CURABLE FIBERGLASS BINDER

Abstract

A curable formaldehyde-free binding composition for use with fiberglass is provided. Such curable composition comprises an addition product of an amine and a reactant to form an amino-amide intermediate. To the amino-amide is added an aldehyde or ketone to form the curable binder composition. The composition when applied to fiberglass is cured to form a water-insoluble binder which exhibits good adhesion to glass. In a preferred embodiment the fiberglass is in the form of building insulation. In other embodiments the product is a microglass-based substrate for use in a printed circuit board, battery separator, filter stock, or reinforcement scrim.

Claims

1. A formaldehyde-free fiberglass product, wherein the fiberglass product is made from: glass fibers; and a binder composition comprising an aldehyde or ketone, and an amino-amide compound, wherein the formaldehyde-free fiberglass product includes a cured binder comprising reaction products of the aldehyde or ketone and the amino-amide compound.

2. The formaldehyde-free fiberglass product of claim 1, wherein the amino-amide compound is an addition product of an amine and a carbonyl-containing compound.

3. The formaldehyde-free fiberglass product of claim 2, wherein the amine includes at least one of an aliphatic amine, a cycloaliphatic amine, or an aromatic amine.

4. The formaldehyde-free fiberglass product of claim 2, wherein the amine includes at least one of 1,2-diethylamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, ,-diaminoxylene, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine.

5. The formaldehyde-free fiberglass product of claim 2, wherein the carbonyl-containing compound includes at least one of an organic acid or an organic anhydride.

6. The formaldehyde-free fiberglass product of claim 2, wherein the carbonyl-containing compound includes at least one of maleic anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride, or tetrahydro phthalic anhydride.

7. The formaldehyde-free fiberglass product of claim 2, wherein the carbonyl-containing compound includes at least one of maleic acid, fumaric acid, glutaric acid, phthalic acid, or tetrahydro phthalic acid.

8. The formaldehyde-tree fiberglass product of claim 1, wherein the aldehyde includes at least one of acetaldehyde, hydroxy acetaldehyde, butyraldehyde, acrolein, furfural, glyoxal, glyceraldehyde, glutaraldehyde, polyfurfural, or polyacrolein.

9. The formaldehyde-tree fiberglass product of claim 1, wherein the aldehyde includes at least one of a monosaccharide, a disaccharide, or a polysaccharide.

10. The formaldehyde-free fiberglass product of claim 1, wherein the aldehyde includes dextrose.

11. The formaldehyde-free fiberglass product of claim 1, wherein the ketone includes at least one of acetone, acetyl acetone, 1,3-dihydroxy acetone, benzyl, benzoin, or fructose.

12. The formaldehyde-free fiberglass product of claim 1, wherein the amino-amide compound is an amino-amide oligomer.

13. The formaldehyde-free fiberglass product of claim 12, wherein the amino-amide oligomer includes at least one of an amino-amide dimer, an amino-amide trimer, or an amino-amide tetramer.

14. The formaldehyde-free fiberglass product of claim 1, wherein the formaldehyde-free fiberglass product is building insulation.

15. A formaldehyde-free fiberglass product comprising a combination of: glass fibers; and a cured binder made from a binder composition that comprises and aldehyde or ketone and an amino-amide oligomer consisting of an addition product of an amine and a carbonyl-containing compound, wherein the cured binder includes reaction products of the aldehyde or ketone and the amino-amide oligomer.

16. The formaldehyde-free fiberglass product of claim 15, wherein the aldehyde or ketone comprises a reducing sugar.

17. The formaldehyde-free fiberglass product of claim 16, wherein the reducing sugar comprises dextrose.

18. The formaldehyde-free fiberglass product of claim 15, wherein the amine includes a diamine having at least one primary amine group.

19. The formaldehyde-free fiberglass product of claim 15, the amine comprises at least one amine selected from the group consisting of 1,2-diethylamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, ,-diaminoxylene, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

20. The formaldehyde-free fiberglass product of claim 15, wherein the carbonyl-containing compound is selected from the group consisting of a saturated or unsaturated anhydride, a carboxylic acid, an ester, and salts and mixtures thereof.

21. The formaldehyde-free fiberglass product of claim 15, wherein the carbonyl-containing compound is selected from the group consisting of maleic acid, fumaric acid, maleic anhydride, mono- and di-esters of maleic acid, mono- and di-esters of fumaric acid, and phthalic anhydride, tetrahydro phthalic anhydride, succinic acid and anhydride, glutaric acid and anhydride, salts and mixtures thereof.

