阅读说明：本技术 组合物、处理方法和经处理的纤维基底 (Composition, treatment method and treated fibrous substrate ) 是由 鲁道夫·J·达姆斯 迪尔克·M·科庞 于 2018-11-26 设计创作，主要内容包括：本发明提供了一种用于处理纤维基底以使所述纤维基底防水的无氟组合物、用所述组合物处理所述纤维基底的方法以及用所述无氟组合物处理的防水纤维基底。(The present invention provides a fluorine-free composition for treating a fibrous substrate to render the fibrous substrate water repellent, a method of treating the fibrous substrate with the composition, and a water repellent fibrous substrate treated with the fluorine-free composition.)

1. A method of treating a fibrous substrate comprising applying a fluorine-free treatment composition in an amount sufficient to render the fibrous substrate water repellent, wherein the treatment composition comprises:

one or more polymeric compounds derived from the polymerization of at least one monomer of formula (I):

R¹-D¹-C(O)C(R²)＝CH₂formula (I)

Wherein:

R¹represents a hydrocarbon group having 4 to 60 carbon atoms; and is

R²Represents H or CH₃；

D¹Selected from:

-C(O)O-L¹-O-；

-OC(O)-L²-O-；

-OC(O)-L³-C(O)O-L⁴-O-；

-C(O)NH-L⁵-O-；

-NHC(O)-L⁶-O-；

-NHC(O)-L⁷-C(O)O-L⁸-O-；

-C(O)-NH-；

-C(O)NHC(O)NH-L⁹-O-；

-C(O)NHC(O)-L¹⁰-O-；

-nhc (o) NH-; and

-NH-; with the proviso that when D¹-NH-, the one or more polymeric compounds are derived from more than 30 wt% of monomers of formula (I), based on the total weight of the monomers; and is

Each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms.

2. The method of claim 1, wherein the one or more polymeric compounds are derived from the polymerization of at least one monomer of formula (I) and at least one monomer of formula (II):

R³-D²-C(O)C(R⁴)＝CH₂formula (II)

Wherein:

R³represents a hydrocarbon group having 4 to 60 carbon atoms; and is

R⁴Represents H or CH₃；

D²Selected from:

-NHC(O)OL¹¹-O-；

-O-C(O)NH-L¹²-O-；

-NHC(O)NH-L¹³-O-; and

-O-; and is

Each L¹¹、L¹²And L¹³Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

wherein the at least one monomer of formula (II) is present in the one or more polymeric compounds in an amount of less than 30% by weight based on the total amount of monomers.

3. The method of claim 1 or 2, wherein applying the composition to a fibrous substrate comprises applying the composition in an amount sufficient to render the fibrous substrate durably waterproof.

4. A fluorine-free treatment composition comprising a component (a), and at least one of a component (B) and a component (C), wherein:

component (a) comprises one or more polymeric compounds derived from the polymerization of at least one monomer of formula (I):

R¹-D¹-C(O)C(R²)＝CH₂formula (I)

Wherein:

R¹represents a hydrocarbon group having 4 to 60 carbon atoms; and is

R²Represents H or CH₃；

D¹Selected from:

-C(O)O-L¹-O-；

-OC(O)-L²-O-；

-OC(O)-L³-C(O)O-L⁴-O-；

-C(O)NH-L⁵-O-；

-NHC(O)-L⁶-O-；

-NHC(O)-L⁷-C(O)O-L⁸-O-；

-C(O)-NH-；

-C(O)NHC(O)NH-L⁹-O-；

-C(O)NHC(O)-L¹⁰-O-；

-nhc (o) NH-; and

-NH-; with the proviso that when D¹(ii) when-NH-, the one or more polymeric compounds are derived from greater than 30 weight percent of a monomer of formula (I), based on the total weight of the monomer; and is

Each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

component (B) comprises:

one or more compounds derived from the reaction of components in one or more steps, the components comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

An alcohol, amine, acid, amide or thiol comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups;

(ii) at least one polyisocyanate;

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound; and

(iv) optionally, at least one isocyanate blocking agent;

wherein the isocyanate-reactive oligomer is prepared from a free radical initiated reaction of at least one (meth) acrylate or (meth) acrylamide monomer in the presence of at least one thiol, wherein the at least one (meth) acrylate or (meth) acrylamide monomer comprises at least one hydrocarbon group having from 4 to 60 carbon atoms; and is

Component (C) comprises one or more polycarbodiimide compounds.

5. The fluorine-free treatment composition of claim 4, wherein, in component (A), the one or more polymeric compounds are derived from the polymerization of at least one monomer of formula (I) and at least one monomer of formula (II):

R³-D²-C(O)C(R⁴)＝CH₂formula (II)

Wherein:

R³represents a hydrocarbon group having 4 to 60 carbon atoms; and is

R⁴Represents H or CH₃；

D²Selected from:

-NHC(O)OL¹¹-O-；

-O-C(O)NH-L¹²-O-；

-NHC(O)NH-L¹³-O-; and

-O-; and is

Each L¹¹、L¹²And L¹³Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

wherein the at least one monomer of formula (II) is present in the one or more polymeric compounds in an amount of less than 30% by weight based on the total amount of monomers.

6. The fluorine-free treatment composition according to claim 4 or 5, wherein the component of the one or more compounds used to prepare component (B) comprises at least one additional mono-, di-or polyfunctional isocyanate-reactive compound.

7. The fluorine-free treatment composition of any one of claims 4 to 6, wherein the one or more polycarbodiimide compounds of component (C) are derived from the carbodiimidization reaction of component(s) in one or more steps comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

An alcohol, amine, acid, amide or thiol comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups;

(ii) at least one polyisocyanate; and

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound;

wherein the isocyanate-reactive oligomer is prepared from a free radical initiated reaction of at least one (meth) acrylate or (meth) acrylamide monomer in the presence of at least one thiol, wherein the at least one (meth) acrylate or (meth) acrylamide monomer comprises at least one hydrocarbon group having from 4 to 60 carbon atoms.

8. A composition comprising component (B), wherein:

component (B) comprises one or more compounds derived from the reaction of components carried out in one or more steps, said components comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

An amine, acid or amide comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups;

(ii) at least one polyisocyanate;

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound; and

(iv) optionally, at least one isocyanate blocking agent;

provided that less than 40% of the isocyanate groups are reacted with acid and/or amide groups;

wherein the isocyanate-reactive oligomer has the formula:

Y¹-[CH₂-C(R²)C(O)-D¹-R¹]_m-S-R¹⁰-(T¹)_pformula (V)

Wherein:

Y¹is H or an initiator residue;

R¹is a hydrocarbon group having 4 to 60 carbon atoms;

R²independently is H or CH₃；

D¹Selected from:

-C(O)O-L¹-O-；

-OC(O)-L²-O-；

-OC(O)-L³-C(O)O-L⁴-O-；

-C(O)NH-L⁵-O-；

-NHC(O)-L⁶-O-；

-NHC(O)-L⁷-C(O)O-L⁸-O-；

-C(O)-NH-；

-C(O)NHC(O)NH-L⁹-O-；

-C(O)NHC(O)-L¹⁰-O-；

-nhc (o) NH-; and

-NH-; with the proviso that when D¹when-NH-, the isocyanate-reactive oligomer comprises greater than 30 weight percent of-NH-containing monomer units based on the total weight of monomer units;

each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

s is sulfur;

R¹⁰is a divalent or trivalent linking group having 1 to 10 carbon atoms;

T¹is-C (O) OH, -C (O) NH₂、–OH、–NH₂or-NH (R)¹¹) Wherein

R¹¹Is H or a hydrocarbon group having 1 to 10 carbon atoms;

m is an integer of 2 to 20; and is

p is independently 1 or 2;

and/or

Component (B) comprises one or more compounds derived from the reaction of components carried out in one or more steps, said components comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

An amine, acid or amide comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups;

(ii) at least one polyisocyanate;

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound; and

(iv) optionally, at least one isocyanate blocking agent;

wherein the isocyanate-reactive oligomer has the formula:

Y²-[CH₂-C(R⁴)C(O)-D²-R³]_m-S-R¹²-(T²)_pformula (VI)

Wherein:

Y²is H or an initiator residue;

R³is a hydrocarbon group having 4 to 60 carbon atoms;

R⁴independently is H or CH₃；

D²Selected from:

-NHC(O)OL¹¹-O-；

-O-C(O)NH-L¹²-O-；

-NHC(O)NH-L¹³-O-; and

-O-; and is

Each L¹¹、L¹²And L¹³Independently a branched or straight chain arylene having 2 to 10 carbon atomsAn alkyl group;

s is sulfur;

R¹²is a divalent or trivalent linking group having 1 to 10 carbon atoms;

T²is-C (O) OH, -C (O) NH₂、-OH、-NH₂or-NH (R)¹¹) Wherein R is¹¹Is H or a hydrocarbon group having 1 to 10 carbon atoms; provided that when T is²is-OH, -NH₂or-NH (R)¹¹) When component (iii) is present and comprises an acid or amide functional group;

m is an integer of 2 to 20; and is

p is independently 1 or 2.

9. The composition of claim 8, further comprising at least one of component (a) and component (C), wherein:

component (a) comprises one or more polymeric compounds derived from the polymerization of at least one monomer comprising at least one hydrocarbon group having from 4 to 60 carbon atoms; and is

Component (C) comprises one or more polycarbodiimide compounds.

10. The composition of claim 9, wherein the at least one monomer used to prepare the one or more compounds of component (a) has at least one of the following formulas:

R¹-D¹-C(O)C(R²)＝CH₂formula (I)

Wherein:

R¹represents a hydrocarbon group having 4 to 60 carbon atoms; and is

R²Represents H or CH₃；

D¹Selected from:

-C(O)O-L¹-O-；

-OC(O)-L²-O-；

-OC(O)-L³-C(O)O-L⁴-O-；

-C(O)NH-L⁵-O-；

-NHC(O)-L⁶-O-；

-NHC(O)-L⁷-C(O)O-L⁸-O-；

-C(O)-NH-；

-C(O)NHC(O)NH-L⁹-O-；

-C(O)NHC(O)-L¹⁰-O-；

-nhc (o) NH-; and

-NH-; with the proviso that when D¹(ii) when-NH-, the one or more polymeric compounds are derived from greater than 30 weight percent of a monomer of formula (I), based on the total weight of the monomer; and is

Each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

R³-D²-C(O)C(R⁴)＝CH₂formula (II)

Wherein:

R³represents a hydrocarbon group having 4 to 60 carbon atoms; and is

R⁴Represents H or CH₃；

D²Selected from:

-NHC(O)OL¹¹-O-；

-O-C(O)NH-L¹²-O-；

-NHC(O)NH-L¹³-O-; and

-O-; and is

Each L¹¹、L¹²And L¹³Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

R⁵-X¹-C(O)NH-L¹⁴-OC(O)C(R⁶)＝CH₂formula (III) or

R⁷-X²-C(O)NH-Q¹-NH-C(O)O-L¹⁵-OC(O)C(R⁸)＝CH₂Formula (IV)

Wherein:

R⁵and R⁷Independently a hydrocarbon group having from 4 to 60 carbon atoms;

R⁶and R⁸Independently is H or CH₃；

L¹⁴And L¹⁵Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms, an arylene group, or a combination thereof;

X¹is S or-N (R)⁹) And X²Is O, S, -NH or-N (R)⁹) Wherein R is⁹Is a hydrocarbon group having 1 to 20 carbon atoms; and is

Q¹Is a divalent isocyanate residue.

