(12) INTERNATIONALAPPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date 25 February 2010 (25.02.2010) WO 2010/021920 Al

(51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C08L 67/00 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, (21) International Application Number: CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, PCT/US2009/053829 DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, 14 August 2009 (14.08.2009) KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, (25) Filing Language: English NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, (26) Publication Language: English SE, SG, SK, SL, SM, ST, SV, SY, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 61/090,283 20 August 2008 (20.08.2008) US (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant (for all designated States except US): RHEIN GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, CHEMIE CORPORATION [US/US]; 145 Parker ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, Court, Chardon, OH 44024 (US). TM), European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, (71) Applicant and ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, MC, MK, MT, NL, NO, PL, PT, RO, SE, SI, SK, SM, (72) Inventor: MCAFEE, Elwin, R. [US/US]; 185b Elton TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, Walker Road, Blythewood, SC 2901 6 (US). ML, MR, NE, SN, TD, TG). (74) Agents: KOHNCKE, Nicanor, A. et al; Lanxess Corpo Published: ration, 111 RIDC Park West Drive, Pittsburgh, PA 15275 (US). — with international search report (Art. 21(3))

(54) Title: POLYOL COMPOSITIONS (57) Abstract: The present invention provides polyester polyol compositions stabilized against hydrolysis and having a reduced acid number, namely, compositions comprising sterically hindered aromatic carbodiimides, the processes of making such compo- sitions, a process for stabilizing against hydrolysis and/or reducing the acid number of polyester polyol compositions, and to the above wherein the polyols are bio-based polyester polyols such as soybean or castor oil based polyols. POLYOL COMPOSITIONS

BACKGROUND OF THE INVENTION

The present invention relates generally to polyester polyol

compositions stabilized against hydrolysis and having a reduced acid number,

as well as compositions comprising sterically hindered aromatic carbodiimides

useful for acid number reduction of polyester polyols as well as for the

stabilization thereof against hydrolysis, to the processes of making such

compositions, and to the process for stabilizing against hydrolysis and/or

reducing the acid number of polyester polyol compositions, and to the above wherein the polyols are bio-based polyester polyols such as soybean or

castor oil based polyols.

Broadly, as is know to one skilled in the art, compositions

may be formed from the reaction of polyisocyanates and polyols (the -

N=C=O/ -OH reaction). Many types of polyol compounds may be used in the formation of and may be, generally, either polyester or

polyether polyols. Polyester based polyols may be used in the production of polyurethane foams useful to, among others, the construction, building, and automotive industries. Conventionally, polyester polyols are derived from petroleum

sources. However, environmental concerns have made the use of

natural renewable sources for polyols of greater importance.

Presently, bio-based polyols can be derived from vegetable oils and,

subsequently, used in the production of polyurethanes. Two important

bio-based sources are soybean oil and castor oil. Significant

ecological savings may be achieved via the use of bio-based polyols

as compared to the use of petroleum based polyols. Bio-based polyols

have found use in, inter alia, the manufacture and production of

polyurethane foams, including rigid and flexible polyurethane foams.

Various methods for the production of bio-based polyols have been

heretofore performed. By way of example reference is made to U.S. Patent

Numbers 6476,244, 6,759,542, 6,686,435, 6,258,869, and 5,482,980, and

U.S. Patent Application Pub. Number 2007/0265459. Generally, for the

production of polyester polyols condensation polymerization is employed,

wherein carboxyl and hydroxyl groups are reacted. Since most renewable feed stocks lack hydroxyl groups, such as soybean oil, the introduction of

hydroxyl groups necessitates a pre-polymerization step to first introduce the

hydroxyl group. For example, the introduction may be carried out by treatment with peroxy acids to form epoxides followed by reaction with

nucleophiles thereby forming the hydroxyl groups. Reference is made for example to U.S. Patent Application Publication Number 2007/0265459

regarding the production of soy-based polyols. One problem associated with bio-based polyol compositions, such as soy based polyols, is the high acid number of such compositions as compared with more conventional petroleum based polyols. The acid number generally being the measure of the amount of carboxylic acid groups in the chemical compound, such as a fatty acid. Furthermore, hydrolytic degradation or breakdown of polyester containing products, for example those produced by polycondensation reactions and/or containing products of polycondensation reactions, such as polyester polyols by water and acids may occur and reduce the useful life span of such materials. As is generally understood the hydrolytic degradation of a polyester containing material is essential the reverse of a condensation reaction and involves the cleavage of an ester group by water and acid to form a carboxylic acid and an alcohol as represented by the following reaction:

