# US 8,785,548 B2 · Styrenic (meth)acrylic oligomers

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- Number: US 8,785,548 B2
- Document ID: US8785548B2
- Status: Granted
- Kind: B2
- Application number: 13/250,162
- Filed: 2011-09-30
- Published: 2012-04-05
- Granted: 2014-07-22
- Earliest claimed: 2010-10-01
- Assignees: BASF SE
- Applicants: Timothy D. Klots; Rafael Galvan; Jon Debling
- Inventors: Timothy D. Klots; Rafael Galvan; Jon Debling
- Web page: https://patentgrep.com/patent/US8785548B2

## CPC

- C08F 220/325: {containing glycidyl radical, e.g. glycidyl (meth)acrylate}
- C08F 4/34: Per-compounds with one peroxy-radical
- C08F 8/04: Reduction, e.g. hydrogenation
- C08F 212/08: Styrene
- C08F 212/12: Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
- C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate}
- C09D 11/106: containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D 11/107: from unsaturated acids or derivatives thereof
- C09D 125/14: with unsaturated esters
- C09D 125/16: Homopolymers or copolymers of alkyl-substituted styrenes
- C09D 133/10: Homopolymers or copolymers of methacrylic acid esters
- C08F 220/1804: {C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate}
- C08F 220/1808: {C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate}
- C08F 220/281: {and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

Styrenic (meth)acrylic oligomers that are prepared at lower temperature than conventional solid grade oligomers, or are hydrogenated, contain fewer terminal vinylic unsaturations, when compared to such conventional styrenic (meth)acrylic oligomers prepared by the customary high temperature processes. Styrenic (meth)acrylic oligomers that contain fewer terminal vinylic unsaturations demonstrate improved thermal stability and may provide improved resistance to UV weathering compared to the conventional and non-hydrogenated styrenic (meth)acrylic oligomers.

## Claims

### Claim 1

A process comprising:
continuously charging into a reactor a mixture comprising:
about 20 wt % to about 80 wt % of a vinylic monomer, the vinylic monomer comprising a styrenic monomer, a (meth)acrylic monomer, or a mixture thereof;
about 0.25 wt % to about 5 wt % of a polymerization initiator; and
about 20 wt % to about 80 wt % of a reaction solvent;
maintaining the reactor at a temperature of from about 120° C. to about 165° C. to produce an oligomer from the vinylic monomer; and
isolating the oligomer;
wherein: the oligomer has an insubstantial amount of olefinic unsaturation and a residence time of the oligomer in the reactor is from about 5 minutes to about 60 minutes.

### Claim 2 (depends on 1)

The process of claim 1, wherein the oligomer is does not exhibit a significant IR absorption in the range of 1645 cm−1 to 1610 cm−1.

### Claim 3 (depends on 1)

The process of claim 1, wherein the oligomer does not exhibit a significant resonance in the range of 4.5 to 5.5 ppm in the 1H NMR, referenced to tetramethylsilane.

### Claim 4 (depends on 1)

The process of claim 1, wherein the vinylic monomer comprises a styrenic monomer and a (meth)acrylic monomer.

### Claim 5 (depends on 1)

The process of claim 1, wherein the vinylic monomer comprises a (meth)acrylic monomer.

### Claim 6 (depends on 1)

The process of claim 1, wherein the oligomer is a styrenic oligomer, a (meth)acrylic oligomer, a styrenic (meth)acrylic oligomer, or a mixture or co-polymer of any two or more thereof.

### Claim 7 (depends on 1)

The process of claim 1, wherein the polymerization initiator comprises an azo compound, a peroxide, or a mixture of any two or more thereof.

### Claim 8 (depends on 1)

The process of claim 1, wherein the polymerization initiator comprises 2,2′-azodi-(2,4-dimethylvaleronitrile); 2,2′-azobisisobutyronitrile (AIBN); 2,2′-azobis(2-methylbutyronitrile); 1,1′-azobis(cyclohexane-1-carbonitrile); tertiary butylperbenzoate; tert-amyl peroxy 2-ethylhexyl carbonate; 1,1-bis(tert-amylperoxy)cyclohexane, tert-amylperoxy-2-ethylhexanoate, tert-amylperoxyacetate, tert-butylperoxyacetate, tert-butylperoxybenzoate, 2,5-di-(tert-butylperoxy)-2,5-dimethylhexane, di-tert-amyl peroxide (DTAP); di-tert-butylperoxide (DTBP); lauryl peroxide; dilauryl peroxide, succinic acid peroxide; or benzoyl peroxide.

### Claim 9 (depends on 1)

The process of claim 1, wherein the reaction solvent comprises acetone, aromatic 100, aromatic 150, aromatic-200, ethyl-3-ethoxypropionate, methyl amyl ketone, methylethylketone, methyl-iso-butylketone, N-methylpyrrolidone, (propylene glycol monomethyl ether acetate, xylene, toluene, ethyl benzene, carbitol, cyclohexanol, dipropylene glycol (mono)methyl ether, n-butanol, n-hexanol, hexyl carbitol, iso-octanol, iso-propanol, methyl cyclohexane methanol, decyl alcohol, lauryl alcohol, myristal alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, or isoparaffins.

### Claim 10 (depends on 4)

The process of claim 4, wherein the (meth)acrylic monomer comprises ethyl acrylate, methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, acrylic acid, (meth)acrylic acid, hydroxy propyl (meth)acrylate, or hydroxy butyl(meth)acrylate.

### Claim 11 (depends on 4)

The process of claim 4, wherein the styrenic monomer comprises styrene or α-methylstyrene.

### Claim 12 (depends on 1)

The process of claim 1, wherein the styrenic monomer comprises styrene and the (meth)acrylic monomer comprises glycidyl (meth)acrylate.

### Claim 13 (depends on 4)

The process of claim 4, wherein the vinylic monomer comprises from about 40 to about 65 wt % of the styrenic monomer; and from about 35 to about 60 wt % (meth)acrylic monomer.

### Claim 14 (depends on 1)

The process of claim 1, wherein the residence time is from about 15 minutes to about 30 minutes.

### Claim 15 (depends on 1)

The process of claim 1, wherein the temperature is from about 120° C. to about 140° C.

### Claim 16 (depends on 1)

The process of claim 1, wherein the temperature is about 140° C.