11. The composition of claim 9 or 10, where the one or more polycarbodiimide compounds of component (C) are derived from the carbodiimidization reaction of component (C) in one or more steps comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

An alcohol, amine, acid, amide or thiol comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups;

(ii) at least one polyisocyanate; and

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound;

wherein the isocyanate-reactive oligomer is prepared from a free radical initiated reaction of at least one (meth) acrylate or (meth) acrylamide monomer in the presence of at least one thiol, wherein the at least one (meth) acrylate or (meth) acrylamide monomer comprises at least one hydrocarbon group having from 4 to 60 carbon atoms.

12. A composition comprising component (C), wherein:

component (C) comprises at least one polycarbodiimide compound derived from the carbodiimidization reaction of components in one or more steps, comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

An amine, acid or amide comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups;

(ii) at least one polyisocyanate; and

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound;

wherein the isocyanate-reactive oligomer has the formula:

Y¹-[CH₂-C(R²)C(O)-D¹-R¹]_m-S-R¹⁰-(T¹)_pformula (V)

Wherein:

Y¹is H or an initiator residue;

R¹is a hydrocarbon group having 4 to 60 carbon atoms;

R²independently is H or CH₃；

D¹Selected from:

-C(O)O-L¹-O-；

-OC(O)-L²-O-；

-OC(O)-L³-C(O)O-L⁴-O-；

-C(O)NH-L⁵-O-；

-NHC(O)-L⁶-O-；

-NHC(O)-L⁷-C(O)O-L⁸-O-；

-C(O)-NH-；

-C(O)NHC(O)NH-L⁹-O-；

-C(O)NHC(O)-L¹⁰-O

-nhc (o) NH-; and

-NH-; with the proviso that when D¹when-NH-, the isocyanate-reactive oligomer comprises greater than 30 weight percent of-NH-containing monomer units based on the total weight of monomer units;

each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

s is sulfur;

R¹⁰is a divalent or trivalent linking group having 1 to 10 carbon atoms;

T¹is-C (O) OH, -C (O) NH₂、–OH、–NH₂or-NH (R)¹¹) Wherein

R¹¹Is H or a hydrocarbon group having 1 to 10 carbon atoms;

m is an integer of 2 to 20; and is

p is independently 1 or 2;

and/or

Component (C) comprises at least one polycarbodiimide compound derived from the carbodiimidization reaction of components in one or more steps, comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

An amine, acid or amide comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups;

(ii) at least one polyisocyanate; and

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound;

wherein the isocyanate-reactive oligomer has the formula:

Y²-[CH₂-C(R⁴)C(O)-D²-R³]_m-S-R¹²-(T²)_pformula (VI)

Wherein:

Y²is H or an initiator residue;

R³is a hydrocarbon group having 4 to 60 carbon atoms;

R⁴independently is H or CH₃；

D²Selected from:

-NHC(O)OL¹¹-O-；

-O-C(O)NH-L¹²-O-；

-NHC(O)NH-L¹³-O-; and

-O-; and is

Each L¹¹、L¹²And L¹³Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

s is sulfur;

R⁷is a divalent or trivalent linking group having 1 to 10 carbon atoms;

T²is-C (O) OH, -C (O) NH₂、-OH、NH₂or-NH (R)¹¹) Wherein R is¹¹Is H or a hydrocarbon group having 1 to 10 carbon atoms; provided that when T is²is-OH, -NH₂or-NH (R)¹¹) When component (iii) is present and comprises an acid or amide functional group;

m is an integer of 2 to 20; and is

p is independently 1 or 2.

13. The composition of claim 12, further comprising at least one of component (a) and component (B), wherein:

component (a) comprises one or more polymeric compounds derived from the polymerization of at least one monomer comprising at least one hydrocarbon group having from 4 to 60 carbon atoms;

and is

Component (B) comprises:

one or more compounds derived from the reaction of components in one or more steps, the components comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

An alcohol, amine, acid, amide or thiol comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups;

(ii) at least one polyisocyanate;

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound; and

(iv) optionally, at least one isocyanate blocking agent;

wherein the isocyanate-reactive oligomer is prepared from a free radical initiated reaction of at least one (meth) acrylate or (meth) acrylamide monomer in the presence of at least one thiol (which may or may not be functionalized), wherein the at least one (meth) acrylate or (meth) acrylamide monomer comprises at least one hydrocarbon group having from 4 to 60 carbon atoms.

14. The composition of claim 13, wherein the at least one monomer used to prepare the one or more compounds of component (a) has at least one of the following formulas:

R¹-D¹-C(O)C(R²)＝CH₂formula (I)

Wherein:

R¹represents a hydrocarbon group having 4 to 60 carbon atoms; and is

R²Represents H or CH₃；

D¹Selected from:

-C(O)O-L¹-O-；

-OC(O)-L²-O-；

-OC(O)-L³-C(O)O-L⁴-O-；

-C(O)NH-L⁵-O-；

-NHC(O)-L⁶-O-；

-NHC(O)-L⁷-C(O)O-L⁸-O-；

-C(O)-NH-；

-C(O)NHC(O)NH-L⁹-O-；

-C(O)NHC(O)-L¹⁰-O-；

-nhc (o) NH-; and

-NH-; with the proviso that when D¹when-NH-, the one or more polymeric compounds are derived from greater than 30 weight percent based on the total weight of the monomers% of monomers of formula (I); and is

Each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

R³-D²-C(O)C(R⁴)＝CH₂formula (II)

Wherein:

R³represents a hydrocarbon group having 4 to 60 carbon atoms; and is

R⁴Represents H or CH₃；

D²Selected from:

-NHC(O)OL¹¹-O-；

-O-C(O)NH-L¹²-O-；

-NHC(O)NH-L¹³-O-; and

-O-; and is

Each L¹¹、L¹²And L¹³Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

R⁵-X¹-C(O)NH-L¹⁴-OC(O)C(R⁶)＝CH₂formula (III) or

R⁷-X²-C(O)NH-Q¹-NH-C(O)O-L¹⁵-OC(O)C(R⁸)＝CH₂Formula (IV)

Wherein:

R⁵and R⁷Independently a hydrocarbon group having from 4 to 60 carbon atoms;

R⁶and R⁸Independently is H or CH₃；

L¹⁴And L¹⁵Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms, an arylene group, or a combination thereof;

X¹is S or-N (R)⁹) And X²Is O, S, -NH or-N (R)⁹) Wherein R is⁹Is a hydrocarbon group having 1 to 20 carbon atoms; and is

Q¹Is a divalent isocyanateAnd (c) a residue.

15. The composition according to claim 13 or 14, wherein the component of the one or more compounds used for preparing component (B) comprises at least one further mono-, di-or polyfunctional isocyanate-reactive compound.

16. The composition according to any one of claims 13 to 15, wherein in component (B) less than 40% of the isocyanate groups are reacted with acid and/or amide groups.

17. The composition of any one of claims 8 to 16, which is a fluorine-free treatment composition.

18. A method of treating a fibrous substrate comprising applying the composition of any one of claims 4 to 17 in an amount sufficient to render the fibrous substrate water repellent.

19. The method of claim 18, wherein applying the composition to a fibrous substrate comprises applying the composition in an amount sufficient to render the fibrous substrate durably waterproof.

20. A fibrous substrate treated by the method of any one of claims 1 to 3 or 18 and 19.

Background

Compositions for treating fibrous substrates to enhance the water repellency of the substrate are well known and described in the literature, for example, "Fluorinated Surfactants and repellants," E.Kissa, Surfactant Science Series, vol.97, Marcel Dekker, New York, Chapter 12, p.516-551(E.Kissa, "Fluorinated Surfactants and water Repellents," Surfactant Science Series, Vol.97, Chapter 12, pp.516-551, Marcel Dekker Press, New York) or "Chemistry and Technology of Silies," by W.Noll, Academic Press, New York, Chapter 10, p.585-595(W.Noll, "Silicone Chemistry and Technology", Academic Press, New York, Chapter 10, pp.585-595). Substrates treated with fluorinated water repellents generally have a high durable water repellency. However, fluorinated treating agents have some disadvantages, including their production price, and they may suffer from some potential environmental problems. In recent years, fluorine-free alternative water repellent agents have received increasing attention. Such water repellents can provide good initial water repellency to fibrous substrates, but are generally unsatisfactory in durability. Thus, there is a continuing need for compositions, particularly fluorine-free compositions, that provide high water repellency (particularly high initial water repellency and, in some cases, high durable water repellency).

Disclosure of Invention

The present disclosure provides compositions, methods, and treated substrates.

In a first embodiment, a method of treating a fibrous substrate is provided. The method comprises applying a fluorine-free treatment composition in an amount sufficient to render a fibrous substrate water repellent, wherein the treatment composition comprises one or more polymeric compounds derived from the polymerization of at least one monomer of formula (I):

R¹-D¹-C(O)C(R²)＝CH₂formula (I)

Wherein:

R¹represents a hydrocarbon group having 4 to 60 carbon atoms; and is

R²Represents H or CH₃；

D¹Selected from:

-C(O)O-L¹-O-；

-OC(O)-L²-O-；

-OC(O)-L³-C(O)O-L⁴-O-；

-C(O)NH-L⁵-O-；

-NHC(O)-L⁶-O-；

-NHC(O)-L⁷-C(O)O-L⁸-O-；

-C(O)-NH-；

-C(O)NHC(O)NH-L⁹-O-；

-C(O)NHC(O)-L¹⁰-O-；

-nhc (o) NH-; and

-NH-; with the proviso that when D¹when-NH-, the one or more polymeric compounds are derived from more than 30% by weight, based on the total weight of monomers, of monomers of formula (I); and is

Each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms.

In a second embodiment, a fluorine-free treatment composition is provided that includes component (a), and at least one of component (B) and component (C). Component (a) comprises one or more polymeric compounds derived from the polymerization of at least one monomer of formula (I):

R¹-D¹-C(O)C(R²)＝CH₂formula (I)

Wherein:

R¹represents a hydrocarbon group having 4 to 60 carbon atoms; and is

R²Represents H or CH₃；

D¹Selected from:

-C(O)O-L¹-O-；

-OC(O)-L²-O-；

-OC(O)-L³-C(O)O-L⁴-O-；

-C(O)NH-L⁵-O-；

-NHC(O)-L⁶-O-；

-NHC(O)-L⁷-C(O)O-L⁸-O-；

-C(O)-NH-；

-C(O)NHC(O)NH-L⁹-O-；

-C(O)NHC(O)-L¹⁰-O-；

-nhc (o) NH-; and

-NH-; with the proviso that when D¹when-NH-, the one or more polymeric compounds are derived from more than 30% by weight, based on the total weight of monomers, of monomers of formula (I); and is

Each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms.

