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Patent US6150492 - Cross-catalyzed phenol-resorcinol adhesive - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsA two-part adhesive is provided wherein the first part comprises a stable aqueous alkaline monohydroxylic phenolic resole resin solution containing a methylene donor such as oxazolidine or a methylolurea and the second part comprises a stable resorcinolic resin precondensate having a shortage of formaldehyde...http://www.google.com/patents/US6150492?utm_source=gb-gplus-sharePatent US6150492 - Cross-catalyzed phenol-resorcinol adhesiveAdvanced Patent SearchPublication numberUS6150492 APublication typeGrantApplication numberUS 08/192,077Publication dateNov 21, 2000Filing dateFeb 4, 1994Priority dateFeb 4, 1994Fee statusPaidAlso published asCA2118079A1, CA2118079C, DE69419242D1, DE69419242T2, EP0666296A1, EP0666296B1, US5684114Publication number08192077, 192077, US 6150492 A, US 6150492A, US-A-6150492, US6150492 A, US6150492AInventorsEarl K. Phillips, William D. Detlefsen, Fred E. CarlsonOriginal AssigneeBorden Chemical, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (22), Non-Patent Citations (5), Referenced by (6), Classifications (16), Legal Events (19) External Links: USPTO, USPTO Assignment, EspacenetCross-catalyzed phenol-resorcinol adhesive
4. The method of claim 2 where the methylene donor is an oxazolidine with or without a methylol group as part of the oxazolidine.
5. The method of claim 2 wherein the methylene donor is a methylolurea.
6. The method of claim 2 wherein the catalyst in the second component is a member selected from the group consisting of an ester functional curing catalyst and a carbamate.
7. The method of claim 6 wherein:A. the ester functional curing catalyst is a member selected from the group consisting of a cyclic organic carbonate, a lactone and a carboxylic acid ester; B. the carbamate is the reaction product of ammonia with a member selected from the group consisting of an alkylene carbonate, glycidol carbonate, and epoxy resin carbonate; C. the quantity of methylene donor is from about 0.3% to 15% by weight of the resole resin; and D. the quantity of the catalyst is from about 1% to 30% by weight of the resorcinolic resin. 8. The method of claim 2 wherein the catalyst for the resole resin is an ester functional curing catalyst.
9. The method of claim 2 wherein the catalyst in the second component is a carbamate, said carbamate being the reaction product of ethylene carbonate or propylene carbonate with ammonia.
10. The method of claim 6 wherein the ester catalyst has from 3 to 9 carbon atoms.
11. The method of claim 2 wherein:A. the methylene donor is a member selected from an oxazolidine represented by the formula ##STR3## wherein R2 is hydrogen, alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 1 to 8 carbon atoms, benzyl, or phenylcarbamyl, and each of R3, R4, and R5 is hydrogen or an alkyl of 1 to 8 carbon atoms; and ##STR4## wherein R is hydrogen, methyl, ethyl, n-propyl, isopropyl, methylol, beta-hydroxyethyl, acetoxymethyl or methoxymethyl; and B. the ester is a member selected from the group consisting of a lactone, a cyclic organic carbonate, a carboxylic acid ester, and mixtures thereof. 12. The method of claim 2 wherein the resole resin is the condensation product of phenol and formaldehyde.
13. The method of claim at wherein the resorcinolic resin is a member selected from the group consisting of: the condensation product of resorcinol and formaldehyde; and the condensation product of phenol, resorcinol and formaldehyde containing up to about 55 parts by weight of phenol per 50 parts of resorcinol.
14. The method of claim 13 wherein the resorcinolic resin is the condensation product of resorcinol and formaldehyde.
15. The method of claim 13 wherein the resorcinolic resin is the condensation product of resorcinol with less than 10 parts of phenol.
16. The method of claim 11 wherein the nitrogen of the oxazolidine is part of a one ring heterocyclic.
17. The method of claim 11 wherein the nitrogen of the oxazolidine is directly attached to a first and a second ring of the oxazolidine.
