WO2013142534A2

WO2013142534A2 - Biobased plasticizer and surface covering employing same

Info

Publication number: WO2013142534A2
Application number: PCT/US2013/033027
Authority: WO
Inventors: Mary Kate DAVIES; Dong Tian
Original assignee: Armstrong World Industries, Inc.
Priority date: 2012-03-19
Filing date: 2013-03-19
Publication date: 2013-09-26
Also published as: CA2866627A1; AU2013235229B2; CA2866627C; CN104284931A; US8609884B2; US9080033B2; KR20170005185A; US20140102335A1; JP2015514143A; EP2828328A2; KR20150000886A; JP2017048396A; WO2013142534A3; EP2828328B1; US20130239852A1; CN104284931B; AU2013235229A1

Abstract

A biobased plasticizer and a surface covering are disclosed. The biobased plasticizer includes an ester formed as a reaction product of a furan derivative selected from the group consisting of furoic acid, furfural and furfuryl alcohol reacted with a carboxylic acid or an alcohol, or includes an ester formed as a reaction product of a biobased aromatic compound and a biobased aliphatic compound. The surface covering is plasticized with a composition comprising an ester formed as a reaction product of a functionalized aromatic heterocyclic compound reacted with a carboxylic acid or an alcohol.

Description

BIO ASED PLASTICIZE AND SURFACE COVERING EMPLOYING SAME

CROSS-REFERNCE TO RELATED PATENT APPLICATIONS

I^'OOOl] The present application claims priority to United States Non-Provisional Patent Application Serial No. 13/423,358, filed March 19, 2012, the entirety of which is hereby incorporated by reference.

FIELD

[0002] The present invention relates to plasticizers and surface coverings. More particularly, the present inventio relates to biobased plasticizers and surface coverings plasticized with biobased plasticizers.

BACKGROUND

[1)003] Ma y plastic materials, including polyvinylchloride (PVC), have a wide variety of uses, inc luding as surface coverings. For many applications, plastic materials can be made softer and more flexible through the use of plasticizers. in particular, phthalates have long been used as plasticizers in PVC and other plastics.

[000 1 Phthalates, such as di-(»2-ethylhexyi)phthaiate and butyl benzyl phihalaie have come under increased scrutiny for a variety of reasons, including their reliance on petroleum- based feedstocks fo production,

[0005] Some plasticizers based on non-petroleum feed stocks are known, including those based on vegetable oils, including soy, castor oil, and acetyl tribiity I citrate. Other non- pefro!eum plasiicizers include those derived from natural sugars, such as sorbitol and mannitol and those that are based on diesters of linear aliphatic hydrocarbons.

[0006] Generally, availability of non-phthaJate and non-petroleum based plasticizers would permit expanded and/or new utilities and performance in known and new applications. [0007 J It would be desirable to increase the available types of non-petroleum plasticizers and particularly to develop new non-petroleum based plasticizers, including some that are useful in floor tiles and other surface coverings.

[ΘΘ08] A biobased piasticizer and a surface covering plasticized by a biobased piasticizer that do not suffer from one or more of the above drawbacks would be desirable in the art.

BRIEF SUMMARY OF THE INVENTION

[Ό009] According to an embodiment, a biobased piasticizer includes an ester formed as a reaction product of a furan derivative selected from the group consisting of firroic acid, furfural and furfuryl alcohol reacted with a carboxylic acid or an alcohol

[§010] According to another embodiment, a biobased piasticizer includes an ester formed as a reaction product of a biobased aromatic compound and a biobased aliphatic compound, the biobased aromatic compound and the biobased aliphatic compound each being derived from a renewable resource.

[0011 J According to another embodiment, a surface covering is plasticized with a composition comprising an ester formed as a reaction product of a funciionai ized aromatic heterocyclic compound reacted with a carboxylic acid or an alcohol .

10012 J Other features and advantages of the present invention will be apparent from the following more detailed description of exemplary embodiments, which, illustrate, by way of example, the principles of the invention .

