Method for preparing (meth)acrylates of biobased alcohols and polymers thereof

Patent metadata

Field	Value
Publication number	US-2016009628-A1
Application number	US-201414769850-A
Country	US
Kind code	A1
Filing date	Mar 13, 2014
Priority date	Mar 15, 2013
Publication date	Jan 14, 2016
Grant date	—

Abstract

Polymers, particularly those used in pressure-sensitive adhesives, are prepared from a mixture of structural isomers of a secondary alkyl (meth)acrylate monomer. The mixture is made by dehydrating a biobased C 2 -C 22 alcohol with a first acid catalyst using a continuous process to form a mixture of olefins, and reacting (meth)acrylic acid with at least some of the mixture of olefins in the presence of a second acid catalyst. The adhesives are characterized by exhibiting an overall balance of adhesive and cohesive characteristics, and containing biobased material.

First claim

1 . A method of making a mixture of structural isomers of a secondary alkyl(meth)acrylate of Formula (I):

wherein:
R 1 and R 2 are each independently a C 1 to C 20 saturated linear alkyl group;
the sum of the number of carbons in R 1 and R 2 is 2 to 21; and
R 3 is H or CH 3 .

wherein the method comprises:
dehydrating a biobased C2-C22 alcohol with a first acid catalyst using a continuous process, thereby forming a mixture of olefins; and
reacting (meth)acrylic acid with at least some of the mixture of olefins in the presence of a second acid catalyst.

2 . The method of claim 1 wherein the first acid catalyst comprises a heterogeneous acid catalyst.

3 . The method of claim 1 wherein the first acid catalyst comprises a cation exchange resin.

4 . The method of claim 1 wherein the mixture of olefins comprises between 80% and 100% by weight biobased olefins, as determined using ASTM D6866-12.

5 . The method of claim 1 wherein the dehydrating occurs at a temperature of 150° C. to 190° C.

6 . The method of claim 1 wherein the C 2 -C 22 alcohol is derived from at least one plant oil.

7 . The method of claim 1 wherein the C 2 -C 22 alcohol comprises a C 8 alcohol, a C 10 alcohol, or a C 12 alcohol.

8 . The method of claim 1 any one of claims 1 wherein the dehydrating is performed in a continuous reactor at a constant weight hourly space velocity (WHSV) of 0.5 h −1 to 10 h −1 , wherein the WHSV is a ratio of mass flow of the C 2 -C 22 alcohol entering the system per hour to the mass of the first acid catalyst.

9 . The method of claim 1 wherein a combination of the mixture of olefins and water is produced at a rate of 0.5 g h −1 to 10 g h −1 per gram of the first acid catalyst.

10 - 15 . (canceled)

16 . A mixture of olefins made by a method comprising reacting a C 2 -C 22 primary alcohol with an acid catalyst at a temperature of 150° C. to 190° C.

17 . The mixture of olefins of claim 16 wherein the olefins comprise a single unsaturation and wherein the olefins are biobased, as determined using ASTM D6866-12.

18 . The mixture of olefins of claim 16 wherein the acid catalyst comprises a cation exchange resin.

19 . A method of making a mixture of olefins comprising reacting a secondary alcohol with an acid catalyst at a temperature of 100° C. to 190° C., wherein the secondary alcohol is a biobased alcohol, as determined using ASTM D6866-12.

20 . The method of claim 19 wherein the secondary alcohol is 2-octanol derived from castor oil.

21 . The method of claim 20 wherein the 2-octanol has a 14 C/C ratio of 1.0×10 −14 or higher.

22 . A method of making a mixture of olefins comprising reacting a biobased C 2 -C 22 primary alcohol with an acid catalyst at a temperature of 150° C. to 190° C., wherein the reaction is performed in a continuous reactor at a constant weight hourly space velocity (WHSV) of 0.5 h −1 to 10 h −1 , wherein the WHSV is a ratio of mass flow of the C 2 -C 22 primary alcohol entering the system per hour to the mass of the acid catalyst.

23 . The method of claim 22 wherein the acid catalyst comprises a cation exchange resin.

24 . The method of claim 22 wherein the mixture of olefins comprises between 80% and 100% by weight biobased olefins, as determined using ASTM D6866-12.

25 . The method of claim 22 wherein the primary alcohol is derived from at least one plant oil selected from the group consisting of almond oil, castor oil, coconut oil, soybean oil, rapeseed oil, cottonseed oil, sunflower seed oil, groundnut oil, palm oil, palm kernel oil, sesame oil, linseed oil, maize oil, peanut oil, olive oil, hemp oil, corn oil, mustard oil, flaxseed oil, apricot oil, argan oil, avocado oil, ben oil, cashew oil, grape seed oil, hazelnut oil, neem oil, pumpkin seed oil, rice bran oil, walnut oil, safflower oil, copra oil, and combinations thereof.

26 . The method of claim 22 wherein a combination of the mixture of olefins and water is produced at a rate of 0.5 g h −1 to 10 g h −1 per gram of the acid catalyst.

Assignees

• 3M Innovative Properties Co

Inventors

• Colby Joshua L
• Hutt Aaron E
• Spawn Terence D
• Clapper Jason D
• Clem Tabitha A

Classifications

• C07C2531/08

  Ion-exchange resins · CPC title

• C09J133/08

  Homopolymers or copolymers of acrylic acid esters · CPC title

• C07C2531/10

  sulfonated · CPC title

• C07C1/24

  by elimination of water · CPC title

• C07C67/04 Primary

  by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds · CPC title