CA2229154A1 - Polycarboxy polymer acid binders having reduced cure temperatures - Google Patents
Polycarboxy polymer acid binders having reduced cure temperatures Download PDFInfo
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- CA2229154A1 CA2229154A1 CA002229154A CA2229154A CA2229154A1 CA 2229154 A1 CA2229154 A1 CA 2229154A1 CA 002229154 A CA002229154 A CA 002229154A CA 2229154 A CA2229154 A CA 2229154A CA 2229154 A1 CA2229154 A1 CA 2229154A1
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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
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2915—Rod, strand, filament or fiber including textile, cloth or fabric
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
Abstract
By carefully adjusting the molecular weight and amounts of methacrylic acid and maleic acid and/or maleic anhydride comonomers in polyacrylic acid-based fiberglass binders, binder-treated fiberglass cured and B-staged product throughput may be maintained at production rates designed for phenol/formaldehyde binders due to the lower thermal requirements for cure as compared to homopolyacrylic acid-based binder systems.
Description
~ , MA~ 0291 PUS
POLYCARBOXY PO~YMER ACID BINDERS
HAV~G REDUCED CURE TE,MPERATURES
Technica~ Field The subjec:t invention pertains to thermo-S settable binding resins. More particularly, the ~ubjectinvention pertains to thermosetting, acrylic acid-based binder re~ins which cure ~y cros~lin~ing with a poly-functional, carboxyl group-reactive curing agent. Such binders are useful as replacements for formaldehyde, based binders in non-woven fiberglass good~.
Ba~k~round Art Polymeric fiberglass binders have a variety of uses ranging from stiffening applications where the binder is applied to wo~en or r.on-woven fiberg'ass sheet goods and cured, producing a ~tiffer product; thermo-forming applications wherein the binder resin is applied to sheet or lofty fibrous product following which it is dried and optionally B-etaged to form an intermediate but yet curable producti and to fully cured sy~tems such as building in6ulat.ion, wherein the binder is fully cured to its thermoset state while the fiberglass is in the lully expanded condition, following which the rolls or batts are compressed for storage and shipment. In the latter case, it is important that upon releasing the compression, that the batt or roll of fi~erglass insula-tion recover a su~stantial part of its precompressed thickness.
~N 0291 PUS -2-Polymeric binders used in the present sense should not be confused with ma~rix resins which are an entirely different and non-analogous field of art.
While ~ometimes termed "binders~, matrix resins act to fill the entire interstitial space between fibers, resulting in a dense, fiber reinforced product where the matrix must translate the fiber strength propertie~ to the composite, whereas "binder resin~'l as used herein are not space-fillin~, but rather coat only the fibers, and particularly the junc~lons of fiber~. 3inder resins in these applications perfor~ no translation of fiber s~rength. Rather, the unique physical properties or these products are rela~ed in general to polymer stiff-ness rather than fibe~ strength. Fiberglass binders also cannot be equated with paper or wood product "binders" where the adhesive properties are tailored to the chemical nature o~ the cellulosic substrates ~any such resins, e.g. urea/formaldehyde and resorcinol/form-aldehyde resin~, are not suitable for use as fiberglass 2G binders. One skilled in the art of fiberglass binders would not look to cellulosic binders to solve any of the known problems associated with fiberglass binder~.
From among the many thermosetting polymers, numerous candidates for suitable thermosetting fiber-glas6 binder resins exict. However, binder-coated fiberglass products are often o~ the commodity type, and thus co~t becomes a driving faceor, ruling out such resins as thermosetting polyurethane3, epoxie~, and others. Due to their excellent co~/performance ratio, ~o ehe resins of choice in the past ha~e been phenol~or-maldehyde resins Phenol/formaldehyde resole resins can be economically produced, and can be extended with urea prior eo use as a binder in many applications. Such CA 02229l54 l998-02-06 urea-extended phenol/~ormaldehyde resole binders have been ~he malnstay of the fiberglass insulation industry for years, for example.
Over the past several decades however, minimi-S zation of volatile organic compound emi~sions (VOCs) both on t~e part of the industry de~iring to provide a cleaner en~ironment, as well as by Federal regul~tion, has led to extensi~e investigation6 into not only reducing emisqions from the current for~aldehyde-based lo binde.s, but also into candidate replacement binders.
For example, subtle changes in the ratios of phenol t~
formaldehyde ,in the preparation of the basic phenol/formaldehyde resole resins, changes in catalysts, and ~ddit1on of different and multiple ~ormaldehyde scavengers, has resulted in considerable improve~ent in emissions from pheno:l/formaldehyde ~inders as compared with the binders previously used. However, with in-creasingly stringent Federal .egulations, more and more attention has been paid to alternati~e binder syseems which are free from formaldehyde.
One such candidate binder sy~tem employs polymers of acrylic acld a~ a first component, and a polyol such as glycerine or a modestly oxyalkylated glycerine as a curing or "cros31inking" component. The preparation and properties of such poly~acrylic acid)-based binders, including informacion relative to the VOC
emisslons, and a comparison o~ binder properties versus urea formaldehyde binders i~ pre6ented in ~l~ormaldehyde-Free Cro~slinking Binders For Non-Woven~", Charles T.
Arkins et al., ~APPI JO~AL, VO1. 78, NO. 11, Page9 161-168, November 1995. ~he Dinders disclosed by the Arkins article, appear to be s-stageable as well as being able CA 02229l54 l998-02-06 .~AN 0291 PUS -4-to pro~ide physical properties similar to ~hose of ~lrea/formaldehyde re5ins. Unfortunately, urea/formalde-hyde resins do not in general offer the same properties as phenol~ormaldehyde resins, the most widely used fiberglass binder ~esins.
U.S. Paten~ No. 4,076,917 discloses ~-hydroxy-alkylamides, more particularly bis(~-hydroxyalkylamide6) as cu.ing asents for polymers containing car~oxyl functionality. Numerous unsaturated monomers are dis-o clo~ed ~or preparation of the carboxyl-functional polymer, lnd copolymers of e~hylacrylate/methacrylic acid, and ter- and tetrapolymers of butylacryl-ate/me~hylmethacrylat~/styrene/methacrylic acid; ethyl-acryla~e/styrene/methacrylic acid; butyl acrylate/meth-i5 acrylic acid/styreneJ'maleic anhydride; and ethylacryl-ate/methylr,ethacrylate/methacrylic acid are among the carboxylic acid group-containing polymers exemplified.
U.S. Patent No. ~,105,798 disclose~ water soluble binders prepared from polyfunctional carboxylic acids and ~-hydrox~urethanes. A~ong the polycarboxylic acids, preference is gi~en to monomeric polycarboxylic acids such as the cycloalkane ~etracarboxylic acids and anhydrides, pyromelli~ic acid and its anhydride, and maleic acid and its anhydride. Polymaleic acid and polymaleic anhydride are also identified. Poly(acrylic acids) are exemplifi~d as not producing cured products with sood tensile strength.
U.S. Patent No. 5,143,5a2 discloses heat resistant non-wo~ens containing ammonia-neutrali2ed polycarboxylic acids, either monomeric or polymeric, and ~-hydroxyalkyl amldes. High molecular wei~h_ CA 02229l54 l998-02-06 ~AN 0291 PUS -5-poly(acrylic acid) is shown to ~e superior to low molecular weight poly(acrylic acid) in these applica-tions. Apparent cure temperature is 204 C. However, the binder compo~itions are belie~ed to liberate ammonia upon cure. Ammonia ~missions are becoming increasingly tightly regulated.
~ .S. Patent No. 5,318,~90 di~close~ fi~erglass insulation produc~s cured with a combination o~ a polycarboxy polymer, a ~-hydroxyalkylamide, and an at least tri~unctional monomeric carboxylic acid such as citric acia. No polyca~boxy polymers other eha~
poly(acrylic acid) are disclosed, although co- and terpoiymer pclycarboxy acids are Droaaly disclosed Published European ~tent Application EP O 593 086 A1 appears to pro~ide details of poly-acrylic binders whose cure i5 catalyzed by a phosphorus-contalniny cataly6t system as di6cussed in the Arkens article pre~iously cited. European Published Applica-tion EP O 651 088 A1 contains a related disclosure pertaining ~o cellulosic substrate binders. The fiber-gla~s binders o~ EP '086 are part~ally neutralized polycarboxy polymers and hydroxyl-functional curing agents wherein the polycarboxy polymers are prepared in the pre~ence of sodium hypopho~phite, incorporatlng the latter into the polymer structure or by incorporating sodium hypophosphite separately i~to the curable mixture of polycarboxy polymers to serve as the curing catalyst.
Terpolymers of acrylic acid, maleic acid, and sodium hypophc,sphite are exemplified but appear to reduce both dry and wet tensile strength as compared to poly(acrylic acid) catalyzed with sodium hypophosphite. Higher mol~c~lar weight ~cly(acrylic acids) are sta~ed to , ~
~N 02~1 PUS -6-pro~ide polymers exhibiting more complete cure. Under the s~me conditions, copolymers of acrylic acid and maleic acid are shown ~o have less complete cure as shown by the swell ratios ~f the polymers, and the copolymer with higher maleic acid content .a~ed wor6e in ~his comparison.
Further, and most importantly, as Arkens indicates, the normal cure temperature of the acrylic binder resins is approximately l~O C, and a final cure doe~ no~ take ~lace without prolonged heating at this tempe-a{ure or by allowing the temperature to rise to the range of 220 C co 240'C. The combination of curing temperature and cure time r.ecessitate~ thermal energy requirements considerably in excess of what is normally lS desirable for phenol~formaldehyde resins. While it might seem ~hat a simple increase ln furnace temperature could Frovlde the additlonal ~hermal energy rec~ired, it mus~ ~ remembered that in a commercial setting, the exceptlonally large ~urnaces, powerful heat supplies, and anc~ ry equipment must all be chansed if a binder with higher thermal enerc3y curing rec~irements is to be used. These changes are no~ minimal, and represent a considerable financial inve~tment, in many case~ requir-ing signlficant additional furnace leng~h. Moreover, it is highly iikely that f~r a considerable period of time at least, a variety of binder resins may be used on the same iine at different times. Thus, any change made to the curing cvens must b~ easily reversible. ~hus, poly(acrylic acid) binder systems having curing energy requirements similar ~o those of phenol/for~aldehyde binders ~ould be desirable.
CA 02229l54 l998-02-06 , ~ he cure eemperatures and rates o~ cure are belie~ed to be ~ependent ~pon a number of factors;
The~e, of course, include the react~ y of the carbox-ylic acid and poiyol and the presence and type of esterification catalyst present. ~he poly(acrylic acid) polymer and the polyol together contain far ~ore theo-retical crosslinking possibilities than is believed neces~ary to provide the necessary crosslinking to a~cain a t:~ermoset binder. Ie is believed that a significan~ frac~ion of carboxylic acid groups from the poly(acrylic acid) and hydroxyl groups f-om the polyol in fac~ do noe esterify, but remain unreaceed in the thermoset product. One of the reason~ for the difficul-,y o- e~eerific~tion of poly~acrylic acid) carboxylic acid groups and polyol hydroxyl groups is that poly(acry~ic acid) i5 believed to form self-as~ociating discrete phases upon loss of ~ater solvent, ~ossibly to the exclusion of the polyol present. Crosslinking via esterificat,on can th~n only occur when sufficient thermal energy is precent to disrupt these dlscrete phases. Such molecular disruption may occur solely via ~hermally-induced molecular motions, and~or by a change in the poly(acrylic acid) molecule caused by internal anhydride forma~ion between neighboring ca~boxylic acid z5 groups.
S11-nm~r~ Of The Invention It has now been surprisingly di3covered that cure tempera~ures of polycarboxy poly~er binders can be significantly lowered through incorporation of maleic acid and~or maleic anhydride into the polyca~boxy polymer. and operating on ~he lower apparene molecular weight end of the 20-100 ~Da range. By these methods, ~AN 0291 PU~ -8-curing temperatures can be lowered from c.a. 1~0'C to temperatures less than 140 C. As a result, the suit-ability of polyacrylic acid bi~.ders as replacements for phenol/formaldehyde and other formaldehyde-~ased resins in current commercial operations is enhanced.
Brief Des~ription Of The Drawin~c FIG-JRE 1 _9 a D~ plot illustrating the temperatures associated with the onset and terminus of cure.
;o r IGU~E 2 is a DMA ploe illustrating a two-step cure.
Detai~ed Description of the Pre~erred Embodiments The polycarboxy polymers useful in the binder sys;e~s of the present invention comprise mini~ally 20 ~eigh~ percent of polymerized poiy~acry~ic acid~ moi-eties and at least 10 weight percent of maleic acid and/or maleic anhydride moieties. Other polymerizable monomers, i.e. styrene, acrylonitrile, and the like may also be present. In general, ~he hi~her the content of acrylic acid, methacrytic acid, maleic an~ydride, and maleic acid, the higher the theoretical crosslink density of the thermosetting resin system. I~ a resin system wi~h less than the highest degree of crosslinking is desired, non-cros~linkable monomers such as s~yrene, acryloni,rile, methylacrylate, and methylmethacrylate, may De added. The polymerization of the monomers preferably occur~ in aqueous solution, for examp~e by the me~hods di~closed in U.S. Patent Nos. 3,658,77~ ~nd 5,412,026.
r ~rL~ 02gI PUS ~9-A s~udy ~as initiated to examine the effec~s of polymer composition, molecular weight, and polyol and esterification catalyst levels in a series o~ copolymers and terpolymers produced by the aqueous polymerizacion of acrylic acid, methacrylic ~cid, ~nd maleic acid utill7ing a free radical polymerization initiator. The polmerizations were carried out at 50~ solids and some of the ves5els actually were gelled after the polymer-ization was complete. Al~hough the gels were due to lQ high molecular weight and not crosslinking (they were still soluble), all ~ffec~s attribuced to molecular weight were suspect ~ue to a probable Tromsdorf~ e~fect Mol~c~1lar weight determination was done using a Waters HPLC with an Ultrahydrogel linear column (Waters). hater, raised to pH 10 with sodium hydroxide, ~as employed as the mobile phas~. Reported molecular ~eights are appa.ent r.umber average molecular weights versus poly~sodiu~ methacrylate) narrow standards (Polysciences) using ~illenium 2010 software for data reduction and a linear calibration curve. The molecular weights determined by this method are actually believed to be lower than che actual molecular weights. The term "apparent" used herein and in the claims i5 reflecti~e o~ molecular ~eight measurement as described herein, in other words, at pH 10 versus poly(sodium methacrylate) standards, a method of mea~urement easily performed by those skiil~d ln the ar~.
Cure profiles were measured us~ng a Polymer Labor.~tories, Inc. Mcdel DMTA III Dynamic Mech~nicai Anaiyzer (D~'~). The ~inders were impregnated in Whatman microfi~erglas3 filter paper strips, about 0.2~ gram~ of binder soluticn on two strips ~bout 20 millime~rs by MAN 02~1 PUS -10-mill~meters in dimension. The strips were then laminat-ed and clam2ed ir.to the DMA. Dynamic moduli were measured from 80 C to 300 C at 4 C/minute in air. The onse~ and completion of cure were determined as shown in Figllre 1 The cure evaluations were done i~ random order.
T:~e cur~ profiles were characterized ~y an onset and a termlnus of cure. The interpretation of several DMA scans wa~ problematic due to an apparent lo cwo-stage cure in many o~ the formuldtions containing maleic aci~. It was possible, ~here~ore, that some residual free maleic acid monomer was contained in those ~ormulatlons which contribu~ed ~o the o~served phenome-non. .~n experiment was conducted to examine the affects of free maleic acld on the cure pro~ile of a polycar-boxypoly~erJglycerol sys~em. A commercial poly(acrylic acid) was bl~ndeà w~th maleic acid at a weight ratio of 1:0.5 and cured with glycerol at a carboxyl:hydroxyl mol ratio of approximately 1:1. 2MA showed a two-step cure (Figure 2) for this ~ystem with ~he ~irst cure being complete at approximately 210-C followed by a second at 260'C. ~he poly~acrylic acld~ binder cured with glycer-ol and no maleic acid cypically has a cure ter~inus of approximately ~lO C, and it thus appeared that che free residual mal~ic acid was responsible for further in-creasing ~odulus by crosslinking thro~gh the un~atura-tiOn present. There~ore, when there were two apparent cures in the DMA scan, the first one was considered ehe "true" cure with respect .o analysis of the experimental data.
This scudy ;n~icated that higher catalyst levels, near stoichlometric polyol, and lower ~olecular ,, , weigh~ ~avored lower cure temperatures. However, the molecular weigh~ effects were suspect as mentioned earller .
Uowever, as a result of some of these uncer-S ~aintle~ thought present in ~he first experimental campaign, in a second experi~encal campaign, a more accurate limitation of molecular weight wa~ achie~ed through t;ne addition of a chain transfer agent, isopro-panol. A potassium persulfate/sodium bisulfite -edox-fr~e rad cal initiator system was employed. The poly-merizations were conduc~ed in septum-sealed 20 mL test ~ubes with no attempt to deoxygenate reagents or reac-tion ~bes. ~he correct amount of wa~er for 80 mL of edch of the three solvent mixeures was added to a 1~ polymeriza.ion tu~e. The initiator was dissolved in the water foliowea by addition 0c the chain transfer agent.
sodiu~ bisulfite waS then ~dded to the solutions and dissolved. The test tubes ~ere charged with 8 mL of the solvent~ini~latorisodiu~ bisulfite mixtures, and the desired monomer amounts added. ~he cubes were septum sealed and placed into a convection oven at 60 C + 5'C.
After three hours, the oven was turned o~f and the tubes allo~ed to cool to room temperature slowly overni~ht inside the oven.
The septa were removed from the test tubes and the con~ents were ~ransferred to scintilla~ion vials Catalyst and polyol was then added If necessary, smail amounts of methanol were added to reduce ~isco~ity and as~i~t in homogenation. In some cases, the vial5 were warmed with hot water for the same rea~on~ The curable binder wag added to glas~ fiber filter strips ac before In the second set ol polymerization~, the solids content CA 02229l54 l998-02-06 was a~proximately 20~ instead of 50~. ~3 a result of the lower solids content, the viscosity cf the polymer solutions were significantly 'ower than those in the first campaig~, and t~.us, the Tromsdorff effect was not ~elieved operable. In the second campaign, the initia-tor level was kept constant at 3 parts per 100 parts of monomer ~phm), and sodium bisulfite was used as a redox catalyst for the initiator at 1.5 phm. The charges for campaisn 2 are presented in Table 1. In the Table, AA
is acrylic acid, MA is methacrylic acid, MaA is maleic acid weight fractions as charged, and iPA is isopropa-noi. The columns iden~ified as X-AA, X-MA, and X-Ma~
are the ln'erred polymer compositions in weight frac-tior,s, ~ased on analysis of residual, ~nreacted monomers in the poiymeri~ation vials.
MUiN 0231 PU~ -13- -~'A~LE I
E~pcrim~nl~l Dcs;~n ~nd ~le~urcd ~e~ponscs Run Tri~ rder- A~ MA MaA X-A~ X-MA X-M~A irA'' O~s~l' Final' ~1w/Mn Mn M~
1 15 O 0.5 O.S 0 0 659 0 341 50 171 237 ~ 41 60,000 14~,000 2 16 0 0.5 0.5 0 0.619 0.3~1 125 176 199 2.49 50,000 125,000 D
POLYCARBOXY PO~YMER ACID BINDERS
HAV~G REDUCED CURE TE,MPERATURES
Technica~ Field The subjec:t invention pertains to thermo-S settable binding resins. More particularly, the ~ubjectinvention pertains to thermosetting, acrylic acid-based binder re~ins which cure ~y cros~lin~ing with a poly-functional, carboxyl group-reactive curing agent. Such binders are useful as replacements for formaldehyde, based binders in non-woven fiberglass good~.
Ba~k~round Art Polymeric fiberglass binders have a variety of uses ranging from stiffening applications where the binder is applied to wo~en or r.on-woven fiberg'ass sheet goods and cured, producing a ~tiffer product; thermo-forming applications wherein the binder resin is applied to sheet or lofty fibrous product following which it is dried and optionally B-etaged to form an intermediate but yet curable producti and to fully cured sy~tems such as building in6ulat.ion, wherein the binder is fully cured to its thermoset state while the fiberglass is in the lully expanded condition, following which the rolls or batts are compressed for storage and shipment. In the latter case, it is important that upon releasing the compression, that the batt or roll of fi~erglass insula-tion recover a su~stantial part of its precompressed thickness.
~N 0291 PUS -2-Polymeric binders used in the present sense should not be confused with ma~rix resins which are an entirely different and non-analogous field of art.
While ~ometimes termed "binders~, matrix resins act to fill the entire interstitial space between fibers, resulting in a dense, fiber reinforced product where the matrix must translate the fiber strength propertie~ to the composite, whereas "binder resin~'l as used herein are not space-fillin~, but rather coat only the fibers, and particularly the junc~lons of fiber~. 3inder resins in these applications perfor~ no translation of fiber s~rength. Rather, the unique physical properties or these products are rela~ed in general to polymer stiff-ness rather than fibe~ strength. Fiberglass binders also cannot be equated with paper or wood product "binders" where the adhesive properties are tailored to the chemical nature o~ the cellulosic substrates ~any such resins, e.g. urea/formaldehyde and resorcinol/form-aldehyde resin~, are not suitable for use as fiberglass 2G binders. One skilled in the art of fiberglass binders would not look to cellulosic binders to solve any of the known problems associated with fiberglass binder~.
From among the many thermosetting polymers, numerous candidates for suitable thermosetting fiber-glas6 binder resins exict. However, binder-coated fiberglass products are often o~ the commodity type, and thus co~t becomes a driving faceor, ruling out such resins as thermosetting polyurethane3, epoxie~, and others. Due to their excellent co~/performance ratio, ~o ehe resins of choice in the past ha~e been phenol~or-maldehyde resins Phenol/formaldehyde resole resins can be economically produced, and can be extended with urea prior eo use as a binder in many applications. Such CA 02229l54 l998-02-06 urea-extended phenol/~ormaldehyde resole binders have been ~he malnstay of the fiberglass insulation industry for years, for example.
Over the past several decades however, minimi-S zation of volatile organic compound emi~sions (VOCs) both on t~e part of the industry de~iring to provide a cleaner en~ironment, as well as by Federal regul~tion, has led to extensi~e investigation6 into not only reducing emisqions from the current for~aldehyde-based lo binde.s, but also into candidate replacement binders.
For example, subtle changes in the ratios of phenol t~
formaldehyde ,in the preparation of the basic phenol/formaldehyde resole resins, changes in catalysts, and ~ddit1on of different and multiple ~ormaldehyde scavengers, has resulted in considerable improve~ent in emissions from pheno:l/formaldehyde ~inders as compared with the binders previously used. However, with in-creasingly stringent Federal .egulations, more and more attention has been paid to alternati~e binder syseems which are free from formaldehyde.
One such candidate binder sy~tem employs polymers of acrylic acld a~ a first component, and a polyol such as glycerine or a modestly oxyalkylated glycerine as a curing or "cros31inking" component. The preparation and properties of such poly~acrylic acid)-based binders, including informacion relative to the VOC
emisslons, and a comparison o~ binder properties versus urea formaldehyde binders i~ pre6ented in ~l~ormaldehyde-Free Cro~slinking Binders For Non-Woven~", Charles T.
Arkins et al., ~APPI JO~AL, VO1. 78, NO. 11, Page9 161-168, November 1995. ~he Dinders disclosed by the Arkins article, appear to be s-stageable as well as being able CA 02229l54 l998-02-06 .~AN 0291 PUS -4-to pro~ide physical properties similar to ~hose of ~lrea/formaldehyde re5ins. Unfortunately, urea/formalde-hyde resins do not in general offer the same properties as phenol~ormaldehyde resins, the most widely used fiberglass binder ~esins.
U.S. Paten~ No. 4,076,917 discloses ~-hydroxy-alkylamides, more particularly bis(~-hydroxyalkylamide6) as cu.ing asents for polymers containing car~oxyl functionality. Numerous unsaturated monomers are dis-o clo~ed ~or preparation of the carboxyl-functional polymer, lnd copolymers of e~hylacrylate/methacrylic acid, and ter- and tetrapolymers of butylacryl-ate/me~hylmethacrylat~/styrene/methacrylic acid; ethyl-acryla~e/styrene/methacrylic acid; butyl acrylate/meth-i5 acrylic acid/styreneJ'maleic anhydride; and ethylacryl-ate/methylr,ethacrylate/methacrylic acid are among the carboxylic acid group-containing polymers exemplified.
U.S. Patent No. ~,105,798 disclose~ water soluble binders prepared from polyfunctional carboxylic acids and ~-hydrox~urethanes. A~ong the polycarboxylic acids, preference is gi~en to monomeric polycarboxylic acids such as the cycloalkane ~etracarboxylic acids and anhydrides, pyromelli~ic acid and its anhydride, and maleic acid and its anhydride. Polymaleic acid and polymaleic anhydride are also identified. Poly(acrylic acids) are exemplifi~d as not producing cured products with sood tensile strength.
U.S. Patent No. 5,143,5a2 discloses heat resistant non-wo~ens containing ammonia-neutrali2ed polycarboxylic acids, either monomeric or polymeric, and ~-hydroxyalkyl amldes. High molecular wei~h_ CA 02229l54 l998-02-06 ~AN 0291 PUS -5-poly(acrylic acid) is shown to ~e superior to low molecular weight poly(acrylic acid) in these applica-tions. Apparent cure temperature is 204 C. However, the binder compo~itions are belie~ed to liberate ammonia upon cure. Ammonia ~missions are becoming increasingly tightly regulated.
~ .S. Patent No. 5,318,~90 di~close~ fi~erglass insulation produc~s cured with a combination o~ a polycarboxy polymer, a ~-hydroxyalkylamide, and an at least tri~unctional monomeric carboxylic acid such as citric acia. No polyca~boxy polymers other eha~
poly(acrylic acid) are disclosed, although co- and terpoiymer pclycarboxy acids are Droaaly disclosed Published European ~tent Application EP O 593 086 A1 appears to pro~ide details of poly-acrylic binders whose cure i5 catalyzed by a phosphorus-contalniny cataly6t system as di6cussed in the Arkens article pre~iously cited. European Published Applica-tion EP O 651 088 A1 contains a related disclosure pertaining ~o cellulosic substrate binders. The fiber-gla~s binders o~ EP '086 are part~ally neutralized polycarboxy polymers and hydroxyl-functional curing agents wherein the polycarboxy polymers are prepared in the pre~ence of sodium hypopho~phite, incorporatlng the latter into the polymer structure or by incorporating sodium hypophosphite separately i~to the curable mixture of polycarboxy polymers to serve as the curing catalyst.
Terpolymers of acrylic acid, maleic acid, and sodium hypophc,sphite are exemplified but appear to reduce both dry and wet tensile strength as compared to poly(acrylic acid) catalyzed with sodium hypophosphite. Higher mol~c~lar weight ~cly(acrylic acids) are sta~ed to , ~
~N 02~1 PUS -6-pro~ide polymers exhibiting more complete cure. Under the s~me conditions, copolymers of acrylic acid and maleic acid are shown ~o have less complete cure as shown by the swell ratios ~f the polymers, and the copolymer with higher maleic acid content .a~ed wor6e in ~his comparison.
Further, and most importantly, as Arkens indicates, the normal cure temperature of the acrylic binder resins is approximately l~O C, and a final cure doe~ no~ take ~lace without prolonged heating at this tempe-a{ure or by allowing the temperature to rise to the range of 220 C co 240'C. The combination of curing temperature and cure time r.ecessitate~ thermal energy requirements considerably in excess of what is normally lS desirable for phenol~formaldehyde resins. While it might seem ~hat a simple increase ln furnace temperature could Frovlde the additlonal ~hermal energy rec~ired, it mus~ ~ remembered that in a commercial setting, the exceptlonally large ~urnaces, powerful heat supplies, and anc~ ry equipment must all be chansed if a binder with higher thermal enerc3y curing rec~irements is to be used. These changes are no~ minimal, and represent a considerable financial inve~tment, in many case~ requir-ing signlficant additional furnace leng~h. Moreover, it is highly iikely that f~r a considerable period of time at least, a variety of binder resins may be used on the same iine at different times. Thus, any change made to the curing cvens must b~ easily reversible. ~hus, poly(acrylic acid) binder systems having curing energy requirements similar ~o those of phenol/for~aldehyde binders ~ould be desirable.
CA 02229l54 l998-02-06 , ~ he cure eemperatures and rates o~ cure are belie~ed to be ~ependent ~pon a number of factors;
The~e, of course, include the react~ y of the carbox-ylic acid and poiyol and the presence and type of esterification catalyst present. ~he poly(acrylic acid) polymer and the polyol together contain far ~ore theo-retical crosslinking possibilities than is believed neces~ary to provide the necessary crosslinking to a~cain a t:~ermoset binder. Ie is believed that a significan~ frac~ion of carboxylic acid groups from the poly(acrylic acid) and hydroxyl groups f-om the polyol in fac~ do noe esterify, but remain unreaceed in the thermoset product. One of the reason~ for the difficul-,y o- e~eerific~tion of poly~acrylic acid) carboxylic acid groups and polyol hydroxyl groups is that poly(acry~ic acid) i5 believed to form self-as~ociating discrete phases upon loss of ~ater solvent, ~ossibly to the exclusion of the polyol present. Crosslinking via esterificat,on can th~n only occur when sufficient thermal energy is precent to disrupt these dlscrete phases. Such molecular disruption may occur solely via ~hermally-induced molecular motions, and~or by a change in the poly(acrylic acid) molecule caused by internal anhydride forma~ion between neighboring ca~boxylic acid z5 groups.
S11-nm~r~ Of The Invention It has now been surprisingly di3covered that cure tempera~ures of polycarboxy poly~er binders can be significantly lowered through incorporation of maleic acid and~or maleic anhydride into the polyca~boxy polymer. and operating on ~he lower apparene molecular weight end of the 20-100 ~Da range. By these methods, ~AN 0291 PU~ -8-curing temperatures can be lowered from c.a. 1~0'C to temperatures less than 140 C. As a result, the suit-ability of polyacrylic acid bi~.ders as replacements for phenol/formaldehyde and other formaldehyde-~ased resins in current commercial operations is enhanced.
Brief Des~ription Of The Drawin~c FIG-JRE 1 _9 a D~ plot illustrating the temperatures associated with the onset and terminus of cure.
;o r IGU~E 2 is a DMA ploe illustrating a two-step cure.
Detai~ed Description of the Pre~erred Embodiments The polycarboxy polymers useful in the binder sys;e~s of the present invention comprise mini~ally 20 ~eigh~ percent of polymerized poiy~acry~ic acid~ moi-eties and at least 10 weight percent of maleic acid and/or maleic anhydride moieties. Other polymerizable monomers, i.e. styrene, acrylonitrile, and the like may also be present. In general, ~he hi~her the content of acrylic acid, methacrytic acid, maleic an~ydride, and maleic acid, the higher the theoretical crosslink density of the thermosetting resin system. I~ a resin system wi~h less than the highest degree of crosslinking is desired, non-cros~linkable monomers such as s~yrene, acryloni,rile, methylacrylate, and methylmethacrylate, may De added. The polymerization of the monomers preferably occur~ in aqueous solution, for examp~e by the me~hods di~closed in U.S. Patent Nos. 3,658,77~ ~nd 5,412,026.
r ~rL~ 02gI PUS ~9-A s~udy ~as initiated to examine the effec~s of polymer composition, molecular weight, and polyol and esterification catalyst levels in a series o~ copolymers and terpolymers produced by the aqueous polymerizacion of acrylic acid, methacrylic ~cid, ~nd maleic acid utill7ing a free radical polymerization initiator. The polmerizations were carried out at 50~ solids and some of the ves5els actually were gelled after the polymer-ization was complete. Al~hough the gels were due to lQ high molecular weight and not crosslinking (they were still soluble), all ~ffec~s attribuced to molecular weight were suspect ~ue to a probable Tromsdorf~ e~fect Mol~c~1lar weight determination was done using a Waters HPLC with an Ultrahydrogel linear column (Waters). hater, raised to pH 10 with sodium hydroxide, ~as employed as the mobile phas~. Reported molecular ~eights are appa.ent r.umber average molecular weights versus poly~sodiu~ methacrylate) narrow standards (Polysciences) using ~illenium 2010 software for data reduction and a linear calibration curve. The molecular weights determined by this method are actually believed to be lower than che actual molecular weights. The term "apparent" used herein and in the claims i5 reflecti~e o~ molecular ~eight measurement as described herein, in other words, at pH 10 versus poly(sodium methacrylate) standards, a method of mea~urement easily performed by those skiil~d ln the ar~.
Cure profiles were measured us~ng a Polymer Labor.~tories, Inc. Mcdel DMTA III Dynamic Mech~nicai Anaiyzer (D~'~). The ~inders were impregnated in Whatman microfi~erglas3 filter paper strips, about 0.2~ gram~ of binder soluticn on two strips ~bout 20 millime~rs by MAN 02~1 PUS -10-mill~meters in dimension. The strips were then laminat-ed and clam2ed ir.to the DMA. Dynamic moduli were measured from 80 C to 300 C at 4 C/minute in air. The onse~ and completion of cure were determined as shown in Figllre 1 The cure evaluations were done i~ random order.
T:~e cur~ profiles were characterized ~y an onset and a termlnus of cure. The interpretation of several DMA scans wa~ problematic due to an apparent lo cwo-stage cure in many o~ the formuldtions containing maleic aci~. It was possible, ~here~ore, that some residual free maleic acid monomer was contained in those ~ormulatlons which contribu~ed ~o the o~served phenome-non. .~n experiment was conducted to examine the affects of free maleic acld on the cure pro~ile of a polycar-boxypoly~erJglycerol sys~em. A commercial poly(acrylic acid) was bl~ndeà w~th maleic acid at a weight ratio of 1:0.5 and cured with glycerol at a carboxyl:hydroxyl mol ratio of approximately 1:1. 2MA showed a two-step cure (Figure 2) for this ~ystem with ~he ~irst cure being complete at approximately 210-C followed by a second at 260'C. ~he poly~acrylic acld~ binder cured with glycer-ol and no maleic acid cypically has a cure ter~inus of approximately ~lO C, and it thus appeared that che free residual mal~ic acid was responsible for further in-creasing ~odulus by crosslinking thro~gh the un~atura-tiOn present. There~ore, when there were two apparent cures in the DMA scan, the first one was considered ehe "true" cure with respect .o analysis of the experimental data.
This scudy ;n~icated that higher catalyst levels, near stoichlometric polyol, and lower ~olecular ,, , weigh~ ~avored lower cure temperatures. However, the molecular weigh~ effects were suspect as mentioned earller .
Uowever, as a result of some of these uncer-S ~aintle~ thought present in ~he first experimental campaign, in a second experi~encal campaign, a more accurate limitation of molecular weight wa~ achie~ed through t;ne addition of a chain transfer agent, isopro-panol. A potassium persulfate/sodium bisulfite -edox-fr~e rad cal initiator system was employed. The poly-merizations were conduc~ed in septum-sealed 20 mL test ~ubes with no attempt to deoxygenate reagents or reac-tion ~bes. ~he correct amount of wa~er for 80 mL of edch of the three solvent mixeures was added to a 1~ polymeriza.ion tu~e. The initiator was dissolved in the water foliowea by addition 0c the chain transfer agent.
sodiu~ bisulfite waS then ~dded to the solutions and dissolved. The test tubes ~ere charged with 8 mL of the solvent~ini~latorisodiu~ bisulfite mixtures, and the desired monomer amounts added. ~he cubes were septum sealed and placed into a convection oven at 60 C + 5'C.
After three hours, the oven was turned o~f and the tubes allo~ed to cool to room temperature slowly overni~ht inside the oven.
The septa were removed from the test tubes and the con~ents were ~ransferred to scintilla~ion vials Catalyst and polyol was then added If necessary, smail amounts of methanol were added to reduce ~isco~ity and as~i~t in homogenation. In some cases, the vial5 were warmed with hot water for the same rea~on~ The curable binder wag added to glas~ fiber filter strips ac before In the second set ol polymerization~, the solids content CA 02229l54 l998-02-06 was a~proximately 20~ instead of 50~. ~3 a result of the lower solids content, the viscosity cf the polymer solutions were significantly 'ower than those in the first campaig~, and t~.us, the Tromsdorff effect was not ~elieved operable. In the second campaign, the initia-tor level was kept constant at 3 parts per 100 parts of monomer ~phm), and sodium bisulfite was used as a redox catalyst for the initiator at 1.5 phm. The charges for campaisn 2 are presented in Table 1. In the Table, AA
is acrylic acid, MA is methacrylic acid, MaA is maleic acid weight fractions as charged, and iPA is isopropa-noi. The columns iden~ified as X-AA, X-MA, and X-Ma~
are the ln'erred polymer compositions in weight frac-tior,s, ~ased on analysis of residual, ~nreacted monomers in the poiymeri~ation vials.
MUiN 0231 PU~ -13- -~'A~LE I
E~pcrim~nl~l Dcs;~n ~nd ~le~urcd ~e~ponscs Run Tri~ rder- A~ MA MaA X-A~ X-MA X-M~A irA'' O~s~l' Final' ~1w/Mn Mn M~
1 15 O 0.5 O.S 0 0 659 0 341 50 171 237 ~ 41 60,000 14~,000 2 16 0 0.5 0.5 0 0.619 0.3~1 125 176 199 2.49 50,000 125,000 D
3 l4 0 0.5 0.5 0 O.GI0 0.390 200 168 192 2 40 46,000 111,000 4 1 ~ I O O I ~ 50 174 205 2.36 31~,000 89,000 l 7 0 \ Q 0 1 0 125 174 207 2.54 26,000 66,000 r 6 i -0 1 0 () I 0 20~) ~ 72 195 2.46 30,000 73,000 7 ~ 0.5 0 0 5 0.621 0 0.379 50 153 182 2.32 ~5,000 81,000 o 12 0.5 0 O.S 0.6l9 0 0.381 l25 146 177 2.D0 25,0110 51,000 O
9 10 0.5 0 0.5 0.609 0 0 3~0 2(~() 145 174 ~.14 25,noU 53,000 9 1 0 0 1 11 0 50 144 197 2.4R 33,01)0 81,000 Il 11 1 0 0 1 0 0 ~25 141 200 2 32 26,000 60,000 12 7 1 0 0 1 0 0 200 145 202 2.~4 25,000 58,000 13 18 0 0.75 0.25 0 0.527 0 473 50 180 222 2.13 56,000 120,000 14 3 0 0.75 0.25 0 0.550 0.44~ 125 175 216 2.52 33,0~0 8~,000 IS 19 0 0.75 0.25 0 0 552 0.448 200 177 226 2.28 39,0D0 ~8,000 16 4 0.75 0 0.25 0.521 0 0.479 S0 146 17R 2.47 30,000 7~,000 Ml~N 0291 PVS 14- (Table 1 Cont'd.
11un TrialOrder' AA MA MaA X-AA X-MA X-MaAirA~Onsel'~inal'1-1w/l~ln Mrl Mw 17 20 0.75 0 0.25 0.626 0 0.374 125 142 169 2.25 34,000 76,000 1~ 3 0.75 0 0.25 0.628 0 0 372 20~ 139 170 2.04 21,000 '14l00 IY 2 0.5 0.5 0 0.4g90.500 0 50 144 197 2.51 44,0(10 110,000 21 0.5 0.5 0 0 4880.512 0 125 149 IR9 2.~14 28,00~ onn O
21 6 0.5 0.5 0 0.4720.52N 0 200 14H 194 2.44 26,000 65,000 22 22 0.250.250.5 0.3790 3810.24050 150 181 2.53 35,000 88,000 r 2~ 23 0.25U25 0.5 0.~740.3800.245125 155 181 2.44 31,000 76,000 1-24 24 0.250.250.5 0.37 1 0.38 10.247200 1~16 1 73 2.43 30,0~1~) 72,~)~0 0.375 0 375 0.250.3500.3500.300SO IS2 220 2.59 51,000 131,000 26 26 0.375 0 375 0.25U.3620.4I50.222 1 141 168 2.56 33,000 84,000 a. Order that ~he DMA e~perimen~i were run b iPA = 2-propanol used as Ihe chau- Irans~er agent in PHM. Bahnce of 400 Plil~1 made up walcr.
c. Measured onset and terrninus Or cure, 'C.
~ e poly~ers ~ere cured with glyce~ol and sodium hypophcsphite hydrate as an est~rification catalyst. The onset and completion of cure are sho~n as mea~ured in Table 1.
Be~t Candidate~ From PredictiYe Equations ~Wei~ht Fr~ctioos l~fonomer a~ Ch~ed) Ro~ AA ~IA MaA ~A- Oo~et~ Finalb 1 0.3SOlS O.S 200146 169 lo ' 0.4 0.1 O.S 162147 169 3 O.q 0.1 O.S 18114S 167 04 0.1 O.S 200l44 166 j O.qS0 05 O.S 125141 169 6 0.450.05 O.S 1~ 146 167 7 0.45O.OS 0.5 162145 165 8 0.45O.OS O.S 181144 164 9 04sO.OS O.S 200l42 162 0.450.~ O.~S 162146 170 Il 0.450.1 0.45 18114S 169 12 o.qS0 1 0.45 200143 168 13 ~.5 0 O.S 1061~6 169 l4 0.5 0 O.S 12S14S 166 O.S 0 O.S 144145 164 16 O.S 0 O.S 162144 162 1~ O.S 0 O.S 181142 161 18 O.S 0 0.5 200141 IS9 19 O.S0 05 0.45 144145 169 0 5O.OS 0.4S 162Iq4 167 ~1 O.SO.os 0.45 1~ 3 ~66 ~AN 0291 ?US -16-Row AA ~IA M&A iPA' On5etb FiDalb 22 0.5 O.OS 0.45 200 14~ 165 23 O.S 01 0.4 200 143 110 'I 0.55 0 O.~S 1~5 1~5 16~
~5 O.Sj 0 0 45 144 1~4 166 26 O.SS 0 0.~5 162 143 16 27 0.55 0 0.45 181 142 163 ~8 0 55 0 0.45 200 141 162 ~9 0.5~ 0 05 0.4 162 144 16~
0.~5 0.0~ 0.4 181 143 168 1~ 31 O.S5 0.05 0.4 ~00 142 168 ~ 0.6 0 0.4 1~1 144 168 3, 0.6 0 0.4 162 143 16~7 ;~ 0.6 0 0,4 181 142 166 0.6 0 0.4 00 1~1 166 36 0.65 0 0.35 162 143 170 37 0.6S 0 0.35 181 112 169 ~8 0.65 0 0.35 200 141 169 a.iPA -'-prop~olused~schain~ansferagentinPH~f.bal~ceof400PHM water.
b. Predicted onsct lnd ~erminu~ of cure, C.
2 0TABLE 3 - Test Points Measured a~d E'redicted Cure Beb~vior~
?00 P~ iPA, Stoichiometric Çl~cerol~ 10 pbb Catal~st A On~c~ t-C) Fin-l l C) (v.t. Frac~(~t. Frac~(v,t. Frac~ r.1casured predicted ~ ured Prodlctrd 0 5 0 0 5 143 141 171 1~9 ~65 o ~)~5 140 l~l 176 169 0. ~5 0 0.'5 1 ~1 141 1~3 1~7 ~375 031~ 0~5 1~6 141 201 1~6 The results of the here~ofore-de6cribed experimentation indicate that addition of maleic acid-andlor male1c anhydride-derived moi~ties to a polycar-boxy poly~er acid component of a curable binder system S is effective in lo~ering the curing temperature signifi-cantly. Without wishing to be bound to any particular t~eory, applicants believe that the ~ici~al carboxylic acid groups of maleic acid tend to prevent or mini~ize the self-associating discrete phases which poly (acrylic 1~ acid) polymers may otherwise adopt, thus increasing the likelihood o~ esterification without requiring disrup-tion of the ;nter- and ln~ramolec~lar order ~y thermal energy. The effect ~r maleic acid on cure temperat~re is far greacer than any effect which might ~e attributed to the number of carboxy groups, a factor which might affect the ultimate crosslink density but should not greatly affect ~ure temperature.
It has been further discovered that faster cures can be achie~ed ~y lowerihg the molecular weight ~o of ~he polycarb~xy polymer~ to below about 6x104 Da (Dal-tons), preferably ~elow 5x104 Da, and most preferably below 3xlO~ Da relative to poly(sodium me~hacrylate) standards. Mo}ecular wei~hts expressed herein are apparent number a~erage molecular weigh~s versus poly(sodi~m methacrylate) standards unles~ otherwise specified. Limiting the molecular weigh~ of the polymer may be achie~ed ~y traditional methods, i.e. through addition of increased levels of initiator and/or chain transfer a~ent. Suita~le chain transf~r agents are 3c those generally ~nown to those 6killed in the art of vinyl polymerizatlcn, e.g. i~opropanol, 2-butanol, c-butanol, ~oluene, n-dodecylmercaptan, trichloroiodo-me~hane, and the li~ ~he e~f~ct of decreased mol~cu-r~AN 0291 PUS -18-lar weigh~ is not as great in lowering curing tempera-eure as the effect of incorporating maleic acid However, th~ effect is significant never~hel~ss.
Wi~hout ~i~hing to ~e bound to any particular theory, t~e effect of decreased molecular weight in lowering cure temperature is believed due to increased molecular mobility.
The polycarboxylic polymers of the 3ubject invention include minimally 20 weight percent ac~ylic o acid, preferably 40-70 weight percent acrylic acid, anà
most pre~erably about 55 to 65 weight percent acrylic acid. "Acrylic acid" and other monomers referred to herein in weight percent are the weight percent of monomers reacted relative to total monomer5.
The polycarboxylic polymers contain minimally 5 weigh~ percent maleic acid and/or maleic anhydride, preferably from 20 weight percent to about 50 weight percent or more, and more preferably fro~ a~out 30 weigh~ percent ~o about 50 weight percent.
2C The polycarboxylic pol~ers may contain methacrylic acid in minor quantity. However, the methac~ylic acid should be present in not more than 30 weight percent, and regardle3s of actual amount, should not exceed 70 percent w/w of the amount of acrylic acid 2S utilized.
r~,ost preferably, the polycar~oxy polymers are composed substantially of the polymerized residues of acryllc acid, maleic acid and/or mal~ic anhydride, and op;ionailf me~hacrylic acid. Ho~ever, it is also possibl~ ~o add minor quan~it~es, noe ~o exceed 50 ~P~ 0291 PUS -19-~eight percent of the total monomer charge, of cne or ~ore non-carboxyl functional molecules, i.e. styrene, ~-methyls~yren~, p-m~thylstyrene, methyl~ethacrylate, acrylonitrile, and the like. Ocher unsaturated carbox-~lic aclds and poly~carboxylic acid~) may also be used.
With respect ~o additional unsaturated carboxylic acids, i.e. itaconic acid, methylmaleic acid, and the like, the ~mounts employed may be greater than 50 weight percent of all monomers.
3 The curlng component of the subject modified polycarboxy polymer binders include polyfunctional carboxylic acid- andJor carboxylic acid anhydride-.eactive functi~nali~ies such as hydroxyl, amino, epoxy, and the like. Preferably, however, the reactive funct:onality is hydroxyl runctionality, i.e. the curing ccmpo.,en~ is ~ polyol. Suitable polyols include but are not limitea to glycerol, trie~hanolam~ne, trimethylol-propane, pentaer~thricol, sorbito~, .etrakis[2-hydroxy-alkyl~ethylene diamines, poly~iinyl alcohol), partially ~0 hydrolyzed poly~inylacetate, and the like.
Th~ co~positicns of the subject application in general require a catalyst for cure to occur at rela-tively low temperature. In the case of cure by esteri-fication with hydroxyl groups, suitable catalysts are t~e known esterifica~ion and transesterification cata-ly~ta. Examples are metal naph~henates, cobaltates, vanadates, terciary amines, etc. A preferred esterifi-_~ticn cataly6t is an alkali metal hyp~phosphite. Lists of suitable cacaly~ts may be ~ound in the re~erences ~o previously cited, which are ~ncorporated herein ~v reference. In the case of ocher reactive functionali-ties, l.e. curing with amino-fun_~ional co~npounds to , form amide or imide linkages, cataly3t~ which promote r~midization or imidi~a~ion may be employed. Such catalysts are r~ell ~nown to the artisdn skil~ed in amidization and/or imidizatiGn reactions.
r~hile the best mode ~or carrying out the in~en~ion has been descri~e~ in detail, those familiar with the art to which th~s invention relates will recognize various alternatlve designs and embodiments for practicing the invention ac de~ined by the following 13 claims.
9 10 0.5 0 0.5 0.609 0 0 3~0 2(~() 145 174 ~.14 25,noU 53,000 9 1 0 0 1 11 0 50 144 197 2.4R 33,01)0 81,000 Il 11 1 0 0 1 0 0 ~25 141 200 2 32 26,000 60,000 12 7 1 0 0 1 0 0 200 145 202 2.~4 25,000 58,000 13 18 0 0.75 0.25 0 0.527 0 473 50 180 222 2.13 56,000 120,000 14 3 0 0.75 0.25 0 0.550 0.44~ 125 175 216 2.52 33,0~0 8~,000 IS 19 0 0.75 0.25 0 0 552 0.448 200 177 226 2.28 39,0D0 ~8,000 16 4 0.75 0 0.25 0.521 0 0.479 S0 146 17R 2.47 30,000 7~,000 Ml~N 0291 PVS 14- (Table 1 Cont'd.
11un TrialOrder' AA MA MaA X-AA X-MA X-MaAirA~Onsel'~inal'1-1w/l~ln Mrl Mw 17 20 0.75 0 0.25 0.626 0 0.374 125 142 169 2.25 34,000 76,000 1~ 3 0.75 0 0.25 0.628 0 0 372 20~ 139 170 2.04 21,000 '14l00 IY 2 0.5 0.5 0 0.4g90.500 0 50 144 197 2.51 44,0(10 110,000 21 0.5 0.5 0 0 4880.512 0 125 149 IR9 2.~14 28,00~ onn O
21 6 0.5 0.5 0 0.4720.52N 0 200 14H 194 2.44 26,000 65,000 22 22 0.250.250.5 0.3790 3810.24050 150 181 2.53 35,000 88,000 r 2~ 23 0.25U25 0.5 0.~740.3800.245125 155 181 2.44 31,000 76,000 1-24 24 0.250.250.5 0.37 1 0.38 10.247200 1~16 1 73 2.43 30,0~1~) 72,~)~0 0.375 0 375 0.250.3500.3500.300SO IS2 220 2.59 51,000 131,000 26 26 0.375 0 375 0.25U.3620.4I50.222 1 141 168 2.56 33,000 84,000 a. Order that ~he DMA e~perimen~i were run b iPA = 2-propanol used as Ihe chau- Irans~er agent in PHM. Bahnce of 400 Plil~1 made up walcr.
c. Measured onset and terrninus Or cure, 'C.
~ e poly~ers ~ere cured with glyce~ol and sodium hypophcsphite hydrate as an est~rification catalyst. The onset and completion of cure are sho~n as mea~ured in Table 1.
Be~t Candidate~ From PredictiYe Equations ~Wei~ht Fr~ctioos l~fonomer a~ Ch~ed) Ro~ AA ~IA MaA ~A- Oo~et~ Finalb 1 0.3SOlS O.S 200146 169 lo ' 0.4 0.1 O.S 162147 169 3 O.q 0.1 O.S 18114S 167 04 0.1 O.S 200l44 166 j O.qS0 05 O.S 125141 169 6 0.450.05 O.S 1~ 146 167 7 0.45O.OS 0.5 162145 165 8 0.45O.OS O.S 181144 164 9 04sO.OS O.S 200l42 162 0.450.~ O.~S 162146 170 Il 0.450.1 0.45 18114S 169 12 o.qS0 1 0.45 200143 168 13 ~.5 0 O.S 1061~6 169 l4 0.5 0 O.S 12S14S 166 O.S 0 O.S 144145 164 16 O.S 0 O.S 162144 162 1~ O.S 0 O.S 181142 161 18 O.S 0 0.5 200141 IS9 19 O.S0 05 0.45 144145 169 0 5O.OS 0.4S 162Iq4 167 ~1 O.SO.os 0.45 1~ 3 ~66 ~AN 0291 ?US -16-Row AA ~IA M&A iPA' On5etb FiDalb 22 0.5 O.OS 0.45 200 14~ 165 23 O.S 01 0.4 200 143 110 'I 0.55 0 O.~S 1~5 1~5 16~
~5 O.Sj 0 0 45 144 1~4 166 26 O.SS 0 0.~5 162 143 16 27 0.55 0 0.45 181 142 163 ~8 0 55 0 0.45 200 141 162 ~9 0.5~ 0 05 0.4 162 144 16~
0.~5 0.0~ 0.4 181 143 168 1~ 31 O.S5 0.05 0.4 ~00 142 168 ~ 0.6 0 0.4 1~1 144 168 3, 0.6 0 0.4 162 143 16~7 ;~ 0.6 0 0,4 181 142 166 0.6 0 0.4 00 1~1 166 36 0.65 0 0.35 162 143 170 37 0.6S 0 0.35 181 112 169 ~8 0.65 0 0.35 200 141 169 a.iPA -'-prop~olused~schain~ansferagentinPH~f.bal~ceof400PHM water.
b. Predicted onsct lnd ~erminu~ of cure, C.
2 0TABLE 3 - Test Points Measured a~d E'redicted Cure Beb~vior~
?00 P~ iPA, Stoichiometric Çl~cerol~ 10 pbb Catal~st A On~c~ t-C) Fin-l l C) (v.t. Frac~(~t. Frac~(v,t. Frac~ r.1casured predicted ~ ured Prodlctrd 0 5 0 0 5 143 141 171 1~9 ~65 o ~)~5 140 l~l 176 169 0. ~5 0 0.'5 1 ~1 141 1~3 1~7 ~375 031~ 0~5 1~6 141 201 1~6 The results of the here~ofore-de6cribed experimentation indicate that addition of maleic acid-andlor male1c anhydride-derived moi~ties to a polycar-boxy poly~er acid component of a curable binder system S is effective in lo~ering the curing temperature signifi-cantly. Without wishing to be bound to any particular t~eory, applicants believe that the ~ici~al carboxylic acid groups of maleic acid tend to prevent or mini~ize the self-associating discrete phases which poly (acrylic 1~ acid) polymers may otherwise adopt, thus increasing the likelihood o~ esterification without requiring disrup-tion of the ;nter- and ln~ramolec~lar order ~y thermal energy. The effect ~r maleic acid on cure temperat~re is far greacer than any effect which might ~e attributed to the number of carboxy groups, a factor which might affect the ultimate crosslink density but should not greatly affect ~ure temperature.
It has been further discovered that faster cures can be achie~ed ~y lowerihg the molecular weight ~o of ~he polycarb~xy polymer~ to below about 6x104 Da (Dal-tons), preferably ~elow 5x104 Da, and most preferably below 3xlO~ Da relative to poly(sodium me~hacrylate) standards. Mo}ecular wei~hts expressed herein are apparent number a~erage molecular weigh~s versus poly(sodi~m methacrylate) standards unles~ otherwise specified. Limiting the molecular weigh~ of the polymer may be achie~ed ~y traditional methods, i.e. through addition of increased levels of initiator and/or chain transfer a~ent. Suita~le chain transf~r agents are 3c those generally ~nown to those 6killed in the art of vinyl polymerizatlcn, e.g. i~opropanol, 2-butanol, c-butanol, ~oluene, n-dodecylmercaptan, trichloroiodo-me~hane, and the li~ ~he e~f~ct of decreased mol~cu-r~AN 0291 PUS -18-lar weigh~ is not as great in lowering curing tempera-eure as the effect of incorporating maleic acid However, th~ effect is significant never~hel~ss.
Wi~hout ~i~hing to ~e bound to any particular theory, t~e effect of decreased molecular weight in lowering cure temperature is believed due to increased molecular mobility.
The polycarboxylic polymers of the 3ubject invention include minimally 20 weight percent ac~ylic o acid, preferably 40-70 weight percent acrylic acid, anà
most pre~erably about 55 to 65 weight percent acrylic acid. "Acrylic acid" and other monomers referred to herein in weight percent are the weight percent of monomers reacted relative to total monomer5.
The polycarboxylic polymers contain minimally 5 weigh~ percent maleic acid and/or maleic anhydride, preferably from 20 weight percent to about 50 weight percent or more, and more preferably fro~ a~out 30 weigh~ percent ~o about 50 weight percent.
2C The polycarboxylic pol~ers may contain methacrylic acid in minor quantity. However, the methac~ylic acid should be present in not more than 30 weight percent, and regardle3s of actual amount, should not exceed 70 percent w/w of the amount of acrylic acid 2S utilized.
r~,ost preferably, the polycar~oxy polymers are composed substantially of the polymerized residues of acryllc acid, maleic acid and/or mal~ic anhydride, and op;ionailf me~hacrylic acid. Ho~ever, it is also possibl~ ~o add minor quan~it~es, noe ~o exceed 50 ~P~ 0291 PUS -19-~eight percent of the total monomer charge, of cne or ~ore non-carboxyl functional molecules, i.e. styrene, ~-methyls~yren~, p-m~thylstyrene, methyl~ethacrylate, acrylonitrile, and the like. Ocher unsaturated carbox-~lic aclds and poly~carboxylic acid~) may also be used.
With respect ~o additional unsaturated carboxylic acids, i.e. itaconic acid, methylmaleic acid, and the like, the ~mounts employed may be greater than 50 weight percent of all monomers.
3 The curlng component of the subject modified polycarboxy polymer binders include polyfunctional carboxylic acid- andJor carboxylic acid anhydride-.eactive functi~nali~ies such as hydroxyl, amino, epoxy, and the like. Preferably, however, the reactive funct:onality is hydroxyl runctionality, i.e. the curing ccmpo.,en~ is ~ polyol. Suitable polyols include but are not limitea to glycerol, trie~hanolam~ne, trimethylol-propane, pentaer~thricol, sorbito~, .etrakis[2-hydroxy-alkyl~ethylene diamines, poly~iinyl alcohol), partially ~0 hydrolyzed poly~inylacetate, and the like.
Th~ co~positicns of the subject application in general require a catalyst for cure to occur at rela-tively low temperature. In the case of cure by esteri-fication with hydroxyl groups, suitable catalysts are t~e known esterifica~ion and transesterification cata-ly~ta. Examples are metal naph~henates, cobaltates, vanadates, terciary amines, etc. A preferred esterifi-_~ticn cataly6t is an alkali metal hyp~phosphite. Lists of suitable cacaly~ts may be ~ound in the re~erences ~o previously cited, which are ~ncorporated herein ~v reference. In the case of ocher reactive functionali-ties, l.e. curing with amino-fun_~ional co~npounds to , form amide or imide linkages, cataly3t~ which promote r~midization or imidi~a~ion may be employed. Such catalysts are r~ell ~nown to the artisdn skil~ed in amidization and/or imidizatiGn reactions.
r~hile the best mode ~or carrying out the in~en~ion has been descri~e~ in detail, those familiar with the art to which th~s invention relates will recognize various alternatlve designs and embodiments for practicing the invention ac de~ined by the following 13 claims.
Claims (15)
1. A thermosettable binder resin having a low onset and terminus of cure, comprising the admixture or curable reaction product thereof of a) a polycarboxylic polymer comprising from about 30 percent to 100 percent acid-functional monomers selected from the group consisting of:
a)i) about 30 to 85 weight percent acrylic acid, (a)ii) about 1 to about 20 weight percent methacrylic acid, and a)iii) about 20 to about 70 weight percent maleic acid and/or maleic anhydride, said weight percents based on the total weight of acid-functional monomers a)i), a)ii), and a)iii), any non-acid functional monomers comprising one or more co-polymerizable, unsaturated, compatible monomers;
b) one or more polyfunctional, carboxylic acid group-reactive curing agent(s);
c) an effective amount of a catalyst which promotes the reaction between carboxylic acid groups and said carboxylic acid group-reactive curing agent(s).
a)i) about 30 to 85 weight percent acrylic acid, (a)ii) about 1 to about 20 weight percent methacrylic acid, and a)iii) about 20 to about 70 weight percent maleic acid and/or maleic anhydride, said weight percents based on the total weight of acid-functional monomers a)i), a)ii), and a)iii), any non-acid functional monomers comprising one or more co-polymerizable, unsaturated, compatible monomers;
b) one or more polyfunctional, carboxylic acid group-reactive curing agent(s);
c) an effective amount of a catalyst which promotes the reaction between carboxylic acid groups and said carboxylic acid group-reactive curing agent(s).
2. The binder of claim 1 wherein at least a substantial portion of functional groups of said carboxylic acid group reactive curing agent(s) comprise hydroxyl groups.
3. The binder of claim 2 wherein said acid-functional monomers are selected from the group consisting of:
a)i) about 35 to about 65 weight percent acrylic acid;
a)ii) from about 5 weight percent to about 10 weight percent methacrylic acid; and a)iii) from about 25 to about 60 weight percent maleic acid and/or maleic anhydride.
a)i) about 35 to about 65 weight percent acrylic acid;
a)ii) from about 5 weight percent to about 10 weight percent methacrylic acid; and a)iii) from about 25 to about 60 weight percent maleic acid and/or maleic anhydride.
4. The binder of claim 1 wherein said modified polyacrylic acid polymer has an apparent number average molecular weight of from about 2x10 4 Da to about 6X10 4 Da.
5. The binder or claim 1 wherein the onset of cure measured by DMA at a temperature ramp of 4°C/min. is below about 155°C and the terminus of cure measured under the same conditions is less than about 200°C.
6. The binder of claim 1 wherein the onset of cure measured by DMA at a temperature ramp of 4°C/min. is below about 150°C and the terminus of cure measured under the same conditions is less than about 180°C.
7. The binder of claim 1 wherein said acid functional reactive curing agent is selected from the group consisting of glycerine, trimethylolpropane, diethanolamine, triethanolamine, polyvinyl alcohol, partially hydrolyzed polyvinylacetate, and mixtures thereof.
8. The binder of claim 1 further comprising one or more ethylenically unsaturated, carboxylic acid group-containing monomers.
