CA2243306C - Solubilized hydrophobically-modified alkali-soluble emulsion polymers - Google Patents
Solubilized hydrophobically-modified alkali-soluble emulsion polymers Download PDFInfo
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- CA2243306C CA2243306C CA002243306A CA2243306A CA2243306C CA 2243306 C CA2243306 C CA 2243306C CA 002243306 A CA002243306 A CA 002243306A CA 2243306 A CA2243306 A CA 2243306A CA 2243306 C CA2243306 C CA 2243306C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
Abstract
Aqueous solutions of hydrophobically-modified alkali-soluble emulsion polymers which exhibit relatively low solution viscosity are disclosed. Such solutions are particularly useful for controlling the viscosity of aqueous systems to which the solutions are added.
Description
SOLUB~ 7.1~n HYDROPHOBICALLY-MODIFIED
ALKALI~OLUBLE EM~ULSION POLYIUFRS
The present invention relates to solubilized hydrophobically-modified all~ali-soluble polymers. In particular the present invention relates to aqueoussolutions of hydrophobic~lly-modi1ied alkali-soluble emulsion polymers. More particularly, the present invention relates to such aqueous solutions which exhibit relatively low solution viscosity. Such solutions are particularly useful for controlling the viscosity of aqueous sys~ems to which the solutions are added.
Hydrophobically-modified alkali-soluble emulsion (UHASE") poly-mers are polymers which are typically utilized for increasing the viscosity of aqueous solutions. The polymer typically is a copolymer which contains an ~ninnic group,a hydrophobic group, and a nor~ nic group. HASE polymers are typically provided as aqueous latex di~percions at low pH with low vi.ccosities.
Surfactants are typically included in the dispersion to st~hili7e the HASE
polymer latex. End users neutralize the low pH HASE polymer with concentrated base such as sodium hydroxide or ~mmonium hydroxide. The handling of concentrated base may be inconv~.~ient for the end user. A
neutralized HASE polymer is desirable so that neutr~li7~tion with concentrated base by the end user is ~limin~ted~
Neutralized HASE polymers have very high viscosities. Due to the high viScosi~ies~ neutralized HASE polymers are difficult to pump. The viscosity of aneutralized HASE polymer may be reduced through diluting the polymer solution, howe~er there is a practical limit on the solids level of a HASE polymer solution. HASE polymer solutions with solids levels below 5% by weight are not pr~G*cal There is a need for pumpable, neutralized, HASE polymers with solids levels of at least 5% by weight.
U.S. Pat. No. 5,476,900 discloses a method for preparing aqueous polymer em~ ion~ useful as t~ Pning agents. The patent discloses the ~ m of up to 1% surfactant to enh~nce t~ rening when the polymer, at a solids level up to 5% is neutralized.
Despite the disdosure of the prior art, there is a continuing need for pumpable, neutralized, HASE polymers ~rith solids levels of at least 5% by weight.
We have surpri.cingly found that the compositions and the process of this invention provide neutralized HASE polymers which have low viscosities, are pumpable, and have solids levels of at least 5% by weight.
The present invention provides a compositinn comprising:
water;
at least 5% by weight neutralized HASE polymer; and less than 1 percent by weight, based on HASE polymer solids, of sllrf~ctg~nt.
The present invention also provides a method for preparing a neutralized HASE polymer comprising:
1) emulsion polym~ri~.ing a mixture of monorners comprising a) from 30 to 75 parts by we~ght of nonionic monomer;
b) from 5 to 75 parts by weight of s-nionic monomer; and c) from 1 to 20 parts by weight of hydrophobic monomer in the presence of less than 1 percent by weight s~lrfsctqnt based on the weight of the monomers, to form a polymer emulsion of HASE polymer;
ALKALI~OLUBLE EM~ULSION POLYIUFRS
The present invention relates to solubilized hydrophobically-modified all~ali-soluble polymers. In particular the present invention relates to aqueoussolutions of hydrophobic~lly-modi1ied alkali-soluble emulsion polymers. More particularly, the present invention relates to such aqueous solutions which exhibit relatively low solution viscosity. Such solutions are particularly useful for controlling the viscosity of aqueous sys~ems to which the solutions are added.
Hydrophobically-modified alkali-soluble emulsion (UHASE") poly-mers are polymers which are typically utilized for increasing the viscosity of aqueous solutions. The polymer typically is a copolymer which contains an ~ninnic group,a hydrophobic group, and a nor~ nic group. HASE polymers are typically provided as aqueous latex di~percions at low pH with low vi.ccosities.
Surfactants are typically included in the dispersion to st~hili7e the HASE
polymer latex. End users neutralize the low pH HASE polymer with concentrated base such as sodium hydroxide or ~mmonium hydroxide. The handling of concentrated base may be inconv~.~ient for the end user. A
neutralized HASE polymer is desirable so that neutr~li7~tion with concentrated base by the end user is ~limin~ted~
Neutralized HASE polymers have very high viscosities. Due to the high viScosi~ies~ neutralized HASE polymers are difficult to pump. The viscosity of aneutralized HASE polymer may be reduced through diluting the polymer solution, howe~er there is a practical limit on the solids level of a HASE polymer solution. HASE polymer solutions with solids levels below 5% by weight are not pr~G*cal There is a need for pumpable, neutralized, HASE polymers with solids levels of at least 5% by weight.
U.S. Pat. No. 5,476,900 discloses a method for preparing aqueous polymer em~ ion~ useful as t~ Pning agents. The patent discloses the ~ m of up to 1% surfactant to enh~nce t~ rening when the polymer, at a solids level up to 5% is neutralized.
Despite the disdosure of the prior art, there is a continuing need for pumpable, neutralized, HASE polymers ~rith solids levels of at least 5% by weight.