18. The method of claim 17 wherein the oxazolidine is 1-aza-5-methylol-3,7-dioxabicyclo[3.3.0]octane.
19. The method of claim 17 wherein the oxazolidine is 1-aza-5-ethyl-3,7-dioxabicyclo[3.3.0]octane.
This invention relates to an adhesive in two parts. The two parts are mixed together immediately prior to use. Part One is a stable aqueous alkaline phenolic resole resin solution containing a methylene donor. Part Two is a stable resorcinolic precondensate resin having a shortage of formaldehyde which optionally contains a catalyst for curing the resole resin. Each part exhibits viscosity stability of the respective resin similar to that without the methylene donor or catalyst until the two parts are mixed. On mixing, the methylene donor of Part One reacts with the resorcinolic resin of Part Two and the catalyst in Part Two reacts with the phenolic resole resin of Part One to cause adhesive gelation and cure of the resins. The adhesive is particularly useful for the manufacture of lignocellulosic panels such as strandboard.
The use of phenolic resole resin curing catalysts are known, e.g., such as those described in U.S. Pat. No. 4,831,067 of May 16, 1989 to Lemon et al; and U.S. Pat. No. 4,961,795 of Oct. 9, 1990 to Detlefsen and Phillips. The above mentioned Detlefsen and Phillips patent is also concerned with methods for accelerating the cure of phenolic resole resins in the manufacture of lignocellulosic panels. The following patents are also concerned with methods for accelerating the cure of phenolic resole resins: U.S. Pat. No. 4,373,062 of Feb. 8, 1983 to Brown which uses a phenol-formaldehyde resole resin to which resorcinol is added and subsequently cured with formaldehyde; and U.S. Pat. No. 4,977,231 of Dec. 11, 1990 to McVay which discusses shortcomings of phenolic resole resins including the use of ester functional curing agents such as propylene carbonate. McVay uses certain carbamate catalysts to solve the problem of slow cure.
Resorcinol is very expensive in relation to phenol and mixtures of resorcinol resin in monohydroxylic phenolic resole resins are not efficient from the standpoint of the increase in performance in relation to the amount of resorcinol resin needed. Additionally, for curing of such resins prepared from both resorcinol and phenol, the prior art added formaldehyde or paraformaldehyde to the mixture.
Another source of methylene donors for resorcinolic resins is a class of chemicals called oxazolidines. These can be reaction products of formaldehyde and certain amino alcohols derived from nitroparaffins. The oxazolidines react with resorcinolic resin solutions which lack formaldehyde, in the manner of formaldehyde, without actually releasing formaldehyde to the solution or to the atmosphere. The use of oxazolidine to catalyze resorcinolic resins, including phenol-resorcinol resins is shown in the following U.S. Pat. No. 3,256,137 of Jun. 14, 1966 to Danielson; U.S. Pat. No. 3,281,310 of Oct. 25, 1966 to Danielson; U.S. Pat. No. 3,698,983 of Oct. 17, 1972 to Bryant; U.S. Pat. No. 3,705,832 of Dec. 12, 1972 to Stephan; and U.S. Pat. No. 3,517,082 of Jun. 23, 1970 to Cockerham. Technical Review, TR No. 4 of the Angus Chemical company also describes oxazolidines as useful curing additives of phenol-formaldehyde and one stage phenolic resins.
The resole resin used in this invention will have a resin pan solids content of about 20% to 75% by weight and preferably about 45% to 60%. Generally, the viscosity should be such as to permit the solution to be sprayed on the cellulosic components such as flakes or strands or to otherwise be applied to the components such as veneer. Thus, the viscosity of the resole resin component will generally vary from about 50 to about 1,000 centipoise at 25� C. as determined by a Brookfield RNTF viscosimeter with a number 2 spindle at 20 revolutions per minute at 25� C. and preferably from about 100 to 300 cps at 25� C. when used with particulate components such as strands.
