Method for preparing polyols and products obtained

Patent metadata

Field	Value
Publication number	US-9556403-B2
Application number	US-201013395027-A
Country	US
Kind code	B2
Filing date	Sep 10, 2010
Priority date	Sep 11, 2009
Publication date	Jan 31, 2017
Grant date	Jan 31, 2017

Abstract

The present invention relates to a method for preparing polyols of formula (I″)

R′ 1 being H or an alkyl group, R″ being especially an alkyl group, A 1 , being an alkylene radical and R 3 , are being especially a group -A 2 -O—Y′, A 2 being an alkylene radical and Y′ being especially H,
said method especially comprising a step of epoxidation of a compound of formula

R″ 1 being H or an alkyl group, A t being defined as above in formula (I″) and
R 4 being especially a group -A 2 -O—Y 1 ′, A 2 being defined as above in formula (I″) and Y′ 1 being especially H,
in order to obtain a compound of formula

A 1 being defined as above, R′″ 1 being H or an alkyl group and R 5 being especially a group of formula -A 2 -O—Y 2 ′, A 2 being as defined above in formula (I″) and Y′ 2 being especially H.

First claim

What is claimed is:

1. A method for preparing a polyol fitting the general formula (I):

wherein:
R 1 represents H or a linear or branched alkyl group, comprising from 2 to 14 carbon atoms,
R′ represents a linear or branched alkyl group, comprising from 1 to 18 carbon atoms,
A 1 represents a linear or branched divalent alkylene radical, comprising from 2 to 14 carbon atoms,
A 2 represents a linear divalent alkylene radical, comprising from 1 to 10 carbon atoms, if necessary comprising one or more substituents,
Y represents a hydrogen atom or a group of formula (A)

A 1 , R′ and R 1 are as defined above,
said method comprising the following steps:
a) a step for transesterification of a compound of the following formula (II):

R 2 represents a branched or linear alkyl group comprising from 1 to 10 carbon atoms, and
R 1- and A 1 being as defined above,
with a diol of the following formula (III):
HO-A 2 -OH  (III)

in order to obtain a compound of the following formula (IV):

A 1 , A 2 and R 1 being as defined above in formula (I),
Y 1 representing a hydrogen atom or a group of formula (A 1 )

A 1 and R 1 being as defined above,
b) a step for epoxidation of the compound of the aforementioned formula (IV) in order to obtain a compound of the following formula (V):

A 1 , A 2 and R 1 being as defined above,
Y 2 representing a hydrogen atom or a group of formula (A 2 )

A 1 and R 1 being as defined above,
c) a step for opening the epoxide ring with an alcohol of formula R′OH, R′ being as defined above, in order to obtain a compound of formula (I) as defined above, and
d) a step for recovering the compound of formula (I) as defined above.

2. The method for preparing a diol according to claim 1 , characterized in that the diol fits the following formula (I-1):

A 1 , A 2 , R 1 and R′ being as defined in claim 1 ,
or the following formula (I-2):

A 1 , A 2 , R 1 and R′ being as defined in claim 1 .

3. The method for preparing a polyol according to any of claim 1 , wherein step a) is carried out in the presence of a catalyst selected from the group consisting of magnesium oxide, zinc acetate and sodium methanolate.

4. The method for preparing a polyol according to claim 3 , wherein step a) is carried out a temperature comprised between from 150 to 200° C. under nitrogen flow.

5. The method according to claim 3 , wherein step a) is carried out without solvent.

6. The method for preparing a polyol according to claim 1 , wherein step b) is carried out in the presence of a peracid.

7. The method for preparing a polyol according to claim 6 , wherein step b) is carried out in the presence of a peracid selected from the group consisting of metachloroperbenzoic acid (m-CPBA) and of magnesium monoperoxyphthalate hexahydrate peracid (MMPP).

8. The method for preparing a polyol according to claim 1 , wherein step c) is carried out in the presence of a catalyst selected from the group consisting of an acid catalyst of the proton ion exchange resin, of heterogeneous catalysts, of para-toluenesulfonic acid (PTSA) and of methanesulfonic acid (MSA), at a temperature comprised between from 20° C. to 120° C.

9. The method for preparing a polyol according to claim 8 , wherein the temperature is 70° C.

10. A compound fitting the following general formula (I):

wherein:
R 1 represents a linear or branched alkyl group comprising from 2 to 14 carbon atoms,
R′ represents a linear or branched alkyl group, comprising from 1 to 18 carbon atoms,
A 1 represents a linear or branched divalent alkylene radical, comprising from 2 to 14 carbon atoms,
A 2 represents a linear divalent alkylene radical, comprising from 1 to 10 carbon atoms, if necessary comprising one or more substituents, and
Y represents a hydrogen atom or a group of formula (A)

A 1 , R′ and R 1 being as defined above.

11. Intermediate compounds chosen from the group consisting of: —compound (3) having the following formula:

wherein Y 2 represents A 2 , A 2 being as defined in claim 1 ; and
compounds having the following formula:

A 1 representing a C 7 H 14 radical, R 1 representing an alkyl group comprising 9 carbon atoms, and A 2 represents a radical selected from the following radicals: C 3 H 6 , C 4 H 8 , C 5 H 10 , C 6 H 12 , H 2 C—(CH 2 OCH 2 ) 6 —CH 2 , H 2 C—(CH 2 OCH 2 ) 13 —CH 2 , H 2 C—(CH 2 OCH 2 ) 45 —CH 2 or H 2 C—C 6 H 4 —CH 2 .

12. Polymers as obtained by polymerization of a compound as defined in claim 10 and of a (poly)isocyanate.

Assignees

• Cramail Henri
• Boyer Aurélie
• Cloutet Eric
• Bakhiyi Rachida
• Alfos Carine
• Centre Nat Rech Scient

Inventors

• Cramail Henri
• Boyer Aurélie
• Cloutet Eric
• Bakhiyi Rachida
• Alfos Carine

Classifications

• C07C67/31

  by introduction of functional groups containing oxygen only in singly bound form · CPC title

• C07C67/03

  by reacting an ester group with a hydroxy group · CPC title

• C07D303/44

  Esterified with oxirane-containing hydroxy compounds · CPC title

• C07D303/42

  Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats · CPC title

• C07C69/732

  of unsaturated hydroxy carboxylic acids · CPC title