In this second embodiment, component (B) comprises one or more compounds derived from the reaction of components in one or more steps, said components comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

An alcohol, amine, acid, amide or thiol comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups;

(ii) at least one polyisocyanate;

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound; and

(iv) optionally, at least one isocyanate blocking agent;

wherein the isocyanate-reactive oligomer is prepared by a free radical initiated reaction of at least one (meth) acrylate or (meth) acrylamide monomer in the presence of at least one thiol, wherein the at least one (meth) acrylate or (meth) acrylamide monomer comprises at least one hydrocarbon group having from 4 to 60 carbon atoms. In this second embodiment, component (C) comprises one or more polycarbodiimide compounds.

In a third embodiment, there is provided a composition comprising component (B), wherein:

component (B) comprises one or more compounds derived from the reaction of components carried out in one or more steps, said components comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

An amine, acid or amide comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups;

(ii) at least one polyisocyanate;

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound; and

(iv) optionally, at least one isocyanate blocking agent;

provided that less than 40% of the isocyanate groups are reacted with acid and/or amide groups;

wherein the isocyanate-reactive oligomer has the formula:

Y¹-[CH₂-C(R²)C(O)-D¹-R¹]_m-S-R¹⁰-(T¹)_pformula (V)

Wherein:

Y¹is H or an initiator residue;

R¹is a hydrocarbon group having 4 to 60 carbon atoms;

R²independently is H or CH₃；

D¹Selected from:

-C(O)O-L¹-O-；

-OC(O)-L²-O-；

-OC(O)-L³-C(O)O-L⁴-O-；

-C(O)NH-L⁵-O-；

-NHC(O)-L⁶-O-；

-NHC(O)-L⁷-C(O)O-L⁸-O-；

-C(O)-NH-；

-C(O)NHC(O)NH-L⁹-O-；

-C(O)NHC(O)-L¹⁰-O-；

-nhc (o) NH-; and

-NH-; with the proviso that when D¹when-NH-, the isocyanate-reactive oligomer comprises greater than 30 weight percent of-NH-containing monomer units based on the total weight of monomer units;

each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

s is sulfur;

R¹⁰is a divalent or trivalent linking group having 1 to 10 carbon atoms;

T¹is-C (O) OH, -C (O) NH₂、–OH、–NH₂or-NH (R)¹¹) Wherein R is¹¹Is H or a hydrocarbon group having 1 to 10 carbon atoms;

m is an integer of 2 to 20; and is

p is independently 1 or 2;

and/or

Component (B) comprises one or more compounds derived from the reaction of components carried out in one or more steps, said components comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

Amines, acids or amides containing at least one straight-chain or branched hydrocarbon radical having from 4 to 60 carbon atoms and optionally one or more ester groups

(ii) At least one polyisocyanate;

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound; and

(iv) optionally, at least one isocyanate blocking agent;

wherein the isocyanate-reactive oligomer has the formula:

Y²-[CH₂-C(R⁴)C(O)-D²-R³]_m-S-R¹²-(T²)_pformula (VI)

Wherein:

Y²is H or an initiator residue;

R³is a hydrocarbon group having 4 to 60 carbon atoms;

R⁴independently is H or CH₃；

D²Selected from:

-NHC(O)OL¹¹-O-；

-O-C(O)NH-L¹²-O-；

-NHC(O)NH-L¹³-O-; and

-O-; and is

Each L¹¹、L¹²And L¹³Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

s is sulfur;

R¹²is a divalent or trivalent linking group having 1 to 10 carbon atoms;

T²is-C (O) OH, -C (O) NH₂、-OH、-NH₂or-NH (R)¹¹) Wherein R is¹¹Is H or a hydrocarbon group having 1 to 10 carbon atoms; provided that when T is²is-OH, -NH₂or-NH (R)¹¹) When component (iii) is present and comprises an acid or amide functional group;

m is an integer of 2 to 20; and is

p is independently 1 or 2.

In a fourth embodiment, there is provided a composition comprising component (C), wherein:

component (C) comprises at least one polycarbodiimide compound derived from the carbodiimidization reaction of components in one or more steps, said component comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

An amine, acid or amide comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups;

(ii) at least one polyisocyanate; and

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound;

wherein the isocyanate-reactive oligomer has the formula:

Y¹-[CH₂-C(R²)C(O)-D¹-R¹]_m-S-R¹⁰-(T¹)_pformula (V)

Wherein:

Y¹is H or an initiator residue;

R¹is a hydrocarbon group having 4 to 60 carbon atoms;

R²independently is H or CH₃；

D¹Selected from:

-C(O)O-L¹-O-；

-OC(O)-L²-O-；

-OC(O)-L³-C(O)O-L⁴-O-；

-C(O)NH-L⁵-O-；

-NHC(O)-L⁶-O-；

-NHC(O)-L⁷-C(O)O-L⁸-O-；

-C(O)-NH-；

-C(O)NHC(O)NH-L⁹-O-；

-C(O)NHC(O)-L¹⁰-O

-nhc (o) NH-; and

-NH-; with the proviso that when D¹when-NH-, the isocyanate-reactive oligomer comprises greater than 30 weight percent of-NH-containing monomer units based on the total weight of monomer units;

each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

s is sulfur;

R¹⁰is a divalent or trivalent linking group having 1 to 10 carbon atoms;

T¹is-C (O) OH, -C (O) NH₂、–OH、–NH₂or-NH (R)¹¹) Wherein R is¹¹Is H or a hydrocarbon group having 1 to 10 carbon atoms;

m is an integer of 2 to 20; and is

p is independently 1 or 2;

and/or

Component (C) comprises at least one polycarbodiimide compound derived from the carbodiimidization reaction of components in one or more steps, said component comprising:

(i) at least one of:

an isocyanate-reactive oligomer comprising from 2 to 20 repeating units; or

An amine, acid or amide comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups;

(ii) at least one polyisocyanate; and

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound;

wherein the isocyanate-reactive oligomer has the formula:

Y²-[CH₂-C(R⁴)C(O)-D²-R³]_m-S-R¹²-(T²)_pformula (VI)

Wherein:

Y²is H or an initiator residue;

R³is a hydrocarbon group having 4 to 60 carbon atoms;

R⁴independently is H or CH₃；

D²Selected from:

-NHC(O)OL¹¹-O-；

-O-C(O)NH-L¹²-O-；

-NHC(O)NH-L¹³-O-; and

-O-; and is

Each L¹¹、L¹²And L¹³Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms;

s is sulfur;

R⁷is a divalent or trivalent linking group having 1 to 10 carbon atoms;

T²is-C (O) OH, -C (O) NH₂、-OH、NH₂or-NH (R)¹¹) Wherein R is¹¹Is H or a hydrocarbon group having 1 to 10 carbon atoms; provided that when T is²is-OH, -NH₂or-NH (R)¹¹) When component (iii) is present and comprises an acid or amide functional group;

m is an integer of 2 to 20; and is

p is independently 1 or 2.

In a fifth embodiment, the present disclosure provides a method of treating a fibrous substrate. The method comprises applying a composition described herein in an amount sufficient to render the fibrous substrate water repellent.

In a sixth embodiment, the present disclosure provides a fibrous substrate treated by the method described herein.

As used herein, a "fluorine-free" treatment composition means a treatment composition that includes less than 1 weight percent (1 wt%) fluorine in the treatment composition (whether in a concentrated or ready-to-use treatment composition) on a solids basis. In certain embodiments, "fluorine-free" treatment compositions means that the treatment composition comprises less than 0.5 wt.%, or less than 0.1 wt.%, or less than 0.01 wt.% fluorine. The fluorine may be in the form of an organic or inorganic fluorine-containing compound.

The term "oligomer" encompasses compounds having at least 2 repeating units and at most 20 repeating units. According to a particular embodiment, the oligomer has 3 to 15 repeating units. According to another embodiment, the oligomer has 4 to 15 repeating units. In certain embodiments, an "oligomer" has a weight average molecular weight of up to 20,000 daltons.

The term "polymeric compound" encompasses compounds having more than 20 repeating units. In certain embodiments, a "polymeric compound" has a weight average molecular weight greater than 20,000 daltons.

The term "residue" means the portion of the original organic molecule remaining after reaction.

The term "hydrocarbon" refers to any substantially fluorine-free organic group comprising hydrogen and carbon. Such hydrocarbon groups can be cyclic (including aromatic), straight chain, and branched. Suitable hydrocarbon groups include alkyl groups, alkylene groups, arylene groups, and the like. Unless otherwise specified, the hydrocarbon group typically contains 1 to 60 carbon atoms. In some embodiments, the hydrocarbon group comprises 4 to 60 carbon atoms, 12 to 50 carbon atoms, 12 to 40 carbon atoms, 12 to 30 carbon atoms, 16 to 60 carbon atoms, 16 to 50 carbon atoms, 16 to 40 carbon atoms, or 16 to 30 carbon atoms. In some embodiments, the hydrocarbon group comprises 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms.

The term "alkyl" refers to a monovalent group that is a residue of an alkane and includes straight chain alkyl groups, branched chain alkyl groups, cyclic alkyl groups, bicyclic alkyl groups, and combinations thereof, including both unsubstituted and substituted alkyl groups. Unless otherwise indicated, alkyl groups typically contain 1 to 60 carbon atoms. In some embodiments, the alkyl group contains 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Examples of "alkyl" groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, tert-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, octadecyl (also known as stearyl), behenyl (also known as behenyl), adamantyl, norbornyl, and the like.

The term "alkylene" refers to a divalent group that is an alkane residue and includes straight chain groups, branched chain groups, cyclic groups, bicyclic groups, or combinations thereof. Unless otherwise indicated, the alkylene group typically has from 1 to 60 carbon atoms. In some embodiments, the alkylene group has 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 2 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Examples of "alkylene" groups include methylene, ethylene, 1, 3-propylene, 1, 2-propylene, 1, 4-butylene, 1, 4-cyclohexylene, 1, 6-hexamethylene and 1, 10-decamethylene.

The term "arylene" refers to a divalent group that is aromatic and optionally carbocyclic. The arylene group has at least one aromatic ring. Optionally, the aromatic ring can have one or more additional carbocyclic rings fused to the aromatic ring. Any additional rings may be unsaturated, partially saturated, or saturated. Unless otherwise specified, arylene groups often have 5 to 20 carbon atoms, 5 to 18 carbon atoms, 5 to 16 carbon atoms, 5 to 12 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.