Illustrative of such methylene donors which do not have a methylol group there can be mentioned: trioxane; hexamine; ethylene diamine/formaldehyde product such as 1,4,6,9-tetrazatricyclo-(4.4.1.1)-dodecane; cyclic triformals such as ethyleneamine triformal, and triformaldehyde glycerine ester; as well as certain oxazolidines.
A review of oxazolidine chemistry appears in Chemical Reviews 53, 309-352 (1953). Illustrative of suitable oxazolidines there can be mentioned the various; 1,3-oxazolidines shown in U.S. Pat. No. 3,281,310 of Oct. 25, 1966 to Danielson which is incorporated herein in its entirety by reference; and those of U.S. Pat. No. 3,256,137 of Jun. 14, 1966 to Danielson which is also incorporated herein in its entirety by reference.
The compounds of the U.S. Pat. No. 3,281,310 patent wherein the nitrogen is part of only one ring can be represented the formula: ##STR1## wherein R2 is hydrogen, alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 1 to 8 carbon atoms, benzyl, or phenylcarbamyl, and each of R3, R4, and R5 is hydrogen or an alkyl of 1 to 8 carbon atoms. Illustrative of such oxazolidines there can be mentioned: 4,4-dimethyl-1,3-oxazolidine; 3-(2-hydroxyethyl)-1,3-oxazolidine; 3-(2-hydroxypropyl)-5-methyl-1,3-oxazolidine; 5-methyl-1,3-oxazolidine; 3-ethyl-1,3-oxazolidine; 3-benzyl-1,3-cyclohexyl-5-methyl-1,3-oxazolidine; 3-phenylcarbamyl-4,4-dimethyl-1,3-oxazolidine; as well as the corresponding bis(1,3-oxazolidino)methanes such as bis(4,4-dimethyl-1,3-oxazolino)methane.
The oxazolidine compounds of the U.S. Pat. No. 3,256,137 patent wherein the nitrogen is directly attached to a first and a second ring of a bicyclic heterocycle can be represented by the formula: ##STR2## wherein R is hydrogen, methyl, ethyl, n-propyl, isopropyl, methylol, beta-hydroxyethyl, acetoxymethyl or methoxymethyl. Illustrative of such oxazolidines there can be mentioned: 1-aza-3,7-dioxabicyclo[3.3.0]octane; 1-aza-5-methyl-3,7-dioxabicyclo[3.3.0]octane; 1-aza-5-ethyl-3,7-dioxabicyclo[3.3.0]octane; 1-aza-5-n-propyl-3,7-dioxabicyclo[3.3.0]octane; 1-aza-5-isopropyl-3,7-dioxabicyclo[3.3.0]octane; 1-aza-5-methylol-3,7-dioxabicyclo[3.3.0]octane; 1-aza-5-acetoxymethyl-3.7-dioxabicyclo[3.3.0]octane; and 1-aza-5-methoxymethyl-3.7-dioxabicyclo[3.3.0]octane.
The preferred oxazolidines are: 1-aza-5-ethyl-3,7-dioxabicyclo[3.3.0]octane such as that under the trademark AMINE CS-1246; 1-aza-5-methylol-3,7-dioxabicyclo[3.3.0]octane such as that under the trademark ZOLDINE ZT-55; and 4,4-dimethyl-1,3-oxazolidine such as that under the trademark AMINE CS-1135, all of which are supplied by Angus Chemical Company. The oxazolidines can be with or without a methylol group attached thereto.
The carbonate catalysts for the resole resin can be a carbamate which is disclosed in U.S. Pat. No. 4,977,231 of T. Mac Vay et al which issued on Dec. 11, 1990 and which is incorporated herein in its entirety by reference. Thus, the carbamate can be a reaction product of (a) a carbonate selected from the group consisting of alkylene, glycidol, and epoxy resin carbonate and (b) ammonia. Of particular interest are the carbamates having 2 to 6 carbon atoms. e.g., hydroxyethyl carbamate, hydroxypropyl carbamate, and the like.