H+ RrCOO-R 2 + H2O -» Rr COOH + R2-OH

Once such a process begins it continues and even accelerates autocatalytically resulting in a substantial break down in the polyester polyol.

As should be appreciated, hydrolysis of the polyester substantially impairs the usability and life span of the polyester containing polyol composition. The acid number reduction and stabilization against hydrolysis of polyester containing polyols is therefore of great importance.

Heretofore various compositions and methods have been attempted to reduce hydrolytic cleavage of polyester containing materials. By way of reference, employment of (poly)carbodiimide compounds as hydrolysis stabilizers are discussed in U.S. Patent Numbers: 3,193,523; 5,434,305; 5,130,360; 6,498,225; 5,210,170; and 6,602,926 and U.S. Application Pub.

Number 2007/0066727.

Carbodiimide hydrolysis stabilization results, generally, from its

reactions with water to form urea and with free carboxyl groups to form acyl

ureas as shown by the following reactions, respectively:

R1-N=C=N-R2 + H2O -» R1-NH-C=O-NH-R2

R1-N=C=N-R2 + R3-COOH - R1-NH-C=O-NR2-C=O-R3

However, various problems exist with the use of carbodiimides as

stabilization additives that reduces the overall stabilization effectiveness. For

example, reactions between carbodiimides themselves are known to occur,

similarly, side reactions with during the production of

polyurethanes may occur, and there is a tendency for carbodiimides to

migrate out of polycondensation products. Furthermore, improper processing

may impact industrial hygiene.

Other compounds known broadly as moisture scavengers capable of

reacting with water in polyurethane systems to thereby remove the same

have been used in polyurethane coating systems. For example, U.S. Patent

Number 5,264,148 discloses the use of oxazolidines as water scavengers in

moisture-curing polyurethane coating systems, wherein these oxazolidines

react with water to form secondary amino alcohols and ketones.

Catalytic compounds have also been used for the of polyurethane reactions, including such as 1-methylimidazole. Such catalysts have been used especially in the production of polyurethane

rigid foams.

In view of the above, it should be appreciated that the need for a bio- based polyester polyol composition having a reduced acid number and stabilized against hydrolysis remains.

BRIEF SUMMARY OF THE INVENTION

Surprisingly, it has now been found that the novel formulations and compositions of the present invention reduce the acid number of a bio-based polyester polyol composition and provide hydrolytic stabilization against hydrolysis, thereby increasing the usability and life span of the bio-based polyester polyol compositions according to the invention. Furthermore it has been found that such formulation may provide synergistic effect.

There is broadly contemplated, in accordance with at least one presently preferred embodiment of the invention, a bio-based polyol composition having a reduced acid number and being effectively stabilized against hydrolysis comprising: a) a bio-based polyol having ester linkages, b) a carbodiimide, and c) at least one of an oxazolidine and an imidazole.

Furthermore, there is contemplated the composition above, wherein the bio-based polyol is a soy-based polyol and/or a castor oil based polyol.

Moreover, in accordance with an embodiment of the invention the carbodiimide may be a sterically hindered carbodiimide, including 2,2',6,6'- tetraisopropyldiphenyl carbodiimide. In addition, there is contemplated the composition above wherein the oxazolidine is 3-ethyi-2-methyl-2-(3-

methy1butyl)-1 -3-oxazolidine and/or wherein the imidazole is 1-

methyiimidazole.

In another embodiment of the present invention there is a process for

the reduction of the acid number of a bio-based polyester polyol, comprising

the steps of: providing a bio-based polyol having ester linkages and mixing

the bio-based polyol with a carbodiimide and at least one of an oxazolidine

and an imidazole.