We have surpri.cingly found that the compositions and the process of this invention provide neutralized HASE polymers which have low viscosities, are pumpable, and have solids levels of at least 5% by weight.
The present invention provides a compositinn comprising:
water;
at least 5% by weight neutralized HASE polymer; and less than 1 percent by weight, based on HASE polymer solids, of sllrf~ctg~nt.
The present invention also provides a method for preparing a neutralized HASE polymer comprising:
1) emulsion polym~ri~.ing a mixture of monorners comprising a) from 30 to 75 parts by we~ght of nonionic monomer;
b) from 5 to 75 parts by weight of s-nionic monomer; and c) from 1 to 20 parts by weight of hydrophobic monomer in the presence of less than 1 percent by weight s~lrfsctqnt based on the weight of the monomers, to form a polymer emulsion of HASE polymer;
2) diluting the HASE polymer to provide a level of HASE polymer solids of from 5 to 70 percent by weight; and 3) neutrsli7.irlg the HASE polymer.
The HASE polymer composition4 of this invention are neutralized emulsion polymers comprising from 30 to 75 parts by weight of nonio~ ic monomer; from 5 to 75 parts by weight of ~qnionic monomer; and from 1 to 20 parts by weight of hydrophobic monomer. The HASE polymer compositions of this invention may be prepared by conventional polyme~ri7.~io-~ te~.~ni~ues. We have surpricingly found that reduction of sllrfs-ctsnt decreases the viscosity of neutralized HASE polymers, and therefore the polymeri7~ r process is typically run in the presence of less than 1 percent by weight sllrf?~ct~nt based on the weight of the monon~ers. The process of this invention requires emulsion polym~7.inE~ a mixt~lre of monomers comprising from 30 to 75 parts of noninni~
.. ... . . .,. . ~.
monomer; from 5 to 75 parts of ~njoni~ monomer; and from 1 to 20 parts of hydrophobic monomer in the presence of less than 1 percent by weight s~ rt~nt based on the weight of the monomers, to form a HASE polymer. The emulsion polymeri~ation may be catalyzed by ~nionic, cationic, or free-radical producing initiators. Free-radical producing ini1i~tors are prefel.ed. The free-radical producing i~iti~tors typically are peloAy~ compounds including inorganic persulfate compounds such as ~mm~nium persulfate, potassium persulfate, and sodium persulfate; peroxides such as hyLogel~ peroxide; organic hydroperoxides such as cllm~ne hydroperoxide and t-butyl hydroperoxide;
organic peroxides such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, peracetic acid, and perbenzoic acid (sometime~ activated by a water-soluble reducing agent such as a ferrous compound or sodium bisulfite); as well as otherfree-radical producing m~teripl.~ such as 2,2'-P7~isi~o~utyronitlile. Other methods of initi~ti~ln such as the use of irr~ tion with Ultra Violet light, Ultr~oI ir, or merh~nicAl means to in~llce free-radical generation are deemed tobe within the scope of this invention.
A macromolecular organic compound having a hydrophobic cavity may be utilized in the process of m~king the HASE polymer. Suitable macromoleclll~r organic compounds include cyclo~ ctrin, cyclo-l~x~rin derivatives, cycloinulohexose, cycloinuloheptose, cycloinuloctose, calyxarene and cavitand.
Cyclo(lext,rin includes a-cydo lextrin, ~-cyclo~ext~in and y-cyclodPYt~in Cyclodextrin derivatives include the methyl, triacetyl, hyd~oAyl~l~yl and hy~lroAyetLyl derivatives of a-cyclo~extr-n, ~-cycloclçx~in and y-cyclodextrin.
Flefel,ed are a-cyclodextrin, ~-cyclo-lext~ in and y-cyclodextrin. More ~ f~lledare the methyl, triacetyl, hy~lloAy~ropyl and hyLoA~ethyl derivatives of a-cyclodextrin, ,B-cyclo-le~rtrin and y-cyclodextrin. The amount of macromolecularorganic compound having a hydrophobic cavity used is typically from 0 to 50 weight percent, preferably 0 to 30 weight percent, more preferably 0 to 10 weight percent based on the total composition to be reacted.
By nonioniC monomer is meant a monomer that does not contain a positive or negative charge when in aqueous solution. The nonionic monomers of this invention have carbon chains that are less than 8 carbon units in length. The ..... . . ..... .. . .. ...
amount of nonionic monomer as polymerized units in the HASE polymer is typically 30 to 75 parts by weight, preferably 35 to 70 parts by weight, more preferably 40 to 65 parts by weight. Suitable nonionic monomers include Cl-C7 alkyl and C2-C7 hydroxyalkyl esters of acrylic and met~rrylic acid including ethyl (meth)acrylate, methyl (meth)acrylate, 2-ethylhexyl acrylate, butyl (meth)acrylate, 2-hy-Lo~yelLyl acrylate, 2-hyd~oxylJlltyl methacrylate, styrene,vinyltoluene, t-butyl styrene, isopropylstyrene, and p-chlorostyrene; vinyl acetate, vinyl butyrate, vinyl caprolate, acrylonitrile, methacrylonitrile, butadiene, isoprene, vinyl r.hl~ri(le, vinylidene rhlor~ , and the like. r~Lelled are ethyl (meth)acrylate, methyl (meth)acrylate, 2-ethylhexyl acrylate, butyl (meth)acrylate, 2-hyd~ yethyl acrylate, and 2-hyLo~yl~utyl methacrylate.
More p.efelled are ethyl acrylate, methyl acrylate, and butyl acrylate.
