WO2020232675A1

WO2020232675A1 - Amine compound with good hydrophilicity

Info

Publication number: WO2020232675A1
Application number: PCT/CN2019/088007
Authority: WO
Inventors: Wanchao Jiang; Renjie JI; Chunyan XIA; Yi Zhang
Original assignee: Huntsman Petrochemical Llc; Wu, Min
Priority date: 2019-05-22
Filing date: 2019-05-22
Publication date: 2020-11-26

Abstract

Amine compounds with good hydrophilicity and more specially amine compounds are useful in textile softeners application. A process for making an amine compound comprises reacting one or more tertiary polyetheramines, one or more polysiloxanes, and one or more acids in a solvent.

Description

AN AMINE COMPOUND WITH GOOD HYDROPHILICITY

FIELD OF THE INVENTION

This invention relates generally to amine compounds with good hydrophilicity and more specially to amine compounds useful in textile softeners application.

BACKGROUND INFORMATION

Methods of improving hydrophilicity and substantivity by introducing quaternary ammonium groups in siloxanes are already known in the art.

US4833225 discloses the use of di-tertiary amine compounds to prepare quaternary ammonium, but the hydrophilicity of these compounds is not ideal.

US8076442 discloses the use of another di-tertiary amine (

ED2003 polyetheramine) to prepare polyammonium polysiloxane copolymers. However, these compounds do not have good hydrophilicity.

US7897716 also discloses the use of

ED2003 polyetheramine to prepare polyammonium polysiloxane copolymers. However, the amine needs to be used together with another di-tertiary amine to enhance hydrophilicity.

US4891166 discloses the use of mono-tertiary amines to prepare diquaternary polysiloxanes. But it does not disclose the use of polyetheramine.

SUMMARY OF THE INVENTION

However, known solutions are not able to provide an amine compound which can significantly enhance the hydrophilicity.

It has now been surprisingly found that the compounds and processes of the present disclosure address the above problem. Advantage of the present disclosure is enhanced hydrophilicity.

The present disclosure is concerned with compounds with enhanced hydrophilicity and processes for preparing these compounds. In one embodiment, the disclosure provides an amine compound of formula (I) :

wherein

each R is independently selected from an unsubstituted or substituted alkyl, alkenyl, aryl, alkylaryl, or alkoxy group;

each R' is independently selected from a hydrogen, a methyl group or an ethyl group;

each R" is independently selected from a hydrogen, an hydroxy group, a methyl group or an ethyl group;

a is in a range of from 0 to 450, more preferred from 13 to 300;

each n is in a range of from 0 to 100, more preferred from 0 to 25;

the sum of p and q is in a range of from 0 to150, more preferred from 10 to 70;

each r is 0 or 1;

when r is 0, R" is a methyl group or ethyl group;

when r is 1, R" is a hydrogen or hydroxyl; and

X is an anion having a charge of -2 or two anions each having a charge of -1.

In another embodiment, the present disclosure provides a process for making an amine compound comprising reacting one or more tertiary polyetheramines, one or more polysiloxanes, and one or more acids in a solvent, wherein the one or more tertiary polyetheramines have the formula (II) :

wherein

R is independently selected from an unsubstituted or substituted alkyl, alkenyl, aryl, alkylaryl, or alkoxy group;

R' is independently selected from a hydrogen, a methyl group or an ethyl group;

R" is independently selected from a hydrogen, an hydroxy group, a methyl group or an ethyl group;

the sum of p and q is in a range of from 0 to150, more preferred from 10 to 70;

r is 0 or 1;

when r is 0, R" is a methyl group or ethyl group;

when r is 1, R" is a hydrogen or hydroxyl;

and the one or more polysiloxanes have the formula:

wherein

a is in a range of from 0 to 400, more preferred from 13 to 300;

each n is in a range of from 0 to 100, more preferred from 0 to 25.

In still another embodiment, the present disclosure provides a method of using the amine compound to form a fabric softener or ironing aid, a hair or skin cosmetic system or an aqueous emulsion.

In yet another embodiment, the present disclosure provides a fabric softener, a hair or skin cosmetic system, and/or an aqueous emulsion comprising the amine compound of the present disclosure.

DETAILED DESCRIPTION

If appearing herein, the term "comprising" and derivatives thereof are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is disclosed herein. In order to avoid any doubt, all compositions claimed herein through use of the term "comprising" may include any additional additive, adjuvant, or compound, unless stated to the contrary. In contrast, the term, "consisting essentially of" if appearing herein, excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability and the term "consisting of" , if used, excludes any component, step or procedure not specifically delineated or listed. The term "or" , unless stated otherwise, refers to the listed members individually as well as in any combination.