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMEN TS

[00131 Ϊ» accordance with exemplary embodiments, biobased plasticizers and surface coverings plasticized by biobased plasticizers are disclosed. Embodiments of the biobased j plasticizers and/or s urface coverings permit use of a non-petroleum based plasticizer in surface coverings and other applications, permit plasticizers and/or surface coverings to be manufactured partially or entirely from renewable resources, permit plasticizers to be used in place of phthalates and/or and other plasticizers under increased scrutiny by consumers,, permit acceptable performance of plasticizers, or combinations thereof.

|0 14| As used herein, the term "biobased" refers to being having at least one material derived from a non-petroleum source. Organic non-petroleum sources include, but are not limited to, plant oils extracted from plant seeds, such as castor oil, linseed oil, soy oil, tall oil (pine oil), lung oil, vernonia oil, lesquerel!a oil (bladderpod oil), cashew shell oil, or other plant oils rich in unsaturated fatty acids, corn, corn sugar, sugar cane, vegetable oil, oats, cellulose, starch, sugar, sugar alcohols, such as xylitol, sorbitol, maltitol, sucrose, glycol, glycerol, erythiitoL arahiiol, rebitol, mannitol, isomait laetitol, fructose, or polysaccharides or

monosaccharides originated from cel lulose, starches, sugars, or combinations thereof inorganic non-petroleum sources include, but are not limited to, ground shells from animals, such as sea shells, clams, coral, or combinations thereof. A composition or product is identifiable as being biobased by having a carbon signature, such as a radioactive CI4 or C1.3 signature, indicating that all or a portion of the carbon is from a non-petroleum source (for example, greater than about 5%, greater than about 25%, greater than about 50%, greater than about 90%, at about .100%. or any suitable combination, subcombination, range, or subrange therein), whethe organic, inorganic, or both, in contrast to a signature indicating the presence of carbon from a petroleum source, such as oil or coal. In some embodiments including .material from such non- petroleum sources, one or more of the above non-petroleum sources are excluded from forming the biobased product of component. In some embodiments, biobased components are also recycled, for example, having material recovered as post-consumer or post-industrial waste utilized in the production of new products, such as, wood- or plants, pecan shells, wood flour, saw dust, walnut shells, rice hulls, cor cob grit, or combinatio s thereof. In other embodiments, biobased components are recycled by including recycled .materials that are not biobased, such as, limestone, quartz, ceramic powders, glass, fly ash, concrete powder, sand, and combinations thereof, so long as additional biobased components are included.

fO015J Biobased plasttcizers in accordance with exemplary embodiments comprise an ester formed as a reaction product of a fimetionalized heterocyclic compound derived from a renewable resource and a carboxyKc acid or an alcohol to form an ester. Such compositions are useful for p!asticizing surface coverings, including flooring tiles and sheets, as well as other vinyl materials.

10016^'} in some embodiments, the fimetionalized heterocyclic compound i a furan derivative, which can be derived from components of naturally occurring materials, thus being a renewable resource and a source of biobased carbon.

|0017| Suitable furan derivatives for use with exemplary embodiments include acids such as furoic acid or furandicarboxylic acid. A particularly suitable turoic acid includes 2 -furoic acid, while a particularly suitable furandicarboxylic acid includes 2,5-f andicarboxylic acid. Other suitable furandicarboxylic acids include, but are not limited to, 3 -furoic acid, 2,3- furandtcarboxylic acid, 2. 4-firrandicarboxylic acid, 3,4~furandicarbo yHc acid, 2,3,5- furantricarboxylic acid, and 2,3,4,5-fttrantetracarboxylic acid.

(00.18] in another embodiment, a biobased piasticizer uses a furan derivative in the form of an aldehyde, such as furfural, as the functional i zed heterocyclic compound. |0Θ19} in yet another embodiment, the furan derivati ve compound used i forrairig a biobased plasticizer is art alcohol such as fwfuryi alcohol.

|002O| Piasticizers in accordance with exemplary^•embodiments are typically esters and formed as the reaction product of the fan.ciionahzed heterocyclic compound with a carboxylic acid or an. alcohol , the selection of which, depends upon the nature of the compound being reacted. That is, alcohols are generally reacted with acids to form the ester, while aldehydes and acids may be reacted with alcohols. Any suitable alcohols or carboxylic acids may be used, although those having in the range of about 6 to about 18 carbon atoms in the main chain are typical. In embodiments in which alcohols are reacted with the functionalized heterocyclic compound to form piasticizers in accordance with exemplary embodiments, the alcohol may be polyols and in particular ma be diols in some cases.

|0O21 J It will further be appreciated that in some embodiments, the alcohol or

carboxylic acid to be reacted with the furan derivative or other functionalized heterocyclic compound may i tself be a biobased component. As a resul t, the formed ester for use as a plasticizer may be entirely or nearly entirely biobased. For example, biobased alcohols such as ! ,3-propanediol or 1 ,4-buianedioJ may be used as the alcohol reactant for use in combination with furan derivates that are acids such as furoic acid and furandicarboxylic acid. Similarly, renewable carboxylic acids, such as sebacic acid, succinic acid, adipic acid, and azelaic acid, may be employed as the acid reactant for use in combination with furan derivatives that are alcohols.