By ~nionic monomer is meant a mo~omer which contains a negative charge when in a basic aqueous solution. The amount of ~nionic monomer as polymerized units in the HASE polymer is typically 5 to 75 parts by weight, preferably 10 to 60 parts by weight, more preferably 20 to 50 parts by weight.
Suitable ~nionic monomers include acrylic acid, met~rrylic acid, crotonic acid, phosphoethyl methacrylate, 2-acryl ~nni 1lo-2-methyl- l-propaneslllfonic acid, sodium vinyl sulfonate, it~conic acid, f~ rie acid, maleic acid, monomethyl it~con~te, monomethyl fumarate, monobutyl fumarate, and maleic anhydride.
Acrylic acid, it~ronic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, film~ric acid, and methacrylic acid are preferred. Methacrylic acid, 2-acryl~mi-1O-2-methyl- 1-propanesl~lfor ic acid, and acrylic acid are more pr~felled.
By hydrophobic mono~er is meant s~ t~nt esters such as C8-Cso alkylphenoxy (ethyleneoxy)6.l00 ethyl (meth)acrylates and C8-C30 alkoxy (ethyleneoxy) 650 ethyl (meth)acrylates; C8-C30 alkylphenoxy ethyl (meth)acrylates; and C8-C30 alkoxy ethyl (meth)acrylates. Other linkages such as, but not limited to ethers, amides and urethanes can be used. Hydrophobic monomers such as, but not limited to vinyl esters of C8-C30 carboxylic acid and C8-C30 alkyl ester of (methyl)acrylate can also be used. The amount of hydrophobic monomer as polymerized units in the HASE polymer is typically 1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 1 to 10 parts by weight. Suitable hydrophobic monomers include ClsH37(E0)20 (meth)acrylate and C~2H2s(E0)23 (meth)acrylate. Preferred are ClsHs7(E0)20 methacrylate and Cl2H2s(E0)2~ methacrylate.
Chain transfer agents may be used to control the molecular weight of the HASE polymer. Suitable chain transfer agents are mercaptans, such as, for example, dodecylmercaptan, methyl mercaptopro~ionate, and mercaptopropionic acid. The chain transfer agent may be used at from 0.05% to 10% based on the total weight of the polymeric compo.cition The HASE polymer may contqin a polyethy1Pnic~11y unsaturated copolymçri7~h1e monomer e~ective for crosslinking~ such as, for example, diallylphthalate, divinylbensene, allyl methacrylate, trimethylol propane triacrylate, ethylene glycol diacrylate or dimethacrylate, l,6-he~nediol diacrylate or dimethacrylate, diallyl ben~ene and lhe lil~e. Typically, from 0.05 weight percent to 20 weight percent of the crosclinlring agent is used, based onthe total weight of the monomers.
By s~ ct~t is meant a compound which reduces surface tenCion when dissolved in water or water solutions, or which reduces interf~-i~1 ten.cio-l between two liquids, or between a liquid and a solid. Included in surfactants are detergents, wetting agents, l1~bri~nts, and em1llcifiers. The total amount of surfactant in the HASE polymer dispersion is typically less than 1 percent by weight, preferably less than 0.5 percent by weight, more preferably less than 0.2 percent by weight based on the total weight of the dry polymer. The level of surfactant present may be controlled through the addition of less than than 1 percent by weight sllrf~q~t~nt, based on the total weight of the dry polymer to the polymerization process. In the event that more than 1 percent by weight s1~ ct~nt based on the total weight of the dry polymer is added to the polymerization process or thereafter, the level of surfactant may be reduced to less than l percent, based on the total weight of the dry polymer through the use of ultrafiltration or ~ fi~ ation.
The HASE polymer is neutralized. By neutralized is meant that greater than 60% of the acidic groups of the HASE polymer are neutralized.
Neutr~1i7.~tion is performed after the polymeri7~tioll is complete. The sample .. ..
may be held and cooled, and is comhined with neutralizer solution comprising base and water to the desired solids level. A macromolecular organic compound having a hydrophobic cavity, may also be utilized in the neutralizer solution.
S~ qhle macromolecular organic compounds include cyclodextrin, cyclo-lextrin derivatives, cycloinulohexose, cycloinuloheptose, cycloinuloctose, calyxarene and cavitand. Cydo(l~Ytrin includes a-cyclodextrin, ~-cyclo-lextrin and y-cyclo~l~Pxt,rin Cydo-lextrin derivatives include the methyl, triacetyl, hydroxypropyl and hydlo~yetl~yl del.val ives of a-cyclo-iextrin, ~-cyclo-l~Pxtrin and y-cycloll~qxtrir~ P~f~rl~d are a-cyclodextrin, ~-cyclo~leYtrin and y-cyclodextrin. More preferlcd are the methyl, triacetyl, hydro~y~ropyl and hy~o~yethyl del;valives of a-cyclodextrin, ,B-cyclo~l~PY~in and r-cYclodeYtrin.
Suitable base includes sodium hydro~de and ~mmonium hydroxide.
The HASE polymer may be d uted to provide a level of HASE polymer solids of typically from 5 to 50 percent by weight, preferably 5 to 30 percent by weight, more preferably 10 to 25 percent by weight.
The viscosity of the neutralized HASE polymer aqueous solutions may be measured by conventional t~hni~-ues~ such as the use of a Broolrfi~
viscometer. When measured by a Brookfielll viscometer, neutralized HASE
polymers typically have visco~ities below 15,000 milli pa~cal seconds. Pl~ferledare neutralized EIASE polymers with vi~cosi~iPs below 10,000 milli pascal seconds. More prefelled are neutralized HASE polymers with viscosities below 5,000 milli pascal seconds.
