CA1067227A - Production of glass fiber products - Google Patents
Production of glass fiber productsInfo
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- CA1067227A CA1067227A CA308,288A CA308288A CA1067227A CA 1067227 A CA1067227 A CA 1067227A CA 308288 A CA308288 A CA 308288A CA 1067227 A CA1067227 A CA 1067227A
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- polymeric component
- phenol
- urea
- starch
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Abstract
ABSTRACT OF THE DISCLOSURE
The production of a bonded glass fiber product is dis-closed. The steps of the method involve forming glass fibers from molten streams of glass; combining the glass fibers with a heat curable aqueous binder composition; consolidating the fibers and he?? curable aqueous binder composition into a lossely packed mass on a foraminous conveyor; and curing the heat curable binder composition in situ on the glass fiber product. The consolidated fibres can be compressed on the foraminous conveyor prior to or during curing of the binder composition, or both. The binder composition comprises: 60-95 percent by weight of a complex polymeric component formed by reacting phenol, formaldehyde, a modifier selected from the group consisting of starch and com-pounds which are degradation products of starch, and urea;
10-80 percent of urea based upon the weight of the phenol originally charged to produce the polymeric component; 0.5-25 percent of a lubricant based on the total weight of the complex polymeric component and any unreacted urea; 0.1-1 percent of a silane, based on the total weight of the complex polymeric component and any unreacted urea; 0.2-3.0 percent of an ammonium salt of a strong acid based on the total weight of the complex polymeric component and any unreacted urea, and water, to dilute the binder to a desired solids content of from 1-40 percent.
The production of a bonded glass fiber product is dis-closed. The steps of the method involve forming glass fibers from molten streams of glass; combining the glass fibers with a heat curable aqueous binder composition; consolidating the fibers and he?? curable aqueous binder composition into a lossely packed mass on a foraminous conveyor; and curing the heat curable binder composition in situ on the glass fiber product. The consolidated fibres can be compressed on the foraminous conveyor prior to or during curing of the binder composition, or both. The binder composition comprises: 60-95 percent by weight of a complex polymeric component formed by reacting phenol, formaldehyde, a modifier selected from the group consisting of starch and com-pounds which are degradation products of starch, and urea;
10-80 percent of urea based upon the weight of the phenol originally charged to produce the polymeric component; 0.5-25 percent of a lubricant based on the total weight of the complex polymeric component and any unreacted urea; 0.1-1 percent of a silane, based on the total weight of the complex polymeric component and any unreacted urea; 0.2-3.0 percent of an ammonium salt of a strong acid based on the total weight of the complex polymeric component and any unreacted urea, and water, to dilute the binder to a desired solids content of from 1-40 percent.
Description
This application relates to the production of bonded glass fiber products, and is a division of application serial number 215,947, filed December 13, 1974.
Glass fiber products of the so-called "wool" and "board"
type have been known for many years. Such products are made by several different methods, all of which involve collecting a mass of fibers randomly intermeshed with one another, associating a binder with the intermeshed fibers, and curing the binder. The apparent density of the finished product can vary from one pound per cubic foot, or even less, if the binder associated with the mass of intermeshed glass fibers is merely cured, for example, in a suitable oven, to 20 pounds per cubic foot, or even higher, if the mass of intermeshed fibers is suitably compressed during cure of the associated binder.
Over the years, various binders and binder systems have been suggested for wool- and board-glass fiber products. For example, U.S. Patent Number 2,225,00~ suggests a carbon bond formed by applying carbohydrates, starches, oils, waxes and re-sins to a wool-like product, and then carbonizing by heating to a suitable temperature in the absence o~ oxygen.
U.S. Patent Number 2,252,157 acknowledges as prior art the use of such materials as asphalt, gypsum, starch, rosin, lin-seed oil, glue, sodium silicate, pitch and the like, indicating, however, that those prior art binders which were water soluble had proved unsatisfactory when subjected to moisture conditions.
This patent then proceeds to disclose "that a fibrous batt having highly superior proper-ties" can be produced by using, as a binder, a small amount of a thermosetting material such as a phenol-formaldehyde, a urea-formaldehyde, or the like condensate.
A review of the more recent patents relating to binders 1()67227 for glass fiber products of the type in question indicates that the art continued to believe that "highly superior properties"
could be achieved by using a thermosetting condensate, particu-larly a phenol-formaldehyde condensate, either alone or in com-bination with an aminoplast, as the resinous component of binders. See, for example, the following U.S. patents:
3,704,199 (barium hydroxide can be used as a condensing agent for producing resins, and barium sulfate formed upon neutralization is advantageous in binders formulated from the resins; amino-plasts, specifically, melamine, dicyandiamide, urea and thioureacan also be reacted with phenol-formaldehyde condensates to produce modified resins that can be used in binders for the production of glass fiber products); 3,223,668 (binders useful for producing glass fiber products can be formulated from a phenol-formaldehyde condensate and unreacted dicyandiamide);
3,380,877 (binders useful for producing glass fiber products can be formulated from a phenol-formaldehyde condensate and unreacted urea); and 3,684,467 (binders useful for producing glass fiber products can advantageously be formulated from a resin produced by condensing phenol and formaldehyde in a comparatively high mole ratio, adding dicyandiamide to the reaction mixture and continuing condensation, adding urea to the reaction mixture and continuing the condensation, cooling and neutralizing).