The articles "a" and "an" are used herein to refer to one or to more than one (i.e. to at least one) of the grammatical object of the article. By way of example, "a resin" means one resin or more than one resin.

The phrases "in one embodiment, " "according to one embodiment, " and the like generally mean the particular feature, structure, or characteristic following the phrase is included in at least one embodiment of the present invention, and may be included in more than one embodiment of the present invention. Importantly, such phrases do not necessarily refer to the same embodiment. If the specification states a component or feature "may" , "can" , "could" , or "might" be included or have a characteristic, that particular component or feature is not required to be included or have the characteristic.

The present disclosure generally provides an amine compound of formula (I) :

In formula (I) , each R is independently selected from an unsubstituted or substituted alkyl, alkenyl, aryl, alkylaryl, or alkoxy group. In embodiments of the disclosure, R may be a methyl group, an ethyl group or a propyl group. In embodiments of the disclosure, R may be a C ₄-C ₁₂ alkyl group.

Each R' in formula (I) may be independently selected from a hydrogen, a methyl group or an ethyl group. In embodiments of the disclosure, R' is a methyl group. In embodiments of the present disclosure, R' is a hydrogen.

Each R" may be independently selected from a hydrogen, an hydroxy group, a methyl group or an ethyl group. In embodiments of the present disclosure R" is a methyl group. In embodiments R" is a hydroxyl group.

In formula (I) , a is in a range of from 0 to 450, more preferred from 13 to 300. According to one embodiment, a is in a range of from 70 to 300. In embodiments of the present disclosure, a may be about 78, 132, 267 and/or 400.

Each n may be in the range of from 0 to 100, more preferred from 0 to 25. In an embodiment of the present disclosure, n is 0.

In formula (I) , the sum of p and q is in a range of from 0 to150, more preferred from 10 to 70. According to still another embodiment, the sum of p and q is in a range of from 20 to 50. In embodiments of the present disclosure, the sum of p and q is 10, 22, 43, 45, and/or 66.

In formula (I) , each r may be 0 or 1. In embodiments, when r is 0, R" is a methyl group or ethyl group. In embodiments, when r is 1, R" is a hydrogen or hydroxyl.

In embodiments of the present disclosure, X is an anion having a charge of -2 or two anions each having a charge of -1. In an embodiment of the present disclosure, X is two acetate radicals. Anions for use in the present disclosure may include F ^-, Cl ^-, ClO ^-, ClO ₃ ^-, ClO ₄ ^-, Br ^-, BrO ₃ ^-, BrO ^-, I ^-, IO ₃ ^-, NO ₃ ^-, NO ₂ ^-, CH ₃COO ^-, CN ^-, SCN ^-, AlO ₂ ^-, MnO ₄ ^-, HSO ₃ ^-, HCO ₃ ^-, CO ₃ ^2-, SO ₄ ^2-, SO ₃ ^2-, S ₂O ₃ ^2-, SiO ₃ ^2-.

In a preferred embodiment, when r is 0, R" is a methyl group.

The present disclosure also provides a process for making an amine compound comprising reacting one or more tertiary polyetheramines, one or more polysiloxanes, and one or more acids in a solvent.

In embodiments of the present disclosure, the one or more tertiary polyetheramines have the formula (II) :

wherein R is independently selected from an unsubstituted or substituted alkyl, alkenyl, aryl, alkylaryl, or alkoxy group;

R' is independently selected from a hydrogen, a methyl group or an ethyl group;

the sum of p and q is in a range of from 0 to150, more preferred from 10 to 70;

r is 0 or 1;

when r is 0, R" is a methyl group or ethyl group;

when r is 1, R" is a hydrogen or hydroxyl

The one or more tertiary polyetheramines may be prepared from various polyether mono-primary-amines of varying molecular weight. In embodiments of the present disclosure, the polyether mono-primary-amines that may be used to form the tertiary polyetheramines may have a molecular weight of about 600, 1000, 2070, 2095 and 3085. Commercial examples of polyether mono-primary-amines that may be used to form the tertiary polyetheramines of the present disclosure may include

M-600 polyetheramine (R, R', and R" are methyl, p + q =10, and r = 0) ,

M-1000 polyetheramine (R, R', and R" are methyl, p + q = 22, and r = 0) ,

M-2070 polyetheramine (R, R', and R" are methyl, p + q = 43, and r =0 ) ,

M-2095 polyetheramine (R, R', and R" are methyl, p + q = 45, and r = 0) , and

M-3085 polyetheramine (R, R', and R" are methyl, p + q = 66, and r = 0) . These polyether mono-primary-amines are commercially available from Huntsman Corporation, USA.

In embodiments of the present disclosure, the one or more polysiloxanes have the formula (III) :

wherein

a is in a range of from 0 to 400, more preferred from 13 to 300;

each n is in a range of from 0 to 100, more preferred from 0 to 25.

In embodiments of the present disclosure, the one or more polysiloxanes may have the molecular weight of 6,000 (a= 78, n = 0) ; 10,000 (a= 132, n = 0) ; 20,000 (a= 267, n = 0) ; and/or 30,000 (a= 400, n = 0) .

Molecular weight (MW) , as used herein, is weight average molecular weight which is defined by Gel Permeation Chromatography (GPC) method with polystyrene as a reference.

The weight ratio of the tertiary polyetheramine to the polysiloxane is in an amount ranging from about 0.01: 1 to about 3: 1, preferably from about 0.05: 1 to about 2: 1, and more preferably from about 0.1: 1 to about 1: 1.

Solvents for use in the present disclosure include alcohols such as isopropyl alcohol.

Acids for use in the present disclosure include, but are not limited to, acetic acid, formic acid or mixtures thereof.

In a preferred embodiment, the polysiloxanes, the acids and the solvent are mixed in a first step and then the one or more tertiary polyetheramines is added in the mixture in a second step. Furthermore, the present disclosure also provides the method of using the amine compound to form a fabric softener, an ironing aid, a hair or skin cosmetic system or an aqueous emulsion. In addition, the present disclosure also provides a fabric softener, a hair or skin cosmetic system and an aqueous emulsion comprising the amine compound of the present disclosure. Embodiments of the present disclosure can also be applied in other industry areas where the treatment is needed for textiles and other natural and synthetic fibrous materials including paper, hair and wool.

The examples which now follow should be considered exemplary of the present disclosure, and not delimitive thereof in any way.

Raw Materials

Tertiary Polyetheramine: a compound of the below formula (II) :

wherein R, R', R", p, q and r are defined in Table 1:

Table 1

Example	R	R'	R"	p+q	r
1	methyl	methyl	methyl	43	0
2	methyl	methyl	methyl	10	0
3	methyl	methyl	methyl	22	0
4	methyl	methyl	methyl	66	0
5	methyl	methyl	methyl	45	0
6	methyl	methyl	methyl	22	0
7	methyl	methyl	methyl	66	0
8	methyl	hydrogen	hydroxyl	45	1

Di-primary Polyetheramine:

ED2003 polyetheramine. Supplier: Huntsman Corporation, USA;

Polysiloxane: a compound of the below formula (III) :

wherein a and n are defined in Table 2:

Table 2

Example	a	n
1	267	0
2	78	0
3	132	0
4	400	0
5	267	0
6	267	0
7	267	0
8	267	0
9	78	0
10	132	0
11	267	0

Solvent: isopropyl alcohol

Examples 1-11:

Examples 1 -11 were produced with the components shown in Table 3. All values listed in Table 3 refer to parts by weight. As shown in Table 3, Examples 9 to 11 were comparative examples that were prepared by Di-primary Polyetheramine.

Table 3

Procedure

For Examples 1 –11, Polysiloxane and solvent (isopropyl alcohol) were added to a 250 mL four-neck flask, equipped with mechanical stirrer, dropping funnel, thermometer and reflux condenser at ambient temperature and mixed with acetic acid. After 10 mins, the temperature was raised to 80 Deg C, polyetheramine was added, the resulting mixture was stirred for another 24 hrs. After cooling down, water was added to give a clear water solution for hydrophilicity test which was performed on cotton woven cloth according to the TEGEWA droplet test method (Melliand textile reports 68 (1987) , 581-583) . The test was performed at 65%relative atmospheric humidity and a temperature of 20 Deg C.