We have surprisingly found that reduction of sllrfqctqnt decreases the viscosity of neutralized HASE polymers. The HASE polymers within the scope of this invention typically have a viscosity of at least 300 milli pascal seconds when measured as a 5 percent by weight aqueous solution of the neutralized HASE polymer in the presence of an added 2 percent by weight based on the weight of the neutralized HASE polymer of sodium lauryl sulfate.
The HASE polymer composi1ion~ of this invention are useful in any applir~tion where ~hirkeners are typically used. Such applications include arrhitectllral and industrial co~ing.C including paints, wood co~ing~, inks;
paper co~ting~; adhesives; mastics; plastics; plastic additives; petroleum additives; nonwovens; texti1Ps; li~lling muds; cosmetics and the like.
The following abbreviations are used throughout this patent applie~tion-LEOMA = Cl2H2s(EO)2~ methacrylate SEOMA = ClsH37(130)20 methacrylate BA ~ butyl acrylate MAA = methacrylic acid SLS = sodium lauryl sulfate CD = methyl-~-cyclo(l~xtrin MPA = mercaptopropionic acid nDDM = n-dodecyl mercaptan Id. = sample i-l~ntific~tion number ~C = degrees centigrade MMP = methyl mercaptopropionate HEM = hyLvAyet~yl mercaptan (meth)acrylate = methacrylate and acrylate pph = parts per hundred BMP = butyl mercaptopropionate g = grams AMPS = 2-acrylamido-2-methyl-1-propaneslllfonir acid The following Table lists some of the m~teri~l~ used in this patent applicatinn and their sources:
~teri~l Fl~nction 50urce Acumer~) 9300 Dispersant Rohm and Haas Company Hydrafine(g) Clay J.M. HuberCorporation HydIa~llnt~ Del~min~ted Clay J.M. Huber Corporation Res~ 4126 Binder Ameripol Synpol Exam~le 1 Polyme~7.~tiQns were carried out in a 3 liter round bottom flask equipped with a merh~nic~l stirrer, temperature control device, condenser, nitrogen inlet, and monomer and initiator feed lines. To the flas~c was added 1,000 g ~leioni7.ed water at room temperature and methyl-~-cyclo-l~xtrin (~CD") as indicated in Table 1 (all weights are in grams). The contents of the flask were heated to 85~C
while stirring under a ni~o~en kl~nket. A monomer mixture was prepared to form the re~rtion mixture in accordance with Table 1. An initial initi~tor consisting of 1 g sodium persulfate dissdved in 10 g deionized water was prepared. A cofeed initi~tor solution of 2.4 g sodium persulfate dissolved in 100 g rlpioIli7ed water was prepared. The initial initi~r solution was added to the flask. The reaction mixture and the cofeed initi~tor solution were fed seperately but simultaneously into the reaction ~ask over a 100 minute period. The sample was held for 10 minutes, cooled to 70~C, and com~ined with neutralizer solution complising 0 to 97.5 grams CD, 200 grams base, and water to the desired solids level.
Table 1 Id. CD EA MAA A nDDM SEOMA LEOMA AMPS
0 275 185 25 0.9 15 0 0 2 2.5 275 190 25 0.9 10 0 0 3 2.5 225 225 25 0.9 18.75 6.25 0 4 2.5 300 155 25 1.2 15 5 0 2.5 250 125 100 0.9 18.75 6.25 0 6 2.5 250 225 0 0.9 18.75 6.25 0 7 2.5 250 195 25 1.2 22.5 7.5 0 8 5 275 190 25 0.9 10 0 0 9' 10 275 185 25 0.9 15 0 0 12 2.5 247199.5 0 0.62 0 25 28.5 13 2.5 247199.5 0 0.63 0 25 28.5 14 2.5 247199.5 0 0.64 0 25 28.5 2.5 247199.5 0 0.6 0 25 28.5 16 2.5 247199.5 0 0.65 0 25 28.5 *176 10 275 175 25 0.9 0 25 0 *18 2.5 291 199 0 1.2 0 10 0 1. 0.2% sodium lauryl sulfate added to kettle.
2. 3-MPA substituted for nDDM (equivalent to 0.9 g nDDM~.
3. BMP substituted for nDDM (c~juiv~lent to 0.9 g nDDM).
4. 2-HEM substituted for nDDM (equivalent to 0.9 g nDDM).
The HASE polymer composition4 of this invention are neutralized emulsion polymers comprising from 30 to 75 parts by weight of nonio~ ic monomer; from 5 to 75 parts by weight of ~qnionic monomer; and from 1 to 20 parts by weight of hydrophobic monomer. The HASE polymer compositions of this invention may be prepared by conventional polyme~ri7.~io-~ te~.~ni~ues. We have surpricingly found that reduction of sllrfs-ctsnt decreases the viscosity of neutralized HASE polymers, and therefore the polymeri7~ r process is typically run in the presence of less than 1 percent by weight sllrf?~ct~nt based on the weight of the monon~ers. The process of this invention requires emulsion polym~7.inE~ a mixt~lre of monomers comprising from 30 to 75 parts of noninni~
.. ... . . .,. . ~.
monomer; from 5 to 75 parts of ~njoni~ monomer; and from 1 to 20 parts of hydrophobic monomer in the presence of less than 1 percent by weight s~ rt~nt based on the weight of the monomers, to form a HASE polymer. The emulsion polymeri~ation may be catalyzed by ~nionic, cationic, or free-radical producing initiators. Free-radical producing ini1i~tors are prefel.ed. The free-radical producing i~iti~tors typically are peloAy~ compounds including inorganic persulfate compounds such as ~mm~nium persulfate, potassium persulfate, and sodium persulfate; peroxides such as hyLogel~ peroxide; organic hydroperoxides such as cllm~ne hydroperoxide and t-butyl hydroperoxide;
organic peroxides such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, peracetic acid, and perbenzoic acid (sometime~ activated by a water-soluble reducing agent such as a ferrous compound or sodium bisulfite); as well as otherfree-radical producing m~teripl.~ such as 2,2'-P7~isi~o~utyronitlile. Other methods of initi~ti~ln such as the use of irr~ tion with Ultra Violet light, Ultr~oI ir, or merh~nicAl means to in~llce free-radical generation are deemed tobe within the scope of this invention.