The term "(meth) acrylate" refers to both acrylates and methacrylates.

The term "polyisocyanate" refers to aliphatic and/or aromatic di-, tri-and higher polyisocyanates.

The term "isocyanate-reactive" refers to a compound or oligomer comprising a group capable of reacting with an isocyanate (i.e., an isocyanate-reactive group such as an alcohol, amine, or amide).

The term "comprising" and its variants have no limiting meaning where these terms appear in the description and claims. Such terms are to be understood to imply the inclusion of a stated step or element or group of steps or elements but not the exclusion of any other step or element or group of steps or elements. By "consisting of … …" is meant to include and be limited to the following of the phrase "consisting of … …". Thus, the phrase "consisting of … …" indicates that the listed elements are required or mandatory, and that no other elements may be present. By "consisting essentially of … …," it is meant to include any elements listed after the phrase, and is not limited to other elements that do not interfere with or contribute to the activity or effect specified in the disclosure for the listed elements. Thus, the phrase "consisting essentially of … …" indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present, depending on whether they substantially affect the activity or effect of the listed elements.

The words "preferred" and "preferably" refer to embodiments of the disclosure that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the disclosure.

In this application, terms such as "a," "an," "the," and "said" are not intended to refer to only a single entity, but include the general class of which a specific example may be used for illustration. The terms "a", "an", "the" and "the" are used interchangeably with the phrases "at least one" and "one or more". The phrases "at least one (kind) in … …" and "at least one (kind) comprising … …" in the following list refer to any one of the items in the list and any combination of two or more of the items in the list.

The term "or" is generally employed in its ordinary sense including "and/or" unless the content clearly dictates otherwise.

The term "and/or" means one or all of the listed elements or a combination of any two or more of the listed elements.

Also herein, all numerical values are assumed to be modified by the term "about" and, in certain embodiments, are preferably modified by the term "exactly. As used herein, with respect to a measured quantity, the term "about" refers to a deviation in the measured quantity that is commensurate with the objective of the measurement and the accuracy of the measurement equipment used, as would be expected by a skilled artisan taking the measurement with some degree of care. Herein, "at most" a number (e.g., at most 50) includes the number (e.g., 50).

Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range and the endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

The term "room temperature" refers to a temperature of 20 ℃ to 25 ℃ or 22 ℃ to 25 ℃.

Herein, when a group appears more than once in a formula described herein, each group is "independently" selected, whether or not explicitly stated. For example, when more than one Q group is present in a formula, each Q group is independently selected. Furthermore, the sub-groups contained within these groups are also independently selected.

Reference throughout this specification to "one embodiment," "an embodiment," "certain embodiments," or "some embodiments," etc., means that a particular feature, configuration, composition, or characteristic described in connection with the embodiment is included in at least one embodiment of the present disclosure. Thus, the appearances of such phrases or in various places throughout this specification are not necessarily referring to the same embodiment of the present disclosure. Furthermore, the particular features, configurations, compositions, or characteristics may be combined in any suitable manner in one or more embodiments.

The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The following description more particularly exemplifies illustrative embodiments. Throughout this application, guidance is provided through lists of examples, which can be used in various combinations. In each case, the lists cited are intended as representative groups only and are not to be construed as exclusive lists.

Detailed Description

The present disclosure provides compositions (e.g., treatment compositions, preferably fluorine-free treatment compositions for fibrous substrates), methods (e.g., treatment methods), and treated fibrous substrates.

The compositions (e.g., treatment compositions) of the present disclosure may be used to treat fibrous substrates to enhance the water repellency of the substrate. In certain embodiments, such treatment compositions may be used in methods of treating fibrous substrates. One method may include applying the composition (preferably, a fluorine-free treatment composition) in an amount sufficient to render the fibrous substrate water repellent. One method may include applying the composition (preferably, a fluorine-free treatment composition) in an amount sufficient to durably waterproof the fibrous substrate.

As used herein, a fibrous substrate is water repellent if the fibrous substrate exhibits a minimum initial water pick-up rating of at least 80 as determined by the water pick-up rating test described in the examples section. In certain embodiments, the initial water pick-up level is at least 90 or at least 100 as determined by the water pick-up level test described in the examples section.

In certain embodiments, the fibrous substrates are treated such that they become durably water repellent. As used herein, a fibrous substrate is durably waterproof if it exhibits a water pick-up rating of at least 50 after 10 washes when treated with a treatment composition of the present disclosure at 1% solids, preferably 0.6% solids, on the fibrous substrate as determined by the water pick-up rating test conducted at wash (and optionally ironing) as described in the examples section. In certain embodiments, when the fibrous substrate is treated with the treatment composition of the present disclosure at 1% solids, preferably 0.6% solids, the water pick-up rating is at least 70 after 10 washes, or at least 80 after 20 washes, as determined by the water pick-up rating test performed with washes (and optionally ironing) described in the examples section.

Generally, the treatment composition is used in an amount to provide a desired initial and/or desired level of pick-up level after multiple washes. In certain embodiments, the amount of treatment composition is at least 0.2 wt.%, or at least 0.3 wt.%, or at least 0.4 wt.%, or at least 0.5 wt.%, or at least 0.6 wt.% SOF (solids on a fibrous substrate, e.g., fabric). In certain embodiments, the amount of treatment composition is at most 2 wt.%, or at most 1.5 wt.%, or at most 1 wt.% SOF (solids on a fibrous substrate, e.g., fabric).

Exemplary fibrous substrates include textiles, leather, carpet, paper, and fabrics (non-woven, or knitted).

The compositions (e.g., treatment compositions) of the present disclosure may be in the form of a concentrate, which may comprise up to 85 weight percent (wt.%) water, based on the total weight of the concentrate composition. The compositions (e.g., treatment compositions) of the present disclosure may be in the form of a concentrate, which may comprise at least 65 wt.% water, based on the total weight of the concentrate composition.

Alternatively, the concentrate compositions of the present disclosure can be diluted to any desired level to form a ready-to-use formulation.

In certain embodiments, the compositions of the present disclosure comprise various combinations of component (a), component (B), and component (C). That is, in certain embodiments, the composition comprises component (a) and component (B). In certain embodiments, the composition comprises component (a) and component (C). In certain embodiments, the composition comprises component (B) and component (C). In certain embodiments, the composition comprises component (a), component (B), and component (C).

Component (A) polymeric compound and preparation thereof

In certain embodiments, component (a) comprises one or more polymeric compounds derived from the polymerization of at least one monomer comprising at least one hydrocarbon group having from 4 to 60 carbon atoms, from 16 to 50 carbon atoms, from 16 to 40 carbon atoms, or from 16 to 30 carbon atoms.

In certain embodiments, component (a) comprises one or more polymeric compounds derived from the polymerization of at least one monomer of formula (I), formula (II), formula (III), or formula (IV), as described below.

Such polymeric compounds may be homopolymers or copolymers (including terpolymers, tetrapolymers, etc.).

In certain embodiments, component (a) comprises one or more polymeric compounds derived from the polymerization of at least one monomer of formula (I):

R¹-D¹-C(O)C(R²)＝CH₂formula (I).

In certain embodiments, the monomer of formula (I) may be a (meth) acrylate monomer or a (meth) acrylamide monomer.

In the formula (I), R¹Represents a hydrocarbon group having 4 to 60 carbon atoms. In certain embodiments of formula (I), R¹Represents a hydrocarbon group having 16 to 60 carbon atoms or 16 to 30 carbon atoms.

In the formula (I), R²Represents H or CH₃。

In the formula (I), D¹Selected from:

-C(O)O-L¹-O-；

-OC(O)-L²-O-；

-OC(O)-L³-C(O)O-L⁴-O-；

-C(O)NH-L⁵-O-；

-NHC(O)-L⁶-O-；

-NHC(O)-L⁷-C(O)O-L⁸-O-；

-C(O)-NH-；

-C(O)NHC(O)NH-L⁹-O-；

-C(O)NHC(O)-L¹⁰-O-；

-nhc (o) NH-; and

-NH-; with the proviso that when D¹When it is-NH-, the one or more polymeric compounds are derived from

More than 30% by weight, based on the total weight of the monomers, of monomers of formula (I).

In D of formula (I)¹Each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms. In D of formula (I)¹In certain embodiments of (a), each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a straight chain (i.e., linear) alkylene group having 2 to 10 carbon atoms. In the formula (I)D¹In certain embodiments of (a), each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently an ethylene, butylene or propylene group.

In certain embodiments of formula (I), D¹is-NH-and the one or more polymeric compounds comprise a homopolymer of formula (I).

In certain embodiments, component (a) comprises one or more polymeric compounds derived from the polymerization of at least one monomer of formula (II):

R³-D²-C(O)C(R⁴)＝CH₂formula (II).

In certain embodiments, at least one monomer of formula (II) is present in the one or more polymeric compounds in an amount of less than 30 weight percent based on the total amount of monomers.

In the formula (II), R³Represents a hydrocarbon group having 4 to 60 carbon atoms. In certain embodiments of formula (III), R³Represents a hydrocarbon group having 16 to 60 carbon atoms or 16 to 30 carbon atoms.

In the formula (II), R⁴Represents H or CH₃。

In the formula (II), D²Selected from:

-NHC(O)OL¹¹-O-；

-O-C(O)NH-L¹²-O-；

-NHC(O)NH-L¹³-O-; and

-O-。

in D of the formula (II)²Each L¹¹、L¹²And L¹³Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms. In D of the formula (II)²In certain embodiments of (a), each L¹¹、L¹²And L¹³Independently a straight chain (i.e., linear) alkylene group having 2 to 10 carbon atoms.

In certain embodiments, component (a) comprises one or more polymeric compounds derived from the polymerization of at least one monomer of formula (III):

R⁵-X¹-C(O)NH-L¹⁴-OC(O)C(R⁶)＝CH₂formula (III).

In certain embodiments, component (a) comprises one or more polymeric compounds derived from the polymerization of at least one monomer of formula (IV):

R⁷-X²-C(O)NH-Q¹-NH-C(O)O-L¹⁵-OC(O)C(R⁸)＝CH₂formula (IV).

In the formulae (III) and (IV), R⁵And R⁷Independently a hydrocarbon group having from 4 to 60 carbon atoms. In certain embodiments of formulae (III) and (IV), R⁵And R⁷Independently a straight or branched hydrocarbon group, and in certain embodiments, a straight hydrocarbon group having 4 to 60 carbon atoms, 16 to 50 carbon atoms, 16 to 40 carbon atoms, or 16 to 30 carbon atoms.

In the formulae (III) and (IV), R⁶And R⁸Independently is H or CH₃。

In formulae (III) and (IV), L¹⁴And L¹⁵Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms, an arylene group (in some embodiments, an arylene group having 5 to 12 carbon atoms), or a combination thereof.