In a further embodiment of the present invention there is contemplated

a polyurethane formed by the reaction of a bio-based polyester containing

polyol and an (the -N=C=O / -OH reaction), wherein said bio-

based polyester polyol has been treated with a carbodiimide and at least one

of an oxazolidine and an imidazole to thereby reduce the acid number and/or

provide hydrolysis stabilization, whereby the bio-based polyester polyol has a

reduced acid number and is stabilized against hydrolytic cleavage of the ester

bonds.

In a further embodiment of the present invention there is contemplated

an article, such as a polyurethane foam, formed from a polyurethane formed

by the reaction of an isocyanate and a bio-based polyester polyol, said polyol

being treated by mixing with a carbodiimide and at least one of an oxazolidine and an imidazole to thereby reduce the acid number and/or provide hydrolysis stabilization

For a better understanding of the present invention, together with other and further features and advantages thereof, reference is made to the following description. The scope of the invention will be pointed out in the

appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In one embodiment of the invention, a carbodiimide and at least one of

an oxazolidine and an imidazole or mixtures thereof are added to a bio-based

polyester polyol composition. The bio-based polyester polyol is one having

an acid content as reflected by its acid number that is greater than the acid

number general found in petroleum based polyester polyols. In one preferred

embodiment, the polyester polyol is derived from a vegetable oil such as from

soybean oil. As used herein, acid number is understood to mean the number

of milligrams of potassium hydroxide required to neutralize the free fatty acids

contained in one ( 1 ) gram of substance.

The carbodiimide of a preferred embodiment is a sterically hindered

carbodiimide according to formula (I)

R1-N=C=N-R2 (I)

in which Ri and R2 independent of one another are optionally

substituted alkyl, cycloalkyl, or aryl groups. In one preferred embodiment, Ri

and R2 are substituted aryl groups. In a preferred embodiment, Ri and R2 are

each diisopropyl phenyl groups, thus forming 2,2',6,6'-tetraisopropyldiphenyl carbodiimide. The oxazolidines of the preferred embodiment correspond to formula

(U)

in which Ri is hydrogen or optionally substituted straight chain or branched alkyl, and R2 through R are, independently of one another, hydrogen or optionally substituted straight chain or branched alkyl.

In a preferred embodiment the oxazolidine is 3-ethyl-2-methyi-2-(3- methylbutyl)-1 -3-oxazolidine.

The imidazoles of the preferred embodiment correspond to formula (III)

(HI)

in which Ri is hydrogen or optionally substituted straight chain or branched alkyl. In a preferred embodiment the imidazole is 1- methylimidazole.

In order to reduce the acid level of the bio-based polyester containing polyol, the addition of the carbodiimide and the at least one of an oxazolidine and an imidazole or mixtures thereof to the bio-based polyol is performed with heating between 500C to 8 O0C for between 2 to 6 hours. It has been found that the addition of the carbodiimide and at least one of an oxazolidine and an imidazole or mixtures thereof may be performed at the end of the polyol

reaction while the polyol product is still under heat thereby increasing the ease and efficiency of the addition. However, it should also be understood to one skilled in the art that the addition could alternatively be preformed after the polyol reaction is completed per a separate process in which the polyol is heated separately from the polyol reaction.

The carbodiimide and at least one of an oxazolidine and an imidazole or mixture thereof may be added separately to the bio-based polyol or they may be together as part of a pre-mixture. It should be noted that carbodiimides are often gel-like solids at room temperature, while oxazolidine and imidazole are generally liquids, thus, the pre-mixture of the carbodiimide and at least one of an oxazolidine and an imidazole or mixture thereof is performed with heating to allow all the compounds to transition to a liquid phase. A phase separation may occur upon cooling of the pre-mixture.

The preferred carbodiimide is present in the mixture of carbodiimide and oxazolidine or imidazole or mixture of oxazolidine and imidazole from 1 to

99 weight percent, preferably between 5 and 80 wt%, more preferably between 10 and 50 wt %.

The amount of the carbodiimide and oxazolidine or imidazole or mixture thereof which may added to the polyol is between 0.1 and 10 wt %, preferably between 0.5 and 5 wt %.