A macromolecular organic compound having a hydrophobic cavity may be utilized in the process of m~king the HASE polymer. Suitable macromoleclll~r organic compounds include cyclo~ ctrin, cyclo-l~x~rin derivatives, cycloinulohexose, cycloinuloheptose, cycloinuloctose, calyxarene and cavitand.
Cyclo(lext,rin includes a-cydo lextrin, ~-cyclo~ext~in and y-cyclodPYt~in Cyclodextrin derivatives include the methyl, triacetyl, hyd~oAyl~l~yl and hy~lroAyetLyl derivatives of a-cyclo~extr-n, ~-cycloclçx~in and y-cyclodextrin.
Flefel,ed are a-cyclodextrin, ~-cyclo-lext~ in and y-cyclodextrin. More ~ f~lledare the methyl, triacetyl, hy~lloAy~ropyl and hyLoA~ethyl derivatives of a-cyclodextrin, ,B-cyclo-le~rtrin and y-cyclodextrin. The amount of macromolecularorganic compound having a hydrophobic cavity used is typically from 0 to 50 weight percent, preferably 0 to 30 weight percent, more preferably 0 to 10 weight percent based on the total composition to be reacted.
By nonioniC monomer is meant a monomer that does not contain a positive or negative charge when in aqueous solution. The nonionic monomers of this invention have carbon chains that are less than 8 carbon units in length. The ..... . . ..... .. . .. ...
amount of nonionic monomer as polymerized units in the HASE polymer is typically 30 to 75 parts by weight, preferably 35 to 70 parts by weight, more preferably 40 to 65 parts by weight. Suitable nonionic monomers include Cl-C7 alkyl and C2-C7 hydroxyalkyl esters of acrylic and met~rrylic acid including ethyl (meth)acrylate, methyl (meth)acrylate, 2-ethylhexyl acrylate, butyl (meth)acrylate, 2-hy-Lo~yelLyl acrylate, 2-hyd~oxylJlltyl methacrylate, styrene,vinyltoluene, t-butyl styrene, isopropylstyrene, and p-chlorostyrene; vinyl acetate, vinyl butyrate, vinyl caprolate, acrylonitrile, methacrylonitrile, butadiene, isoprene, vinyl r.hl~ri(le, vinylidene rhlor~ , and the like. r~Lelled are ethyl (meth)acrylate, methyl (meth)acrylate, 2-ethylhexyl acrylate, butyl (meth)acrylate, 2-hyd~ yethyl acrylate, and 2-hyLo~yl~utyl methacrylate.
More p.efelled are ethyl acrylate, methyl acrylate, and butyl acrylate.
By ~nionic monomer is meant a mo~omer which contains a negative charge when in a basic aqueous solution. The amount of ~nionic monomer as polymerized units in the HASE polymer is typically 5 to 75 parts by weight, preferably 10 to 60 parts by weight, more preferably 20 to 50 parts by weight.
Suitable ~nionic monomers include acrylic acid, met~rrylic acid, crotonic acid, phosphoethyl methacrylate, 2-acryl ~nni 1lo-2-methyl- l-propaneslllfonic acid, sodium vinyl sulfonate, it~conic acid, f~ rie acid, maleic acid, monomethyl it~con~te, monomethyl fumarate, monobutyl fumarate, and maleic anhydride.
Acrylic acid, it~ronic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, film~ric acid, and methacrylic acid are preferred. Methacrylic acid, 2-acryl~mi-1O-2-methyl- 1-propanesl~lfor ic acid, and acrylic acid are more pr~felled.
By hydrophobic mono~er is meant s~ t~nt esters such as C8-Cso alkylphenoxy (ethyleneoxy)6.l00 ethyl (meth)acrylates and C8-C30 alkoxy (ethyleneoxy) 650 ethyl (meth)acrylates; C8-C30 alkylphenoxy ethyl (meth)acrylates; and C8-C30 alkoxy ethyl (meth)acrylates. Other linkages such as, but not limited to ethers, amides and urethanes can be used. Hydrophobic monomers such as, but not limited to vinyl esters of C8-C30 carboxylic acid and C8-C30 alkyl ester of (methyl)acrylate can also be used. The amount of hydrophobic monomer as polymerized units in the HASE polymer is typically 1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 1 to 10 parts by weight. Suitable hydrophobic monomers include ClsH37(E0)20 (meth)acrylate and C~2H2s(E0)23 (meth)acrylate. Preferred are ClsHs7(E0)20 methacrylate and Cl2H2s(E0)2~ methacrylate.
Chain transfer agents may be used to control the molecular weight of the HASE polymer. Suitable chain transfer agents are mercaptans, such as, for example, dodecylmercaptan, methyl mercaptopro~ionate, and mercaptopropionic acid. The chain transfer agent may be used at from 0.05% to 10% based on the total weight of the polymeric compo.cition The HASE polymer may contqin a polyethy1Pnic~11y unsaturated copolymçri7~h1e monomer e~ective for crosslinking~ such as, for example, diallylphthalate, divinylbensene, allyl methacrylate, trimethylol propane triacrylate, ethylene glycol diacrylate or dimethacrylate, l,6-he~nediol diacrylate or dimethacrylate, diallyl ben~ene and lhe lil~e. Typically, from 0.05 weight percent to 20 weight percent of the crosclinlring agent is used, based onthe total weight of the monomers.
