhesive composition comprises a polyurethane prepolymer having residues of (i) a polyester polyol comprising residues of 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) and (ii) at least one isocyanate;
(b) contacting at least a portion of the adhesive layer with a second surface of a second substrate; and
(c) adhering said first substrate and said second substrate to one another via said adhesive layer thereby forming a layered article.

### Claim 18 (depends on 17)

The method of claim 17, wherein at least a portion of said applying includes heating said adhesive composition to form said adhesive layer, wherein at least a portion of said heating is carried out at a temperature of at least 50° C.

### Claim 19 (depends on 17)

The method of claim 17, wherein said first and second substrates comprise a material selected from the group consisting of metal, polymer, wood, fabric, leather, and combinations thereof.

### Claim 20 (depends on 17)

The method of claim 17, wherein said polyester polyol has an acid component comprising 5 to 100 mole percent of residues of a dicarboxyl monomer selected from the group consisting of 1,4-cyclohexanedicarboxylic acid, adipic acid, isophthalic acid, and hexahydrophthalic anhydride, based on the total moles of said acid component, and wherein said diol component further comprises 5 to 95 mole percent of residues of said at least one diol monomer is selected from the group consisting of 1,4-cyclohexanedimethanol, neopentyl glycol, and combinations thereof, based on the total moles of said diol component, wherein said polyester polyol has a hydroxyl number of 5 to 60 mg KOH/g and a glass transition temperature of from about 20 to about 70° C. and wherein said isocyanate is selected from the group consisting of 4,4′-MDI, 2,4′-MDI, and combinations thereof.