Biodegradable Graft Polymers

Abstract

A novel graft polymer can include a block copolymer backbone (A) as a graft base having polymeric sidechains (B) grafted thereon. The polymeric sidechains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally N-vinylpyrrolidone as optional further monomer (B2). For example, the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). Also included is a process for obtaining such a graft polymer, the process is preferably carried out by free-radical polymerization.

1 . A graft polymer comprising:
 (A) a block copolymer backbone as a graft base, wherein said block copolymer backbone (A) comprises at least two monomers comprising ethylene oxide; 1,2-propylene oxide; 1,2-butylene oxide; 2,3-butylene oxide; 1,2-pentene oxide; 2,3-pentene oxide; or a combination thereof, where said block copolymer backbone (A) has three or more alkylene oxide blocks;   (B) polymeric sidechains grafted onto the block copolymer backbone (A), wherein said polymeric sidechains (B) comprise at least one vinyl ester monomer (B1),   wherein the vinyl ester monomer (B1) comprises at least 50%, by weight of B1 monomers,   wherein the polymer has an OG of greater than 0, wherein
     OG=a   X   EO+b   X   M   n   2   −c   X ( M   n   ×SUB )− d   X   M   n   +e   X   SUB+h   X  
 
   wherein:   “M n ” is the number average molecular weight of the block copolymer backbone (A);   “EO” is the molar ratio of ethylene oxide moieties to total alkylene oxide moieties present in the backbone (A), wherein EO is in the range of from 0 to less than 1.00,   “SUB” is the weight percentage, by weight of the polymer, of polymeric sidechains B);   “a X ” is a coefficient and equals 7.06;   “b X ” is a coefficient and equals 5.63×10 −7 ;   “c X ” is a coefficient and equals 1.25×10 −3 ;   “d X ” is a coefficient and equals 7.03×10 −3 ;   “e X ” is a coefficient and equals 3.66; and   “h X ” is a coefficient and equals 16.3.   
     
     
         2 . The graft polymer according to  claim 1 , wherein the graft polymer also has a FJ of greater than 0, wherein
     FJ=a   Y   EO−b   Y   M   n   2   +d   Y   M   n   +e   Y   SUB−f   Y   SUB   2   −g   Y ( EO×SUB )− h   Y  
   wherein:   “a Y ” is a coefficient and equals 446;   “b Y ” is a coefficient and equals 4.02×10 −6 ;   “d Y ” is a coefficient and equals 0.0168;   “e Y ” is a coefficient and equals 281;   “f Y ” is a coefficient and equals 229;   “g Y ” is a coefficient and equals 1140; and   “h Y ” is a coefficient and equals 83.6.   
     
     
         3 . The graft polymer according to  claim 1 , wherein said polymeric sidechains (B) comprise at least one vinyl ester monomer (B1) and at least one N-vinylpyrrolidone monomer (B2). 
     
     
         4 . The graft polymer according to  claim 1 , wherein “SUB” is the weight percentage, by weight of the polymer, of vinyl ester monomer side chains (B1). 
     
     
         5 . The graft polymer according to  claim 1 , where the graft polymer comprises from 20% to 95% by weight of the block copolymer backbone (A) and from 5% to 80% by weight of the polymeric sidechains (B) (in relation to the total weight of the graft polymer). 
     
     
         6 . The graft polymer according to  claim 1  wherein the block copolymer backbone (A) comprises:
 (i) at least two monomers selected from ethylene oxide; 1,2 propylene oxide; or 1,2-butylene oxide; and/or 
 (ii) one of the at least two monomers is ethylene oxide; and/or 
 (iii) the number of individual alkylene oxide blocks (x) within the block copolymer backbone (A) is an integer, wherein x has a value of from 3 to 10. 
 
     
     
         7 . The graft polymer according to  claim 6 , wherein block copolymer backbone (A) comprises ethylene oxide. 
     
     
         8 . The graft polymer according to  claim 6 , wherein the number of individual alkylene oxide blocks (x) within the block copolymer backbone (A) is an integer, wherein x has a value of from 3 to 5. 
     
     
         9 . The graft polymer according to  claim 1 , wherein
 (i) the graft polymer has a weight average molecular weight M w  of from 800 to 10,000 g/mol; and/or   (ii) the graft polymer has a polydispersity M w /M n  of less than 3.0, wherein:
 “M w ”=weight average molecular weight [g/mol]; and 
 “M n ”=number average molecular weight [g/mol]; and/or 
   (iii) the block copolymer backbone (A) is capped at one or both endgroups, and/or   (iv) the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide and polypropylene oxide.   
     
     
         10 . The graft polymer according to  claim 1 , wherein the block copolymer backbone (A) has the structure according to formula (A1) and/or formula (A2),
 wherein formula (A1) is defined as follows:   
       
         
           
           
               
               
           
         
         wherein: 
         “n” is an integer in the range of 2 to 100, and 
         “m” is an integer in the range of 2 to 100; and 
         wherein formula (A2) is defined as follows: 
       
       
         
           
           
               
               
           
         
         wherein: 
         “o” is an integer in the range of 2 to 100, and 
         “p” is an integer in the range of 2 to 100. 
       
     
     
         11 . The graft polymer according  claim 1 , wherein the polymeric sidechains (B) comprise:
 (B1) from 50 to 100% by weight (in relation to the sum of (B1) and (B2)) of at least one vinyl ester monomer (B1), and   (B2) from 0 to 50% by weight (in relation to the sum of (B1) and (B2)) of N-vinylpyrrolidone as further monomer (B2),   
       wherein the polymeric sidechains (B) are optionally fully or partially hydrolyzed after polymerization. 
     
     
         12 . A process for obtaining at least one graft polymer according to  claim 1 , wherein at least one monomer (B1) is polymerized in the presence of at least one block copolymer backbone (A),
 wherein the process comprises the polymerization of at least one monomer (B1) selected from vinyl acetate or vinyl propionate in order to obtain the polymer sidechains (B) in the presence of at least one block copolymer backbone (A), a free radical-forming initiator (C) and at least one organic solvent (D), at a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 min to 500 min, in such a way that the fraction of unconverted graft monomers (B1) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the block copolymer backbone (A),   and optionally, wherein the polymeric sidechains (B) are obtained by radical polymerization.   
     
     
         13 . A fabric and home care product comprising at least one graft polymer according to  claim 1 . 
     
     
         14 . The product according to  claim 13 , wherein the product is a composition in the form of a liquid, a gel, a powder, a hydrocolloid, an aqueous solution, a granule, a tablet, a capsule, a single compartment sachet, a pad, a multi-compartment sachet, a single compartment pouch, or a multi-compartment pouch. 
     
     
         15 . The product of  claim 13 , wherein the product is a composition that further comprises a surfactant, an enzyme, a detergent builder, a complexing agent, a polymer, a soil release polymer, a surfactancy-boosting polymer, a bleaching agent, a bleach activator, a bleaching catalyst, a fabric conditioner, a clay, a foam booster, a suds suppressor, an anti-corrosion agent, a soil-suspending agent, an anti-soil re-deposition agent, a dye, a bactericide, a tarnish inhibitor, an optical brightener, a perfume, a saturated or unsaturated fatty acid, a dye transfer-inhibiting agent, a chelating agent, a hueing dye, a calcium cation, a magnesium cation, a visual signaling ingredient, an anti-foam, a structurant, a thickener, an anti-caking agent, a starch, sand, a gelling agent, or a combination thereof. 
     
     
         16 . The product of  claim 14 , wherein the product is a composition that further comprises a surfactant, an enzyme, a detergent builder, a complexing agent, a polymer, a soil release polymer, a surfactancy-boosting polymer, a bleaching agent, a bleach activator, a bleaching catalyst, a fabric conditioner, a clay, a foam booster, a suds suppressor, an anti-corrosion agent, a soil-suspending agent, an anti-soil re-deposition agent, a dye, a bactericide, a tarnish inhibitor, an optical brightener, a perfume, a saturated or unsaturated fatty acid, a dye transfer-inhibiting agent, a chelating agent, a hueing dye, a calcium cation, a magnesium cation, a visual signaling ingredient, an anti-foam, a structurant, a thickener, an anti-caking agent, a starch, sand, a gelling agent, or any combination thereof.