Suitable additives can be used in coating the raw lignocellulosic material. Thus, from 0.25 to 3% by weight, based on the weight of the oven dry wood on the board product, of molten slack wax as well as emulsified wax can be used. Still further, from 5% to 20% by weight, based on the weight of the oven dry wood in the board product, of a suitable plasticizer may be included. Suitable plasticizers include glycol esters, glycerine esters, phosphate esters and the like.
The invention will be demonstrated by the following examples. In these examples and elsewhere through the specification, parts and percentages are by weight unless expressly indicated otherwise. Also, the term "resin solids" refers to pan solids according to an industry accepted test where one gram of resin is placed in an aluminum pan and heated in ;a forced air oven at 125� C. for one hour and 45 minutes. Such solids include catalysts, e.g. esters and carbamates well as well as methylene donors such as oxazolidine and urea-formaldehyde complexes.
Boiling Water Gel Tests. The boiling water gel tests to determine gel time were conducted with a Gel Time Meter, Catalog No. 22 of Sunshine Scientific Instrument of 1810 Grant Avenue, Philadelphia, Pa. The gel-time meter essentially consists of a motor-driven, rotating spindle suspended in the test sample. The sample is maintained at constant temperature by a boiling bath surrounding the sample cell. In this case, the boiling bath was that of water so that the temperature was 100� C. At the gel point, the very pronounced increase in viscosity of the sample stops the rotating spindle, closing an electrical switch which actuates the timing and alarm circuits. In operation, the sample tube containing a 10 gram sample, unless otherwise indicated, and the spindle are placed in the briskly boiling water bath. At the same time, the power switch is turned on, starting the counter and the slowly rotating spindle device. The spindle is locked into the spindle drive by magnetic coupling. The test switch is turned on, setting up the automatic counter stop and alarm circuits. The instrument needs no further attention for the duration of the test. When the gel point is reached, the increased viscosity of the test sample stops the rotating spindle and the actuating switch is closed. This switch shuts off the spindle motor and the counter, and actuates the visible and audible signal. The gel time and the bath temperature are then recorded by the operator, and the test is complete.
This example illustrates preparation of the two-part adhesive wherein the first part is that of a mixture of an aqueous alkaline monohydroxylic phenolic resole resin solution (PF) and an oxazolidine and the second part is phenol-resorcinol-formaldehyde co-condensed aqueous resin solution (PRF) without ester catalyst for the resole resin. The resole resin is referred to as WS474-101 and is made with phenol, formaldehyde, water, and sodium hydroxide, with 7.2% urea added in the finished polymer. The pH of this resole resin was 11.95. AMINE CS 1246, namely, 1-aza-5-ethyl-3,7-dioxabicyclo[3.3.0]octane, an oxazolidine supplied by Angus Chemical Company, is added to attain a 10% by weight concentration in the resin. The final resin has a pan solids of 51%, an alkalinity of 7% NaOH, molar ratio of 2.25:1 of formaldehyde to phenol, and 150 cps Brookfield viscosity. The phenol-resorcinol resin, referred to as WS453-88, is made with phenol, resorcinol, formaldehyde, water and sodium hydroxide. The resulting resorcinolic resin has pan solids of 50%, alkalinity of 3.5% NaOH, a molar ratio of 0.95:1 of formaldehyde to phenol-resorcinol, and 200 cps Brookfield viscosity.