While the present invention has been described with reference to specific details of particular embodiments above and particular examples below, it is not intended that such details be regarded as limitations upon the scope of the invention except insofar as and to the extent that they are

included in the accompanying claims, and it is to be understood that various other changes and modifications may be affected therein by one skilled in the art without departing from the scope or spirit of the invention.

As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. Examples:

Two blends were prepared comprising 2,2\6,6 >-tetraisopropyldipheny1 carbodiimide and 3-ethyl-2-methyl-2-(3-methylbutyi)-1 -3-oxazolidine, the carbodiimide being in the amount of 25 wt% and 50 wt%, Table 1 and Table 2

respectively. The blends were then each added to a soy-based polyester

polyol at various amounts and the acid number and color index measured.

As shown in Tables 1 and 2, the acid number of the soy-based polyester polyols were reduced and the color index increased.

Table 1;

2,2',6,6'-tetraisopropyldiphenyl carbodiimide and 3-ethyl-2-methyl-2-(3- methylbutyl)-l-3-oxazolidine (25 wt% Carbodiimide)

Table 2:

2,2',6,6'-tetraisopropyldiphenyl carbodiimide and 3-ethyl-2-methyl-2-(3- methylbutyl)-l-3-oxazolidine (50 wt% Carbodiimide)

CLAIMS

What is claimed is:

1. A bio-based polyol composition having ester linkages formed by mixing a polyester bio-based polyol with a carbodiimide and at least one of an oxazolidine and an imidazole.

2. The bio-based polyol composition according to Claim 1, wherein the polyester bio-based polyol is formed from soybean oil or castor oil.

3. The bio-based polyol composition according to Claim 1, wherein the carbodiimide is 2,2',6,6'-tetraisopropyldiphenyl carbodiimide.

4. The bio-based polyol composition according to Claim 1, wherein the oxazolidine is 3-ethyl-2-methyl-2-(3-methylbutyl)-1 -3-oxazolidine.

5. The bio-based polyol composition according to Claim 1, wherein the imidazole is 1-methylimidazole.

6. A process for reducing the acid number of a bio-based polyol having polyester linkages, comprising: providing a bio-based polyester polyol and mixing the bio-based polyol with a carbodiimide and at least one of an oxazolidine and an imidazole.

7 . The process according to Claim 6, further comprising heating the polyol during the mixing step to between 50 and 80 degrees Celsius for between 2-6 hours.

8. A bio-based polyol acid inhibitor comprising a mixture of a carbodiimide and at least one of an oxazolidine and an imidazole. A. CLASSIRCATION OF SUBJECT MATTER INV . C08L67/00

According to International Patent Classitication (IPC) or to both national classification and IPC

B. RELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) C08L

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practical, search terms used) EPO-Internal , WPI Data

c. DOCUMENTS CONSIDERED TO BE RELEVANT

Category Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No

US 2007/166344 A l (QU XIN [US] ET AL) 1-8 19 July 2007 (2007-07-19) claims 1-58; examples 1-24

US 2006/036007 Al (HSIEH BING [US] ET AL) 1-8 16 February 2006 (2006-02-16) claims 1-71; examples 1-25

US 2007/129452 A l (CLATTY JAN L [US] ET 1-8 AL) 7 June 2007 (2007-06-07) claims 1-37; examples 1-6

US 2006/258762 A l (DOBRANSKY MICHAEL A 1-8 [US] ET AL) 16 November 2006 (2006-11-16) claims 1-24; examples 1,2

-/--

Further documents are listed in the continuation of Box C See patent family annex

* Special categories of ctted documents ' later document published after the international filing date or pπoπty date and not in conflict with the application but 'A' document defining the general state of the art which is not cited to understand the principle or theory underlying the considered to be of particular relevance invention 'E' earlier document but published on or after the international 'X' document of particular relevance, the claimed invention filing dale cannot be considered novel or cannot be considered to "L" document which may throw doubts on pπonly claιm(s) or involve an inventive step when the document is taken alone which is cited to establish the publication date of another • Y" document of particular relevance, the claimed invention citation or other special reason (as specified) cannot be considered Io involve an inventive step when the 'O" document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu olher means ments, such combination being obvious to a person skilled 'P' document published prior to the international filing date but in the art later than the priority dale claimed "&" document member of the same patent family

