Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1999-08-05
2001-04-03
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S384000, C525S327400, C525S207000, C525S404000, C252S008620, C510S529000
Reexamination Certificate
active
06211299
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to an in situ solvent free method for making anhydride based graft copolymers. The graft copolymers are especially useful as soil release agents in detergent and textile applications.
BACKGROUND OF THE INVENTION
Styrene-maleic anhydride copolymers are typically made by solution polymerization in the presence of aromatic hydrocarbon solvents or ketone solvents. In addition to the solvents being environmentally undesirable, recovering the styrene-maleic anhydride copolymers from the solvent requires additional process steps. For example, aromatic solvents used in the solution polymerization generally require a decanting and drying step prior to recovering the copolymer product, and ketone solvents generally require a solvent-stripping step prior to recovering the copolymer product.
U.S. Pat. No. 3,485,762 describes a process for preparing styrene-maleic anhydride copolymers which are used in a detergent formulation containing polyethylene glycol. The styrene-maleic anhydride copolymers are prepared by solution polymerization using incremental feed addition of the styrene and maleic anhydride monomers and catalyst into a reactor containing an aromatic solvent. The polymerization is conducted at the reflux temperature of the monomers and solvent mixture. The copolymer is isolated and mixed with polyethylene glycol in a detergent formulation. The styrene-maleic anhydride copolymers are present as a physical mixture with the polyethylene glycol and as a partial ester of the polyethylene glyol and styrene-maleic anhydride copolymer.
U.S. Pat. No. 5,158,996 describes a process for preparing styrene-maleic anhydride graft copolymers by solution polymerization in a ketone solvent. The copolymer is isolated and reacted with polyethylene glycol to form a copolymer product containing a styrene-maleic anhydride main backbone chain having polyethylene glycol side chains.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the invention to provide a method for making anhydride based graft copolymers.
It is another object of the invention to provide an environmentally safe and economical method for making anhydride based graft copolymers.
It is also an object of the invention to provide an in situ method for making anhydride based graft copolymers.
It is an additional object of the invention to provide a polymer which improves the cleaning properties of cleaning compositions by removing soil.
It is another object of the invention to provide a polymer which imparts soil resistance to an article.
With regard to the foregoing and other objects, the present invention provides an in situ solvent free method for making an anhydride based graft copolymer, said method comprising
(I) mixing from about 50 to about 90 mole percent, based on the total moles of monomer, of an ethylenically unsaturated monomer, from about 10 to about 50 mole percent, based on the total moles of monomer, of an anhydride monomer selected from the group consisting of maleic anhydride, itaconic anhydride, and mixtures thereof, either a monofunctional polyglycol having a hydroxyl or amine terminal group or a polyfunctional polyglycol having a weight average molecular weight of greater than 5,000 and at least one terminal hydroxyl group, and a free radical initiator to form a mixture;
(II) heating the mixture at a temperature of from about 30° C. to about 150° C. for a sufficient period of time to form a copolymer having repeat units derived from the ethylenically unsaturated monomer and anhydride monomer, and a copolymer grafted polyglycol comprising a main polyglycol backbone having copolymer side chains, wherein the copolymer and copolymer grafted polyglycol are dispersed in unreacted polyglycol; and
(III) heating the copolymer, copolymer grafted polyglycol and unreacted polyglycol at a temperature of from about 50° C. to about 300° C. for a sufficient period of time to form an anhydride based graft copolymer,
wherein the anhydride based graft copolymer is selected from the group consisting of a polyglycol grafted copolymer comprising a main copolymer backbone chain having polyglycol side chains, a copolymer grafted polyglycol comprising a main polyglycol backbone having copolymer side chains, a polyglycol and copolymer grafted copolymer comprising a main copolymer backbone chain having polyglycol side chains and copolymer side chains attached to the polyglycol side chains, and mixtures thereof.
According to another aspect the invention provides a method of cleaning which involves preparing a cleaning composition comprising the anhydride based graft copolymer, contacting the cleaning solution with one or more articles, wherein at least one of the articles contains soil, and removing at least a portion of the soil from the article containing soil.
According to a further aspect the invention provides a method of imparting soil resistance to an article which involves preparing a cleaning composition comprising the anhydride based graft copolymer, and contacting the cleaning composition with the article to provide soil resistance to the article.
The anhydride based graft copolymers when used in a cleaning process, remove soil from articles, inhibit soil deposition on articles, and provide soil resistance to articles. Examples of cleaning compositions containing the anhydride based graft copolymers are laundry detergents, prespotters, dishwashing detergents, and hard surface cleaners. The anhydride based graft copolymers are sufficiently hydrophobic to absorb to an article such as cloth either in a washing process, yet retain enough hydrophilic character to decrease the hydrophobic nature of an article such as polyester.
DETAILED DESCRIPTION OF THE INVENTION
The method of the invention for making the anhydride based graft copolymer involves three steps. In the first step, a mixture is prepared which contains an ethylenically unsaturated monomer, an anhydride monomer, a monofunctional polyglycol having a hydroxyl or amine terminal group, and a free radical initiator. The ethylenically unsaturated monomer is selected from vinyl esters, alpha olefins, alkyl esters of acrylic and methacrylic acid, substituted or unsubstituted mono and dialkyl esters of unsaturated dicarboxylic acids, unsaturated carboxylic acids, vinyl aromatics, unsubstituted or substituted acrylamides, cyclic monomers, sulfonated monomers, and vinyl amide monomers. A combination of ethylenically unsaturated monomers may also be used in the method of the invention.
Suitable vinyl esters are, for example, vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl 2-ethyl-hexanoate, etc. Suitable alkyl esters of acrylic and methacrylic acid are, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, etc. Suitable substituted or unsubstituted mono and dialkyl esters of unsaturated dicarboxylic acids are, for example, substituted and unsubstituted mono and dibutyl, mono and diethyl maleate esters as well as the corresponding fumarates. Suitable unsaturated carboxylic acids are, for example, crotonic acid, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, and their alkyl esters etc.
Suitable vinyl aromatic monomers are, for example, styrene, 3-isopropenyl-&agr;, (&agr;-dimethylbenzyl isocyanate 1-vinyl napthalene, 2-vinyl napthalene, 3-methyl styrene, 4-propyl styrene, t-butyl styrene etc. Suitable acrylamide based monomers are, for example, acrylamide, N, N dimethylacrylamide, N-octyl acrylamide, N-methylol acrylamide, dimethylaminoethylacrylate etc. Suitable cyclic monomers are, for example, vinyl pyrrolidone, vinyl imidazolidone, vinyl pyridine etc. Suitable sulfonated monomers are, for example, 2-acrylamido-2-methyl propane sulfonic acid, sodium methallyl sufonate, sodium vinyl sulfonate, sulfonated sytrene etc. Suitable vinyl amidemonomers are, for example, N-vinyl formamide, N-vinyl acetamide, etc. Suitable &agr;-olefin based monomers are, for example, C
4
-C
20
based alkyl monomers
Moss, III Thomas H.
Rodrigues Klein A.
Asinovsky Olga
National Starch and Chemical Investment Holding Corporation
Roland, Esq. Thomas F.
Seidleck James J.
LandOfFree
In situ solvent free method for making anhydride based graft... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with In situ solvent free method for making anhydride based graft..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and In situ solvent free method for making anhydride based graft... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2446092