This example shows a two-part adhesive wherein the first part it that of an aqueous alkaline monohydroxylic phenolic resole resin solution and the second part is an aqueous polymerizable resorcinolic resin (RF) wherein each part carries a catalyst for the other part. The resole resin (PF), referred to as WS421-110, is made with phenol, formaldehyde, water, and sodium hydroxide, with urea added to the finished polymer to provide a resin having 10.8% urea and a pH of 12. ZOLDINE ZT55, namely, 1-aza-5-methylol-3,7-dioxabicyclo[3.3.0]octane, an oxazolidine supplied by the Angus Chemical Company, is added within the preferred range. The final resin, including the oxazolidine and urea has pan solids of 50%, alkalinity of 7% NaOH, molar ratio of 2.3:1 of formaldehyde to phenol, and a viscosity of 110 cps at 25� C. Brookfield viscosity. Part two is a resorcinolic resin, referred to as WS 421-109, which is made with resorcinol, formaldehyde, water, and sodium hydroxide. Triacetin, an ester, is added to the resorcinolic resin to provide a resin having 17% of triacetin. The resorcinolic resin had pan solids of 51%, alkalinity of 1.5% NaOH, a molar ratio of 0.58:1, formaldehyde to resorcinol, a pH of 7.6, and a viscosity of 80 cps at 25� C. Brookfield viscosity.
TABLE 3______________________________________RF : PF     Boiling Water Gel Test______________________________________ 0 : 100    28 min.   5 : 95 13.1 min.  10 : 90 4.8 min.  15 : 85 1.7 min.  20 : 80 1.5 min.______________________________________
Laboratory strandboards were made with the phenolic resole resin mixture of Example 1, also referred to as PF in Table 4, with the resorcinolic resin of Example 1, also referred to as PRF in Table 4. These were mixed in the ratio of 50:50 by weight. The pH of the mixed resins was at least about 10. Resole Resin A was also tested for comparison purposes and as a control. Resin A is an aqueous solution of a phenol-formaldehyde resole resin having: a molar ratio of about 2.2 moles of formaldehyde per mole of phenol; 47% solids; Brookfield viscosity of about 200 cps at 25� C.; a pH of about 12.5; less than 0.5% of free phenol; less than 0.2% of free formaldehyde; which was made with sodium hydroxide as the base and which contains 8% of urea which was added after the resin cooled. The dimensions of the boards were 14�14�0.75 inches. They were pressed in an oil-heated laboratory hot press set at 390� F. Target board density was 40 pcf, and the wood was southern pine strands with minor amounts of mixed southern hardwoods. The wood moisture before resin application was 9% and 14% after resin application. The boards had random strand orientation, and were homogeneous in construction. The resins were mixed by hand just prior to use and applied to the strands in a laboratory rotating blender using air atomization. The resins were applied at the rate of 5% resin solids to dry wood weight. Press cycle times, including press closing and board degas, were adjusted to determine cure speed of the resins. This was done by examining board edges and corners for weakness immediately out of the press. The results of this example are shown in Table 4 wherein the first three series of results are for the Resin A and the second three series are for the mixture of the two-part adhesive of Example 1.
TABLE 4______________________________________     Cycle  IB       MOR  6-Cycle MOR                                     TS  Resin (min) (psi) (psi) (psi) (%)______________________________________Resin A   7.5    39       2971 1296       12.7   7.0 46 2033 1711 11.4   6.5 26 1780 1389 13.2  PRF : PF 5.0 39 2852 1452 10.5  50 : 50 4.5 40 2648 1793 11.0   4.0 26 2049 1527 12.6______________________________________
Laboratory strandboards were made with the resins from Example 2 mixed in various ratios by weight, using a monohydroxylic phenolic resole resin solution designated as Resin B as a control resin. The pH of the mixture of resins was about 10 to 11. Resin B has a molar ratio of about 2.2 moles of formaldehyde per mole of phenol; 47% solids; brookfield viscosity of about 100 cps at 25� C.; a pH of about 13; less than 0.5% free phenol; less than 0.1% of free formaldehyde; and which was made with sodium hydroxide as the base. Resin B contains 9.4% formaldehyde which was added after the condensation of the phenol and formaldehyde. The boards were manufactured as in Example 4, except that a press temperature of 400� F. was used, and wood moisture was lower, i.e., 3% before resin application.