The present invention is an improvement over the inven-tion disclosed and claimed in the above-mentioned U.S. Patent No.
3,684,467. Both inventions are concerned with providing phenolic binder compositions which can be used in producing glass fiber products of the wool-like and board types, which binder composi-tions are especially formulated to minimize the total air pollu-tion occasioned by use thereof in producing glass fiber products, - ~067Z27 and to keep the percentage of especially noxious pollutants, phenol and formaldehyde, in particular, as low as possible. In both cases, a part of the method involves using a higher than normal molecular proportion of formaldehyde to phenol in carrying out an initial phenol-formaldehyde condensation; as a consequence of the high mole ra-tio, free phenol is reduced to a minimum during this initial condensation. A second reactant which is also condensable with formaldehyde is then added, according to both inventions, and further condensation occurs. Urea is added according to both inventions and there is limited condensation between the added urea and the previously formed condensate. In the case of the prior art process, the second reactant capable of condensation with formaldehyde is dicyandiamide.
The present invention is based upon the discovery that the prior art condensates briefly described above can be improved in several significant respects by substituting for the dicyandi-amide, starch or a compound which is a decomposition product of starch. The compound which is a decomposition product of starch can be dextrose (a C6 sugar) or a solution thereof in water, usu-ally called a glucos~e solution, or can be an intermediate betweenstarch and dextrose, e.g. dextrin.
In accordance with this invention the production of bonded glass fiber products includes the steps of forming glass fibers from molten streams of glass; combining the glass fibers with a heat-curable aqueous binder composition; consolidating the fibers and heat-curable aqueous binder composition into a loosely packed mass; and curing the heat-curable binder composition in situ on the glass fiber product. The consolidated fibers can be compressed prior to or during curing of the binder composition, or both. The binder composition according to this invention 1~6~Z27 comprises: (1) 60-95 percent: by weight of a complex polymeric component foxmed by reacting phenol, formal-dehyde, a modifier selected from the group consisting of starch and compounds which are degradation pro-ducts of starch, and urea. The polymeric component is prepared by charging a reactor with a mixture of formaldehyde and phenol in a mole ratio of formal-dehyde to phenol between 2.9 and 4.2/1., reacting the mixture in the presence of a condensing agent until it has a free formaldehyde content between about 7% and 15% based on the total weight of formaldehyde, phenol and water, then adding to the reactor the starch or starch decomposition product in an amount ranging from about 5% to about 50% of the phenol charged, and cooling the reactor contents. (2) 10-80 percent of urea (preferably at least 20 percent) based upon the weight of the phenol originally charged to produce the polymeric component. (3) 0.5-25 percent of a lubricant based on the total weight of the complex polymeric component and any unreacted urea. (4) 0.1-l percent of a silane, based on the total weight of the complex polymeric component and any unreacted urea. (5) 0.2-3.0 percent of an ammonium salt of a strong acid based on the total weight of the complex polymeric component and any unreacted urea, and (6) water, to dilute the binder to a desired solids content of from 1-40 percent. In the bonded glass fiber prod-ucts produced utilizing the binder composition of this invention, the amount of cured binder in the ~B ~ 4 -72~7 product varies between about 0.5% and 25~, based on the combined weight of glass fibers and binder composition.
The following examples illustrate preferred embodiments of the present invention. In the examples, as elsewhere herein, including the appended claims, the terms "percent" and "parts" refer to percent and parts by weight, unless otherwise indicated.
EXAMæLE 1 A mixing tank provided with a propeller-type agitator was charged with 10 parts of water, and the water and subsequently charged ingredients were stirred during the formulation of a binder composi-tion according to the invention. A 0.04 part portion of sodium hexametaphosphate and a 0.004 part portion of an aminoalkysilane* were added to the tank, follow-ed by a 0.07 part portion of ammonium sulfate, a 1.86 part portion of a 50 percent aqueous solution of urea, a 7.46 part portion of a Condensate A** and a 0.05 part portion of an oil emulsified with a non-ionic surfactant. Sufficient additional water was added to provide a binder composition of 16 percent solids.
The binder composition produced as described in the preceding paragraph was sprayed into a region through which glass fibers were being projected onto foraminous conveyor. The fibers were collected in * The particular aminoalkylsilane used had the formula NH2c2H4NHc3H6si ( O CH2CH3)3 ** Subsequently identified.
B 4a -the form of a wool-like mass associated with the binder composition. The relative proportions of binder composition and fibers were such that the binder, after cure thereof, constituted approximate-ly 11 percent of the total product. Cure was accom-plished in an oven maintained at a temperature of about 400F through which the glass fibers and asso-ciated binder were passed in a period of about two minutes, and in which the product was compressed suffi-ciently that the final product was a board-like mass of glass fibers bonded to one another at points of contact by a resite formed by cure of the binder com-position, and had an apparent density of about nine pounds per cubic foot, on the average.