22. The formaldehyde-free fiberglass product of claim 15, wherein the formaldehyde-free fiberglass product is building insulation.

23. A formaldeyde-free fiberglass product comprising a combination of: glass fibers; and a cured binder made from a binder composition that comprises and aldehyde or ketone and an amino-amide, wherein the amino-amide is a dimer, trimer, or tetramer, and wherein the amino-amide consists of an addition product of an aqueous solution of a diamine and a reactant comprising at least one of an unsaturated anhydride, a carboxylic acid, an ester or salts thereof.

24. The formaldehyde-free fiberglass product of claim 23, wherein the aldehyde or ketone comprises a reducing sugar.

25. The formaldehyde-free fiberglass product of claim 24, wherein the reducing sugar comprises dextrose.

26. The formaldehyde-free fiberglass product of claim 23, wherein the diamine comprises 1,6-hexanediamine.

27. The formaldehyde-free fiberglass product of claim 23, wherein the aqueous solution of the diamine and the reactant are reacted at a temperature ranging from 120 C. to 150 C. to form the addition product.

28. The formaldehyde-free fiberglass product of claim 23, wherein the formaldehyde-free fiberglass product is building insulation.

Description

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0023] The novel fiberglass binder composition of the present invention is a curable composition comprising the reaction product of an amine and a saturated or unsaturated reactant to form an amino-amide intermediate.

[0024] In accordance with one embodiment of the invention, amine reactants are selected which are capable of undergoing conjugate addition to form the requisite amino-amide, which forms a water-insoluble polyimide upon curing. In such an embodiment the amine is a di- or multi-functional primary or secondary amine. More preferably, the amine is a diamine having at least one primary amine group.

[0025] Example of amines include, but are not limited to, aliphatic, cycloaliphatic and aromatic amines. The amines may be linear or branched. The amine functionalities may be di- or multifunctional primary or secondary amines. The amines can include other functionalities and linkages such as alcohols, thiols, esters, amides, acids, ethers and others.

Representative amines that are suitable for use in such an embodiment include 1,2-diethylamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and mixtures of these. A preferred diamines for use in this embodiment of the invention are 1,4-butanediamine and 1,6-hexanediamine. Natural and synthetic amino acids such as lysine, anginine, hestidine, etc. can also be used.

[0026] The curable amino-amide is formed through the selection of an unsaturated or saturated reactant that is an anhydride, carboxylic acid, ester, and salts and mixtures of such reactants. Representative unsaturated reactants are maleic acid, fumaric acid, maleic anhydride, mono- and di-esters of maleic acid and fumaric acid, and salts and mixtures of these. Ammonium salts of the unsaturated acids of their monoesters conveniently can be utilized. A preferred unsaturated reactant is maleic anhydride. Representative saturated reactants include, but are not limited to, succinic anhydride, succinic acid, mono and diesters of succinic acid, glutaric acid and anhydride, phthalic acid and anhydride, tetrahydro phthaic acid and anhydride, mono and diesters of acid anhydrides and salts of the acids, and their mono esters. A preferred saturated reactant is phthalic anhydride or tetrahydro phthalic anhydride.

[0027] The amino-amide addition products can be readily formed by mixing the components in an aqueous medium at room temperature. The resulting addition products are either water-soluble, water-dispersible, or are present as an emulsion. To the solution of amino-amide, the carbonyl functional materials can be added, especially an aldehyde or ketone. Due to their higher reactivity, aldehydes are preferred to ketones. The composition comprises the amino-amide and the aldehyde and/or ketone. Some reaction does take place within the composition between the components. However, the reaction is completed during the curing step, followed by the cross-linking reaction of curing.

[0028] Examples of suitable aldehydes include, but are not limited to, mono- and multifunctional aldehydes including acetaldehyde, hydroxy acetaldehyde, butyraldehyde, acrolein, furfural, glyoxal, glyceraldehyde, glutaraldehyde, polyfurfural, polyacrolein, copolymers of acrolein and others. Reducing mono, di- and polysaccharides such as glucose, maltose, etc. can be used, with reducing monosaccharides such as glucose being preferred.

[0029] Examples of ketones include, but are not limited to, acetone, acetyl acetone, 1,3-dihydroxy acetone, benzyl, benzoin, fructose, etc.

[0030] The aldehydes and ketones react with the amino-amide intermediate, which contains an amic acid function, i.e., an amide linkage in the vicinity of a carboxylic acid. An amic acid function is more reactive than a simple carboxylic acid. The amount of aldehyde and/or ketone added is generally such that the molar ratio of carboxylic acid in the amino-amide to carbonyl or ketone is from 1:5 to 50:1. A ratio of 1:20 to 20:1 is more preferred, with a ratio of 1:10 to 10:1 being most preferred.

[0031] One advantage is that the presence of all functional groups, i.e., amine, amide and carboxylic acid, on the same molecule eliminates the potential need for the addition of external crosslinkers or binders such as polycarboxylic acids and/or polyvinyl alcohol. Such crosslinkers can be added, however if desired.

[0032] In an embodiment, the amino-amide can be first oligomerized prior to adding the aldehyde or ketone. The amino-amide can be heated until an oligomer is obtained, e.g., a dimer, trimer or tetramer of the amino-amide intermediate. An example of suitable conditions for making the oligomer involves heating in the range of from 120-150 C. for up to 5 hours.

[0033] Using the oligomerized product has been found to result in a more robust binder product upon curing. This manifests itself in the strength of the binder, and allows for better storage results, higher tensile strength and rigidity, and better recovery for products made with the binder.

[0034] The composition when applied to the fiberglass optionally can include adhesion prompters, oxygen scavengers, solvents, emulsifiers, pigments, fillers, anti-migration aids, coalescent aids, wetting agents, biocides, plasticizers, organosilanes, anti-foaming agents, colorants, waxes, suspending agents, anti-oxidants, crosslinking catalysts, secondary crosslinkers, and combinations of these.

[0035] The fiberglass to which the composition according to the present invention is applied may take a variety of forms and in a preferred embodiment is building insulation. Roofing membranes is also a useful application due to good characteristics. In other embodiments the fiberglass is a microglass-based substrate useful in applications such as printed circuit boards, battery separators, filter stock, and reinforcement scrim.

[0036] The composition of the present invention can be applied to the fiberglass by a variety of techniques. In preferred embodiments these include spraying, spin-curtain coating, and dipping-roll coating. The composition can be applied to freshly-formed fiberglass, or to the fiberglass following collection. Water or other solvents can be removed by heating.

[0037] Thereafter the composition undergoes curing wherein a polymeric coating is formed which exhibits good adhesion to glass. The polymeric composition obtained upon curing is a combination of a polyamino-amide and a polyamino-imide. The polyimide is the primary product, but some of the amide in the intermediate is believed to not form the imide. Thus, some polyamino-amide is also present in the cured composition/binder.

[0038] Such curing can be conducted by heating. Elevated curing temperatures on the order of 100 to 300 C. generally are acceptable. Satisfactory curing results are achieved by heating in an air oven at 200 C. for approximately 20 minutes.

[0039] The cured binder at the conclusion of the curing step commonly is present as a secure coating on the fiberglass in a concentration of approximately 0.5 to 50 percent by weight of the fiberglass, and most preferably in a concentration of approximately 1 to 10 percent by weight of the fiberglass.

[0040] The present invention provides a formaldehyde-free route to form a securely bound formaldehyde-free fiberglass product. The binder composition of the present invention provides advantageous flow properties, the elimination of required pH modifiers such as sulfuric acid and caustic and improved overall economics and safety. The binder also has the advantages of being stronger and offering lower amounts of relative volatile organic content during curing, which ensures a safer work place and environment. The cure time of the binder is also seen to be much faster and therefore does favor the economics, while reducing the energy consumption during the curing process and lowering the carbon footprint. The binder also contains a high level of sustainable raw materials further reducing the dependency on fossil based sources for the resin. Also, due to the hydrophobic nature of the binder, the need for a water repellant such as silicones is eliminated or greatly reduced.

[0041] The following examples are presented to provide specific examples of the present invention. In each instance the thin glass plate substrate that receives the coating can be replaced by fiberglass. It should be understood, however, that the invention is not limited to the specific details set forth in the Examples.

Preparation of Intermediates

[0042] To 116 g 1, 6 diaminohexane (HMDA) dissolved in 214 g water, 98 g maleic anhydride (MAn) was added slowly (molar ratio of 1:1) and the solution was stirred for 10 min. The intermediate was labeled HM.

[0043] To 116 g HMDA dissolved in 264 g water was added to 148 g phthalic anhydride. After the anhydride dissolved, the intermediate was labeled HP.