TABLE 5______________________________________     Cycle  IB        MOR  6-CYCLE MOR  Adhesive (min) (psi) (psi) (psi)______________________________________Resin B   6.0    69        3516 1358   5.5 58 3164 1817   5.0 45 2520 1165   4.5 29 1659 1268  RF : PF 4.5 73 3298 1927  12 : 88 4.0 73 3916 2234   3.5 58 3157 1863   3.0 45 2452 1640  RF : PF 4.5 77 3059 2153  15 : 85 4.0 68 3479 1971   3.5 63 3161 1651   3.0 46 2614 1918  RF : PF 4.5 75 3732 2174  18 : 82 4.0 79 3620 2054   3.5 66 3497 2034   3.0 58 3021 2026______________________________________
Laboratory boards were made as in Example 5 with the following changes: aspen strands were used with moisture content of 9-10% before resin application; press temperature was 260� F.; Resin A, which was also used in Example 4, was again used as a control. Wood moisture was 14% after resin application. The results of this example are shown in Table 16.
TABLE 6______________________________________     Cycle  IB        MOR  6-CYCLE MOR  Adhesive (min) (psi) (psi) (psi)______________________________________Resin A   13     37        2840  802   12 36 2459  790   11 24 1492  575   9  8  653  331  RF : PF 10 60 2760 2013  18 : 82 9 51 2932 2095   8 47 2776 1864   7 29 2178 1331______________________________________
______________________________________Sample     Components                Boiling Water Gel Time______________________________________Hexamine  1            A 85 parts                    1.3 minutes   E 15 parts  2 B 85 parts 1.2 minutes   E 15 partsMethylolurea  3            C 100 parts                    25 minutes  4 C 80 parts 19.9 minutes   F 12.5 parts  5 D 85 parts 2.2 minutes   F 12.5 parts  6 D 85 parts 1.0 minute   E 15 parts______________________________________
TABLE 8______________________________________Sample              Boiling Water Gel Time______________________________________1 PF + oxazolidine  29.1 minutes  2 PF + triacetin 11.3 minutes  3 PF + RF + oxazolidine  3.3 minutes  4 PF + RF + oxazolidine + triacetin  1.3 minutes______________________________________
TABLE 9______________________________________          Percent      Boiling water  Additive Addition Gel Time______________________________________Dimethylolurea 20%          1.9 minutes  N-Methylolacrylamide 15% 11.4 minutes  Tris-hydroxy- 20% 3 minutes.  methyl-nitromethane______________________________________
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HauptRapid curing aldehyde resin-polyisocyanate composition and method for producing hybrid polymerUS20090149624 *Sep 19, 2008Jun 11, 2009Saint-Gobain Abrasives, Inc.Phenolic resin formulation and coatings for abrasive productsUS20110151180 *Aug 12, 2009Jun 23, 2011Haupt Robert ARapid curing aldehyde resin-polyisocyanate composition and method for producing hybrid polymerWO2004029119A1 *Feb 20, 2003Apr 8, 2004Shea Lawrence ENon-formaldehyde reinforced thermoset plastic composites* Cited by examinerClassifications U.S. Classification528/144, 525/507, 524/501, 528/145, 525/508, 525/504, 524/508, 525/480, 524/509International ClassificationC08L61/06, C08L97/02, C09J161/06Cooperative ClassificationC08L97/02, C09J161/06, C08L61/06European ClassificationC09J161/06Legal EventsDateCodeEventDescriptionFeb 4, 1994ASAssignmentOwner name: BORDEN, INC., OHIOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PHILLIPS, EARL K.;DETLEFSEN, WILLIAM D.;CARLSON, FRED E.;REEL/FRAME:006859/0233Effective date: 19940201Jun 27, 1996ASAssignmentOwner name: BORDEN CHEMICAL, INC., OHIOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BORDEN, INC.;REEL/FRAME:008011/0357Effective date: 19960620Apr 8, 2002ASAssignmentOwner name: BORDEN CHEMICAL, INC. 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