By s~ ct~t is meant a compound which reduces surface tenCion when dissolved in water or water solutions, or which reduces interf~-i~1 ten.cio-l between two liquids, or between a liquid and a solid. Included in surfactants are detergents, wetting agents, l1~bri~nts, and em1llcifiers. The total amount of surfactant in the HASE polymer dispersion is typically less than 1 percent by weight, preferably less than 0.5 percent by weight, more preferably less than 0.2 percent by weight based on the total weight of the dry polymer. The level of surfactant present may be controlled through the addition of less than than 1 percent by weight sllrf~q~t~nt, based on the total weight of the dry polymer to the polymerization process. In the event that more than 1 percent by weight s1~ ct~nt based on the total weight of the dry polymer is added to the polymerization process or thereafter, the level of surfactant may be reduced to less than l percent, based on the total weight of the dry polymer through the use of ultrafiltration or ~ fi~ ation.
The HASE polymer is neutralized. By neutralized is meant that greater than 60% of the acidic groups of the HASE polymer are neutralized.
Neutr~1i7.~tion is performed after the polymeri7~tioll is complete. The sample .. ..
may be held and cooled, and is comhined with neutralizer solution comprising base and water to the desired solids level. A macromolecular organic compound having a hydrophobic cavity, may also be utilized in the neutralizer solution.
S~ qhle macromolecular organic compounds include cyclodextrin, cyclo-lextrin derivatives, cycloinulohexose, cycloinuloheptose, cycloinuloctose, calyxarene and cavitand. Cydo(l~Ytrin includes a-cyclodextrin, ~-cyclo-lextrin and y-cyclo~l~Pxt,rin Cydo-lextrin derivatives include the methyl, triacetyl, hydroxypropyl and hydlo~yetl~yl del.val ives of a-cyclo-iextrin, ~-cyclo-l~Pxtrin and y-cycloll~qxtrir~ P~f~rl~d are a-cyclodextrin, ~-cyclo~leYtrin and y-cyclodextrin. More preferlcd are the methyl, triacetyl, hydro~y~ropyl and hy~o~yethyl del;valives of a-cyclodextrin, ,B-cyclo~l~PY~in and r-cYclodeYtrin.
Suitable base includes sodium hydro~de and ~mmonium hydroxide.
The HASE polymer may be d uted to provide a level of HASE polymer solids of typically from 5 to 50 percent by weight, preferably 5 to 30 percent by weight, more preferably 10 to 25 percent by weight.
The viscosity of the neutralized HASE polymer aqueous solutions may be measured by conventional t~hni~-ues~ such as the use of a Broolrfi~
viscometer. When measured by a Brookfielll viscometer, neutralized HASE
polymers typically have visco~ities below 15,000 milli pa~cal seconds. Pl~ferledare neutralized EIASE polymers with vi~cosi~iPs below 10,000 milli pascal seconds. More prefelled are neutralized HASE polymers with viscosities below 5,000 milli pascal seconds.
We have surprisingly found that reduction of sllrfqctqnt decreases the viscosity of neutralized HASE polymers. The HASE polymers within the scope of this invention typically have a viscosity of at least 300 milli pascal seconds when measured as a 5 percent by weight aqueous solution of the neutralized HASE polymer in the presence of an added 2 percent by weight based on the weight of the neutralized HASE polymer of sodium lauryl sulfate.
The HASE polymer composi1ion~ of this invention are useful in any applir~tion where ~hirkeners are typically used. Such applications include arrhitectllral and industrial co~ing.C including paints, wood co~ing~, inks;
paper co~ting~; adhesives; mastics; plastics; plastic additives; petroleum additives; nonwovens; texti1Ps; li~lling muds; cosmetics and the like.
The following abbreviations are used throughout this patent applie~tion-LEOMA = Cl2H2s(EO)2~ methacrylate SEOMA = ClsH37(130)20 methacrylate BA ~ butyl acrylate MAA = methacrylic acid SLS = sodium lauryl sulfate CD = methyl-~-cyclo(l~xtrin MPA = mercaptopropionic acid nDDM = n-dodecyl mercaptan Id. = sample i-l~ntific~tion number ~C = degrees centigrade MMP = methyl mercaptopropionate HEM = hyLvAyet~yl mercaptan (meth)acrylate = methacrylate and acrylate pph = parts per hundred BMP = butyl mercaptopropionate g = grams AMPS = 2-acrylamido-2-methyl-1-propaneslllfonir acid The following Table lists some of the m~teri~l~ used in this patent applicatinn and their sources:
~teri~l Fl~nction 50urce Acumer~) 9300 Dispersant Rohm and Haas Company Hydrafine(g) Clay J.M. HuberCorporation HydIa~llnt~ Del~min~ted Clay J.M. Huber Corporation Res~ 4126 Binder Ameripol Synpol Exam~le 1 Polyme~7.~tiQns were carried out in a 3 liter round bottom flask equipped with a merh~nic~l stirrer, temperature control device, condenser, nitrogen inlet, and monomer and initiator feed lines. To the flas~c was added 1,000 g ~leioni7.ed water at room temperature and methyl-~-cyclo-l~xtrin (~CD") as indicated in Table 1 (all weights are in grams). The contents of the flask were heated to 85~C
while stirring under a ni~o~en kl~nket. A monomer mixture was prepared to form the re~rtion mixture in accordance with Table 1. An initial initi~tor consisting of 1 g sodium persulfate dissdved in 10 g deionized water was prepared. A cofeed initi~tor solution of 2.4 g sodium persulfate dissolved in 100 g rlpioIli7ed water was prepared. The initial initi~r solution was added to the flask. The reaction mixture and the cofeed initi~tor solution were fed seperately but simultaneously into the reaction ~ask over a 100 minute period. The sample was held for 10 minutes, cooled to 70~C, and com~ined with neutralizer solution complising 0 to 97.5 grams CD, 200 grams base, and water to the desired solids level.