[0044] To 116 g HMDA dissolved in 268 g water was added 152 g tetrahydro phthalic anhydride. The solution was stirred until all anhydride dissolved. The intermediate was labeled HT.

[0045] These intermediates were utilized to make the following resins with glucose.

Example 1

[0046] To 42.8 g of solution of the HM intermediate anhydrous dextrose (alpha-D-glucose) and water were added. The mass of added water was chosen to be equal to that of the corresponding dextrose. The mass of dextrose (and corresponding water) was 18 g, 36 g, 54 g, 72 g 90 g, 108, 144, 180 g and 216 g. The various solutions were stirred at ambient temperature for 10 mn. The solutions were applied as a thin film on glass and A1 panel, dried in an oven at 100 C. for 5 min and cured at 200 C. for 20 min. Each of the solutions formed a cured brown polymer which was hard and insoluble in water and solvents, and showed an excellent adhesion to glass.

Example 2

[0047] To 52.8 g of solution of the HP intermediate, anhydrous dextrose (alpha-D-glucose) and water were added. The mass of added water was chosen to be equal to that of the corresponding dextrose. The mass of dextrose (and corresponding water) was 18 g, 36 g, 54 g, 72 g, 90 g, 108, 144, 180 g and 216 g. The various solutions were stirred at ambient temperature for 10 min. The solutions were applied as a thin film on a glass and A1 panel, dried in an oven at 100 C. for 5 min and cured at 200 C. for 20 min. Each solution formed a cured brown polymer which was hard and insoluble in water and solvents and showed an excellent adhesion to glass.

Example 3

[0048] To 53.6 g of solution of the HT intermediate, anhydrous dextrose (alpha-D-glucose) and water were added. The mass of added water was chosen to be equal to that of corresponding dextrose. The mass of dextrose (and corresponding water) was 18 g, 36 g, 54 g, 72 g, 90 g, 108, 144, 180 g and 216 g. The various solutions were stirred at ambient temperature for 10 min. The solutions were applied as a thin film on glass and A1 panel, dried in an oven at 100 C. for 5 min and cured at 200 C. for 20 min. Each solution formed a cured brown polymer which was hard and insoluble in water and solvents, and showed an excellent adhesion to glass.

Example 4

[0049] Examples 1-3 were repeated in the presence of 5% by weight ammonium sulfate. The polymers became insoluble in water in less than 10 min.

Example 5

[0050] To 116 g HMDA dissolved in 214 g water was added slowly 98 g maleic anhydride (Man), this was a molar ratio of 1:1. The resulting solution was refluxed for 60 minutes to prepare an amino-amide oligomer. The solution was opaque with 50% solids. The solution was then used to repeat example 1 with the observed results being the same, i.e., the cured polymer was hard and insoluble in water and solvents, and showed excellent adhesion to glass.

Example 6Plant Trial

[0051] To examine the performance of the binder on an insulation batt, a binder solution was prepared and applied in the manufacture of the insulation batt. Processing and performance of the batts made with the binder of this invention was compared with the batts manufactured with a polyacrylic acid binder cured with triethanol amine.

[0052] To prepare the binder, 116 g HMDA was dissolved in 754 kg water. To this solution was added 98 kg maleic anhydride with stirring until dissolved. To this solution was added 540 kg anhydrous dextrose. When the dextrose dissolved, 37.7 kg ammonium sulfate was added. After all the ingredients dissolved, the clear binder solution was utilized in the manufacture of R-19 and R-13 insulation batt.

[0053] The binder was applied at the rate of 4.5% binder on glass fiber containing 1% (based on binder) of an amino-propyl silane coupling agent and about 0.5% dedusting oil. The batt was cured at 210 C. with an oven residence time of two minutes. The 32 droop (sag) and recovery data for R-19 insulation batt products are presented in Table 1 and Table 2 below respectively:

TABLE-US-00001 TABLE 1 32 Droop Data for R-19 Unaged 7 Day 14 Day Control (Acrylic) 1.1 1.7 2.2 HP 1.0 1.3 1.6

TABLE-US-00002 TABLE 2 Recovery fir R-19 Unaged 7 Day 14 Day Control (Acrylic) 6.91 6.48 6.38 HP 6.85 6.55 6.41

[0054] As seen from Table 1 and Table 2, the R-19 insulation product of the new formaldehyde free binder of this invention (HP) has better performance compared to the commercial acrylic control.

[0055] The principles, preferred embodiments, and modes of operation of the present invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.