Dale of the actual completion of the international search Date of mailing of the international search report

9 October 2009 21/10/2009

Name and mailing address of the ISA/ Authorized officer European Patent Office, P B 5818 Patentlaan 2 NL - 2280 HV Rl|Swi|k TeI (+31-70) 340-2040, Gl omm, Fax (+31-70) 340-3016 Bernhard

Form PCT/ISA/210 (second sheet) (April 2005) C(Contlnuatlon). DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

DE 10 2005 011572 A l (BASF AG [DE]) 1-8 14 September 2006 (2006-09-14) claims 1-13; examples 1-5

US 2005/282017 A l (JIBRAIL JOSEPH [US]) 1-8 22 December 2005 (2005-12-22) claims 1-52; examples A-O

EP 1 162 222 A (SMITHERS OASIS CO [US]) 1-8 12 December 2001 (2001-12-12) claims 1-11; examples 1-8

WO 00/29459 A (HUNTSMAN ICI CHEM LLC [US]; 1-8 CHEOLAS EVAN H [US]; ELING BEREND [BE]; JO) 25 May 2000 (2000-05-25) claims 1-47; examples 1-36

WO 99/51430 A (SEYDEL RESEARCH INC [US]; 1-8 SALSMAN ROBERT KEITH [US]; WANG TIMOTHY SHOU) 14 October 1999 (1999-10-14) claims 1-40; examples 1-12

DATABASE WPI Week 199332 1-8 Thomson Scientific, London, GB; AN 1993-252794 XP002549487 & JP 05 170862 A (TEIJIN LTD) 9 July 1993 (1993-07-09) abstract

Form PCT/ISA/210 (continuation ol second sheet) (April 2005) Patent document Publication Patent family Publication cited in search report date member(s) date

US 2007166344 Al 19-07-2007 AU 2007207708 Al 26-07-2007 CA 2636975 Al 26-07-2007 CN 101374607 A 25-02-2009 EP 1984121 A2 29-10-2008 J P 2009523890 T 25-06-2009 K R 20080110578 A 18-12-2008 WO 2007084452 A2 26-07-2007

US 2006036007 Al 16-02-2006 US 2009011124 Al 08-01-2009 US 2006247341 Al 02-11-2006

US 2007129452 Al 07-06-2007 AR 058846 Al 27-02-2008 CA 2632128 Al 05-07-2007 CN 101316875 A 03-12-2008 J P 2009517533 T 30-04-2009 KR 20080077964 A 26-08-2008 WO 2007075251 A2 05-07-2007

US 2006258762 Al 16-11-2006 CA 2608008 Al 23-11-2006 CN 101175785 A 07-05-2008 EP 1883664 Al 06-02-2008 J P 2008540767 T 20-11-2008 K R 20080015404 A 19-02-2008 WO 2006124364 Al 23-11-2006

DE 102005011572 Al 14-09-2006 NONE

US 2005282017 Al 22-12-2005 CA 2507201 Al 22-12-2005 MX PA05006698 A 11-01-2006

EP 1162222 A 12-12-2001 NONE

WO 0029459 A 25-05-2000 AU 760158 B2 08-05-2003 AU 1721200 A 05-06-2000 BR 9915380 A 31-07-2001 CA 2359560 Al 25-05-2000 CN 1326476 A 12-12-2001 EP 1131369 Al 12-09-2001 J P 2002530445 T 17-09-2002 T W 482780 B 11-04-2002

WO 9951430 A 14-10-1999 AU 743591 B2 31-01-2002 AU 3219399 A 25-10-1999 AU 747282 B2 09-05-2002 AU 3219499 A 25-10-1999 CA 2327294 Al 14-10-1999 CN 1298347 A 06-06-2001 EP 1084030 Al 21-03-2001 WO 9951431 Al 14-10-1999

J P 5170862 A 09-07-1993 NONE

Form PCT/ISA/210 (patent family annex) (April 2005)