Polyurethanes derived from non-fluorinated or partially fluorinated polymers

Patent metadata

Field	Value
Publication number	US-9957661-B2
Application number	US-201715617272-A
Country	US
Kind code	B2
Filing date	Jun 8, 2017
Priority date	Sep 26, 2014
Publication date	May 1, 2018
Grant date	May 1, 2018

Abstract

Polymers are described having repeat units of Formula (I):

wherein R 3 is H or alkyl group; x and t are positive integers; Q is C(O)O, C(O)NH, or direct bond; D is alkylene, arylene, or (CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m ; E is O, S, NR 5 , or direct bond; R 5 is H or alkyl; G is the residue of a polyisocyanate; V is a urethane, urea, or thiourea that bonds to other parts of the polymer compound or to a monovalent blocking group; s is 1 to 5; Y is O or a substituted or unsubstituted arylene group; A is an alkylene group; w, v, and y are 0 or 1; X is the residue of a cyclic or acyclic sugar alcohol which is substituted with —R 1 , —C(O)R 1 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 , or mixtures thereof; n and m are independently 0 to 20; R 1 is independently an alkyl group; and R 2 is independently —H or alkyl group.

First claim

What is claimed is:

1. A method of preparing a polymer compound comprising
(i) reacting (a) at least one compound selected from Formula (IV)

with (b) at least one compound selected from Formula (V)

(ii) optionally reacting at least one additional ethylenically unsaturated monomer;
(iii) subsequently reacting the product of step (i) or (ii) with at least one diisocyanate or polyisocyanate; and
(iv) optionally reacting at least one isocyanate-reactive compound during step (iii) or following step (iii);

wherein
R 3 is selected from H or a C 1 to C 4 alkyl group;
Q is C(O)O, C(O)NH, or a direct bond;
D is a C 1 to C 6 linear or branched alkylene, an arylene group, or (CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m ,
J is H, OH, N(R 5 ) 2 , C(O)OH, or SH;
provided that J is H only when D is (CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m ;
R 5 is H or a C 1 to C 6 alkyl;
Y is selected from O, a substituted arylene group, or an unsubstituted arylene group;
A is a linear or branched C 1 to C 10 alkylene group;
w is 0 or 1;
v is 0 or 1;
y is 0 or 1;
provided that w+y is at least 1; if w is 0 then Y is a substituted or unsubstituted arylene group; and if Y is O then v is 1;
X is the residue of a cyclic or acyclic sugar alcohol which is substituted with at least one —R 1 , —C(O)R 1 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 , or mixtures thereof;
where the cyclic or acyclic sugar alcohol is selected from a saccharide, reduced sugar, aminosaccharide, aldonic acid, or aldonic acid lactone; wherein
each n is independently 0 to 20;
each m is independently 0 to 20;
m+n is greater than 0;
each R 1 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; and
each R 2 is independently H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or mixtures thereof.

2. The method of claim 1 , where X is selected from Formulas (IIa), (IIb), or (IIc):

wherein each R is independently a direct bond to C═O of Formula I, H, —R 1 , —C(O)R 1 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ;
n and m are defined as above;
m+n is greater than 0;
r is 1 to 3;
a is 0 or 1;
p is independently chosen from 0 to 2;
provided that a is 0 when r is 3;
each R 1 and R 2 are defined as above;
provided when X is Formula (IIa), then one R is a direct bond to C═O of Formula 1; and at least one R is a —R 1 , —C(O)R 1 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ;
each R 4 is independently a direct bond to C═O of Formula I, —H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond or combinations thereof, —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ;
provided when X is Formula (IIb), then one R or R 4 is a direct bond to C═O of Formula 1; and at least one R or R 4 is a linear or branched alkyl group optionally comprising at least 1 unsaturated bond or combinations thereof, —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ; and
each R 19 is a direct bond to C═O of Formula I, —H, —C(O)R 1 , or —CH 2 C[CH 2 OR] 3 , provided when X is Formula (IIc), then one R 19 or R is a direct bond to C═O of Formula I; and at least one R 19 or R is —C(O)R 1 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 .

3. The method of claim 1 where at least one additional ethylenically unsaturated monomer is used, having a functional group selected from a linear or branched hydrocarbon, linear or branched fluorocarbon, ether, anhydride, oxyalkylene, ester, formate, carbamate, urea, amide, sulfonate, sulfonic acid, sulfonamide, halide, saturated or unsaturated cyclic hydrocarbon, morpholine, pyrrolidine, piperidine, or mixtures thereof.

4. The method of claim 3 , wherein the additional ethylenically unsaturated monomer is selected from linear or branched alkyl (meth)acrylates, linear or branched fluoroalkyl (meth)acrylates optionally interrupted by O, CH 2 , CH 2 CH 2 , or SO 2 NH, alkoxylated (meth)acrylates, (meth)acylic acid, vinyl or vinylidene chloride, glycidyl (meth)acrylate, vinyl acetate, hydroxyalkylene (meth)acrylate, urethane or urea (meth)acrylates, (meth)acrylamides including N-methyloyl (meth)acrylamide, alkoxyalkyl (meth)acrylamide, styrene, alpha-methylstyrene, chloromethyl-substituted styrene, ethylenediol di(meth)acrylate, 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS), and maleic anhydride.

5. A method of treating a fibrous substrate comprising applying to the surface of a substrate a polymer made by the method of claim 1 .

6. The method of claim 5 wherein the applying step is performed by exhaustion, foam, flex-nip, nip, pad, kiss-roll, beck, skein, winch, liquid injection, overflow flood, roll, brush, roller, spray, dipping or immersion.

7. The method of claim 2 , wherein X is selected from Formula (IIa) to be Formula (IIa′):

wherein R is further limited to independently a direct bond to C═O, —H, —R 1 , or —C(O)R 1 .

8. The method of claim 2 , wherein X is selected from Formula (IIa) to be Formula (IIa′):

wherein R is further limited to independently a direct bond to C═O, —H, —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 .

9. The method of claim 1 , comprising the step of reacting at least one isocyanate-reactive compound following step (iii), where the isocyanate-reactive compound is water.

Assignees

• Chemours Co Fc Llc

Inventors

• Sworen John Christopher
• Brown Gerald Oronde
• Haidzinskaya Tatsiana
• Kohler Ewa

Classifications

• D06M2200/12

  Hydrophobic properties · CPC title

• C08G18/284

  Compounds containing ester groups, e.g. oxyalkylated monocarboxylic acids · CPC title

• C08G18/8116

  esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group · CPC title

• D06M15/273

  of unsaturated carboxylic esters having epoxy groups · CPC title

• C08G18/7831

  containing biuret groups · CPC title