10022] Embodiments in which the functionalized heterocyclic compound is an aldehyde (such as furfural) may be converted to the ester product for use as a plasticizer directly by reacting the aldehyde with an alcohol in the presence of bromine or other catalyst to ^"form the ester. Additionally or alternatively, the aldehyde may be directly esterified using aluminum. trieihoxySate, with or without a catalyst Alternatively, a tw step process may be employed. n the first step, the furfural can be cata!ytica!ly converted to 2-foroic acid. Any suitable catalyst may be employed, including potassium . permanganate for example. The 2-furoic acid is further reacted with an alcohol in the presence of a catalyst, such as a strong acid, for example, to form the ester. The use of a two step process may be preferred over the use of a one step process in which bromine is the catalyst as a result of the bromine's toxicity.

f 0023] 2~fiirfiiryl alcohol may be converted to an ester in a one step reaciion with a suitable acid, such as sebacic acid, adipic acid, and azeiaic acid, for example. The reaction may be catalyzed using a strong acid.

f 0G24] In one embodiment, 2-furoic acid is reacted with a bis-diol in the presence of heat and a catalyst to yield an ester having the following: structure:

(0025] in another embodiment, the bis-diol is replaced by poiyois in the reaction. Exemplary poiyois include, but are not limited to, aliphatic polyether poiyois and aliphatic polyester poiyois, either of which, can include components derived, from renewable resources, such as biobased I,3~propanediol or i ,4-butauedi.oL sebacic acid, succinic acid, adipic acid, and azeiaic acid. [0026j In another embodiment,

is reacted with two organic alcohols (ROH and R'OH) to yield an ester having the following structure, where R and R' may or may not be the same aliphatic carbon change:

f002?j The presence of the functional groups at particular numerical positions of the far derivatives used as reactants can result in providing plasticizer compounds thai are structural analogs to those formed with non-renewable materials currently used in plasticizer formation having, for example, a benzoate or dibenzoate-type structure. For example,, two functionalities at the 2,5 position of furandicarboxyiic acid can be used to form a terephthalate analog when reacted with an alcohol as described above, as can readily be seen in the following comparison:

10 281 In a like manner, two adjacent functionalities from the furan ring at the 2,3 positions or the 3,4 positions of furandicarboxyiic acid can be used to form an orthophthalate analog when reacted with an alcohol as described above,

f^§029] Unlike a phthalate, however, furandicarboxyiic acid is derived from renewable resources, not from petroleum feedstock. It has the additional advantage of being more polar than phthalates and other similar compounds and as a result may provide better solvation as a plasticizer. In addition to increased solvation capability, the heteroatomic aromatic ring of a furan-based material, may exhibit a lower rate of migration from a plasticized article than the comparable phthaSate or benzoate. The polarity of the ring provides increased opportunity for intermolecular bonding between the resin and the plasticizer, thus decreasing the chance for migration away from the resin.

f 0030 j Similarly, an ester resulting from the reaction of furoic acid or furfural with an alcohol restsits in a compound that has a structure analogous to a benzoate, but also provides the benefit of being derived from a renewable resource and thus providing a biobased plasticizer:

10031] Although described primarily herein in terms of reactions using renewable heterocyclic compounds, other aroma tics may be used in place of such compounds, including lignin, porphyrins and amino acids. For example, a porphyrin may be reacted at a double bond with an oxidizing agent, such as Os04 or dilute KMn(>4, resulting in a diol product, which may then be reacted with a earboxylic acid to produce a diester, which may be used as a plasticizer. Additionally or alternatively, amino acids, which include a earboxylic acid group, may be reacted with an alcohol to form the ester, analogous to a benzoate.

[0032] The surface coverings plastieized by the plasticizer may be any suitable surface covering. For example, suitable surface coverings include, but are not limited to, vinyl compositio tile, luxury vinyl tile, other suitable tile products, cushion vinyl, sheet products, or combinations thereof

EXAMPLES

[0033] The invention is further described by way of the following examples, which are presented by way of illustration, not of limitation. EXAMPLE 1

f 0034] A biobased plasticizer was formed using 2-furoic acid, i 20 g of furoic acid (commercially obtained, from Pennakem) was reacted with 123,3 g of isooctyl alcohol, in 70mL of toluene and 1.2 g p-tol enesul fon i c acid. The reaetants were stirred under heat to dissolve t he acid, then heated to boiling during which 2-octyl furanoate (C14H2 O3) and water were formed as reaction products. Because of an azeotrope formed by the toluene solvent and the water byproduct, the reaction was cooled and dried over magnesium sulfate to remove water, then Jittered. The organic componenis were then distilled under vacuum to separate the furanoate product. A clear liquid was obtained and its identit as 2-octyl furanoate was confirmed by FTIR.