Results

Amine compound prepared by Example 1-8 have a structure of formula (I)

wherein R, R', R", p, r, a and n are defined in Table 4:

Table 4

Example	R	R'	R"	p+q	r	a	n
1	methyl	methyl	methyl	43	0	267	0
2	methyl	methyl	methyl	10	0	78	0
3	methyl	methyl	methyl	22	0	132	0
4	methyl	methyl	methyl	66	0	400	0
5	methyl	methyl	methyl	45	0	267	0
6	methyl	methyl	methyl	22	0	267	0
7	methyl	methyl	methyl	66	0	267	0
8	methyl	hydrogen	hydroxyl	45	1	267	0

Hydrophilicity

Table 5

Example	Hydrophilicity ¹⁾ (second)
1	1
2	2
3	2
4	1
5	2
6	1
7	1
8	1
9	>5 mins
10	>5 mins
11	>5 mins

1) Test according to TEGEWA droplet test method (Melliand textile reports 68 (1987) , 581-583)

Table 5 shows the enhanced hydrophilicity for Examples 1 –8 as tested according to the TEGEWA droplet test method. When mono-tertiary polyetheramine are used, there is a significant good performance of hydrophilicity. In Examples 9-11 (where di-primary polyetheramine is used) , one can see it takes longer for the droplet completely sunk into the fabric compared to Example 1-8 when mono-tertiary polyetheramine are used.

As can be seen from the data above, the advantage of the disclosed composition is enhanced hydrophilicity.

Claims

An amine compound having the formula:

wherein

each R is independently selected from an unsubstituted or substituted alkyl, alkenyl, aryl, alkylaryl, or alkoxy group;

each R' is independently selected from a hydrogen, a methyl group or an ethyl group;

each R" is independently selected from a hydrogen, an hydroxy group, a methyl group or an ethyl group;

a is in a range of from 0 to 450, more preferred from 13 to 300;

each n is in a range of from 0 to 100, more preferred from 0 to 25;

the sum of p and q is in a range of from 0 to150, more preferred from 10 to 70;

each r is 0 or 1;

when r is 0, R" is a methyl group or ethyl group;

when r is 1, R" is a hydrogen or hydroxyl; and

X is an anion having a charge of -2 or two anions each having a charge of -1.
The amine compound of claim 1 wherein a is in a range of from 70 to 300.
The amine compound of any one of claims 1 to 2, wherein n is 0.
The amine compound of any one of claims 1 to 3, wherein the sum of p and q is in a range of from 20 to 50.
The amine compound of any one of claims 1 to 4, wherein R is a methyl group.
The amine compound of any one of claims 1 to 5, wherein R' is a methyl group.
The amine compound of any one of claims 1 to 6, wherein r is 0 and R" is a methyl group.
The amine compound of any one of claims 1 to 7, wherein X is two acetate anions.
A process for making an amine compound comprising reacting one or more tertiary polyetheramines, one or more polysiloxanes, and one or more acids in a solvent, wherein the one or more tertiary polyetheramines have the formula:

wherein

R is independently selected from an unsubstituted or substituted alkyl, alkenyl, aryl, alkylaryl, or alkoxy group;

R' is independently selected from a hydrogen, a methyl group or an ethyl group;

R" is independently selected from a hydrogen, an hydroxy group, a methyl group or an ethyl group;

the sum of p and q is in a range of from 0 to150, more preferred from 10 to 70;

r is 0 or 1;

when r is 0, R" is a methyl group or ethyl group;

when r is 1, R" is a hydrogen or hydroxyl;

and the one or more polysiloxanes have the formula:

wherein

a is in a range of from 0 to 400, more preferred from 13 to 300; and

each n is in a range of from 0 to 100, more preferred from 0 to 25.
The process of claim 9, wherein the weight ratio of the tertiary polyetheramine to the polysiloxane is in an amount ranging from about 0.01: 1 to about 3: 1, preferably from about 0.05: 1 to about 2: 1, and more preferably from about 0.1: 1 to about 1: 1.
The process of any one of claims 9 to 10, wherein the solvent is alcohol.
The process of any one of claims 11, wherein the alcohol is isopropyl alcohol.
The process of any one of claims 9 to 12, wherein the at least one acid is acetic acid, formic acid or mixtures thereof.
The process of claim 9, wherein reacting the one or more tertiary polyetheramines, one or more polysiloxanes, and one or more acids in a solvent comprises mixing the polysiloxanes, the acids and the solvent in a first step and then adding the one or more tertiary polyetheramines in a second step.
A fabric softener comprising the amine compound of any one of claims 1 to 8.
A hair or skin cosmetic system comprising the amine compound of any one of claims 1 to 8.
An aqueous emulsion comprising the amine compound of any one of claims 1 to 8.