In the formulae (III) and (IV), X¹Is S or-N (R)⁹) And X²Is O, S, -NH or-N (R)⁹) Wherein R is⁹Are hydrocarbon groups having from 1 to 20 carbon atoms (in certain embodiments, straight or branched chain hydrocarbon groups, and in certain embodiments, straight chain hydrocarbon groups).

In the formula (IV), Q¹Is a divalent isocyanate residue.

In certain embodiments of component (a), the one or more polymeric compounds have an average of greater than 20 repeat units (or at least 30 repeat units, or at least 50 repeat units, or at least 100 repeat units, or at least 200 repeat units, or at least 300 repeat units, or at least 400 repeat units, or at least 500 repeat units, or at least 600 repeat units, or at least 700 repeat units, or at least 800 repeat units, or at least 900 repeat units, or at least 1000 repeat units) of at least one monomer of formula (I), formula (II), formula (III), or formula (IV). In certain embodiments of component (a), the one or more polymeric compounds have an average of greater than 20 repeat units (or at least 30 repeat units, or at least 50 repeat units, or at least 100 repeat units, or at least 200 repeat units, or at least 300 repeat units, or at least 400 repeat units, or at least 500 repeat units, or at least 600 repeat units, or at least 700 repeat units, or at least 800 repeat units, or at least 900 repeat units, or at least 1000 repeat units) of at least one monomer of formula (I).

In certain embodiments, such polymeric compounds comprise up to 10,000 repeat units.

In certain embodiments of component (a), the one or more polymeric compounds are derived from the polymerization of at least one monomer of formula (I) and at least one monomer of formula (II).

In certain embodiments of component (a), the one or more polymeric compounds are derived from at least one monomer of the formula:

C₁₈H₃₇-NH-C(O)C(R²)＝CH₂；

C₁₈H₃₇-NH-C(O)OCH₂CH₂OC(O)C(R²)＝CH₂；

C₁₈H₃₇-NH-C(O)-NH-C(O)-C(R²)＝CH₂(ii) a And

C₁₇H₃₅-C(O)OCH₂CH₂OC(O)C(R²)＝CH₂。

wherein R is²Represents H or CH₃。

In certain embodiments of component (a), the one or more polymeric compounds are derived from at least one monomer of the formula:

C₁₈H₃₇-NH-C(O)C(R²)＝CH₂；

C₁₈H₃₇-NH-C(O)-NH-C(O)-C(R²)＝CH₂(ii) a And

C₁₇H₃₅-C(O)OCH₂CH₂OC(O)C(R²)＝CH₂。

wherein R is²Represents H or CH₃。

In certain embodiments of component (a), the one or more polymeric compounds are derived from at least one monomer of the formula:

C₁₈H₃₇-NH-C(O)C(R²)＝CH₂

wherein R is²Represents H or CH₃. In certain embodiments of component (A), one or more polymeric compounds comprise C₁₈H₃₇-NH-C(O)C(H)＝CH₂A homopolymer of (a).

In certain embodiments of component (a), the one or more polymeric compounds additionally comprise units derived from monomers having one or more functional groups capable of undergoing additional reactions. In certain embodiments, the functional group capable of undergoing additional reactions is selected from the group consisting of polymerizable olefinic groups, olefinic groups capable of undergoing hydrosilylation reactions, epoxy groups, hydroxyl groups, halo groups, haloformyl groups, aziridinyl groups, acid groups, salts of acid groups, amino groups, salts of amino groups, quaternary ammonium groups, salts of quaternary ammonium groups, blocked isocyanate groups, hydroxyalkyl chloride groups, N-hydroxymethyl groups, acetoacetoxyalkyl groups, and combinations thereof. Examples of such monomers include 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, N-methylolacrylamide, glycidyl methacrylate, 3-chloro-2-hydroxypropyl acrylate or the reaction product of 2-isocyanatoethyl (meth) acrylate with Methyl Ethyl Ketoxime (MEKO).

In certain embodiments of component (a), the one or more polymeric compounds have a weight average molecular weight greater than 20,000 daltons. In certain embodiments of component (a), the one or more polymeric compounds have a weight average molecular weight of up to 500,000 daltons.

The techniques and conditions for preparing the monomers of formula (I), formula (II), formula (III) and formula (IV) described herein are well known to those skilled in the art. For example, suitable monomeric reactants (e.g., (meth) acrylic acid, (meth) acrylamide, hydroxyalkyl acrylate) and isocyanate reactants (e.g., stearyl isocyanate) may be combined in the presence or absence of a suitable catalyst.

Suitable amounts of catalyst (e.g., 500ppm) can be used, but this is not mandatory (especially where higher temperatures are used). exemplary catalysts include dibutyl tin dilaurate (DBTD L) and bismuth neodecanoate (e.g., shepherdbcatt 8108M, ABCR bismuth (III) neodecanoate, superconducting grade, about 60% in neodecanoate (15-20% Bi), or Strem Chemicals bismuth (III) neodecanoate, superconducting grade, about 60% in neodecanoate (15-20% Bi)).

The reaction to form the (meth) acrylate containing isocyanate-derived groups (as used below in components (B) and (C)) may for example generally be carried out at a temperature in the range of from 40 ℃ to 100 ℃ or from 70 ℃ to 100 ℃ or from 75 ℃ to 95 ℃, preferably under drying conditions (e.g. dry air). If no catalyst is used, reaction temperatures of from 70 ℃ to 100 ℃ are preferred. Typically, the reaction takes place within 1 to 24 hours or 4 to 15 hours.

To prevent unwanted free radical polymerization during synthesis of the monomers, stabilizers such as 3, 5-di-tert-butyl-4-hydroxy-toluene (BHT), 4-Methoxyphenol (MOP), or Hydroquinone (HQ) may be used, but not mandatory, in appropriate amounts (e.g., 50 to 500 ppm).

Further examples of the preparation of suitable monomers are detailed in the examples section.

In certain embodiments, the polymeric compound of component (a) may be prepared by free radical polymerization.

To prepare the polymeric compound, a free radical initiator may be used to initiate polymerization. Free radical initiators include those known in the art, and specifically include: azo compounds such as 2,2 '-azobis (2-methylpropionamidine) dihydrochloride, 2' -azobis (2-methylbutyronitrile), 2 '-Azobisisobutyronitrile (AIBN), 2' -azobis (2-cyanopentane), and the like; hydroperoxides such as cumene, tert-butyl-and tert-amyl-hydroperoxide, and the like; peroxyesters such as t-butyl perbenzoate, di-t-butylperoxyphthalic acid, and the like; and diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, and the like.

The polymerization can be carried out in a variety of solvents suitable for organic free radical reactions. Examples of suitable solvents include: aliphatic and alicyclic hydrocarbons (e.g., hexane, heptane, cyclohexane), ethers (e.g., diethyl ether, glyme, diglyme, diisopropyl ether), esters (e.g., ethyl acetate, butyl acetate), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone), and mixtures thereof.

The polymerization can also be carried out in aqueous media, such as in emulsion polymerization or microemulsion polymerization, using suitable emulsifiers and initiators known to those skilled in the art. Emulsifiers include nonionic, cationic, amphoteric or anionic surfactants such as sodium alkyl sulfonates, sodium alkyl benzene sulfonates, sodium dialkyl sulfosuccinates, (C12-C18) alkyl alcohol-ethylene oxide adducts, polyethoxylated nonylphenols or alkyl quaternary ammonium ethoxylates.

The polymerization reaction may be carried out at a temperature suitable for carrying out a radical polymerization reaction. The particular temperature and solvent employed can be readily selected by one of skill in the art based upon considerations such as the solubility of the reagents, the temperature required to use a particular initiator, the desired molecular weight, and the like. Although it is not practical to enumerate specific temperatures for all initiators and all solvents, generally a suitable temperature is from 30 ℃ to 150 ℃. In certain embodiments, the temperature is from 55 ℃ to 95 ℃ or from 75 ℃ to 85 ℃. The reaction time is usually within 1 to 24 hours, usually within 4 to 15 hours.

Component (B) polymeric compound and preparation thereof

In certain embodiments, component (B) comprises one or more compounds derived from the reaction of components in one or more steps, said components comprising:

(i) at least one isocyanate-reactive (i.e., functionalized) oligomer comprising from 2 to 20 repeating units, or an alcohol, amine, acid, amide, or thiol comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups (in certain embodiments, at least one isocyanate-reactive oligomer comprising from 2 to 20 repeating units, or an amine, acid, or amide comprising at least one straight or branched chain hydrocarbon group having from 4 to 60 carbon atoms and optionally one or more ester groups, and in certain embodiments, at least one isocyanate-reactive oligomer comprising from 2 to 20 repeating units);

(ii) at least one polyisocyanate;

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound; and

(iv) optionally, at least one isocyanate blocking agent.

Typically, one or more compounds of component (B) used in the compositions of the present disclosure may be prepared in a one-step reaction, a two-step reaction, or optionally a three-step reaction, but typically the reaction product will not need to be isolated after each step. That is, the reaction can be carried out in three steps in a single reactor.

IN certain embodiments, an alcohol comprising at least one straight or branched chain hydrocarbon group having from 16 to 40 carbon atoms and optionally one or more ester groups (e.g., ISOFO L28, ISOFO L32, ISOFO L36, UNI L IN350, sorbitan tristearate, and the reaction product of 1 mole citric acid and 3 moles stearyl alcohol) will be reacted with an equivalent amount of polyisocyanate.

In certain embodiments, in the first step, a functionalized oligomer having from 2 to 20 repeating units is prepared. In a second step, the functionalized oligomer is reacted with a polyisocyanate, optionally in the presence of an additional isocyanate-reactive compound. Thus, the term "functionalized oligomer" (also referred to as isocyanate-reactive oligomer) means an oligomer comprising functional groups capable of reacting with isocyanate. Examples of such groups include alcohol, amine, thiol, acid or amide groups.

In certain embodiments, in the first step, a functionalized oligomer having from 2 to 20 repeating units is prepared. In a second step, the functionalized oligomer is reacted with an excess of isocyanate (typically a polyisocyanate) to form an isocyanate-containing oligomer (i.e., an oligomer having at least one isocyanate terminal group). In a third step, the isocyanate-containing oligomer (i.e., the oligomer having isocyanate end groups) is further reacted with an isocyanate blocking agent. Thus, the reaction product of the second step, i.e., the oligomer comprising at least one isocyanate group (e.g., an isocyanate terminal group), may be formed in the reaction mixture without being isolated (i.e., it is formed in situ).

In certain embodiments of component (B), less than 40% of the isocyanate groups are reacted with acid and/or amide groups.

In certain embodiments, the isocyanate-reactive oligomer is prepared from a free radical initiated reaction of at least one (meth) acrylate or (meth) acrylamide monomer in the presence of at least one thiol, which may or may not be functionalized. In certain embodiments, the thiol is functionalized with at least one isocyanate-reactive group (e.g., an alcohol, amine, acid, or amide group). In certain embodiments, the molar ratio of thiol to (meth) acrylate or (meth) acrylamide monomer is from 1:4 to 1:20, or from 1:8 to 1: 16.