EXAMPLES 2-6 and Comparative Example 1

10035} The 2-octyl furanoate of Example .1 was then used as biobased plasticizer to formulate a floor covering composition and formed into tiles. Table 1 provides five formulations used in creating tiles using the plasticizer of Example 1 and a control formulation using a conventional phthaiate plasticizers as a comparative example. In each case, 1 kg batches were formed and the amounts in Table 1 reflect grams of each component.

TABLE 1

epoxkiized soy oil)

2-octyi fiiranoate 0 40.0 36.0 30.0 32.0 20.0

Di-propy^'lheptyl 8.0 0 0 0 0 0

phthalate

Diocfyl ierephtlialate o 0 0 10 0 0

Di-isononyl 0 0 0 0 8.0 20.0 eyclohexarioate

Limestone 823.7 831 ,7 831 .7 831 .7 831.7 831.7

(0036] The resulting compositions were processed into floor tiles and except for a strong odor in nearly every case, generally demonstrate acceptable results with respect to mill feed, roll tack, hot strength, blanket formation, moisture curl and light stability, as shown in Table 2, and that achieve the additional advantage of utilizing a biobased plasticizer.

TABLE 2

EXAMPLE 7 f 0037] A second biobased plasticizer was formed by reacting 286 g 1 ,3-propanediol isophthalic acid, 156 g phthalic anhydride, 151 g sebacic acid, and 24 g 2,5- furaadicarboxylic acid in the presence of 0,4 g dibutytin bis-lauryi mercaptide as catalyst (obtained as T-20 from Air Products of Al!eiito n, PA).

10038] The foregoing illustrates some of the possibilities for practicing the invention. Many other embodiments are possible within the scope and spirit of the invention. It is, therefore, intended that the foregoing description be regarded as illustrative rather than limiting, and that the scope of the invention is given by the appended claims together with their foil range of equivalents.

Claims

WHAT IS CLAIMED IS:

1. A biobased plasticizer comprising an ester formed as a reaction produc t of a furan derivative selected from the group consisting of furoic acid, furfural and furfhryt alcohol reacted with a carboxylic acid or an alcohol.

2. The biobased plasticizer of claim I , wherein the furan derivative is 2- furoic acid.

3. The biobased plasticizer of claim 1 , wherein the alcohol reacted with the furan derivative is a poIyoL

4. The biobased plasticizer of claim 3, wherein the alcohol reacted with the furan derivative is a dioL

5. The biobased plasticizer of claim 1 , wherein the polyester has the formula:

6. The biobased plastic izer of claim 1 , wherein the carboxylic acid or alcohol reacted, with the furan derivative is derived from a renewable resource.

7. The biobased plasticizer of claim 1 , wherein the carboxylic acid is sebacie acid.

8. The biobased plasticizer of claim I , wherein the alcohol reacted with the furan derivati ve is 1 ,3-propane diol or 1,4-butane dioL

9. The biobased plasticizer of claim 1 , wherein the alcohol reacted with the furan derivative has six to eighteen carbon atoms.

10. A. biobased plasticizer comprising an ester formed as a reaction product of a biobased aromatic compound and a biobased aliphatic compound, the biobased aromaiic compound and the biobased aliphatic compound each being derived from a renewable resource.

1 1 . The plasticizer of claim 10, wherein the biobased aromaiic compound is selected from the group consisting, of furoic acid, fnrandioar ox lic acid, fnraldehyde, furfural, and- furfuryl alcohol.

12. The plasticizer of claim 10, wherein the biobased aromatic compound is 2,5- furandicarboxylic acid.

13. The plasticizer of claim 50, wherein the biobased aromatic compound is selected from the group consisting of lignin, porphyrins, and amino acids.

14. The plasticizer of claim 10, wherein the biobased aliphatic compound is .1 ,3 -propane diol or 1 ,4-hutane diol.

15, The plasticizer of claim 10, wherein the biobased plasticizer is greater than 25% biobased.

16, The plasticizer of claim 10, wherein the biobased plasticizer is substantially 100% biobased.

17. The plasticizer of claim 10, further compri sing at least one nonrenewable component.

18. A surface covering plastieized with a composition comprising an. ester formed as a reaction product of a fimctionalized aromatic heterocyclic compound reacted with a carboxyiic acid or an alcohol,

19. The surface covering of claim I S, wherein the funetiooalized aromatic heterocyclic compound is a fimctionalized furan derivative.

20. The surface covering of claim 1 , wherein the functiooalized fiuan derivative is selected from the group consisting of furoic acid, furandi carboxyiic acid, furaldehyde, furfural and fm uryl alcohol.