The glass fiber product produced as described in the preceding paragraph substantially the same properties and characteristics as an analogous pro-duct made from a binder containing a condensate pre-pared by the procedure described in U.S. Patent No.
3,684,467, column 8, lines 1-27.
Condensate A was prepared from 363.6 parts 52 percent formaldehyde, 160 parts phenol, 52 parts water, 14.4 parts calcium hydroxide, 48 parts dextrin and 160 parts 50 percent urea solu-tion in water. The condensate was produced in a stainless steel reactor equipped with a propeller-type agitator and an interior, indirect heat trans-fer coil through which steam or cooling water was circulated, as required, to control temperature.
~.~67ZZ7 Agitation was used throughout. The phenol and formaldehyde were added to the reactor first, and were heated to 110F, which tem-perature was maintained for 3~ hours, during which time the cal-cium hydroxide, as a slurry in the water, was added gradually.
The reaction mixture was then heated to 125F and maintained at that temperature for a period of one hour counting the time, approximately ten minutes, required to reach 125F. The tempera-ture was then increased to 150F, and that temperature was main-tained for a total of 2~ hours. The dextrin was charged two hours af-ter the reaction mixture reached 150F. At the end of the 2~ hour period at 150F, cooling water was c:irculated through the indirect heat exchanger to lower the reaction temperàture, and the urea solution was added rapidly. Cooling water was cir-culated until the condensate reached a temperature of about 80F.
The proportion of volatiles in Condensate A was found to be 20 units, as measured by an arbitrary test which has been found to correlate well with emission experience under commercial conditions when binders made with that resin are being used. The test involves distilling a predetermined volume of the resin, di-luted to about 25 percent solids with distilled water, collecting the distillate, and determining colorimetrically the proportion of low molecular weight condensates in the distillate collected.
Volatility is then determined by reference to an empirical chart.
The correlation between emissions, under commercial conditions, and "volatility" of a resin by the test just described, occurs in the sense that resins which are found to have low "volatility"
are found to give fewer emissions under commercial conditions, other factors being equal, than do resins which are found to have a high "volatility".
A condensate prepared by the procedure described in U.S.
~7227 Patent No. 3,684,467, column 8, lines 1-27, using barium hydrox-ide as the condensing agentand formaldehyde and phenol in a mole ratio of 3.1:1 had a volatility of 200 units by the test des-cribed above, while the same condensate, produced with calcium hydroxide as the condensing agent, had a volatility of 85.
In the procedure described above for producing Conden-sate A, urea was added to the phenol-dextrin-formaldehyde condensate duriny cooling thereof. This is a preferred procedure because an adequate degree of reaction between the added urea and formaldehyde, partial condensates or both in the reaction mixture occurs during the cooling. The same result can be achieved, however, by any other proc~dure according to which at least 5 percent of urea, based upon the weight of the phenol originally charged, is dissolved in the condensation products for at least 15 minutes at a temperature of at least about 90 F. For example, Condensate A could be cooled to about 800F without making any urea addition. The condensate could then be reheated, and the urea could be added. Alternatively, a binder could be formulated from the phenol-dextrin-formaldehyde condensate and urea, and the binder can be aged for at least 15 minutes at a temperature 90F or higher to provide the requisite degree of reaction.
Reaction between added urea and formaldehyde is required in order to minimize the lower molecular weight binder constituents used in producing glass fiber products and, as a consequence, to minimize the volatiles in the binder and effluent from the process.
It has been found that a part of the pheno~dextrin-urea-formaldehyde or the like condensate can be replaced by a compara-tively high molecular weight additive reactive with formaldehydein order to reduce still further the volatiles in a glass fiber 10~72Z7 binder system. Lignin sulfonate, a by-product of the paper in-dustry, polyvinyl acetate, polyvinyl alcohol and mixtures thereof can all be used for this purpose. These materials, usually in an amount ranging from 5 to 25 percent, based upon total solids, can be added to the condensate during cooling, as described above for the urea addition, or can be used in formulating binders accord-ing to the invention. Examples of binders containing lignin sul-fonate and polyvinyl acetate which can be produced and used in connection with the production of glass fiber products as des-cribed above in Example 1 are given in the following ~able:
TABLE I
ExcorlpZe 2 Ex~np~e 2 Water ............................. (As in Example 1) (As in Example 1) Sodium hexametaphosphate .......... 0.03 part 0.03 part Gamma-aminopropyltriethoxysilane 0.01 " 0.01 "
Ammonium sulfate .................. 0.05 " 0.05 "
Condensate A ...................... 6.06 " 6.06 "
Lignin sulfonate .................. 0.70 "
Polyvinyl acetate ................. 0.70 "
50% aqueous solution of urea ...... 1.86 " 1.86 "
Oil emulsified with non-ionic surfactant ...................... 0.23 " 0.23 "
It has been found that starch derivatives other than dex-trins can be used in the manner described above in connection with the preparation of Condensate A, and that starch itself can be so used, although the condensates have a somewhat higher vis-cosity when made with starch, rather than a starch derivative, so that larger quantities of more dilute binders should be used when the condensate is starch modified, as distinguished from modified with a starch derivative. Starch derivatives including dextrose 1()672Z7 are all equally operable in practicing the instant invention, and whether made enzymatlcally, by heating an aqueous system under acid conditions, an aqueous system under basic conditions or by a combination of heat and pressure under acid or basic conditions.