Examples of thiols include monofunctional or difunctional hydroxyl, amino, acid or amide functional thiols (as chain transfer agents) to prepare monofunctional or difunctional oligomers, respectively. Examples of monofunctional thiols (as chain transfer agents) include 2-mercaptoethanol, 3-mercapto-2-butanol, 3-mercapto-2-propanol, 3-mercapto-1-propanol, 2-mercaptoethylamine, 3-mercaptopropionic acid, and 16-mercaptohexadecanoic acid. Particularly suitable monofunctional chain transfer agents include 2-mercaptoethanol, 3-mercaptopropionic acid, and 16-mercaptohexadecanoic acid. Examples of difunctional thiols (as chain transfer agents) include those having two hydroxyl or amino groups or one hydroxyl and one amino group. An example of a suitable bifunctional chain transfer agent is 3-mercapto-1, 2-propanediol (thioglycerol).

In certain embodiments, a non-functional thiol is used, i.e., a thiol that does not contain additional isocyanate-reactive groups. To prepare functionalized oligomers with such thiols, non-functional thiols are reacted with a mixture of (meth) acrylic acid and/or (meth) acrylamide, wherein at least one (meth) acrylate and/or (meth) acrylamide has a functional group capable of reacting with an isocyanate group. Examples of non-functional mercaptans include octyl mercaptan, dodecyl mercaptan, octadecyl mercaptopropionate, and octadecyl mercaptan. Examples of functionalized (meth) acrylates capable of reacting with isocyanate groups include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate and 2-carboxyethyl acrylate.

In certain embodiments, the at least one (meth) acrylate or (meth) acrylamide monomer used to prepare the isocyanate-reactive oligomer comprises at least one hydrocarbon group (in certain embodiments, a straight or branched hydrocarbon group, and in certain embodiments, a straight chain hydrocarbon group) having 4 to 60 carbon atoms, 16 to 50 carbon atoms, 16 to 40 carbon atoms, or 16 to 30 carbon atoms. In certain embodiments, the at least one (meth) acrylate or (meth) acrylamide monomer comprises at least one hydrocarbon group (in certain embodiments, a straight or branched hydrocarbon group, and in certain embodiments, a straight hydrocarbon group) having 4 to 60 carbon atoms, 16 to 50 carbon atoms, 16 to 40 carbon atoms, or 16 to 30 carbon atoms, and at least one isocyanate-derived group.

Herein, the "isocyanate-derived group" is a chemical linking group obtained by the reaction of an isocyanate-containing compound with a compound containing a functional group capable of reacting with isocyanate in the presence or absence of a catalyst. Examples of such groups include, for example, a urethane group (obtained by reaction of an isocyanate-containing compound with an alcohol-containing compound), a urea group (obtained by reaction of an isocyanate-containing compound with an amine-containing compound), an amide group (obtained by reaction of an isocyanate-containing compound with a carboxylic acid-containing compound), or a ureide group (obtained by reaction of an isocyanate-containing compound with an amide-containing compound).

In certain embodiments, the monomer used to prepare the isocyanate-reactive oligomer (which is the compound or compounds used to prepare component (B)) is at least one of formula (I), formula (II), formula (III), and formula (IV) (described above for component (a)). In certain embodiments, if the monomer of formula (II) is used to prepare the isocyanate-reactive oligomer, it is used in an amount of less than 30% by weight, based on the total amount of monomers.

To prepare the functionalized oligomer (i.e., the isocyanate-reactive oligomer), a free radical initiator may be used to initiate the oligomerization. Free radical initiators include those known in the art, and specifically include: azo compounds such as 2,2' -azobis (2-methylbutyronitrile), 2' -Azobisisobutyronitrile (AIBN), 2' -azobis (2-cyanopentane), and the like; hydroperoxides such as cumene, tert-butyl-and tert-amyl-hydroperoxide, and the like; peroxyesters such as t-butyl perbenzoate, di-t-butylperoxyphthalic acid, and the like; and diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, and the like.

The oligomerization reaction to form the functionalized (i.e., isocyanate-reactive) oligomer can be carried out in a variety of solvents suitable for organic free radical reactions. Particularly suitable solvents are those which do not interfere with the isocyanate reaction in the subsequent step. The reactants can be present in the solvent at any suitable concentration (e.g., about 5 wt.% to about 90 wt.%, based on the total weight of the reaction mixture). Examples of suitable solvents include: aliphatic and alicyclic hydrocarbons (e.g., hexane, heptane, cyclohexane), ethers (e.g., diethyl ether, glyme, diglyme, diisopropyl ether), aromatic hydrocarbons (e.g., toluene), esters (e.g., ethyl acetate, butyl acetate), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone), and mixtures thereof.

The oligomerization reaction to form the functionalized (i.e., isocyanate-reactive) oligomer may be carried out at a temperature suitable for carrying out the free radical oligomerization reaction. The particular temperature and solvent employed can be readily selected by one of skill in the art based upon considerations such as the solubility of the reagents, the temperature required to use a particular initiator, the desired molecular weight, and the like. Although it is not practical to enumerate specific temperatures for all initiators and all solvents, generally, a suitable temperature is between 30 ℃ and 150 ℃. In certain embodiments, the temperature is between 55 ℃ and 90 ℃, or between 75 ℃ and 85 ℃. The reaction time is usually within 1 to 24 hours, usually within 3 to 15 hours.

In certain embodiments, the isocyanate-reactive oligomer is represented by formula (V):

Y¹-[CH₂-C(R²)C(O)-D¹-R¹]_m-S-R¹⁰-(T¹)_pformula (V).

In formula (V), Y¹Is H or an initiator residue.

In the formula (V), R¹Is a hydrocarbon group having 4 to 60 carbon atoms, 16 to 50 carbon atoms, 16 to 40 carbon atoms, or 16 to 30 carbon atoms.

In the formula (V), R²Independently is H or CH₃。

In the formula (V), D¹Selected from:

-C(O)O-L¹-O-；

-OC(O)-L²-O-；

-OC(O)-L³-C(O)O-L⁴-O-；

-C(O)NH-L⁵-O-；

-NHC(O)-L⁶-O-；

-NHC(O)-L⁷-C(O)O-L⁸-O-；

-C(O)-NH-；

-C(O)NHC(O)NH-L⁹-O-；

-C(O)NHC(O)-L¹⁰-O-；

-nhc (o) NH-; and

-NH-; with the proviso that when D¹When it is-NH-, the isocyanate-reactive oligomer comprises a monomer based on

(ii) greater than 30 weight percent of-NH-containing monomer units based on the total weight of monomer units.

In certain embodiments, D¹is-NH-and the oligomer comprises 100% of-NH-containing monomer units.

In D of formula (V)¹Each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms in certain embodiments, each L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰Independently a straight chain (i.e., linear) alkylene group having 2 to 10 carbon atoms.

In formula (V), S is sulfur.

In the formula (V), R¹⁰Is a divalent or trivalent linking group having 1 to 10 carbon atoms.

In formula (V), T¹is-C (O) OH, -C (O) NH₂、–OH、–NH₂or-NH (R)¹¹) Wherein R is¹¹Is H or a hydrocarbon group having 1 to 10 carbon atoms;

in formula (V), m is an integer of 2 to 20.

In formula (V), p is independently 1 or 2.

In certain embodiments, the isocyanate-reactive oligomer is represented by formula (VI):

Y²-[CH₂-C(R⁴)C(O)-D²-R³]_m-S-R¹²-(T²)_pformula (VI).

In the formula (VI), Y²Is H or an initiator residue.

In the formula (VI), R³Is a hydrocarbon group having 4 to 60 carbon atoms, 16 to 50 carbon atoms, 16 to 40 carbon atoms, or 16 to 30 carbon atoms.

In the formula (VI), R⁴Independently is H or CH₃。

In the formula (VI), D²Selected from:

-NHC(O)OL¹¹-O-；

-O-C(O)NH-L¹²-O-；

-NHC(O)NH-L¹³-O-; and

-O-。

in formula (VI), each L¹¹、L¹²And L¹³Independently a branched or straight chain alkylene group having 2 to 10 carbon atoms in certain embodiments, each L¹¹、L¹²And L¹³Independently a straight chain (i.e., linear) alkylene group having 2 to 10 carbon atoms.

In formula (VI), S is sulfur.

In the formula (VI), R¹²Is a divalent or trivalent linking group having 1 to 10 carbon atoms.

In the formula (VI), T²is-C (O) OH, -C (O) NH₂、-OH、NH₂or-NH (R)¹¹) Wherein R is¹¹Is H or a hydrocarbon group having 1 to 10 carbon atoms; provided that when T is²is-OH, -NH₂or-NH (R)¹¹) When component (iii) is present and comprises an acid or amide functional group.

In formula (VI), m is an integer of 2 to 20.

In formula (VI), p is independently 1 or 2.

In certain embodiments, the functionalized (i.e., isocyanate-reactive) oligomer has a weight average molecular weight of at least 600, or at least 1500, or at least 2000 daltons. In certain embodiments, the functionalized oligomer has a weight average molecular weight of at most 20,000, or at most 10,000, or at most 5,000 daltons.

In the second step, an isocyanate-containing oligomer (i.e., an isocyanate oligomer having at least one isocyanate terminal group) is prepared by a condensation reaction of a functionalized (i.e., isocyanate-reactive) oligomer with a polyisocyanate. The reaction product of such condensation reactions is typically a mixture of isocyanate-containing oligomers.

In certain embodiments, in the components of the one or more compounds used to prepare component (B), the at least one polyisocyanate comprises an aromatic and/or aliphatic polyisocyanate, such as an aromatic or aliphatic diisocyanate, an aromatic or aliphatic triisocyanate, an aromatic or aliphatic polymeric isocyanate, or mixtures thereof. Examples of such polyisocyanates include: 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, o-, m-and p-xylylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 4-isophorone diisocyanate, 4' -diisocyanatodiphenyl ether, 3' -dichloro-4, 4' -diisocyanatodiphenylmethane, 4' -diphenyl diisocyanate, 4' -diisocyanatodibenzyl, 3' -dimethoxy-4, 4' -diisocyanatodiphenyl, 3' -dimethyl-4, 4' -diisocyanatodiphenyl, 2' -dichloro-5, 5' -dimethoxy-4, 4' -diisocyanatodiphenyl, 2, 4' -diisocyanatodiphenyl, 1, 3-diisocyanatobenzene, 1, 2-naphthylene diisocyanate, 4-chloro-1, 2-naphthylene diisocyanate, 1, 3-naphthylene diisocyanate, 1, 8-dinitro-2, 7-naphthylene diisocyanate, tris- (4-isocyanatophenyl) -methane, polymethylene polyphenyl isocyanates (PAPI) and their respective biurets or isocyanurates.

In certain embodiments, the component(s) of one or more compounds used to prepare component (B) include (iii) at least one additional mono-, di-, or polyfunctional isocyanate-reactive compound.

In certain embodiments, additional mono-, di-or polyfunctional isocyanate-reactive compounds include compounds comprising: a hydrocarbon group having from 4 to 60 carbon atoms (or from 16 to 60 carbon atoms, or from 16 to 50 carbon atoms, or from 16 to 40 carbon atoms, or from 16 to 30 carbon atoms): a polydimethylsiloxane segment having a weight average molecular weight of at least 200; a divalent polyoxyalkylene group comprising 2 to 100 alkylene oxide repeat units wherein the alkylene oxide units have 2 to 10 carbon atoms; or a combination thereof.

In certain embodiments, the additional mono-, di-, or polyfunctional isocyanate-reactive compound comprises a mono-, di-, or polyfunctional alcohol, thiol, amine, acid, or amide.

Examples of alcohol-containing compounds include: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, tert-pentanol, 2-ethylhexanol, glycidol, stearyl alcohol, (iso) stearyl alcohol, behenyl alcohol, branched chain long chain alkanesAlcohols such as ISOFO L alcohol (2-alkyl alkanols having C-14 to C-32 alkyl chains, available from Sasol, Germany)), alcohols containing poly (oxyalkylene) groups such as methyl or ethyl ethers of polyethylene glycol, hydroxy-terminated methyl or ethyl ethers of random or block copolymers of ethylene and/or propylene oxide with alcohols containing polysiloxane (e.g., polydimethylsiloxane) groups other examples include diols, triols and polyols such as 1, 4-butanediol, 1, 6-hexanediol, 1-10-decanediol, 4' -isopropylidenediphenol (bisphenol A), glycerol, pentaerythritol, dipentaerythritol, polyester glycols such as polycaprolactone glycol, fatty acid dimer glycols and poly (oxy) alkylene glycols having oxyalkylene groups having 2 to 4 carbon atoms, such as-OCH₂CH₂-,-O(CH₂)₄-,-OCH₂CH₂CH₂-,-OCH(CH₃)CH₂-and-OCH (CH)₃)CH(CH₃) The poly (oxy) alkylene glycol of (a) (the oxyalkylene units in the poly (oxyalkylene) may be the same, such as in polypropylene glycol or present as a mixture); and ester diols such as glyceryl monostearate and silicone-containing (e.g. polydimethylsiloxane-containing) diols.

Examples of thiol-containing compounds include octadecyl mercaptan, dodecyl mercaptan, octadecyl mercaptopropionate, 1, 4-butanedithiol, and 1, 6-hexanedithiol.

Examples of amine-containing compounds include octadecylamine, dioctadecylamine, 1, 6-hexamethylenediamine, amino-terminated polyethylene oxide or propylene oxide or copolymers thereof, amino-terminated methyl or ethyl ethers of polyethylene oxide or polypropylene oxide or copolymers thereof, and amino group-terminated polysiloxanes such as polydimethylsiloxane.

Examples of the acid-containing compound include octadecyl (stearic) acid, behenic acid (or behenic acid), adipic acid, dodecanedioic acid, and octadecanedioic acid.

Examples of the amide-containing compound include octadecyl (stearyl) amide, isostearyl amide, and octyl amide.

The condensation reaction of the functionalized (i.e., isocyanate-reactive) oligomer with the polyisocyanate (in one embodiment, an excess of polyisocyanate) may be carried out under conventional conditions well known to those skilled in the art. In certain embodiments, the condensation reaction is carried out under dry conditions in a polar solvent such as ethyl acetate, acetone, methyl isobutyl ketone, and the like. One skilled in the art will readily determine the appropriate reaction temperature depending on the particular reagents, solvents and catalysts used. Although it is impractical to enumerate specific temperatures for all cases, generally suitable temperatures are from room temperature to 120 ℃.

In certain embodiments, the condensation reaction is carried out in the absence of a catalyst. In certain embodiments, the condensation reaction is carried out in the presence of a catalyst; these catalysts are well known to those skilled in the art. Depending on the isocyanate-reactive groups, suitable catalysts may be selected from, for example, tin catalysts such as dibutyltin dilaurate or stannous octoate, zirconium catalysts such as zirconium isopropoxide; or a magnesium halide such as magnesium chloride.

The condensation reaction typically produces a mixture of compounds. These compounds can be used directly in the treatment compositions of the present disclosure.

In certain embodiments, the component of the one or more compounds used to prepare component (B) comprises (iv) blocked isocyanate groups. Such blocked isocyanate groups are the result of the reaction of an isocyanate-containing oligomer (obtained from the condensation reaction of an isocyanate-reactive oligomer in the presence of an excess of polyisocyanate) with a blocking agent.

Such blocked isocyanates are particularly preferred because they impart durable properties when such blocked compounds are applied to a fibrous substrate. This is generally because the blocking agent is removable from the isocyanate under the thermal conditions used in curing the fibrous substrate treated with the compound containing blocked isocyanate groups.

Conventional isocyanate blocking agents include aryl alcohols (e.g., phenol, cresols, nitrophenols, o-and p-chlorophenols, naphthols, 4-hydroxybiphenyl); c2 to C8 alkanone oximes (e.g., acetoxime, butanone oxime); aromatic thiols (e.g., thiophenol); organic active hydrogen compounds (e.g., diethyl malonate, acetylacetone, ethyl acetoacetate, ethyl cyanoacetate, -caprolactam); sodium bisulfite; and hydroxylamine.

Particularly preferred blocked isocyanates include those blocked with oxime blocking agents such as C2 to C8 alkanone oximes, particularly 2-butanone oxime. That is, the preferred blocked isocyanate group is an oxime-derived group. Such blocked isocyanates can be unblocked at relatively low temperatures, for example during the process of curing a fibrous substrate that has been treated with a compound comprising blocked isocyanate groups.

Various combinations of capping agents can be used to prepare the compounds of component (B) of the present disclosure, if desired. In certain embodiments, if a blocking agent is used, up to 70% or up to 60% of the isocyanate equivalents will be blocked by one or more blocking groups. In certain embodiments, if a blocking agent is used, at least 10%, or at least 20%, or at least 30%, or at least 40% of the isocyanate equivalent weight will be blocked by one or more blocking groups.

This step of blocking the isocyanate-containing oligomer under conventional conditions is well known to those skilled in the art. In certain embodiments, the capping reaction is carried out under dry conditions in a polar solvent such as ethyl acetate, acetone, methyl isobutyl ketone, and the like. One skilled in the art will readily determine the appropriate reaction temperature depending on the particular reagents, solvents and catalysts used. Although it is not practical to enumerate a particular temperature suitable for all cases, a temperature of room temperature to 120 ℃ is generally suitable.

Polycarbodiimide as component (C) and its preparation

Component (C) comprises one or more polycarbodiimide compounds (i.e. compounds comprising one or more groups of the formula (-N ═ C ═ N-).

In certain embodiments, the one or more polycarbodiimide compounds of component (C) are derived from the carbodiimidization reaction of component (C) in one or more steps comprising:

(i) at least one isocyanate reactive oligomer (i.e., a functionalized oligomer) comprising 2 to 20 repeating units, or an alcohol, amine, acid, amide, or thiol comprising at least one linear or branched hydrocarbon group having 4 to 60 carbon atoms (or 16 to 60 carbon atoms, or 16 to 50 carbon atoms, or 16 to 40 carbon atoms, or 16 to 30 carbon atoms) and optionally one or more ester groups (in certain embodiments, at least one isocyanate reactive oligomer comprising 2 to 20 repeating units, or an amine, acid, or amide comprising at least one linear or branched hydrocarbon group having 4 to 60 carbon atoms and optionally one or more ester groups, and in certain embodiments, at least one isocyanate reactive oligomer comprising 2 to 20 repeating units);

(ii) at least one polyisocyanate; and

(iii) optionally, at least one additional mono-, di-or polyfunctional isocyanate-reactive compound.

Generally, the polycarbodiimide compounds of the present disclosure and mixtures thereof may be prepared by a three-step reaction, but generally, the reaction product need not be isolated after each step. That is, the reaction can be carried out in three steps in a single reactor.

IN certain embodiments, an alcohol comprising at least one straight or branched chain hydrocarbon group having from 16 to 40 carbon atoms and optionally one or more ester groups (e.g., ISOFO L, ISOFO L, ISOFO L, UNI L IN350, sorbitan tristearate, and the reaction product of 1 mole of citric acid and 3 moles of stearyl alcohol) will react with an isocyanate to form an isocyanate-containing compound.

In certain embodiments, in the first step, a functionalized oligomer having at least two repeating units is prepared. In a second step, the functionalized oligomer is reacted with a polyisocyanate to form an isocyanate-containing oligomer (i.e., an oligomer having at least one isocyanate terminal group and at least two repeat units) as described above for component (B). In the third step, the isocyanate-containing oligomer (i.e., the oligomer having isocyanate end groups) is further reacted in a carbodiimidization reaction to form polycarbodiimide. Thus, the reaction product of the second step (i.e., the oligomer comprising at least one terminal isocyanate group and at least two repeat units) may be formed in the reaction mixture without isolation (i.e., formed in situ).

The isocyanate-reactive oligomers (i.e., functionalized oligomers) of the polycarbodiimide compound or compounds used in the preparation of component (C) can be prepared as described above for component (B) using monomers as described above for component (a). In addition, isocyanate-containing oligomers that further undergo a carbodiimidization reaction (i.e., oligomers having isocyanate end groups) can be prepared as described above for component (B).

In certain embodiments, the isocyanate-reactive oligomer is prepared from a free radical initiated reaction of at least one (meth) acrylate or (meth) acrylamide monomer in the presence of at least one thiol, which may or may not be functionalized. In certain embodiments, the thiol is functionalized with at least one isocyanate-reactive group (e.g., an alcohol or amine group). In certain embodiments, the molar ratio of thiol to (meth) acrylate or (meth) acrylamide monomer is from 1:4 to 1:20, or from 1:8 to 1: 16.

Examples of thiols include those listed above in component (B).

In certain embodiments, the at least one (meth) acrylate or (meth) acrylamide monomer used to prepare the isocyanate-reactive oligomer comprises at least one hydrocarbon group (in certain embodiments, a straight or branched hydrocarbon group, and in certain embodiments, a straight chain hydrocarbon group) having 4 to 60 carbon atoms, 16 to 50 carbon atoms, 16 to 40 carbon atoms, or 16 to 30 carbon atoms. In certain embodiments, the at least one (meth) acrylate or (meth) acrylamide monomer comprises at least one hydrocarbon group (in certain embodiments, a straight or branched hydrocarbon group, and in certain embodiments, a straight hydrocarbon group) having 4 to 60 carbon atoms, 16 to 50 carbon atoms, 16 to 40 carbon atoms, or 16 to 30 carbon atoms, and at least one isocyanate-derived group.

In certain embodiments, the monomer used to prepare the isocyanate-reactive oligomer (which is the compound or compounds used to prepare component (C)) is at least one of formula (I), formula (II), formula (III), and formula (IV) (described above for component (B)). In certain embodiments, if the monomer of formula (II) is used to prepare the isocyanate-reactive oligomer, it is used in an amount of less than 30% by weight, based on the total amount of monomers.

To prepare the functionalized oligomer (i.e., the isocyanate-reactive oligomer), a free radical initiator may be used to initiate the oligomerization, as described above for component (B).

In certain embodiments, the isocyanate-reactive oligomer used to prepare the polycarbodiimide compound of component (C) is represented by formula (V) and/or formula (VI) (as described above for component (B)).

In the second step, the isocyanate-containing oligomer (i.e., an isocyanate oligomer having at least one isocyanate terminal group) is prepared by condensation reaction of a functionalized (i.e., isocyanate-reactive) oligomer with an excess of polyisocyanate, as described above for component (B). The reaction product of such condensation reactions is typically a mixture of isocyanate-containing oligomers.

In certain embodiments, the component(s) of one or more compounds used to prepare component (C) comprise (iii) at least one additional mono-, di-, or polyfunctional isocyanate-reactive compound. In certain embodiments, additional mono-, di-or polyfunctional isocyanate-reactive compounds include those described above for component (B).

In the third step, the polycarbodiimide compound (component (C)) used in the composition of the present disclosure may be formed by a carbodiimidization reaction in the presence of a suitable catalyst.

Representative examples of suitable catalysts are described in, for example, U.S. Pat. No.2,941,988, U.S. Pat. No.3,862,989, and U.S. Pat. No.3,896,251. Examples include 3-methyl-1-phenyl-2-phosphorus-1-oxide (MPPO), 1-ethyl-3-diethylphosphonothiocholine, 1-ethyl-3-methyl-3-diethylphosphonothiocholine-1-oxide, 1-ethyl-3-methyl-3-diethylphosphonothiocholine-1-sulfide, 1-ethyl-3-methyl-phosphidine, 1-ethyl-3-methyl-phosphidine-1-oxide, 3-methyl-1-phenyl-3-diethyloxyphosphonothiocholine-1-oxide and a bicycloalkyl or alkylaryl phosphine oxide or camphenylphosphine oxide.

The specific amount of catalyst used will depend to a large extent on the reactivity of the catalyst itself and the isocyanate. A concentration range of 0.05 to 5 parts of catalyst per 100 parts of oligomer having at least one isocyanate group is generally suitable.

This third step of the carbodiimidization reaction can be carried out under conventional conditions well known to those skilled in the art. In certain embodiments, the carbodiimidization reaction is carried out under dry conditions in a polar solvent such as ethyl acetate, acetone, methyl isobutyl ketone, and the like. One skilled in the art will readily determine the appropriate reaction temperature depending on the particular reagents, solvents and catalysts used. Although it is impractical to enumerate specific temperatures for all cases, a temperature of 70 ℃ to 100 ℃ is generally suitable. In certain embodiments, the reaction is carried out at a temperature of 75 ℃ to 95 ℃.

In one embodiment of the three-step process, steps 2 and 3 are performed simultaneously. That is, the condensation reaction (step 2) and the carbodiimide reaction (step 3) occur simultaneously.

In certain embodiments, the one or more polycarbodiimide compounds of component (C) have the formula:

Q²-(X³-C(O)NH-(A¹-(N＝C＝N))_r-A²-NHC(O)-X⁴)_s-Q³formula (VII).

In the formula (VII), X³Is a chemical bond, -O-, -NH-, -N (R)¹⁴) -S-or-C (O) NH-, and X⁴Is a chemical bond, -O-, -NH-, -N (R)¹⁴) -S-or-NHC (O) -, wherein R is¹⁴Are hydrocarbon groups (e.g., alkyl groups) having 1 to 20 carbon atoms (e.g., methyl, ethyl, octyl, and octadecyl).

In the formula (VII), A¹And A²Each represents a residue of an organic diisocyanate compound.

In formula (VII), s is 1 or 2.

In formula (VII), r is 2 to 10.

In formula (VII), Q²And Q³Independently selected from: a hydrocarbon group (in certain embodiments, a straight or branched chain hydrocarbon group) having at least 2 carbon atoms (in certain embodiments, 2 to 60 carbon atoms); and has the formula- (CH)₂)_a-a group of S-U (formula (VIII)).

In formula (VIII), a is an integer of 1 to 10.

In formula (VIII), S is sulfur.

In formula (VIII), U is an oligomeric group comprising from 2 to 20 repeat units of a monomer selected from at least one of formula (I), formula (II), formula (III) and formula (IV) (as described above for component (a)). In certain embodiments, if the monomer of formula (II) is used to prepare the isocyanate-reactive oligomer, it is used in an amount of less than 30% by weight, based on the total amount of monomers.

In certain embodiments of formula (VII), X³And X⁴Each is-O-, s is 1, and r is 3.

Treatment composition

The compositions of the present disclosure are typically treatment compositions. In certain embodiments, such treatment compositions are fluorine-free treatment compositions. In certain embodiments, such treatment compositions are aqueous dispersions.

In certain embodiments, the fluorine-free treatment composition further comprises one or more additives selected from the group consisting of paraffin waxes, surfactants, coalescing solvents, antifreeze solvents, emulsifiers, and stabilizers against one or more microorganisms.

Component a, component B and/or component C may be dispersed in water using a surfactant or mixture of surfactants in an amount sufficient to stabilize the dispersion. If one or more components are prepared in solution in a solvent, the component(s) can be dispersed in water by vigorous mixing and homogenization with the aid of surfactants or emulsifiers and subsequent homogenization, for example by means of a Manton Gaulin homogenizer or an ultrasonic homogenizer. The dispersion free of organic solvent can then be obtained by subsequent distillation of the solvent.

A typical dispersion will contain water in an amount of 100 to 1000 parts by weight based on 100 parts by weight of component a, component B and/or component C. In certain embodiments, the surfactant or surfactant mixture is present in an amount of 1 to 25 parts by weight, or 5 to 15 parts by weight, based on 100 parts by weight of component a, component B, and/or component C.

The treatment compositions of the present disclosure may comprise conventional cationic, nonionic, anionic and/or zwitterionic (i.e., amphoteric) surfactants (i.e., emulsifiers.) mixtures of surfactants may be used, e.g., mixtures comprising nonionic and ionic surfactants suitable nonionic surfactants may have a high or low H L B value, such as TERGITO L, TWEEN, etc.

In certain embodiments, surfactants suitable for use in the treatment compositions of the present disclosure are described in international publication WO 2013/162704.

In certain embodiments of the present disclosure, the treatment composition comprises component (a). In certain embodiments, the treatment composition comprises component (a), and at least one of component (B) and component (C).

Certain embodiments of the compositions of the present disclosure (e.g., fluorine-free treatment compositions) comprise: 1 to 99 wt% of component (a), based on the total weight of component (a) and component (B) and/or component (C); and from 1 to 99 weight percent of component (B), component (C), or both, based on the total weight of component (a) and component (B) and/or component (C).

Certain embodiments of the compositions of the present disclosure (e.g., fluorine-free treatment compositions) comprise: 10 to 90 wt% of component (a), based on the total weight of component (a) and component (B) and/or component (C); and 10 to 90 weight percent of component (B), component (C), or both, based on the total weight of component (a) and component (B) and/or component (C).

Certain embodiments of the compositions of the present disclosure (e.g., fluorine-free treatment compositions) comprise: 20 to 80 wt% of component (a), based on the total weight of component (a) and component (B) and/or component (C); and 20 to 80 weight percent of component (B), component (C), or both, based on the total weight of component (a) and component (B) and/or component (C).

Certain embodiments of the compositions of the present disclosure (e.g., fluorine-free treatment compositions) comprise: 30 to 70 wt% of component (a), based on the total weight of component (a) and component (B) and/or component (C); and 30 to 70 weight percent of component (B), component (C), or both, based on the total weight of component (a) and component (B) and/or component (C).

In certain embodiments of the present disclosure, the treatment composition comprises component (B). In certain embodiments, the treatment composition comprises component (B) and at least one of component (B) and component (C).

Certain embodiments of the compositions of the present disclosure (e.g., fluorine-free treatment compositions) comprise: 1 to 99 wt% of component (B), based on the total weight of component (B) and component (a) and/or component (C); and from 1 to 99 weight percent of component (a), component (C), or both, based on the total weight of component (B) and component (a) and/or component (C).

Certain embodiments of the compositions of the present disclosure (e.g., fluorine-free treatment compositions) comprise: 10 to 90 wt% of component (B), based on the total weight of component (B) and component (a) and/or component (C); and 10 to 90 weight percent of component (a), component (C), or both, based on the total weight of component (B) and component (a) and/or component (C).

Certain embodiments of the compositions of the present disclosure (e.g., fluorine-free treatment compositions) comprise: 20 to 80 wt% of component (B), based on the total weight of component (B) and component (a) and/or component (C); and 20 to 80 weight percent of component (a), component (C), or both, based on the total weight of component (B) and component (a) and/or component (C).

Certain embodiments of the compositions of the present disclosure (e.g., fluorine-free treatment compositions) comprise: 30 to 70 wt% of component (B), based on the total weight of component (B) and component (a) and/or component (C); and 30 to 70 weight percent of component (a), component (C), or both, based on the total weight of component (B) and component (a) and/or component (C).

In certain embodiments of the present disclosure, the treatment composition comprises component (C). In certain embodiments, the treatment composition comprises component (C) and at least one of component (a) and component (B).

Certain embodiments of the compositions of the present disclosure (e.g., fluorine-free treatment compositions) comprise: 1 to 99 wt% of component (C), based on the total weight of component (C) and component (a) and/or component (B); and from 1 to 99 weight percent of component (a), component (B), or both, based on the total weight of component (C) and component (a) and/or component (B).

Certain embodiments of the compositions of the present disclosure (e.g., fluorine-free treatment compositions) comprise: 10 to 90 wt% of component (C), based on the total weight of component (C) and component (a) and/or component (B); and 10 to 90 weight percent of component (a), component (B), or both, based on the total weight of component (C) and component (a) and/or component (B).

Certain embodiments of the compositions of the present disclosure (e.g., fluorine-free treatment compositions) comprise: 20 to 80 wt% of component (C), based on the total weight of component (C) and component (a) and/or component (B); and 20 to 80 weight percent of component (a), component (B), or both, based on the total weight of component (C) and component (a) and/or component (B).

Certain embodiments of the compositions of the present disclosure (e.g., fluorine-free treatment compositions) comprise: 30 to 70 wt% of component (C), based on the total weight of component (C) and component (a) and/or component (B); and 30 to 70 weight percent of component (a), component (B), or both, based on the total weight of component (C) and component (a) and/or component (B).

Exemplary embodiments