Table 1 Id. CD EA MAA A nDDM SEOMA LEOMA AMPS
0 275 185 25 0.9 15 0 0 2 2.5 275 190 25 0.9 10 0 0 3 2.5 225 225 25 0.9 18.75 6.25 0 4 2.5 300 155 25 1.2 15 5 0 2.5 250 125 100 0.9 18.75 6.25 0 6 2.5 250 225 0 0.9 18.75 6.25 0 7 2.5 250 195 25 1.2 22.5 7.5 0 8 5 275 190 25 0.9 10 0 0 9' 10 275 185 25 0.9 15 0 0 12 2.5 247199.5 0 0.62 0 25 28.5 13 2.5 247199.5 0 0.63 0 25 28.5 14 2.5 247199.5 0 0.64 0 25 28.5 2.5 247199.5 0 0.6 0 25 28.5 16 2.5 247199.5 0 0.65 0 25 28.5 *176 10 275 175 25 0.9 0 25 0 *18 2.5 291 199 0 1.2 0 10 0 1. 0.2% sodium lauryl sulfate added to kettle.
2. 3-MPA substituted for nDDM (equivalent to 0.9 g nDDM~.
3. BMP substituted for nDDM (c~juiv~lent to 0.9 g nDDM).
4. 2-HEM substituted for nDDM (equivalent to 0.9 g nDDM).
5. MMP substituted for nDDM (equivalent to 0.9 g nDDM).
6. 1.6% sodium lauryl sulfate added to kettle.
* = Comparative Sample m~le 2 Some of the samples from Table 1 were tested for viscosity on a Brookfield RV viscometer. S~nples were tested at 20~C with the instrument set at 100 rot~io~.~ per minute. The results are in Tables 2, 3, and 4.
Table 2 Sam~le15% With 5% CD
2 12,720 3 1,808 4 6,930 4,520 6 1,178 7 2,580 8 1,104 9 4,390 1,250 11 1,100 *17 > 100,000 * = Comparative Sample Table 3 Sam~le 5%
*17 > 100,000 * = Comparative Sample Table 4 Sam~le 5% With 2% SLS
6 12,640 *18 260 * = Compa~clive Sample F.x~mple 3 Some of the compositions of this invention were tested for t~ içk~ning properties in a typical pigmented paper co~ting. A pigm~nted paper co~ting was prepared by combining 80 pph Hydrap~nt~ tlel~nin~ted clay, 20 pph Hydrafine~ #1 clay, 7 pph Res~ 4126, and 0.15 pph Acumer~ 9300 dispersant.
The pH was adjusted to 8.5-9 with ~mmoni7~ The compositions o~this invention were added at the levels indicated in Table 3, and the viscosity of the sample was measured using the Brookfield viscomet,er at 100 rotations per _inute. The results are shown in Table 5.
Table 5 Sam~le Level (p~h) Viscosity 6 0.35 998 7 o.~ 1,000 The data above demonstrate the compQcitionc of this invention are efEective ~ keners in pigmented paper o~ g~.
* = Comparative Sample m~le 2 Some of the samples from Table 1 were tested for viscosity on a Brookfield RV viscometer. S~nples were tested at 20~C with the instrument set at 100 rot~io~.~ per minute. The results are in Tables 2, 3, and 4.
Table 2 Sam~le15% With 5% CD
2 12,720 3 1,808 4 6,930 4,520 6 1,178 7 2,580 8 1,104 9 4,390 1,250 11 1,100 *17 > 100,000 * = Comparative Sample Table 3 Sam~le 5%
*17 > 100,000 * = Comparative Sample Table 4 Sam~le 5% With 2% SLS
6 12,640 *18 260 * = Compa~clive Sample F.x~mple 3 Some of the compositions of this invention were tested for t~ içk~ning properties in a typical pigmented paper co~ting. A pigm~nted paper co~ting was prepared by combining 80 pph Hydrap~nt~ tlel~nin~ted clay, 20 pph Hydrafine~ #1 clay, 7 pph Res~ 4126, and 0.15 pph Acumer~ 9300 dispersant.
The pH was adjusted to 8.5-9 with ~mmoni7~ The compositions o~this invention were added at the levels indicated in Table 3, and the viscosity of the sample was measured using the Brookfield viscomet,er at 100 rotations per _inute. The results are shown in Table 5.
Table 5 Sam~le Level (p~h) Viscosity 6 0.35 998 7 o.~ 1,000 The data above demonstrate the compQcitionc of this invention are efEective ~ keners in pigmented paper o~ g~.
Claims (9)
1. A composition comprising:
water;
at least 5 % by weight neutralized hydrophobically modified alkali-soluble emulsion (HASE) polymer; and from 0 to less than 1 % by weight, based on hydrophobically modified alkali-soluble emulsion polymer solids, of surfactant, wherein the viscosity of the composition is below 15,000 millipascal seconds.
water;
at least 5 % by weight neutralized hydrophobically modified alkali-soluble emulsion (HASE) polymer; and from 0 to less than 1 % by weight, based on hydrophobically modified alkali-soluble emulsion polymer solids, of surfactant, wherein the viscosity of the composition is below 15,000 millipascal seconds.
2. The composition of claim 1 wherein the HASE polymer is selected from the group consisting of HASE polymers which have a viscosity of at least 300 millipascal seconds when measured as a 5 % by weight aqueous solution of the neutralized HASE
in the presence of an added 2 % by weight based on the weight of the neutralized HASE polymer of sodium lauryl sulfate.
in the presence of an added 2 % by weight based on the weight of the neutralized HASE polymer of sodium lauryl sulfate.
3. The composition of claim 1, further comprising a macromolecular organic compound having a hydrophobic cavity.
4. The composition of claim 3 wherein the macromolecular organic compound is selected from the group consisting of cyclodextrin, cyclodextrin derivative, cycloinulohexose, cycloinuloheptose, cycloinuloctose, calyxarene and cavitand.
5. The composition of claim 4 wherein the macromolecular organic compound is a cyclodextrin selected from the group consisting of .alpha.-cyclodextrin, .beta.-cyclodextrin and .gamma.-cyclodextrin.
6. The composition of claim 4 wherein said macromolecular organic compound is a cyclodextrin derivative selected from the group consisting of methyl, triacetyl, hydroxypropyl and hydroxyethyl derivatives of .alpha.-cyclodextrin, .beta.-cyclodextrin and y-cyclodextrin.
7. A method for preparing a neutralized hydrophobically modified alkali-soluble emulsion (HASE) polymer comprising:
1) emulsion polymerizing a mixture of monomers comprising:
a) from 30 to 75 parts by weight of nonionic monomer;
b) from 5 to 75 parts by weight of anionic monomer; and c) from 1 to 20 parts by weight of hydrophobic monomer;
in the presence of less than 1 % by weight surfactant based on the weight of the monomers, to form a polymer emulsion of hydrophobically modified alkali-soluble emulsion polymer;
2) diluting the hydrophobically modified alkali-soluble emulsion polymer to provide a level of hydrophobically modified alkali-soluble emulsion polymer solids of from 5 to 70 % by weight; and 3) neutralizing the hydrophobically modified alkali-soluble emulsion polymer.
1) emulsion polymerizing a mixture of monomers comprising:
a) from 30 to 75 parts by weight of nonionic monomer;
b) from 5 to 75 parts by weight of anionic monomer; and c) from 1 to 20 parts by weight of hydrophobic monomer;
in the presence of less than 1 % by weight surfactant based on the weight of the monomers, to form a polymer emulsion of hydrophobically modified alkali-soluble emulsion polymer;
2) diluting the hydrophobically modified alkali-soluble emulsion polymer to provide a level of hydrophobically modified alkali-soluble emulsion polymer solids of from 5 to 70 % by weight; and 3) neutralizing the hydrophobically modified alkali-soluble emulsion polymer.
8. The method of claim 7 wherein the surfactant is present at a level of from 0 to 0.5 % by weight based on the weight of the monomers.
9. The composition of claim 1 wherein the level of surfactant is from 0 to 0.5 %
by weight, based on the hydrophobically modified alkali-soluble emulsion solids.
by weight, based on the hydrophobically modified alkali-soluble emulsion solids.
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| US5383297P | 1997-07-29 | 1997-07-29 | |
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| US5530056A (en) * | 1995-05-03 | 1996-06-25 | National Starch And Chemical Investment Holding Corporation | latex binders and paints which are free of volatile coalescents and freeze-thaw additives |
| US5686024A (en) * | 1995-12-18 | 1997-11-11 | Rhone-Poulenc Surfactants & Specialties, L.P. | Aqueous dispersion of a surface active polymer having enhanced performance properties |
| DE19548038A1 (en) * | 1995-12-21 | 1997-06-26 | Basf Ag | Process for the preparation of polymers by emulsion polymerization |
-
1998
- 1998-07-09 MX MX9805571A patent/MX200986B/en unknown
- 1998-07-15 AU AU76192/98A patent/AU749553B2/en not_active Ceased
- 1998-07-16 CA CA002243306A patent/CA2243306C/en not_active Expired - Fee Related
- 1998-07-16 NZ NZ331019A patent/NZ331019A/en unknown
- 1998-07-17 EP EP98305722A patent/EP0896027B1/en not_active Expired - Lifetime
- 1998-07-17 DE DE69800268T patent/DE69800268T2/en not_active Expired - Lifetime
- 1998-07-20 US US09/119,500 patent/US6063857A/en not_active Expired - Lifetime
- 1998-07-23 TH TH9801002823A patent/TH34258A/en unknown
- 1998-07-24 ID IDP981045A patent/ID20646A/en unknown
- 1998-07-24 KR KR1019980029819A patent/KR100590815B1/en not_active IP Right Cessation
- 1998-07-27 JP JP10211191A patent/JPH11152411A/en active Pending
- 1998-07-28 BR BR9802609-7A patent/BR9802609A/en not_active Application Discontinuation
- 1998-07-28 CN CNB981166342A patent/CN1165576C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11152411A (en) | 1999-06-08 |
| BR9802609A (en) | 2000-02-08 |
| EP0896027A1 (en) | 1999-02-10 |
| DE69800268D1 (en) | 2000-09-28 |
| CN1208745A (en) | 1999-02-24 |
| US6063857A (en) | 2000-05-16 |
| EP0896027B1 (en) | 2000-08-23 |
| KR100590815B1 (en) | 2006-10-11 |
| AU7619298A (en) | 1999-02-11 |
| MX9805571A (en) | 1999-01-31 |
| ID20646A (en) | 1999-02-04 |
| AU749553B2 (en) | 2002-06-27 |
| TH34258A (en) | 1999-08-06 |
| KR19990014137A (en) | 1999-02-25 |
| DE69800268T2 (en) | 2001-03-15 |
| CN1165576C (en) | 2004-09-08 |
| NZ331019A (en) | 2000-01-28 |
| MX200986B (en) | 2001-03-07 |
| CA2243306A1 (en) | 1999-01-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |