CA2136095A1 - Glass fiber binding compositions, process of binding glass fibers, and glass fiber compositions - Google Patents

Abstract

The present invention relates to a glass fiber binding composition comprising an effective binding amount of an aqueous soluble furan resin, 15 to 99 percent by weight water, and an effective amount of a catalyst for curing the furan resin. The invention further pertains to a process of binding glass fibers at junctions of the fibers comprising the steps of providing newly formed glass fibers, applying an effect binding amount of an aqueous soluble furan resin to the junctions of the glass fibers, and curing the resin at the junctions of the glass fibers. Finally, the invention also discloses a glass fiber composition comprising a plurality of glass fibers having a plurality of junctions where two or more fibers meet, and an effective binding amount of an aqueous soluble furan resin comprising 15 to 99 % water applied to the junctions of the glass fibers.

Description

W093/ 5490 ~ PCr/~IS93/04786 GLASS FIBEK E31NDliN(; COMPOSITIONS, PROCESS OF BINDING C;l ASS FIE~ERS, .4ND
GLASS FIBFR COIU~POSITlO~J5 _ eld of thç Invention This applicaiion relates to aqueous compatible furan binder compositions for glass fibers, a process for binding glass fibers, and also to glass fiber compositions utilizing the bindQrs.

Background ~f the Invention Fiber glass comes in many shapes and sizes and can be used for a variety of applications. A
general discussion of fiber glass technology is pro-vided in "Fiber ~lass" by J. Gilbert Mohr and William P. ~owe, Van Nostran ~einhold Co., New York 1978 which is herein incorporated by reference.

As disGussed in "Fiber Glass", glass fibers are generally mass produced in two types: ~ulk or blown fiber for insulation and allied applications, and continuous-filament, or reinforcin~ ~ibers. In either form raw fiber glass is abrasive and easily fragmentized. Damage to the individual glass fibe-rs ~~
can occur as a result of the self-abrasive motion o~
one fiber passinq over or interac_ing with another fiber. The resulting surface defects cause reductions -~5 in overall mechanical strength~

- Consequently, binders have been develop~
prevent these problems. A typical bin~er may prevent ~he destructive effects of self-abrasion without in-- 2~'~609~

hibiting the overall flexibility of the finished glass fiber product. Extremely gOQ~ resistancP and resilience to conditions of elevated humidity and heat are ben ficial in view of ~h~ wide variety of end use S applications for glass fiber/~inder compositions.

One of the most important performance prop-erties is a conse~uence of ~he practical realities of the glass fiber manufacturing busines. Cured giass fiber/binder composition~ are normally very bulky and voluminous. Batts ~nd rolls used as insulation in buildings have densities rangi~g from 8 to 16 kg/m3 and generally require binder contents of 3 to 7% by weight. Since it is prohibitively expenslve to ship such materia 15 in an uncompressed state, the ~atts and rolls are bundled and compressed in packages to 8 to 25% of their manufactured thic~ness. During the shipping process these packages are normally subjected to conditions OL elevated temperature and humidity.
Once the compressed batt or roll reaches the consumer and is removed from its packaging, it should recover between 40% to 100% of its original volume.
Insulation materials not achievi~g such recovery values normally have difficulty meeting ad~ertised thermal resistivity (R) ~alues. In general, the ~- ~~
better the recovery value of the glass fiber/bi~der composition, the better insulating properties the composition will possess.

Fiber glass products denser than 11.2 ks/m3 generally ha~e load bearing requir~ments, ei~her ~n-~~ `-the form of compressive or flexural strength, as wellas thermal and sound attenuation restrictions.

~MEN :)ED SHEET

2~3~Q95 Th~ amount of binder present in a f iber glass product is dependent on several f actors inGluding the product shape, t~e type of service requirad, compress ive strength requirements and anticipated environmental variables ~uch as temperatureO 3inder content is determined by the loss on ignition testr des~~ribed b~low, and is given . s %
L. O . I . In general, binder cor~tents may range from to 25% L.O.I., depending on the specific end use application. Applications include sound control batts :
with low binder content; industrial-grade thermal lnsulation for driers, ovens, boilers, furnaces, and other heat generators; low-to-intermediate L.O.I. duct liners and fiber glass ~lexi~le ducts and high-L.O.I.
rigid ducts; and pipe insulation with intermediate to hi~h binder le~els. Moided fiber gla~s parts (e.g.-,' automoti~e topliners~ are generally thin pieces of high density ( 240-352 kg/m3 at 3.175 to 9.525 mm thick, for example) and require binders to provide excellent flexural strength. Fiber glass products used for filtration have wide ranges of fiber diameter and binder levels.

Traditionally, high compressibility ratios, recovery v~lues and other desirable properties have ~ ~- -been obtainable only with phenol formaldehyde resins.
As a result, for many years glass ~iber binders have been al~ost exclusively based upon phenol formaldehyde -resins. These systems typically include aminoplast -resins such as melamine and urea, silicone compounds,._ 39 soluble or emulsified oils, wetting agents, and ex~
tenders or stabilizers.

AMEN~2 SffEET

. , . . ,, ,, .. , ., . ~ , .,, , . , .. , , . .. , . ... . .. ,, . . . ~ . . . . .

21~6~95 Although widespread, the use of phenol fo~m-aldehyde re~ins in binders for fiber glass involves numerous problems and disadvantaqes.

Chief among these is the difficulty in complying with ever stricter environmental regulations. Typirally these phenolic binders contain large amounts of low molecular weight species including phenol, formaldehyde and volatile 1:1 and 1:2 phenol formaldehyde adducts such as 2 methylolphenol and 4-methylolphenol. During the curing process, these volatile low molecular weight components are relea~ed nto the atmosphere in substantial volumes as volatile organic compounds (YOC). Since the process of manufacturing fiber glass typically involves spraying large ~olumes of phenol formaldehyde binders into high volume air streams, and then curing the product in convection ov~ns that involve high volumes of air, fiber glass manufacturers have an ur~ent need to reduce their VoC emissions, particularly with regard to formaldehyde.

Attempts ~t reducing the free fo~maldehyde content of typical phenol f~rma-i~e~*e binders have been unsuccessful because excass formal~ehyde is essen~ial to curing and bonding in such systems.
Techni~ues such as scrubbing and incineration would require substantial financial.expenditures with the potential for uncertain results.

Attempts to convert free foxmaldehyde int~
less obnoxious and dangerous chemicals have invol~ed the addition of ammonia or urea. Such additions were intended to convert free formaldehyde into hexamethy-lenetetramine or a mixture of mono and dimethylol :; , , W093/25490 PCT/US93/~4786 ~136Q9.S

ureas. Unfortuna~ely however, urea, hexamethylenete~
tramine, and mono and dimethylol ureas can all con-tribute to the production of trimethylamine, which gives the cured phenolic binder and finished prod~c~
an undesirable "fishy" odor. In addition, nitrogen containing compounds can decompose to yi~ld ammonia and other potentially harmful volatile compoundsO

Phenol formaldehyde resin~ also require careful handling procedures. Since the cooked resin must be refrigerated until use, refrigerated trucks and holding tanks are required. EYen with refrigeration, the storaqe life of a phenolic resin is typically 15 days.

Adding to these problems is the fact that phenol formaldehyde resins have a short life span.
Finished binders based on such resins must used within 2 to 12 hours o~ their initial formulation.

Finally, because phenol formaldehyde resins are petroleum based, they are particularly vulnQrable to fluctuations in price and availability.
, As a result, an alternative to phenol form- ~ ~
aldehyde based fiber glass binders has long been sou~ht.

The present in~ention solves the problems caused by the use of phenol formaldehyde resins~in~~
binders f sr f iber glass by pro~iding binders based on a~ueous compatible furan resins. The furan binders of the instant invention provide many of the advantages of phenolic binders while resulting in subs~antially reau~ed VOC emissions. What ic ~articularly desirable W093/25490 P~T/VS93/04786 ~,~3699~ -6-about the furan binders disclosed herein is the use of water as a significant component.

The furan binders of the present invention have several advantages. Formaldehyde is not a sig-nificant curing or decomposition product and the f uranresins for~ very rigid thermos~ts. Since furan resins are derived from vegetable cellulose, a renewable resource, ~hey are ineXpensive and readily available.

It is, therefore, a~ object of the present invention to proYide a binder for fiber glass which will provide substantially all of the advantages of phenol formaIdehyde binders while simultaneously re- ¦
sulting in signif icantly reduced omissions of volatile organic compounds, particularly formaldehyde.

Another object of the presen~ invention is to provide methods of applying the novel furan binder to r~w or bare glass fibers so as to provide the re-~uired perfo~mance characteristics.

Finally, another object of the invention is to provide glass fiber compositions employing the novel binders which are suitable for incorporation into a variety of end use applications~

Summarv of the Inventi~n The present invention relates to a glass fiber binding camposition comprisin~ an e~fective binding amount of an aqueous soluble furan resin and 15 to 99 percent by weight wate~ The invention fur-ther pertains to a process of bindin~ glass ~ibers at 2 ~ 9 5 MAN 023~ PUS -7-junctions of the fibers, comprising the steps of pro-viding newly formed glass fibers, applying an effec-tive binding amount of an aqueous compatible furan .
resin to the junctions of the glass fibers, and curing the resin at the junctions of the gl2ss fibers.
Fin lly, the invention also discloses a glass fiber composition comprising a plurality of glass fibers ha~ing a plurality of junctions where two or more fibers meet, and an effective binding amount of an aqueous compatible furan resin applied to thejunctions of the glass fibers.

Brief Des~ri~tio~ of the Dra~ihqs Figure l illustrates a desired distribution :~
of a 66% non-volatiles bis(hydroxmethyl)furan resin based binder applied to glass fibers; and Figure 2 illustrates a desired distribution of a 40~ N.V. bisthydroxm2thyl)furan resin bzsed binder applied to glass fibers.

Detailed De~r~Ption Of The Preferred Embodi~e~t The present invention broadly provides glass~
fiber binding campositions comprised of agueous compatible furan resins which provide finished products with properties similar to that achi~ved with ~raditional phenol formaldehyde binders. Compatible as use~ herein is def ined as any aqueous mixture comprised of water and a polymeric component forming~ ~~
either a true solution, an emulsion or a sol. The use of furan resins greatly reduces the emissions of particular VOCs such as f ormald~ de during the curing AMEN~3ED SHEET

21~3~Q95 MAN ~238 PUS -8-cycle. The present invention also pro~ides a process of ~inding glass fibers and further provides for glass fiber compositions having app~icability for use in a wide variety of end products.

Furan is traditionally defined ~s a heterocyolic ring compound wi~h two carbon double bonds linking an oxygen atom on one side with a single carbon-carbon bond on the other. As used herein, furan resin is defined to inc~ude resinous products which are comprised o polymer molecules which contain the traditional furan ring structure as described above as well as the saturated analogs th~reof. Such analogs will consist of fi~è me~bered rin~s having ~our carbons and one o~ygen and 0 or 1 carbon-carbon double bonds. The structures encompassed by this definition are illustrated below: ¦

wherein R may be methylene; methylidyne; - --methylcarbonyl; methylester; methylene . . .
ether; methylene dioxy, ethylene; polymeric methylene _ .
ether wherein R is (-CH2-(OCH~) n-) and n may be from 1-- -to 10; ethylene methyl carbonyl; ethylene methyl ester; me~hylene oxy; ethyl oxy; and hydroxy methyl. -O~ these, it is most preferred th~;. R be methylene, AMENDED SHEET

W093/25490 2 ~ ~ 6 ~ 9 ~ PCT/US93/04786 methylene ether, or polymeric methylene ether wherein n is 1 to 5.

R may also be characteri7ed as the residue resulting from the polymerization of at least one reactant selected from the group consisting ~f:

furan, furfural, furfuryl alcohol~
5-hydroxymethyl-2-furancarboxyaldehyde, 5-methyl-2-furancarboxyaldehyde; 2-vinyl furoate, 5-methyl-2-vinylfuroate, 5-tert~utyl-2-~inyl furoa~e, 2-furfurylmethacrylate, 2-furfuryl methylmethacrylate, 2-vinyl furan, 5-methyl-2-vinyl furan, 2-(2-propylene)furan (or 2-methyl vinylidene furan) I j 5-methyl-2-methyl vinylidenefuran, ~urfurylidene acetone, 5-methyl-2-furfurylidene acetone t 2-vinyl tetrahydrofuran, 2-furyl oxirane, 5-methyl-2-furyloxirane, furfuryl vinyl ether, 5-methyl-furfuryl vinyl ether, vinyl 2-furyl ~etone, bis-2,5 carboxyaldehyde furan, bis-2,5-hydroxymethyl furan, 5-hydroxymetAyl-2-ethyl furanacrylate, .
2,5-furandicarboxylic acid, 2,5-furan diacid dichloride, 2,5-furan dicar~oxylic acid dimethyl es~er, 2,5-furan methylamine, 5-carboxy-2-furan amine, 5-methylester-2-furan amine, -~
~is-(2,5-methylene isocyanate)furan, ~ ~
bis(2,5-isocyante)furan, 2-isocyanatefuryl, and 2-methylene isocyanate furyl.

WO93/2~gO PC~US93/04786 9~

It will be appreciated that the composition of R will vary greatly as it is dependent upon the identity of the starting reactants and the mecAanism of polym rization; "n" may be any value greater than 1 but will most prefera~ly be no greater than 2S.

Gne of the chief advantages in using furan-based binders stems from the fact that they are derived from vegetable cellulose. Suita~le sources of vegetable cellulose are corn cobs, sugar cane bagasse, oat hulls, paper mill byproducts, ~iomass refinery eluents, co~ton seed hulls, rice hulls, and food stuffs such as saccharides and starch. These materials undergo acid digestion to produce furfural.
Furfural is the chief reagent used to produce materials such as furfuryl alcohol, 5-hy~roxymethyl-2-furancarboxyaldehyde ~HMF), 2,5 r dicarboxyaldehyde furan, and bis(hy~roxymethyl)furan (BHMF). These furan containing monomers in turn can undergo - reactions to produce various furan containing monomers with a wide variety of substituents at-~the C2 and C5 positions.

Although furan resins may~be~ identified via the names of the starting reactan~s (i~e., furfural-phenol resin or furfuryl alcohol resin) the term furan resin as used herein is intended to-describe resins derived from a variety of starti-ng reactants.
Typically at least one of these-re~ctants will contain the basic furan ring structure or-=-the saturated analogs thereof. Accordingly, `he term furan resin is further defined as a mixture.- comprised of oligomers resulting from the polymerization reac~ion wherein at least one of the reactants is selected from the group 2~0g5 consisting of the f~ran containing molecule having the general formula:

~, X~

and its saturated analogs thereof having 0 or ~.
carbon-carbon double bonds, wharein X and Y are independently organic substituent groups. Thi.s group is illustrated below:

X~ X~y X~y X~ Y X ~ y .

- Suitable X and Y groups are those comprised of molecular species comprising one or more functional moieties selected ~rom ~he group consisting of~
hydrogen; C1-C10 alkyl groups; mono, di- or tri- sub- -stituted vinyl radicals; di- or tri- substituted aromatic rings; ketones; anhydrides; polysubstituted . furfuryl; hydroxyls; aldehydes; carboxylic acids;
esters; ethers; amines; imines; alkynes; alkyl halides; aromatic h~lides; olefin c halides; ethers; -~
thiols; sulfides; nitriles; nitro ~roups; sulfone~; -~- =-~~
a~d sulfonic aci~s. It will be appreciated that combinations of these various functional groups can be employed to form either X or Y.

AMENDE~ SHE~T

WO93/2~gO PCT/US~3/04786 36'`9~

consisting of the furan containing molecule having the general formula:

X~Y

and its saturated analogs thereof having 0 to 1 carbon-carbon double bonds, wherein X and Y are independently organic substituent groups~ This group is illustrated below:

X~Y X~y X~y X~Y X~Y

Suitable X and Y groups are those comprised of molecular spe~ies comprising one or more functional moieties selected from the group consisting of:
hydrogen; Cl-C10 alkyl ~roups; mono, di- or tri- sub- ~.
stituted vinyl radicals; di- or tri- substituted ;:
aromatic rings; ketones; anhydrides; polysubstitu~ed :
furfuryl; hydroxyls; aldehydes; car~oxylic acids; .
esters; ethers; amines; imines; a~`.kynes; alkyl =_~- -~`
halides; aromatic halides; olefinic halides; ethers; -~-~ _.
thiols; sulfides; nitriles; nitro ~roups; sulfones;
and sulfonic acids. It will be appreciated that ~
combinations of the~e various functional groups can be employed to form either X or Y.

NCELLED/A~Nl~L~

W093~2~9~ 2 1 ~ ~ ~ g 5 PCT/US93/04786 Examples of specific compounds containing suitable X and Y groups include:

furan, furfural, furfuryl alcohol, 5-hydroxymethyl-2-Eurancarboxyaldehyde, 5-methyl-2-furancarboxyaldehyde, 2-vinyl furoate, 5-me~hyl-2-vinylfuroate; 5-tertbutyl-2-vinyl furoate, 2-furfurylmethacrylate, 2-furfuryl methylmethacrylate, 2-vinyl furan, 5-methyl-2-vinyl ~uran, 2-(2-propylene)furan (or 2-methyl vinylidene furan), 5-methyl-2-methyl vinylidenefuran;
furfurylidene acetone, 5-methyl-2-furfurylidene, acetone, 2-vinyl tetrahydrofuran, 2-furyl oxirane, 5-methyl-2-furyloxirane, furfuryl ~inyl ether, 5-methyl-furfuryl ~inyl ether, vinyl 2-furyl ketone, bis-2,5 carboxyaldehyde furan, bis 2,5-hydroxymethyl furan, 5-hydroxymethyl-2-ethyl furanacrylate, 2,5-furandicar~oxylic acid, 2,5-furan diacid dichloride, 2,S-furan dicarboxylic acid dimethyl ester, 2,5furan methylamine, 5-carboxy-2-furan amine, Z5 5-methylester-2-furan amine, bis-(2,5-methylene isocyanate~ furan, bis(2,5-isocyante) furan, --2-isocyanate furyl, and 2-methylene isocyanate furyl~
.
It is preferred that X and Y be comprised of molecular species containing one or more functional moieties selected from the group consisting of hydro~en; C1-C6 alkyl groups; mono, di-, or tri-W093/25490 ~ ~3 6 ~ 9 S P~T/US93~04786 substituted vinyl radicals; ketones; hy~roxyls; alde-hydes; carboxylic acids; esters; ethers; amines;
imines, and polysubstituted furfurylc.

It is furthermore particularly desired that at least one of X and Y be comprised of a molecular species comprising an oxygen containing functional moiety such as a ketone, hydroxyl, aldehyde, carboxylic acid, ester or e~her.

It i~ most preferred that X and Y be com-prised of methylol (-C~OH) termLnated groups.
Accordingly, the most preferred fur~n resin for use in the glass fiber binding compositions described herein are those resins resulting from the polymerization of 2,5-bis(hydroxymethyl~furan. Such rPsins may be further defined as 'BHMF' resins.

These f uran containing monomers can polymerize through two well known ~echanisms. The first inYol~es chain or poly~ddition polymerization . ~:
which is initiated by well known free radical, cationic or anionic promoters. This method of polymerization produces macromolecules with furan rings branching from the main chain. A comprehen ive -discussion of such raactions is provided by A~ricultural and Synthetic Polymers, Biodegrad~ility and Utilization; edited by J. ~. ,lass and ~. Swift, Symposium sponsored by Divisions of Cellulosa, Paper and Textile Chemistry; and Polymeric Materials~
Science and Engineering at the 197th National Meeting of the American Chemical Society, Dallas, Texas, April 9-14, 1989, herein incorporated by reference.

`

~l3~ng~
MAN 0238 PUS ~14-The second method i5 typically known as condensation polymerization. Polymers and copolymers resulting from acid catalyzed condeAsation reactions result in macromolecules with f ur~n rin~s in the main chain. As a general rule, the furan resins ~ormed by polycondensation reactions have stiffer chains and higher glass tr nsition temperatures. T~ese r actio~s may involve self condensation of the furan monomers described above, as well as condensation reactions of such monomers with aminoplast resins, or~anic anhydrides~ aldehyd~s such as formaldehyde, ketones, urea, phenol and other suitable reagents. Most preferably the binder compositions described hPrein will contain f~ran resins produced by acid-catalyzed condensation reactions.

The most preferred furan resin for use here-in is Farez~ M, a commercially available composition ~rom Q0~ Chemicals, a-division of Great Lakes Chemical Corporation, located in West Lafaye~te, Indiana. The material safety data sheet ~MSDS) for Farez~ M indi-cat~s that it is a furfuryl alcohol-urea formaldehyde-resin containing about 6~ free furfuryl alcohol and 0O4 to 1.1~ by weight free formaldehyde. This resin is believed to be based on the most preferred fura~
monomer wherein X and Y are terminal ~ethylol groups;
i.e. bis(hydroxymethyl)furan ("BHMF").

Although Farez~ M has been found to be most suitable for use in the present invention, another material supplied by QO~ Chemicals, Inc. has a~~so~been fou~d suitable. Quacorr~ 1300 is a commerciaily avai-lable resin believed to result fro~ the acid catalyzed self condensation of furfu~yl alcohol. Quacorr~ 1300 is receiv~d with a viscosity of zbout 2.000 to 17.000 AMEN~D SHEET -2136~9S

~ Pa s at 25~C. It contains between 2 to 18~ free furfuryl alcohol and is believed to have a substantial fraction of high~r molecular weight oligomers. It has a percent nonvolatile between 72 to ~8%.

~arez~ M, as recei~ed from QO~ Chemicals, - Inc., has a p~ of be~ween 4,0 to 7.0, 13 to 17~ by weight water and 4-7% by wei~ht unreact-d furfuryl alcohol. Because furfuryl alcohol volatilizes at 160C it is most preferred that its presence be minimized to decrease overall VOC. ~arez~ M normally has a percent nonvolatile (~ N.V.) of approxima~ely 75%-90% and is received at a viscosity of be~ween 250 t~ 2.000 m Pa-s at 25C. A hydroxyl number of 17 to 21% has been measured for different batches of this material. Lower viscosities are strongly pre~er~e~d~.

The hydroxyl number or percent hydroxyl was determined using the following testing procedure.
Approximately 1.2 grams of binder was dissolved in 25 m~ iters of pyridine in a ~olumetric ~lask.
Sufficien~ 3A mole&ular sieve was added to cover the bottom of the flask. The flask was shaken and left ~o stand overnight in order to remove any water present in the binder sample. Residual wa~er was determined by the presence of a shoulder at 3560cm~l and corrected by the ad~ition of more 3A molecular sieve. A Perkin-- Elmer 621 Grating Spectrophotometer, equipped with an infrared absorbance mode, was ~sed to determine the hydroxyl number~- The s2mple a~ reference cell were a pair of matching NaCl liguid cells with 0.05 to 0.10 ~m path lengths and were scanned from 4000 cm-l to 3200 cm~l. Absorbance was read at a peak maximum of 3 2 4 o C~-l . Standard curve5 for each sample cell were generated by analyzing solutions containing 1.25, '4~E~EG ~HC-ET

~J ~ 9 5 0.625, 0.313, and 0.156 grams of furf~ryl zlcohol or bis(hydroxymethyl)fur~n per 25 ml dry pyridine.
Solutions w~re scanned in NaCl liquid cells of path lengths 0.075 mm. A standard curve absorbance vers~s concentration was plotted and the percent hydroxyl calculated by extrapolating ~rams of hydroxyl per 25 ml sample and then dividing this value by the sample weight in grams and multiplying by 100.

. Additional water is added to the material as received from Q0~ C~emicals, Inc to make the glass fiber binders of the invention. Addition of water ~e-tween 1~% to 70%-by weight produces acceptable ~is~
co~ities of between 50 to 600 .m Pa . However, it has been f ound that adding more than 15 to 17% by weight water to Farez~ M may produce nonhomogeneous mixtures. Although two-phase binders can pro~ide desired properties, one-phase systems are most preferred. Thus, in the absence of the co solvents discucsed below, it is preferable that 13 to 17% by weigh~ of water be added to the m terial as recei~ed - - from Q0~ Chemi als, Inc. Such an addition results in approximately 30% total water by weight.

- - - HoweYer, lQWer Yi5COSities are norma~ly pre-ferred and viscosities in the range of 2 to 200 25 ~Pa s at 25~ are most preferred. These lower ~iscosities may be achieved by the additivn of organic mono-, di-, and poly~cids as co-sol~ent~. Co sol~ent is defined herein as any material which upon addition to the composition allows for the addition of greater amounts of water. These co-solvents are generally added in an amount equal to 2 to 10~ by weight.
Examples o~ suitable organic ~ono-, di-, and polyacids are methacrylic acid, propionic acid, levulinic acid, ~/~E~ S

'J1 ~ 6 ~ g S

maleic acid, citric acid and succinic acid. of these maleic acid is most preferred in an amount from 4 to 8% by weight.

A preferred binder c~mposition will have a %NV ~rom 50-6~% resulting from the addition of 35-45%
by weight o~ water, 5-6~ by weight maleic acid and a final viscosity betwe~n 70-150 nnPa-s at 25~C.

In addition to water and a co-solvent, an effective amsunt of .one or more materials lo traditionally known as acid catalysts may be added to the ~uran resin as received from Q0~ Chemicals. Acid catalysts for curing furan resins are well known in I
the art. S~lection of a particular catalyst ultimate- !
ly depends upon th~ desired rate of c~re and desired `
end properties. A feature of the present inventio~ is the choice of particular combi~ations of catalysts to minimize the release of VoC's originating from dif f erent resin components.

Materials known ~o be suitable for curing -furan resins include inorganic and organic acids.
Suitable organic acids include aliphatic saturated monocarboxylic acids, aliphatic unsaturated ~
monocarboxylic acids, saturated and unsaturated dicarboxcylic acids, hydroxy acids, aromatic acids and ! :
diacids, and alicyclic acids. Exa~ples o~ suitable - I
acids include hydrochloric acid, s~lfuric acid, nitric. . ¦ :
acid, phosphoric acid, benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, napthalene sulfonic acid, oleic acid, benzoic acidj salicylic ~0 acid, acetic acid, propionic acid, maleic acid, fumaric acid, oxalic acid, malonic acîd, phthalic acid, lactic acid, succinic acid, glutaric acid, ~E~E S~EET

W093~25490 ~ 9 ~ PCT/VS~3/0478 adipic acid, citric acid and levulinic acid. Of these toluene sulfonic acid and maleic acid are most preferred.

Friedel-Crafts type catalysts such as aluminum chloride, zinc chloride, aluminum bromide, and boron fluoride are also suitable.

Salts of both inorganic and organic acids may also be used. Examples of suitable inorgan.ic acid salts are ammonium chloride, ammonium sulfate, ammonium hydrogen su~fate, ammonium nitrate, alumin~m chloride, aluminum nitrate, aluminum sulfate, copper chloride, copper nitrate, copper sulfate. Of these, ammonium sulfate is most preferred.

Salts of orqanic acids are likewise expected to be suitable. Suita~le salts are the urea salt of toluene sulfonic acid and the diammonium salts of citric acid.

Acid anhydrides are also suitable for use as catalysts in the presen~ invention. In particu~ar, cyclic anhydrides resulting from the dehydration-o~
dicarboxylic acids are suitable for use in the present invention. Suitable acid a~hydr:..des includ~ acetic anhydride, maleic anhydride, succlnic anhydride and.
phthalic anhydride. Of these maleic anhydride is most preferred. Although not wishing to be ~ound to ~ny particular theory, it i5 believed that in addi~lon~t~
functisning as a catalys~, polyether co-polymers are formed ~etween the anhydride and the free hydroxylated species presen~ in the resin.

W093~25490 ~ 9 ~ P~T/~Sg3/04786 The most preferred materials are those which m~y be defined as latent catalysts which become active -.
at approximately 110 - 150C. As discussed above, preferred materials are ammonium sulfate, the urea salt of tol~ene sulfonic acid, maleic acid and mixtures thereof. In particular, ammonium sulfate has been observed to preferentially reduce free formaldehyde emissions. :

Although not wishing to be bound to any ~ :~
particular theory, it is believed that maleic acid, in --addition to functioning as a co-solvent, also promo~es --the polymerization reaction. Furthermore, it is believed that maleic acid may preferentially reduce ¦-.
the emission of BHMF monomer during the curing process~ Since it is desira~le to maximize the - reduc~ion o~ VoC~s, the most preferred 'catalyst' ~
co~bination will be comprised of maleic acid and -am~onium sulfate~

- In addition to function~ng as a true j -catalyst and a~ a co-solYent, it is further bëlieved ¦ `
that maleic acid may modify the molecular structure of the fflOSt desirable BKMF resin via the foll~w-rnq re~ctlon: -t L '~ X ~ ~C- `C~ .
al HEAT - ~ `:
~ ~o ~ ~ ~
X may be ither (-C~OH) or a polymer chain. The remaining free acid group may act to 'ca~alyze' the reaction at conditions of elevated temperatures.
Alternatively, howe~er, the reaction may reverse it-W093/2~49n - PCT/US93/04786 self under normal curing conditions to release free maleic acid. Although a catalyst has been tradition-ally defined as a su~stance whose presence changes the rate of a chemical reaction without undergoing permanent chan~e in its composition, catalyst as used herein is further defined to include materials such as maleic acid and maleic anhydride whose molecular structure ~ay be altPred via reaction with ~he macromolecules of the f uran resin .

of couxse, it will b~ appreciated by those skilled in the art that this is an expected mechanism only.

It has been found that the catalyst or catalyst c~mbination should be present in the binder in an a~ount e~ual to 1 - 15% by weight. Preferably, however the amount will be from 5 to 12% and most preferably 8 - 10% by w~ight. In par~icular, ammonium sulfate should be present in an amount of 8% by wei~ht.--_Maleic acid should be present in the amount as previously describe~ above.

, ~ In addition to the above, the aqueous compatible furan binder composition may further comprise compounds such as ammo~ia or urea in an amount:-equal to 0 to 5% by weight. Most preferred is the~incorporation of urea in amounts from 0 to 2~ by we~gh~ It has been found that the incorporation o~
urea-to the disclosed binder compositions can cause further reductions in the emission of free formalde- --hydeA It will be appreciated by those s~illed in the art that other formaldehyde scavengers may be utilized.

W093/2~90 2 ~ ~ 5 0 ~ ~ PCT/US93/0~7~

In addition, silanes may be incorporated to improve the overall characteristics of the cured glass fiber/binder composition~ Silanes appear to have the ability to improve recuvery properties by facilitating an adhesive bond between the glass fiber surface and .
the furan rasin. ::~
'~.
Suitable silane coupling agents arP Union Carbide A1100~, Union Carbide~ A1160, Union Carbide~
A-187, Alpha~ 41B, Dow-Corning~ Z6026 and Wac~er~
B.S.-20. Wacker~ B.5.-20 is siloxane based.
Experimental data showed a general trend in wh.ich all of t~he tested silanes narrowed the variability of recovery results from 40-70~ to 60-70%. Reactive silanes are pre~erred for use in the present ~-invention. In particular those silanes with reactive groups such as primary amines and -uriedo are most .
preferred.

Accordingly, it is most preferred that the aqueous compatible furan binder compositions of the in~ention contain reacti~e silanes in an a~ount from 0.05 - 0.50% by weight and most preferably approximately-O.~S-~by weight. However, the actual amount incorporated wi-ll be dependent upon the reac-tivity of the sila~e and can be determined by one skilled in- the art.
.. .
It is-also anticipated that coupling agents such an-oryano~itanates and organozirconates are suitable for use in the present invention. The amounts of such coupling agents to be incorporated will depend upon the agent's particular chemistry.

2136n,~

It will be appreci~ted by t~ose skilled in the art that additional materials such as extenders to reduce cost and coloring agents may alss be incorp~-rated without departing from ~he spirit of the invention. Examples of suitable extenders are silica r alumina, and calci~m carbonate~ Examples of suitable coloring agents are red dye 42 and similar s~1ch materials.

Surfactants may also be added to the furan binder compositions of the instant inventisn. ~:t has been found that sodium dodecyl sulfonate is a suitable surfactant. It may be ad-ded in an amount e~ual to O.OS to 1.0% ~y weight.

The most preferred glass fiber binding compositlons are illustrated in Table 1 below.

TABLE l - Material Example A Ex~mple ~ . Example C
~ E~Y_Weic~ht ~y~~ V Weiaht Farez~ ~5/3E~F Re~ 69.9 . 68.4 79.4 2 0 Wate~ ~ ~ ~ 2~ . 4- - 23 . g ~5 . 8 Maleic Acid - 3 . 5 5 . 4 0 . 0 Ammoniu:n Sulf ate 2 . 1 2 . 1 4 . 7 SLlane (AllO0) 0.2 0.2 0.2 .
~h~ invention ~urther comprises gla~s fiber compositions made according to the present invention.
.
As discussed above, the amount of bind~r present on the glass fiber co~p~sition depends in large part on-thë performance re~uirem~nts of the finished product. The amount of resin on a cured glass f iber mat is typically determined by the loss on ignition test (L.O~I.). After ignition of a weighed, cured glass fiber/binder sample at 510C, the total '4~ENi~EU ~ ET

,~ .~,, .,, ., ", " , ` - - -,- , . ~, . . . , , ~.
,. ~ .. . .

5~ g5 per~ent weight 105s is determi~ed. This value repre-sents the amount of thermoset ~inder originally present. The compositions of this invention should .
contain 1 to 25% by weight cured resin or % L.O.I.
Preferably, such systems will ~ontain 2 to 18~ L.O.I.
It is most preferred that L.O~I. values for the compositions of the instant invention range from 4 to 12%.

- It is anticipated that thç glass fiber/binder composi~ions of the instant invention :~
will be darker in color than glass fiber batts pro~uced with traditional phenol formiald~hyde binders.
However, in many cases the dark color and thermal resistance of furan based binders are fa~ored for many QEM and industrial fiber glass markets r such as duct and furnace liners and automotive hoodliners.
, One of the most desirable properties re-~uired of ~lass-fiber/binder compositions is a high compressibility ratio of between 4-12 :1 and recovery . values of between 40-'co~ 100~--. -This is especially true of glass fiber products with densities of approximate-ly 8 ts 16 kg/m3. As p~eviously discussed, such materials have great appllcability for use in insulation.

The recovery~o-f-a glass fiber/binder composition is generally tested via the followin~
method known as the "RecRvery test". Cured glass fiber/binder compositi~n~ having densities of between 8 to 16 kg/m~ are compres5ed to densities of approximately 32 to-64 kg/m3. Th~ compressed materials are ins~rted into humidity cabinets and are subjected to temperatures of AM~N~ED S~E~T

W~93/2~90 P~T/US93/04786 ~9~ -23-percent weight loss is determined. This value repre-sents the amount of thermoset binder originally ~;
present. The ~ompositions of this inYention should contain 1 to 25% by w~ight cured resin or % L.O.I.
Preferably, such sy-tems will contain 2 to 18~ L~OoI~
It is most preferred that L.O.I. values for the compositions of the instant invention range from 4 to 12%.

It is anticipated that the glass fiber/binder compositions of the instant invention will be darker in color than glass fiber batts produce~ with traditional ph2nol formaldehyde binders.
However, in many cases the dark color and thermal resist nce of furan based binders are favored for many OEM and industrial fiber glass markets, such as duct and furnace liners and automotive hoodlin~rs.

One of the most desirable properties re- :
quired of glass fiber/binder compositions is a high compressibility ratio of between 4-12:1 and recovery valu~s of between 40 to 100%. This is especially true of glass fiber products with densities of approxi~ate-ly 1/2 pound to 1 pound per cubiG foot. As preYiously di~cussed, such materials hav@ ~reat applicability for use in insulation.

The recovery of a glass fiber/binder compositio~ is generally tested ~ia the following method known as the "R~covery test". Cured glass fiber/binder compositions ha~ing densities of between 0.5 to 1~0 pound per cubic foot are compressed ~o densities of approximate~y 2.0 to 4.0 pounds per -~bic foot. Th~ eompressed materials are inserted in~
humidity cabinets and are subjected to temperatures Oî
~AN'eELLED,f,~ 3~V~E

W093/2~90 ~ 9 5 PCT/VS93/04786 :

between 25 to 70 C at 95~ R.H. After 2 to 500 hours, the samples are uncompressed and left to recover for a period of 1.0 hour. Their resultant "recovered"
thic~nesses are measured and the percent recovery calculated as a percentage of the initial thiokness.

Most preferably, the glass fiber composi-tions disc~osed herein will recovex between 60 to 100~
of their initial thickness and most preferably between 70-100~.

Although not wishing to be ~ound to any particular theory, it is believed that the ability of the glass fiber compositions to recover is substan- ¦ ;
tially influenced by the modulus of the glass fibers themselYes. As a result, the distri~ution of the binder on the glass fibers affects not only the move- i ment of the indi~idual glass fibers but also the col- !
lective overall move~ent and hence the r~covery characteristics.

_ - Accordi~gly, it i5 most preferred that the aqueous compatible furan resins of the instant inven-~ ti-onrbe present mainly at the gl~u,s fibers junctions.
--Furthermore, the number and size of the binder-junction furan resin particles appears to have - a- direct effect on recovery properties. It is also believed that some sheathing of the glass fibers by ~the binder may contribu~e to the recovery properties ~ ~ of the fiber glass batt. Kowever, it will be appreciated that in the ~lass fiber/binder compositions of the instant invention, the binder does not completely fill the interstitial space surrou~ding the individual glass fibers.

W093~25490 P~T/US93/~47~6 ~1~ 6~9~

Figures 1 and 2 illustrate acceptable distributions of binder on glass fibers. Figures 1 and 2 illustrate acceptable distributions of bis(hydroxymethyl)furan resin-based binders. The 5 binder of Figure 1 has ammonium sulfat~ as catalyst.
The binder of Figure 2 contains a co~bination of maleic acid and ammonium sulfate. Composition of the binders used to produce the il~ustrated distributions are given in Table 2.

Figures 1 and 2 also represent different methods of binder application. Figure 1 illust:rates binder distribution derived from applying the binder t~r~gh a fiberglass column expander whereas Figure 2 shows distribution resulting from application through ~n air assisted spray nozzle.

As Table 3 shows, bo~h binder systems and application methods produced fiberglass produot with zcceptable recoveries. There is a sufficient proportion of bon~ed junction points to non-bonded junction points in both figures to provide adequate product recovery. It is believ~ th~t the average - size of such binder-junction particles should mos~
~~ ~~ preferably be no larger than 1 to 20 tlmes t~e average fi~er diameter.
i _ .

. .: - . . . .

W093~25¢9~ PCT/VS93/04786 3;~ --26- :

Binder ComPositions of Fiaures 1 and 2 Figure 1 Figure 2 Raw Materials !66%_N.V.) Farez~ M 7g.23 69.34 Catalysts :
-Maleic Acid -- 3.47 - ~NH4) _S04 4.75 2.77 ~H.O Added 15.85 24.27 Silane A-1100 0.17 0.15 Binder Junction % Recovery Binder System$ LOI Size ~2) _ 2 Hrs _ Figure 1 5.8 1000 ~0.8 Figure 2 8.3 6'~0 74.0 :
Some coating of the shafts of the individual fibers is advantageous i~ that it diminishes abrasion among individual ~ibers. Thi~ destructive self-abra-sion reduces overail strength and hence recovery of -- -the composition because it increases the likelihood of fiber breakage. However, it is not desirable for the _-furan binder to coat all fibers nor to fill all interstitial space between and around the individual glass fibers in a mat of the same.

s -The invention further comprises a process for binding glass fiber compositions with the aqueous compatible furan resin compositions described herein.
Glass fiber compositions made according to this pro-cess have recovery properties sufficient to allow them.to be used in a wide variety ~f end use applications including insulation and or filtration and or separa-~ion applications. In addition, the high acid resistance of furan based binders makes them suitable for filtration appllcations~

It is mos~ preferred that the furan binder compocitions discl~sed herein and intended to be used in the procesg of the invention have a viscosity from 2 to 200 nnPa s at a % non-volatiles from 2 to 70~.
It is desirabl~ that such compositions be homogeneous one phase mixtures. However, mixtures having a two phase composition can provide the desired performance properties.

Application of the previously disclosed furan binder compositions will br to newly formed glass fibers using known prior art fiber manufacturing me~hods. Most preferably, the binder will be applied ~~ to the newly formed glass fibers in mid air prior ~o their collection as described below.

Suitable manufacturing processes are the well known rotary process or pot and marbl~ process.
- The rotary process is described on pages 12014 of --- "Fiber Glass" by Mohr & Rowe previously re~erenced ~ abo~e~

Delivery of the bind~r in such processes may be achieved via the use of standard (air less) spray ~~o s~ ~

- -W093~90 ~ 1 3 ~ PCT/US93/04786 -28~

systems, column expanders or con~entional air assistPd spray equipment. It is most preferred that conventional air assisted spray equipment be used as ::
described in U.S. Patent No. 4,832,723, issued May 23, 1989 to ShislPr et al., which is incorporated by ;
reference. :

Most preferably, the newly formed glass fi-~ers wit~ a binder sprayed thereon are collected on a moving chain as a loose blanket. This chain is pulled into an oven wherein the blanket is partially com-pressed as it is going throug~ the oven to a~hieve ~~
desired blanket thickness. As the blanket is s~ueezed ~etween the oven flights, ho~ air is pumped through the blanket via a series of internal plenums or air ducts.

Although not wishing to be bound to a par-ticular theory, it is believed that cure may be a variable effecting reduced V.O.C. emissions. A desir- -able cure for VOC purposes is a cure cycle wherein the temperature is increased from am~,e~t of a rate of between 10--20C per minute up to as low as a final a temperature as po~sible, preferably 150~. -.Tkis type of cure cycle is defined herein as a Iramp cure'.-Given appropriate oven conditions this should result ~5 in an op~imum cure cycle of 10 minutes or less at 150C. However, oven temperatures between 7SC -250C may be used as long as the residence time i~ the .
oven is adjusted accordingly. Curre~t~y,--the most preferred cure cycle for t~e compositions illustrated in Table 1 is 8 minutes at an oven temperature of 177C.

. ~ n 9 ~

of course it will be appreciated that the desired cure cycle is affected by the strength of th chosen acid catalyst. ~or example, in some situations such as the preparation of blown wool (i.e. ~iber glass that is to be blown into position in order to give a particular form of insulation~, a relatively strong acid catalyst such as para-toluene sulfoni~
acid ~PTSA) may be chosen. With a PKa of approxi-mately .5 to 2.5, this acid cau~es the ~ur n resin ~o cure almost instantly on the glass fiber. Such a cure - rate is acceptable because ~he glas~ fiber/binder com-position does not need to undergo ~ny forming process in the oven. In many cases this type of fiber glass will be reduced in 5iZ8 prior to its e~d use applica-1-~ tion.

In another application, the fiber glass and binder will be collected and packaged prior to cure.
This material is known as uncured wool and is cured via a molding process. It may be molded in house or packaged and transported to an outside molding f cility~ Suitabl~ catalysts for this application zre the latent oatalysts discussed ab~ve. Most preferably - the catalyst will be a 5:3 wt:w~, maleic acid and ammonium sulfate mixture, present in an amount e~ual to 7% by weight. 5uch molded glass fiber compositions normally have 5 to 25~ by weight cured resin or %
L.O.I. It is preferred that they have 5 t~ 20% by weight catalyst.

This unc~red wool is typically molded in a 149-260C flat press at 4S second or le~s in~er~als. --The resulting materials may be utilized in various automotive applications such as headliners. Although csmpressed, it should be noted that the resulting glass fibe~ composi~ions are air permeable. Although, ~El:) S~tE~T

. , ... ,,, . -W093/2~90 PCT/US93/0$7~6 ~ e9~ -30 the individual glass fibers may be coated, the furan binder does not fill the interstitial space in the finished article~

The following examples are provided to il-lustrate the invention but are not intended to limitthe invention. All degrees are centigrade and all parts are by weight percent unless otherwise indicatPd .
Examp!e 1 Fsrmaldehyde emissions were initially stud-ied with tube furnace tests.

Compositions of the various samples tested are illustrated below in Ta~le 4. 1'Farez M~" denotes the resin previously described and supplied by QQ
Chemicals, while '1300' denotes the use of Quacorr~
1300 ac received from Q0 Chemicals. Any catalysts - used or other ma~erials added are identi-f ied to the ri~ht of the resin. Preparation of th~~samp-Ies consis~ed of mixing the various components together under a typical laboratory mixing apparatus.

.

WO ~3/~549~ PCr/US93/04786 ~'.136~9~

~5 8 5 ~ 8 ~ 8 8 8 8 8 8 8 8 8 g 8 8 o ~ o _ ~ 8 8 ~ 8 7 ~ ~ ~ '1 0 0 ~ 8 ~ 'g O O i ~ :1 ~ j, j o V~ X ~O ~0 I C10 ~ 5 0 ~ O

E B 5-- ^ ~ ~ X ~ 8 ~ x . 8 8 8 _ ~ ~ ~ 8 Y ~ æ
r q W O~ ~ ~ ~ _ _ O ~ ~ ~

^ O O O O O, O O O O O O O O O O

V ~ o ~ O

o ~ ~ 8 8 e ~ q ", 8 8 0 8 8 8 8 8 8 ~ ~ ", 8 ~ ~ ~ 8 e ~ ~ ~ ~ ~ ~ _ ~ O ~ o O ~
0 ~ a -- - o o o o o o o o o o ? o ? o ? --u U ~ i 3 ~, o = ~ ~ . ~

; ~, ~ , . .

W~".3~?n~

The tube furnace i5 ~sed to h~at samples in a controlled environm~nt designed to simulate a fiber glass binder curing process. It consists of a glass tube, about one foot long and with a one inch i~side diameter, wrapped with a nick~l-chromium wire heater and surrounded with a ~acuum 3acket. The temperature inside the furnace can be mon~tored by a thermocouple in the thermocouple well placed between the heater wire and the wall of the inside tube.

Sample support conslsted of a glass microfiber filter (Whatman 5.5 cm GF/B) inside a carrier consisting of a 38.1 mm long piece of 19.05 mm diameter Pyrex~ glass tubing. Between 0.15 and 0.90 gram of the final binder solution was placed and weighed to the nearest 0.1 mg on the filter. The sample support and 5ample were placed near the outlet end of the tube furnace and the cap replaced. Dry air or an inert gas was used to sweep the inside of the tube.

Volatile formaldehyde, ~leased by the curing sample, was trapped and measured using two impingers connected in series downstream from the exit of the tube furnace. Into each of impingers was - - - placed 20 ml of ~ trapping solution comprised of 2.50 ~~ ~ 25 gm of 2,4-dinitrophenylhydrazine in 1000 ml of acetonitrile solvent that also contained 5 ml o~
glacial acetic acid ~to facilitate the reaction between the 2,4-dinitrsphenylhydrazine and formaldehyde), and a small, accurately known quantity, of diethyl phthalate as an internal standard. The reaction between 2,4-dinitrophenylhydrazine and formaldehyde to form a stable 2, 4-dinitrophenyl-hydrazone de~i~ative is well known to those skilled in ,~MENDED SHEET

W093/2~90 ~ n 5 PCT/US93/0478 the art of analytical organic chemistry and need not be discussed further here.

In initial work (see Tables 5 and 6), these trapping solutions were used directly. However, it was subsequently observed that the acetic acid caused some polymerization of the furfural alcohol and BH~F
monomer trapped in the impinger solutions. In la~er work, (see Table 7), a "Split Impinger Solution"
technique was used where the solution used in the impingers was solely acetonitrile. After the tube ~urnac~ run a portion of the impinger solutlon wals analyzed directly for furfuryl alcohol and BHMF
mono~er, and a second accurately measured aliquo~ was diluted 1:1 with the 2,4-dinitrophenylhydrazine solution described above and analyzed for formaldehyde. ;

Two methods were used to determine the con-centration of formaldehyde, furfur-l alcohol and BHMF
monome~ captured ~y the impinger solutions. A GC mass _ spectrometer (GCJMS) was utiliz~d with a 30 meter DB-5 column wi~h 0.25 micron film thickness, an oven temperature-p~ogram of 70 C for three minutes. then ramped-to 260' C for 4.7 minutes at 30 C/minute. The injector temperature was 280 C with a transfer line and trzp-temperature of 270' C. The scan rate was one scan per second and the range 45 to 450 AMU. Alterna-ti~ely-, hi~h pressure liquid chromatography (HPLC) could be utilized with a one Nova-Pak phenyl column, a mobile phase comprised of a linear gradient 10%
methanol, 90% water and 1% acetic acid. A W
de~e~tor was used at 274nm for phenols and 360nm for the formaldehyde-2,4-d~nitrophenylhydrazone terivative.

,,,, . , , , ,, . , i ~ - .

WO 93J~5490 PCI /US~3~047~6 36Q9~3 -34-Representative results from tube furnace burns of the compositions in Table 4 are illustrated below in Table 5:

S~lc ~um Tin~c ~UrD Dcg. l~n w~ ,m No. S~nplclC ull~aMis. C ~nnu gla~su~p. olid I F-rcznqUUCi~ic30 150 0.0983 0.0361 2969 Fano~q4UCiu~c30 125 0.1013 0.0368 3144 3 F~ro~1UVCiLnc15 125 0.1018 0.0337 2514 0 ~ ~uRo~lUUCiLnc30 100 0.1002 0.0321 200 F~n~lUUCiunc 30 150 0.2779 0.1854 4g9t 6 13001Ci~ic 30 100 0.2582 O.Z112 158 ~ 1300rZs~ 30 10~ 0.2509 0.2~31 3~8 8 1300/~a 30 100 0.2643 0.1885 t25 9 1300nH P~ 30 125 0~2438 0.196~ 159~
1300rH,PY~/ACN' 30 125 0.25560.11?~ 3595 Il 130011H~P~,/urc~ 30 125 0. ~0 0.1840 o - 1~ 1300~H~FY~,/urc- ~ 150 0.25390.~654 193 13 13~0/lH PC)~u~ ~ 4 125 0.25Ui7O.I~S~ 0 - - 2 0 1~ 1300M Y1~/ure~25 125 02567 0.1~57 0 ~ ~ t5 F~rG~SnH Pt)llUrc~ ~ 125 0.26790.1826 0 16 F~n~ hllH P~llJrc~ 2~ 125 0.26950.1869 0 17 F~rc~ M~H ~SO30 1~5 0.2676 0.1666 196 18 130C~Nn{ ~SO 30 125 0.2516 0.1953 6~6 19 P~c~ ~inH~P~,'5 1~ 0.3346 0.2063 9255 - ~0 ~rc~ (Dc~l) 25 125 0.23g9 0.1757 3411 AC3N 8 ~u~o~i~ile u~od ~o il Iprovc olubility of ~u~crf~ 1300.
The results illustrated above indicatPd that su~stantial reductions in formaldehyde emissions are possible with the use of aqueous soluble furan based binder compositions.

WO 93/254gO PCr/l~g3/04786 ? 1 ~ g s Example 2 Additional tube furnace studies were condu~ted .

Samples consisted of QO Chemicals ' Fareæ~M M
~3HMF resin (identified as "Farez M" below) and various catalysts and cure cycles. Compositions consisted of 100. û grams of Farez~ M and the amount of cal:al.yst identif ied below . 15 gm of water was added to each sample. The tut:~e ~urnace apparatus utilized was iden-tical to that described in Example 1. Results are illustrated in Table 6.

Emissions of formaldehyde, furfuryl alcohol, and monomeric BHMF are reported in the sixth, se~renth, and eighth columns and are given in unlts of micrograms (~g) of material per : ~ram of sample solids .

.
Su~ S4nple ~ ~ O/~ m FA ~i~m 131MP ~/~
2 0 ~ m -(NNJHSO, ISOC~30~is 0~575 10 3150.15 ?993.a2 17.~ 81.62 ' - ~{,)HSO, 150C130~02759 10868.50983.614.73 82.75 25-3 -- (NH,~So, 15~30~ o.l~ Iqo.~o23~23.67'33~1 76.47 "---(NH,)~SO, I~OC130~0.1277 100.~ ~537.1~'01.09 7~.65 - -3 ~~- H~PO, 150C/30mi~ 0:~2~ 10 3864.91 l6so.n 37.-1 70.57 6 ~I~K), 1.50C~30n~i~ 0~54 10 4239.39 180~.01 0.00 71.06 7 H,PO, ISOC130~i~ 02~39 5 ~035.61 1 1950.98 30.93 70.~0 3 0 8 H~PO, 15~3~ 02~8 5183.-9168~.6a n.~s 70.69 9 Ci~nc ~ci~ 150Ct30~in/2-0.24~9 5 5829.97 16012.63 739.92 S6.97 W093t2~90 PCT/US93/04786 ~ 36- -ci~nc ~c~ 1~OC130D~? 0.2~33 5 5452.56 1~806.18 842.8~ 6~.0 ~bn Il Gonc Acid 150C/30n~ 0.2479 10 3913.9~ 13560.88 114.03 75,3g 12 C;L;C ~c~ 150C/30~un 0:245 10 3939.~3 13529.~2 134.10 75.61 13 (Nl~"~SO, 150CI30mil10.25~5 5 ?75.58 13130.89 98.34 ~1.16 14 ~HJ~SO, I~OCi30c~ 0.2U9 5 264.60 16143.65 216.60 70.72 LANU~CISOCnO~u~ 0.2508 10 3678.54 1728~.21 5~.T7 Aod 16 8~ 150C130u~0.243 0 993.01 1~113.46 218.34 6~.n 0 1~ ~u~150C/3~nuo0.2431 0 93S.14 13904.83 300.60 68.65 * Acidified impinged solution may have caused some polymerization of the trapped FA and B~MF monomers, thus aotual values may be higher than shown in Table 6.

The above studies illustrate that sVerall VOC emissions can be controlled by catalyst selection and choice of cure cycle.

Exampie 3 Further tube furnace studies using refined analytical technigues involving the split impinger solutions described in Example 1 gave improved results as to the amounts of furfuryl alcohol and BHM~ monomer and are present d in Table 7. In all of these examples, 15 gm of water was added to 100 gm of resin.
It will be appreciated that by judicious choice of - catalyst(s) the amount of either formaldehyde or B~MF
monomer released c~n be reduced to almost zero.

The illustrated catalysts were added to Farez~ M samples in the amounts provided below. No additional water was added. All samples underwent a burn temperature cure of 30 mlnutes at 150 C. In W093/2~90 ~,J ~ bO~ ~ PCTJUSg3/04786 Table 7, the values "wt. cat. gm" refer to the amount of catalyst added p r 10 ~m of resin and the "sample wt in gm" refers to the amount of catalyzed material placed in the tube furnace.

TABLE ?
BHnUP
Su~le ~ C~OI~glFm F~ ~E/gnn Yg/tm % n~i~
C~ q~ g~ c~ ~m n~in n~i~ re-i~ no~
~NnH ~SO 0.25620.60 0.00 45175.56 163.12 6!.J4 ~H ~SO 0.251 0.60 0.00 41455.27 276822 60.00 ~NnH ~SO 0.255~~.60 0.00 44993.64 24~8.01 60.67 1 0 ~2 ~3 0~6S4 0.40 0~8.r ~4212.22 348-.99 57.12 fN11i ~SO 0.23250.40 2126.68 ~ 6.15 3Sg2.42 57.73 CNllH ~SO 0.25050.40 ~936.44 4422~i.18 4018.40 57.20 ~NIl~ ~SO 0.2633 020 3-96.-8 ~22~.3~ 9230.41 ~7.38 ~H~30~ 0.2586 020 3040.60 41266.S7 83R2~ 48.8S
~H,)2so, 02705 0.20 2~Z ~0 403~S.31 8332.m ~797 SO~c ~cid 0.2~7 0.90 10~4.02 16336.16 0.0~ 69.8~ t ~N~2 ~SO~ kic ~od 0.2~360.90 928.24 2936S.0~ 0.00 67.g2 ~NIIH ~SO~nMk~ac ~cit 0.24980.90 1220.66 28l14.19 0.00 68.~8 ~NilH ~SO~QUbJae ~cid2 0.2B420.70 2269.22 86597.94 143.09 68.3~
2 0 (NH )~So ~c ~ cid 0.24~ o.~o 2~87.~7 49540.46 0.00 67.32 ~NH ) SO ~lac Acid~ 02562 0.70 1851.48 35812.46 0.00 68.66 c ~cid 0.24S~O.S0 6~0.02 6036S.50 91Q35 63.61 Mabic Acict 02578 O.S0 9212.m 40S16.11 9tS.0S 62.61 M lc~c ~cid 0.26060.50 63~0.30 55027.20 550.68 65.9 M-l~c Acict 02~79 0.7S 6CQ3.~2 17118 10 0.00 69.99 M~;c Acxt 0.25U 0.7S 75~.n ~6208.22 0.00 71.03 ACit (~.267~0.7S 709~.98 12705.87 0.00 71. 13 Mclcic Acit 02571 1.00 5507.66 11453.49 0.00 72.46 cisl 02.S7~t.00 5~31.58 13558.01 0.00 n.~3 3 0 M bic hcid 0.26981.00 527a.~0 96~t0.45 0.00 7325 CN~ 2SO~c /~citl 02~U 0.~3 3285.0~ 4~005.~5 0.00 ~9.96-(NH )~SO /M~leic .~cit 03041 0.-3 2309.06 ~.9~9.~3 0.00 50.~4-(2~H )~SO /bWcic Ac ctJ- 02651 0.~3 3279.16 538S5.73 0.00 4529-0.?~9~0.00 4261.02 72?7.61 6913.63 ~632 3 5 31~- ~ _ 0.251~0.00 ~197.82 42848.13 6029.06 J9.~3 E~c 0.2~930.~0 ~4V.52 533 t3 .74 59~0.6 1 ~9.83 ~ho F~ M ~i~ iu ~c ~pbJ couus~l of ~ ~o~u e~ froul Fu~( ~iu ~ ~ceivet ~ QO
C~ . E~ puu ~ ~ Fuez~ M, ~rc ~i~ visorou~ly for ooe ~our u~d Ihco ~llo~ lo u~l ~ out for-o~ cur. ~c ~ ponio~ D~ off ~1 u~od P~ ~hc b~ io.

4 0 1 l~c ~ uo of ~i~ ~ulfu~ to ~kiG ~cid ~u oqu~ to 4:5.
2 ~6 ~io cl u~uu~ ~U~tc lo ~kic ~d ~ ~ ~> 2:5.
- 3 hc r~uo of ~o~lium ~ulfue to ~ic ci~ l to 3:5.
, .
Example 4 The purpose of this experiment was to estab lish the ability of silanes to improve moisture resis-r?~~)1Q5 tanc~ in the bonded fibers~ Samples without silane had been showing recovery results ranging ~rom 40 to 7~.

Binderless flber glass batts were prepared by sub-jectin~ commercial insulation batts from Schuller International, Inc., type "R-19", to 510C ~o burn ~-out the binder. The "burne~ out" batts w re slioed horizontally into strips approximately 9~525 mm in thickness. Furan binders consisting of 100 grams FarezTM M resin, 6 grams ammonium sulfate, 20 grams water, and a ~uantity of silane based on its . individual ac~ivity was sprayed onto both sides of each strip. The three strips were combined and cured at 218C for 10 minutes to make up one sample. The brand and quantlty of silane ~sed were as follows:
Union Carbide A1100, 0.2 parts; Union Carbide A1160, 0.4 parts; Union Carbide A-187l, 0.2 parts; ~lfa 41B2, Q.2 parts; Dow-Corning Z-60263, 0.1 part; and Wacker BS-204,-0.5 parts.

-- 20 -- Four 15.24-x 15.Z4 cm test specimens were cut from each prepared sampl~, wei~hed, and measured for _ thickness. Then the specimens were compressed to one ~ --~- guarter of their original thickness and placed in a humidity cabine~ at 68C and 95~ R.H. for two hours.
After removal, the specimens were left to cool undis-- -- turbed for 30 minutes and then allowed to expand.
- Following an hour of specimen eguilibration, their , - _ 1 A1100 and A1160 are tradenames o~ Union Carbid~r 2 41B is a tradename of Alfa.
3 Z-5026 is a tradename of Dow-Corning.
4 BS-Z0 is a ~radenam~ of Wack~r Silicones.

AMENCD StlEE~T

, .. . . . .

~13~gS

thicknesses were again measured. The samples were then reheated to 510~C ~or binder determination. (%
L.O.I.) Sample recovery, density and binder values are summarized below.
8ampl~ %
De~ i~Y O.I ~_~ecovery ~ilane UC A-187 0.51 7.85 59.6 BS-20 ~.55 6.04 67.1 UC A-1100 . 0.~4 4.19 65.5 UC A-1160 0.50 6.94 59.9 DCZ6026 0.56 5.08 68.0 Alfa 41B 0.58 4.26 63.4 Samples containing A-187 5ilanes stuck to t~e compression plat~s and those wi~h Z6026 ~ended to stick although not as tenaciously as the A-187 samples. Ho~ever~- none of the silane con~:aining samples bonded to the plates as strongly as previ-ously tes~ed samples wit~out silane.
_ .
A ~eneral trend ~ an be seen and summarized in that all silanes tested reduced recovery variability from 40-70~ to 60-7D%.-A pilo trial using the furan resin based binders of the invention was eonducted. Compositions of the Z5 ~arious binders tested are illustra~ed in Table 8.

AMEh~DED SHEEr Y~ 9 5 ~!
M~c S~e Fue~M fNH,) S0, ~.~ W8~r Scb~
tt L U~L tb~ S~ OL~r V~
_S~ 1.7a~ O 5.5~6 A~lttO. oa ~-: 30 I.t 0 6 ~Q55c~
3 3L.9 1.9~ 0 63~ ~IIOt. 0 ~
2~6 ;.7~6 ~ 5.~2 ~lt6~. O.~ -31:~ 1~72 0 6~ BS2~1. 1 96CcP~ ;
6 31 5 1.~9 0 6~ ~1101, 0 ~ ::
~1 7 3~ 9 1.97~ 0 6~ ~.1101. 0-- R~ ~c :!LI a.7t3 1~05 9.1- ~ t~. O~
9 30.~ 1.. ~ 1~ IOS5 AllOl. 0.14 ''9.~ 0 1.~7 J029 AllOI. 0 ~' 19tePS ~:
Il ~0 1~ .0 140 All~0. 0.~ ~3S- ePS ~::
1~ ~00 16 :0 I~O ~1101. ~3 AOS'.Q9 ~t~35~cPS
13 ~00 16 , "~t 144 C ' ~35~ c~S
t~ ~0 16 'O 140 AllOI. C~ ~8.3SJ.cP~
~ . .
,~.
* AOS = Witconate AOS (Witco Inc.) olefin sulfonate ethanolated ~lkylgua~idine amine complex.
** C61 - Aerosol C-61 surfactant produced by American Cyanamid tEthenylate~ Amine Complex).

T~ g :
- Sample Platen Oven ~ ~OI_~ Recovery No. * ~ mP C Temp C _ ~

1 246 232 5.6. 74.4 3 246 232 5.8-- 70.~
4A 246 232 4.873.5 4B 246 232 3.575.5 4C 246 232 5.2- - - -66.4 246 2~2 3.0 -:. 74.1 8R 246 232 4.3 - 71.4 - 8~ ~46 232 5.0 . -_. 78.0 9 246 232 5.6 76.3 246 232 7. æ 72.9 ll 246 232 9 D 6 76.1 ~MENI~ED S~lEET

2i ~119~

12 246 23~ 7.5 74.9 13 246 232 7.9 7~.4 14A 288 246 8.8 75~5 14B 260 232 8.6 75.2 14C 246 218 7.8 74.3 14D 232 204 8.1 73.5 14E 232 l91 8.6 74.5 14F 232 177 8.6 72.3 * The sample numbers in Table 9 refer to the lQ composltions of the same sample number given in Table 8. The suffix letters in the Table 9 - sample numbers refer to di.ferent procese;
conditions.

The above results indicate that the furan resin based bind~rs of the instant invention produced fiber glass binder campositions that l~roduce commercially acceptable recovery Yalues.

AMENDCO SHEET

.~, . , . ' ... .

Claims (34)

What Is Claimed Is:

1. A glass fiber binding composition compris-ing:
an effective binding amount of an aqueous compatible furan resin and 15 to 99 percent by weight water, the total being 100% by weight.

2. The glass fiber binding composition of claim 1 wherein the aqueous compatible furan resin comprises oligomers resulting from the polymerization reaction wherein at least one reagent is selected from the group consisting of the furan containing molecule having the general formula:
and its saturated analogs thereof having 0 or 1 carbon-carbon double bonds, wherein X and Y are independently comprised of organic molecular groups comprising one or more functional moieties selected from the group consisting of hydrogen, C1-C10 alkyl groups, polysubstituted vinyl radicals, pslysubstituted aromatic groups, ketones, anhydrides, polysubstituted furfuryl, hydroxyls, aldehydes, carboxylic acids, es-ters, ethers, amines, imines, alkynes, alkyl halides, aromatic halides, olefinic halides, ethers, thiols, sulfides, nitriles, nitro groups, sulfones, sulfonic acids, and mixtures thereof.

3. The glass fiber binding composition of claim 2 wherein X and Y are comprised of terminal methylol (-CH2OH) groups.

4. The glass fiber binding composition of claim 1 having a viscosity between 2 to 600 mPa?s at 25°C.

5. The glass fiber binding composition of claim 4 having a % non-volatiles of 45 to 65.

6. The glass fiber binding composition of claim 1 further comprising an effective amount of a catalyst for curing the furan resin.

7. The glass fiber binding composition of claim 6 comprising a catalyst selected from the group consisting of inorganic and organic acids and salts thereof, acid anhydrides, metal halides, and mixtures thereof.

8. The glass fiber binding composition of claim 6 comprising 1 to 20% catalyst.

9. The glass fiber binding composition of claim 1 further comprising a co-solvent.

10. The glass fiber binding composition of claim 9 wherein the co-solvent is selected from the group consisting of organic acids, and the anhydrides thereof.

11. The glass fiber binding composition of claim 1 further comprising urea.

12. The glass fiber binding composition of claim 1 further comprising silane.

13. The glass fiber binding of claim 1 further comprising maleic acid and ammonium sulfate.

14. A process of binding glass fibers at junc-tions of the fibers comprising the steps of:
providing newly formed glass fibers;
applying an effective binding amount of an aqueous compatible furan resin containing binder to the junctions of the glass fibers said binder comprising an effective binding amount of an aqueous compatible furan resin and 15 to 99 percent by weight water, the total being 100% by weight and;
curing the binder at the junctions of the glass fibers.

15. The process of claim 14 wherein the aqueous compatible furan resin is comprised of oligomers resulting from the polymerization reaction wherein at least one reagent is selected from the group consisting of the furan containing molecule having the general formula:
and its saturated analogs thereof having 0 or 1 carbon-carbon double bonds, wherein X and Y are independently comprised of organic molecular groups, comprising one or more functional moieties selected from the group consisting of hydrogen, C1-C10 alkyl groups, polysubstituted vinyl radicals, polysubstituted aromatic groups, ketones, anhydrides, polysubstituted furfuryl, hydroxyls, aldehydes, carboxylic acids, es-ters, ethers, amines, imines, alkynes, alkyl halides, aromatic halides, olefinic halides, ethers, thiols, sulfides, nitriles, nitro groups, sulfones, sulfonic acids, and mixtures thereof.

16. The process of claim 15 wherein X and Y
are comprised of terminal methylol (-CH2OH) groups.

17. The process of claim 14 wherein the aqueous compatible furan resin containing binder has a viscosity of 2 to 600 mPa?s at 25° C.

18. The process of claim 14 wherein the aqueous compatible furan resin containing binder further comprises a catalyst for curing the binder.

19. The process of claim 18 wherein the catalyst is selected from the group consisting of inorganic and organic acids and salts thereof, acid anhydrides, metal halides, and mixtures thereof.

20. The process of claim 18 wherein the aqueous compatible furan resin containing binder further comprises 1 to 20% by weight catalyst.

21. The process of claim 14 wherein the aqueous compatible furan resin containing binder further comprises a co-solvent.

22. The process of claim 14 wherein the aqueous compatible furan resin containing binder further comprises maleic acid and ammonium sulfate.

23. The process of claim 14 wherein the furan resin containing binder further comprises urea.

24. The process of claim 14 wherein the furan resin containing binder comprises silane.

25. The process of claim 14 wherein the effective binding amount of the aqueous compatible furan resin containing binder comprises from 1 to 25%
L.O.I. as determined by the Loss On Ignition test.

26. The process of claim 14 wherein the step of curing the resin at the junctions of the glass fibers further comprises subjecting the glass fibers and applied binder to temperatures equal to or greater than 110° C for at least 5 minutes.

27. A glass fiber composition comprising:
a plurality of glass fibers having a plurality of junctions where two or more fibers meet and;
an effective binding amount of an aqueous compatible furan resin containing binder comprising 15 to 99% water, applied to the junctions of the glass fibers.

28. The glass fiber composition of claim 27 wherein the aqueous compatible furan resin containing binder has been cured.

29. The glass fiber composition of claim 27 wherein an effective binding amount of the aqueous compatible furan resin containing binder comprises an amount from 1 to 25% L.O.I.

30. The glass fiber composition of claim 27 wherein the aqueous compatible furan resin is comprised of oligomers resulting from the polymerization reaction wherein at least one reagent is selected from the group consisting of the furan containing molecule having the general formula:
and its saturated analogs thereof having 0 or 1 carbon-carbon double bonds, wherein X and Y are independently comprised of organic molecular groups comprising one or more functional moieties selected from the group consisting of hydrogen, C1-C10 alkyl groups, polysubstituted vinyl radicals, polysubstituted aromatic groups, ketone, anhydrides, polysubstituted furfuryl, hydroxyls, aldehydes, carboxylic acids, es-ters, ethers, amines, imines, alkynes, alkyl halides, aromatic halides, olefinic halides, ethers, thiols, sulfides, nitriles, nitro groups, sulfones, sulfonic acids, and mixtures thereof.

31. The composition of claim 30 wherein the X
and Y are comprised of terminal methylol (-CH2OH) groups.

32. The composition of claim 27 wherein the furan containing binder is in the B-stage.

33. The composition of claim 27 wherein the furan resin is in the C-stage.

34. The glass fiber composition of claim 28 wherein the furan resin has been cured at temperatures greater than or equal to 110°C for at least 5 minutes.