Optimum results have been achieved using, as the silane coupling agent, aminoalkylalkoxysilanes, for example those listed in U.S. Patent No. 3,684,467.
,~
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Glass fiber products of the so-called "wool" and "board"
type have been known for many years. Such products are made by several different methods, all of which involve collecting a mass of fibers randomly intermeshed with one another, associating a binder with the intermeshed fibers, and curing the binder. The apparent density of the finished product can vary from one pound per cubic foot, or even less, if the binder associated with the mass of intermeshed glass fibers is merely cured, for example, in a suitable oven, to 20 pounds per cubic foot, or even higher, if the mass of intermeshed fibers is suitably compressed during cure of the associated binder.
Over the years, various binders and binder systems have been suggested for wool- and board-glass fiber products. For example, U.S. Patent Number 2,225,00~ suggests a carbon bond formed by applying carbohydrates, starches, oils, waxes and re-sins to a wool-like product, and then carbonizing by heating to a suitable temperature in the absence o~ oxygen.
U.S. Patent Number 2,252,157 acknowledges as prior art the use of such materials as asphalt, gypsum, starch, rosin, lin-seed oil, glue, sodium silicate, pitch and the like, indicating, however, that those prior art binders which were water soluble had proved unsatisfactory when subjected to moisture conditions.
This patent then proceeds to disclose "that a fibrous batt having highly superior proper-ties" can be produced by using, as a binder, a small amount of a thermosetting material such as a phenol-formaldehyde, a urea-formaldehyde, or the like condensate.
A review of the more recent patents relating to binders 1()67227 for glass fiber products of the type in question indicates that the art continued to believe that "highly superior properties"
could be achieved by using a thermosetting condensate, particu-larly a phenol-formaldehyde condensate, either alone or in com-bination with an aminoplast, as the resinous component of binders. See, for example, the following U.S. patents:
3,704,199 (barium hydroxide can be used as a condensing agent for producing resins, and barium sulfate formed upon neutralization is advantageous in binders formulated from the resins; amino-plasts, specifically, melamine, dicyandiamide, urea and thioureacan also be reacted with phenol-formaldehyde condensates to produce modified resins that can be used in binders for the production of glass fiber products); 3,223,668 (binders useful for producing glass fiber products can be formulated from a phenol-formaldehyde condensate and unreacted dicyandiamide);
3,380,877 (binders useful for producing glass fiber products can be formulated from a phenol-formaldehyde condensate and unreacted urea); and 3,684,467 (binders useful for producing glass fiber products can advantageously be formulated from a resin produced by condensing phenol and formaldehyde in a comparatively high mole ratio, adding dicyandiamide to the reaction mixture and continuing condensation, adding urea to the reaction mixture and continuing the condensation, cooling and neutralizing).
The present invention is an improvement over the inven-tion disclosed and claimed in the above-mentioned U.S. Patent No.
3,684,467. Both inventions are concerned with providing phenolic binder compositions which can be used in producing glass fiber products of the wool-like and board types, which binder composi-tions are especially formulated to minimize the total air pollu-tion occasioned by use thereof in producing glass fiber products, - ~067Z27 and to keep the percentage of especially noxious pollutants, phenol and formaldehyde, in particular, as low as possible. In both cases, a part of the method involves using a higher than normal molecular proportion of formaldehyde to phenol in carrying out an initial phenol-formaldehyde condensation; as a consequence of the high mole ra-tio, free phenol is reduced to a minimum during this initial condensation. A second reactant which is also condensable with formaldehyde is then added, according to both inventions, and further condensation occurs. Urea is added according to both inventions and there is limited condensation between the added urea and the previously formed condensate. In the case of the prior art process, the second reactant capable of condensation with formaldehyde is dicyandiamide.
The present invention is based upon the discovery that the prior art condensates briefly described above can be improved in several significant respects by substituting for the dicyandi-amide, starch or a compound which is a decomposition product of starch. The compound which is a decomposition product of starch can be dextrose (a C6 sugar) or a solution thereof in water, usu-ally called a glucos~e solution, or can be an intermediate betweenstarch and dextrose, e.g. dextrin.
In accordance with this invention the production of bonded glass fiber products includes the steps of forming glass fibers from molten streams of glass; combining the glass fibers with a heat-curable aqueous binder composition; consolidating the fibers and heat-curable aqueous binder composition into a loosely packed mass; and curing the heat-curable binder composition in situ on the glass fiber product. The consolidated fibers can be compressed prior to or during curing of the binder composition, or both. The binder composition according to this invention 1~6~Z27 comprises: (1) 60-95 percent: by weight of a complex polymeric component foxmed by reacting phenol, formal-dehyde, a modifier selected from the group consisting of starch and compounds which are degradation pro-ducts of starch, and urea. The polymeric component is prepared by charging a reactor with a mixture of formaldehyde and phenol in a mole ratio of formal-dehyde to phenol between 2.9 and 4.2/1., reacting the mixture in the presence of a condensing agent until it has a free formaldehyde content between about 7% and 15% based on the total weight of formaldehyde, phenol and water, then adding to the reactor the starch or starch decomposition product in an amount ranging from about 5% to about 50% of the phenol charged, and cooling the reactor contents. (2) 10-80 percent of urea (preferably at least 20 percent) based upon the weight of the phenol originally charged to produce the polymeric component. (3) 0.5-25 percent of a lubricant based on the total weight of the complex polymeric component and any unreacted urea. (4) 0.1-l percent of a silane, based on the total weight of the complex polymeric component and any unreacted urea. (5) 0.2-3.0 percent of an ammonium salt of a strong acid based on the total weight of the complex polymeric component and any unreacted urea, and (6) water, to dilute the binder to a desired solids content of from 1-40 percent. In the bonded glass fiber prod-ucts produced utilizing the binder composition of this invention, the amount of cured binder in the ~B ~ 4 -72~7 product varies between about 0.5% and 25~, based on the combined weight of glass fibers and binder composition.
The following examples illustrate preferred embodiments of the present invention. In the examples, as elsewhere herein, including the appended claims, the terms "percent" and "parts" refer to percent and parts by weight, unless otherwise indicated.
EXAMæLE 1 A mixing tank provided with a propeller-type agitator was charged with 10 parts of water, and the water and subsequently charged ingredients were stirred during the formulation of a binder composi-tion according to the invention. A 0.04 part portion of sodium hexametaphosphate and a 0.004 part portion of an aminoalkysilane* were added to the tank, follow-ed by a 0.07 part portion of ammonium sulfate, a 1.86 part portion of a 50 percent aqueous solution of urea, a 7.46 part portion of a Condensate A** and a 0.05 part portion of an oil emulsified with a non-ionic surfactant. Sufficient additional water was added to provide a binder composition of 16 percent solids.
The binder composition produced as described in the preceding paragraph was sprayed into a region through which glass fibers were being projected onto foraminous conveyor. The fibers were collected in * The particular aminoalkylsilane used had the formula NH2c2H4NHc3H6si ( O CH2CH3)3 ** Subsequently identified.
B 4a -the form of a wool-like mass associated with the binder composition. The relative proportions of binder composition and fibers were such that the binder, after cure thereof, constituted approximate-ly 11 percent of the total product. Cure was accom-plished in an oven maintained at a temperature of about 400F through which the glass fibers and asso-ciated binder were passed in a period of about two minutes, and in which the product was compressed suffi-ciently that the final product was a board-like mass of glass fibers bonded to one another at points of contact by a resite formed by cure of the binder com-position, and had an apparent density of about nine pounds per cubic foot, on the average.
The glass fiber product produced as described in the preceding paragraph substantially the same properties and characteristics as an analogous pro-duct made from a binder containing a condensate pre-pared by the procedure described in U.S. Patent No.
3,684,467, column 8, lines 1-27.
Condensate A was prepared from 363.6 parts 52 percent formaldehyde, 160 parts phenol, 52 parts water, 14.4 parts calcium hydroxide, 48 parts dextrin and 160 parts 50 percent urea solu-tion in water. The condensate was produced in a stainless steel reactor equipped with a propeller-type agitator and an interior, indirect heat trans-fer coil through which steam or cooling water was circulated, as required, to control temperature.
~.~67ZZ7 Agitation was used throughout. The phenol and formaldehyde were added to the reactor first, and were heated to 110F, which tem-perature was maintained for 3~ hours, during which time the cal-cium hydroxide, as a slurry in the water, was added gradually.
The reaction mixture was then heated to 125F and maintained at that temperature for a period of one hour counting the time, approximately ten minutes, required to reach 125F. The tempera-ture was then increased to 150F, and that temperature was main-tained for a total of 2~ hours. The dextrin was charged two hours af-ter the reaction mixture reached 150F. At the end of the 2~ hour period at 150F, cooling water was c:irculated through the indirect heat exchanger to lower the reaction temperàture, and the urea solution was added rapidly. Cooling water was cir-culated until the condensate reached a temperature of about 80F.
The proportion of volatiles in Condensate A was found to be 20 units, as measured by an arbitrary test which has been found to correlate well with emission experience under commercial conditions when binders made with that resin are being used. The test involves distilling a predetermined volume of the resin, di-luted to about 25 percent solids with distilled water, collecting the distillate, and determining colorimetrically the proportion of low molecular weight condensates in the distillate collected.
Volatility is then determined by reference to an empirical chart.
The correlation between emissions, under commercial conditions, and "volatility" of a resin by the test just described, occurs in the sense that resins which are found to have low "volatility"
are found to give fewer emissions under commercial conditions, other factors being equal, than do resins which are found to have a high "volatility".
A condensate prepared by the procedure described in U.S.
~7227 Patent No. 3,684,467, column 8, lines 1-27, using barium hydrox-ide as the condensing agentand formaldehyde and phenol in a mole ratio of 3.1:1 had a volatility of 200 units by the test des-cribed above, while the same condensate, produced with calcium hydroxide as the condensing agent, had a volatility of 85.
In the procedure described above for producing Conden-sate A, urea was added to the phenol-dextrin-formaldehyde condensate duriny cooling thereof. This is a preferred procedure because an adequate degree of reaction between the added urea and formaldehyde, partial condensates or both in the reaction mixture occurs during the cooling. The same result can be achieved, however, by any other proc~dure according to which at least 5 percent of urea, based upon the weight of the phenol originally charged, is dissolved in the condensation products for at least 15 minutes at a temperature of at least about 90 F. For example, Condensate A could be cooled to about 800F without making any urea addition. The condensate could then be reheated, and the urea could be added. Alternatively, a binder could be formulated from the phenol-dextrin-formaldehyde condensate and urea, and the binder can be aged for at least 15 minutes at a temperature 90F or higher to provide the requisite degree of reaction.
Reaction between added urea and formaldehyde is required in order to minimize the lower molecular weight binder constituents used in producing glass fiber products and, as a consequence, to minimize the volatiles in the binder and effluent from the process.
It has been found that a part of the pheno~dextrin-urea-formaldehyde or the like condensate can be replaced by a compara-tively high molecular weight additive reactive with formaldehydein order to reduce still further the volatiles in a glass fiber 10~72Z7 binder system. Lignin sulfonate, a by-product of the paper in-dustry, polyvinyl acetate, polyvinyl alcohol and mixtures thereof can all be used for this purpose. These materials, usually in an amount ranging from 5 to 25 percent, based upon total solids, can be added to the condensate during cooling, as described above for the urea addition, or can be used in formulating binders accord-ing to the invention. Examples of binders containing lignin sul-fonate and polyvinyl acetate which can be produced and used in connection with the production of glass fiber products as des-cribed above in Example 1 are given in the following ~able:
TABLE I
ExcorlpZe 2 Ex~np~e 2 Water ............................. (As in Example 1) (As in Example 1) Sodium hexametaphosphate .......... 0.03 part 0.03 part Gamma-aminopropyltriethoxysilane 0.01 " 0.01 "
Ammonium sulfate .................. 0.05 " 0.05 "
Condensate A ...................... 6.06 " 6.06 "
Lignin sulfonate .................. 0.70 "
Polyvinyl acetate ................. 0.70 "
50% aqueous solution of urea ...... 1.86 " 1.86 "
Oil emulsified with non-ionic surfactant ...................... 0.23 " 0.23 "
It has been found that starch derivatives other than dex-trins can be used in the manner described above in connection with the preparation of Condensate A, and that starch itself can be so used, although the condensates have a somewhat higher vis-cosity when made with starch, rather than a starch derivative, so that larger quantities of more dilute binders should be used when the condensate is starch modified, as distinguished from modified with a starch derivative. Starch derivatives including dextrose 1()672Z7 are all equally operable in practicing the instant invention, and whether made enzymatlcally, by heating an aqueous system under acid conditions, an aqueous system under basic conditions or by a combination of heat and pressure under acid or basic conditions.
Optimum results have been achieved using, as the silane coupling agent, aminoalkylalkoxysilanes, for example those listed in U.S. Patent No. 3,684,467.
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Claims (14)
1. A method of preparing a bonded glass fiber product, which method comprises the steps of:
(a) forming glass fibers from molten streams of glass;
(b) combining the glass fibers with a heat-curable aqueous binder composition comprising (1) 60-95 percent by weight of a complex polymeric compo-nent formed from a reaction mixture consisting of phenol, formaldehyde, a modifier selected from the group consisting of starch and compounds which are degradation products of starch, and urea, wherein said polymeric component is pro-duced by (a) charging a reactor with a mixture of formaldehyde and phenol in a mole ratio of formaldehyde/phenol of from 2.9-4.2/1;
(b) reacting the mixture in the presence of a conden-sing agent until it has a free formaldehyde content of from 7-15 percent of the total weight of formaldehyde, phenol and water;
(c) adding to the reactor the starch or starch decom-position product in an amount ranging from 5 to 50 per-cent of the phenol charged; and (d) cooling the reactor contents;
(2) 10-80 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric compo-nent, with the proviso that at least 5 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric component, is dissolved in the polymeric component for at least fifteen minutes at a tem-perature of at least 90°F, (3) 0.5-25 percent of a lubricant based upon the total weight of the complex polymeric component and any unreacted urea, (4) 0.1-1 percent of a silane, based on the total weight of the complex polymeric component and any unreacted urea, (5) 0.2-3.0 percent of an ammonium salt of a strong acid based on the total weight of the complex polymeric component and any unreacted urea, and (6) water, to dilute the binder to a desired solids content of from 1-40 percent, (c) consolidating the fibers and heat-curable aqueous binder composition into a loosely-packed mass on a foraminous conveyor;
and (d) curing the heat-curable binder composition in situ on the glass fiber product.
(a) forming glass fibers from molten streams of glass;
(b) combining the glass fibers with a heat-curable aqueous binder composition comprising (1) 60-95 percent by weight of a complex polymeric compo-nent formed from a reaction mixture consisting of phenol, formaldehyde, a modifier selected from the group consisting of starch and compounds which are degradation products of starch, and urea, wherein said polymeric component is pro-duced by (a) charging a reactor with a mixture of formaldehyde and phenol in a mole ratio of formaldehyde/phenol of from 2.9-4.2/1;
(b) reacting the mixture in the presence of a conden-sing agent until it has a free formaldehyde content of from 7-15 percent of the total weight of formaldehyde, phenol and water;
(c) adding to the reactor the starch or starch decom-position product in an amount ranging from 5 to 50 per-cent of the phenol charged; and (d) cooling the reactor contents;
(2) 10-80 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric compo-nent, with the proviso that at least 5 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric component, is dissolved in the polymeric component for at least fifteen minutes at a tem-perature of at least 90°F, (3) 0.5-25 percent of a lubricant based upon the total weight of the complex polymeric component and any unreacted urea, (4) 0.1-1 percent of a silane, based on the total weight of the complex polymeric component and any unreacted urea, (5) 0.2-3.0 percent of an ammonium salt of a strong acid based on the total weight of the complex polymeric component and any unreacted urea, and (6) water, to dilute the binder to a desired solids content of from 1-40 percent, (c) consolidating the fibers and heat-curable aqueous binder composition into a loosely-packed mass on a foraminous conveyor;
and (d) curing the heat-curable binder composition in situ on the glass fiber product.
2. A method as defined in claim 1, wherein at least 20 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric component, is added to the reac-tor during the cooling step, and is dissolved in the polymeric component for at least fifteen minutes at a temperature of at least 90°F while in the reactor.
3. A method as defined in claim 2, wherein at least 20 percent of unreacted urea, based upon the weight of the phenol originally charged to produce the polymeric component, is mixed with the polymeric component and other ingredients in producing the binder.
4. A method as defined in claim 1, 2, or 3, wherein the binder composition additionally contains from 5-25 percent of lignin sulfonate, polyvinyl acetate, polyvinyl alcohol or a mix-ture of at least two thereof.
5. A method as defined in claim 1, 2, or 3, wherein the third-named reactant used to produce the complex polymeric compo-nent is a starch degradation product containing dextrose.
6. A method as defined in claim 1, 2 or 3, wherein the third-named reactant used to produce the complex polymeric com-ponent is dextrin.
7. A product formed of glass fibers and a cured binder, wherein the glass fibers are bonded together by said cured binder in a random arrangement to form a substantially rigid structure and wherein the cured binder results from heating together on the glass fiber surfaces a binder composition comprising:
(1) 60-95 percent by weight of a complex polymeric component formed from a reaction mixture consisting of phenol, formalde-hyde, a modifier selected from the group consisting of starch and compounds which are degradation products of starch, and urea, wherein said polymeric component is produced by (a) charging a reactor with a mixture of formaldehyde and phenol in a mole ratio of formaldehyde/phenol of from 2.9-4.2/1;
(b) reacting the mixture in the presence of a condensing agent until it has a free formaldehyde content of from 7-15 percent of the total weight of formaldehyde, phenol and water;
(c) adding to the reactor the starch or starch decomposition product in an amount ranging from 5 to 50 per-cent of the phenol charged; and (d) cooling the reactor contents;
(2) 10-80 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric component, with the proviso that at least 5 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric component, is dissolved in the polymeric component for at least fifteen min-utes at a temperature of at least 90°F, (3) 0.5-25 percent of a lubricant based upon the total weight of the complex polymeric component and any unreacted urea, (4) 0.1-1 percent of a silane, based on the total weight of the complex polymeric component and any unreacted urea, (5) 0.2-3.0 percent of an ammonium salt of a strong acid based on the total weight of the complex polymeric component and any unreacted urea, and (6) water, to dilute the binder to a desired solids content of from 1-40 percent, wherein the amount of cured binder in the product is between 0.5 and 25 percent, based upon the combined weight of glass fibers and binder.
(1) 60-95 percent by weight of a complex polymeric component formed from a reaction mixture consisting of phenol, formalde-hyde, a modifier selected from the group consisting of starch and compounds which are degradation products of starch, and urea, wherein said polymeric component is produced by (a) charging a reactor with a mixture of formaldehyde and phenol in a mole ratio of formaldehyde/phenol of from 2.9-4.2/1;
(b) reacting the mixture in the presence of a condensing agent until it has a free formaldehyde content of from 7-15 percent of the total weight of formaldehyde, phenol and water;
(c) adding to the reactor the starch or starch decomposition product in an amount ranging from 5 to 50 per-cent of the phenol charged; and (d) cooling the reactor contents;
(2) 10-80 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric component, with the proviso that at least 5 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric component, is dissolved in the polymeric component for at least fifteen min-utes at a temperature of at least 90°F, (3) 0.5-25 percent of a lubricant based upon the total weight of the complex polymeric component and any unreacted urea, (4) 0.1-1 percent of a silane, based on the total weight of the complex polymeric component and any unreacted urea, (5) 0.2-3.0 percent of an ammonium salt of a strong acid based on the total weight of the complex polymeric component and any unreacted urea, and (6) water, to dilute the binder to a desired solids content of from 1-40 percent, wherein the amount of cured binder in the product is between 0.5 and 25 percent, based upon the combined weight of glass fibers and binder.
8. A product as defined in claim 7, wherein the binder composition additionally contains from 5-25 percent of lignin sulfate, polyvinyl acetate, polyvinyl alcohol or a mixture of at least two thereof.
9. The product of claim 7 or 8, wherein the third-named reactant used to produce the complex polymeric component is a starch degradation product comprising dextrose.
10. The product of claim 7 or 8, wherein the third-named reactant used to produce the complex polymeric component is dex-trin.
11. A heat-curable aqueous binder composition comprising:
(1) 60-95 percent by weight of a complex polymeric component formed from a reaction mixture consisting of phenol, formaldehyde, a modifier selected from the group consisting of starch and com-pounds which are degradation products of starch, and urea, where-in said polymeric component is produced by:
(a) charging a reactor with a mixture of formaldehyde and phenol in a mole ratio of formaldehyde/phenol of from 2.9-4.2/1;
(b) reacting the mixture in the presence of a condensing agent until it has a free formaldehyde content of from 7-15 percent of the total weight of formaldehyde, phenol and water;
(c) adding to the reactor the starch or starch decomposi-tion product in an amount ranging from 5 to 50 percent of the phenol charged; and (d) cooling the reactor contents;
(2) 10-80 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric component, with the proviso that at least 5 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric component, is dissolved in the polymeric component for at least fifteen min-utes at a temperature of at least 90°F, (3) 0.5-25 percent of a lubricant based upon the total weight of the complex polymeric component and any unreacted urea, (4) 0.1-1 percent of a silane, based on the total weight of the complex polymeric component and any unreacted urea, (5) 0.2-3.0 percent of an ammonium salt of a strong acid based on the total weight of the complex polymeric component and any unreacted urea, and (6) water, to dilute the binder to a desired solids content of from 1-40 percent.
(1) 60-95 percent by weight of a complex polymeric component formed from a reaction mixture consisting of phenol, formaldehyde, a modifier selected from the group consisting of starch and com-pounds which are degradation products of starch, and urea, where-in said polymeric component is produced by:
(a) charging a reactor with a mixture of formaldehyde and phenol in a mole ratio of formaldehyde/phenol of from 2.9-4.2/1;
(b) reacting the mixture in the presence of a condensing agent until it has a free formaldehyde content of from 7-15 percent of the total weight of formaldehyde, phenol and water;
(c) adding to the reactor the starch or starch decomposi-tion product in an amount ranging from 5 to 50 percent of the phenol charged; and (d) cooling the reactor contents;
(2) 10-80 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric component, with the proviso that at least 5 percent of urea, based upon the weight of the phenol originally charged to produce the polymeric component, is dissolved in the polymeric component for at least fifteen min-utes at a temperature of at least 90°F, (3) 0.5-25 percent of a lubricant based upon the total weight of the complex polymeric component and any unreacted urea, (4) 0.1-1 percent of a silane, based on the total weight of the complex polymeric component and any unreacted urea, (5) 0.2-3.0 percent of an ammonium salt of a strong acid based on the total weight of the complex polymeric component and any unreacted urea, and (6) water, to dilute the binder to a desired solids content of from 1-40 percent.
12. A binder composition as defined in claim 11, which additionally contains from 5-25 percent of lignin sulfonate, polyvinyl acetate, polyvinyl alcohol or a mixture of at least two thereof.
13. A binder composition as claimed in claim 11 or 12, wherein the third-named reactant used to produce the complex polymeric component is a starch degradation product containing dextrose.
14. A binder composition as claimed in claim 11 or 12, wherein the third-named reactant used to produce the complex polymeric component is dextrin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA308,288A CA1067227A (en) | 1974-03-18 | 1978-07-27 | Production of glass fiber products |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/452,293 US4014726A (en) | 1974-03-18 | 1974-03-18 | Production of glass fiber products |
| CA215,947A CA1067226A (en) | 1974-03-18 | 1974-12-13 | Production of glass fiber products |
| CA308,288A CA1067227A (en) | 1974-03-18 | 1978-07-27 | Production of glass fiber products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1067227A true CA1067227A (en) | 1979-11-27 |
Family
ID=27163746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA308,288A Expired CA1067227A (en) | 1974-03-18 | 1978-07-27 | Production of glass fiber products |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1067227A (en) |
-
1978
- 1978-07-27 CA CA308,288A patent/CA1067227A/en not_active Expired
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