9. A non-neutralized low temperature cure, thermosettable fiberglass binder resin, comprising:
a) an acid-functional polymer comprising from 30 to 100 percent moieties derived from polymerization of unsaturated monomers selected from the group consisting of:
a)i) from about 35 weight percent to about 75 weight percent acrylic acid-derived moieties, a)ii) from 0 to about 20 weight percent methacrylic acid moieties;
a)iii) from 25 weight percent to about 70 weight percent maleic acid and/or maleic anhydride moieties; and a)iv) mixtures thereof, with the proviso that at least a)i) and a)iii) must be present, and any non-acid-functional monomers comprise copolymerizable compatible monomers, said weight percents based on the weight of total acid-functional polymer;
b) one or more curing agent(s) bearing a plurality of reactive functionalities reactive with a carboxylic acid group;
c) an amount of a catalyst effective to catalyze the reaction between said carboxylic acid groups of said acid-functional polymer and said curing agent,
a) an acid-functional polymer comprising from 30 to 100 percent moieties derived from polymerization of unsaturated monomers selected from the group consisting of:
a)i) from about 35 weight percent to about 75 weight percent acrylic acid-derived moieties, a)ii) from 0 to about 20 weight percent methacrylic acid moieties;
a)iii) from 25 weight percent to about 70 weight percent maleic acid and/or maleic anhydride moieties; and a)iv) mixtures thereof, with the proviso that at least a)i) and a)iii) must be present, and any non-acid-functional monomers comprise copolymerizable compatible monomers, said weight percents based on the weight of total acid-functional polymer;
b) one or more curing agent(s) bearing a plurality of reactive functionalities reactive with a carboxylic acid group;
c) an amount of a catalyst effective to catalyze the reaction between said carboxylic acid groups of said acid-functional polymer and said curing agent,
10. The binder of claim 9 wherein said acrylic acid-derived moieties are present in an amount of from about 40 weight percent to about 65 weight percent and said maleic acid and/or maleic anhydride moieties are present in an amount of from about 40 weight percent to about 60 weight percent.
11. The binder of claim 9 wherein said acrylic acid-derived moieties are present in an amount of from about 45 weight percent to about 60 weight percent and said maleic acid and/or maleic anhydride moieties are present in an amount of from about 15 weight percent to about 50 weight percent.
12. The binder or claim 9 wherein the onset of cure measured by DMA at a temperature ramp of 4°C/min. is below about 155°C and the terminus of cure measured under the same conditions is less than about 200°C.
13. The binder of claim 9 wherein the onset of cure measured by DMA at a temperature ramp of 4°C/min. is below about 150°C and the terminus of cure measured under the same conditions is less than about 180°C.
14. The binder of claim 9 wherein said acid functional reactive curing agent is selected from the group consisting of glycerine, trimethylolpropane, diethanolamine, triethanolamine, polyvinyl alcohol, partially hydrolyzed polyvinylacetate, and mixtures thereof.
15. A process for increasing the throughput of a polyacrylic acid-based binder-treated fiberglass cured or B-staged product, comprising:
selecting as a binder a modified polyacrylic acid-based binder having moieties derived from acrylic acid and maleic acid such that the onset of cure measured by DMA at a temperature ramp of 4°C/min. is below about 155°C and the terminus of cure measured under the same conditions is less than about 200°C.
15. The process of claim 15 wherein said binder comprises the admixture or curable reaction product thereof of a) a modified polyacrylic acid polymer comprising from about 30 percent to 100 percent acid-functional monomers selected from the group consisting of:
a)i) about 30 to 85 weight percent acrylic acid, (a)ii) about 1 to about 20 weight percent methacrylic acid, and a)iii) about 20 to about 70 weight percent maleic acid and/or maleic anhydride, and a)iv) mixtures thereof, said weight percents based on the total moles of acid-functional monomers, any non-acid functional monomers comprising one or more copolymerizable, unsaturated, compatible monomers;
b) one or more polyfunctional, carboxylic acid group-reactive curing agent (s);
c) an effective amount of a catalyst which promotes the reaction between carboxylic acid groups and said carboxylic acid group-reactive curing agent.
17. The process of claim 15 wherein said binder comprises a) an acid-functional polymer comprising from 30 to 100 percent moieties derived from polymerization of unsaturated monomers selected from the group consisting of:
a)i) from about 35 weight percent to about 75 weight percent acrylic acid-derived moieties, a)ii) from 0 to about 20 weight percent methacrylic-derived moieties;
a)iii) from 25 weight percent to about 70 weight percent maleic acid-derived moieties and/or maleic anhydride-derived moieties; and a)iv) mixtures thereof, with the proviso that at least a)i) and a)iii) must be present, and any non-acid-functional monomers comprise copolymerizable compatible monomers, said weight percents based on the moles or total acid-functional polymer;
b) a curing agent bearing a plurality of reactive functionalities reactive with a carboxylic acid group;
c) an amount of a catalyst effective to catalyze the reaction between said carboxylic acid groups of said acid-functional polymer and said curing agent.
18. The process of claim 17 wherein said acid functional polymer has an apparent number average molecular weight below 100 K Da.
19. The process of claim 17 wherein said acid functional polymer has an apparent number average molecular weight between about 20,000 Da and 60,000 Da.
20. The process of claim 17 wherein said acid functional polymer has an apparent number average molecular weight between about 20,000 Da and 30,000 Da.
selecting as a binder a modified polyacrylic acid-based binder having moieties derived from acrylic acid and maleic acid such that the onset of cure measured by DMA at a temperature ramp of 4°C/min. is below about 155°C and the terminus of cure measured under the same conditions is less than about 200°C.
15. The process of claim 15 wherein said binder comprises the admixture or curable reaction product thereof of a) a modified polyacrylic acid polymer comprising from about 30 percent to 100 percent acid-functional monomers selected from the group consisting of:
a)i) about 30 to 85 weight percent acrylic acid, (a)ii) about 1 to about 20 weight percent methacrylic acid, and a)iii) about 20 to about 70 weight percent maleic acid and/or maleic anhydride, and a)iv) mixtures thereof, said weight percents based on the total moles of acid-functional monomers, any non-acid functional monomers comprising one or more copolymerizable, unsaturated, compatible monomers;
b) one or more polyfunctional, carboxylic acid group-reactive curing agent (s);
c) an effective amount of a catalyst which promotes the reaction between carboxylic acid groups and said carboxylic acid group-reactive curing agent.
17. The process of claim 15 wherein said binder comprises a) an acid-functional polymer comprising from 30 to 100 percent moieties derived from polymerization of unsaturated monomers selected from the group consisting of:
a)i) from about 35 weight percent to about 75 weight percent acrylic acid-derived moieties, a)ii) from 0 to about 20 weight percent methacrylic-derived moieties;
a)iii) from 25 weight percent to about 70 weight percent maleic acid-derived moieties and/or maleic anhydride-derived moieties; and a)iv) mixtures thereof, with the proviso that at least a)i) and a)iii) must be present, and any non-acid-functional monomers comprise copolymerizable compatible monomers, said weight percents based on the moles or total acid-functional polymer;
b) a curing agent bearing a plurality of reactive functionalities reactive with a carboxylic acid group;
c) an amount of a catalyst effective to catalyze the reaction between said carboxylic acid groups of said acid-functional polymer and said curing agent.
18. The process of claim 17 wherein said acid functional polymer has an apparent number average molecular weight below 100 K Da.
19. The process of claim 17 wherein said acid functional polymer has an apparent number average molecular weight between about 20,000 Da and 60,000 Da.
20. The process of claim 17 wherein said acid functional polymer has an apparent number average molecular weight between about 20,000 Da and 30,000 Da.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/796,832 US5932665A (en) | 1997-02-06 | 1997-02-06 | Polycarboxy polymer acid binders having reduced cure temperatures |
| US796,832 | 1997-02-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2229154A1 true CA2229154A1 (en) | 1998-08-06 |
Family
ID=25169176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002229154A Abandoned CA2229154A1 (en) | 1997-02-06 | 1998-02-06 | Polycarboxy polymer acid binders having reduced cure temperatures |
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| Country | Link |
|---|---|
| US (1) | US5932665A (en) |
| CA (1) | CA2229154A1 (en) |
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| MX2022015000A (en) | 2020-05-29 | 2023-01-04 | Bmic Llc | Polymer reinforced glass mat with enhanced nail shank shear resistance, shingles including the same, and methods of manufacturing the same. |
| CA3136446A1 (en) | 2020-10-27 | 2022-04-27 | Bmic Llc | Low penetration point asphalt reinforced glass mat and articles including the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3658772A (en) * | 1966-10-20 | 1972-04-25 | Dow Chemical Co | Acrylic acid polymers |
| US4076691A (en) * | 1972-08-18 | 1978-02-28 | Ceskoslovenska Akademie Ved | Polyacrylates containing primary amino groups |
| US5108798A (en) * | 1989-06-08 | 1992-04-28 | American Cyanamid Company | Water soluble binder compositions containing beta-hydroxy urethanes and polyfunctional carboxylic acids |
| US5143582A (en) * | 1991-05-06 | 1992-09-01 | Rohm And Haas Company | Heat-resistant nonwoven fabrics |
| US5268437A (en) * | 1992-01-22 | 1993-12-07 | Rohm And Haas Company | High temperature aqueous polymerization process |
| US5661213A (en) * | 1992-08-06 | 1997-08-26 | Rohm And Haas Company | Curable aqueous composition and use as fiberglass nonwoven binder |
| US5318990A (en) * | 1993-06-21 | 1994-06-07 | Owens-Corning Fiberglas Technology Inc. | Fibrous glass binders |
| US5427587A (en) * | 1993-10-22 | 1995-06-27 | Rohm And Haas Company | Method for strengthening cellulosic substrates |
-
1997
- 1997-02-06 US US08/796,832 patent/US5932665A/en not_active Expired - Lifetime
-
1998
- 1998-02-06 CA CA002229154A patent/CA2229154A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| US5932665A (en) | 1999-08-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |