Source: http://www.google.com/patents/US4543405?dq=%22melissa+white%22
Timestamp: 2013-12-06 09:36:26
Document Index: 600340813

Matched Legal Cases: ['art 1', 'art 2', 'art 1', 'art 1', 'art 1', 'art 2', 'art 1', 'art 2', 'art 3', 'art 4']

Patent US4543405 - High solids polyurethane polyols and coating compositions thereof - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Advanced Patent Search | Sign inAdvanced Patent SearchPatentsThere are disclosed herein polyurethane polyols and coating compositions formulated therewith. The polyurethane polyols are prepared by typically reacting low molecular weight polyols in amounts sufficient to produce reaction products containing a significant amount of unreacted starting polyols which...http://www.google.com/patents/US4543405?utm_source=gb-gplus-sharePatent US4543405 - High solids polyurethane polyols and coating compositions thereofPublication numberUS4543405 APublication typeGrantApplication numberUS 06/656,559Publication dateSep 24, 1985Filing dateOct 1, 1984Priority dateOct 1, 1984Fee statusLapsedPublication number06656559, 656559, US 4543405 A, US 4543405A, US-A-4543405, US4543405 A, US4543405AInventorsRonald R. Ambrose, Wen-Hsuan Chang, David T. McKeough, John R. PefferOriginal AssigneePpg Industries, Inc.Patent Citations (2), Referenced by (33), Classifications (27), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetHigh solids polyurethane polyols and coating compositions thereofUS 4543405 AAbstract There are disclosed herein polyurethane polyols and coating compositions formulated therewith. The polyurethane polyols are prepared by typically reacting low molecular weight polyols in amounts sufficient to produce reaction products containing a significant amount of unreacted starting polyols which can be subsequently removed by means such as vacuum distillation.
What is claimed is: 1. A polyurethane polyol having a number average molecular weight of up to about 1000 which is prepared by reacting a low molecular weight starting polyol with a polyisocyanate, wherein the starting polyol is in an amount sufficient to produce a reaction product containing about 5 percent or higher unreacted starting polyol.
DETAILED DESCRIPTION OF THE INVENTION The claimed invention encompasses in one aspect, polyurethane polyols containing "significantly high" amounts, i.e., about 16 percent or higher and preferably 21 percent or higher of unreacted starting polyols wherein the unreacted starting polyols are not removed. As fully explained hereinafter, these polyurethane polyols are advantaged by the preponderance of low molecular weight and narrow molecular weight distribution of the polyurethane polyol species. They can have utility as intermediates for the preparation of other resinous materials, and they can have utility in their own right as film-formers.
nA+mB&#8417;A.sub.1 +B.sub.1 +A.sub.1 B.sub.1 +A.sub.2 B.sub.1 +A.sub.1 B.sub.2 +A.sub.2 B.sub.2 +A.sub.3 B.sub.2 + . . . (1)
where A and B denote a starting glycol and diisocyanate, respectively, n and m are the number of moles of A and B charged, and the subscripts denote the number of A and B units in a particular species. If the reaction is carried out with excess glycol (n&gt;m) and the reaction is carried out to completion (--NCO equivalent weight of infinity), the species which contain --NCO functional groups become negligible, and equation (1) simplifies to:
nA+mB&#8417;A.sub.1 +A.sub.2 B.sub.1 +A.sub.3 B.sub.2 +A.sub.4 B.sub.3 +A.sub.5 B.sub.4 . . .                            (2)
The mole fraction distribution, F(r), and the weight fraction distribution, W(r), of the polyurethane glycol can be calculated as follows: ##EQU2## where β is the extent of reaction of hydroxyl groups and this is m/n when the reaction is carried to completion, i.e., to the --NCO equivalent weight of infinity, r is the number of diisocyanate species, i.e., B units per molecule, and MW is the molecular weight of the A.sub.r+1 B.sub.r species. As would be realized, the species such as A.sub.2 B.sub.1 and to some extent A.sub.3 B.sub.2 which are low molecular weight species are more desirable for high solids compositions.
To obtain these polyurethane polyols, it would have been theorized that one would have to employ relatively higher quantities of starting polyols. This theory would have had a limited practical use because the high quantities of starting polyols would result in correspondingly high quantities of unreacted starting polyols which are believed to have the following associate negatives. The unreacted starting polyols which are in the nature A.sub.1 are of relatively lower molecular weight. Hence, they may volatilize during heat curing of coatings containing same. When cured into coatings with curing agents such as melamines, they may impart brittleness to the coating.
TABLE I______________________________________   Weight    Weight Percent                          Weight Percent   Percent of             of Desired Low                          of HigherMole Ratio   Unreacted Molecular Weight                          Molecular WeightDiol/NCO   Diol A.sub.1             Species A.sub.2 B.sub.1                          Species A.sub.3 B.sub.2 + . .______________________________________                          .(i) 1.5:1   5.3       13.4         81.3(ii) 1.7:1   8.7       19.4         71.9(iii) 2.0:1   13.9      26.3         59.8(iv) 2.3:1   18.8      30.9         50.3(v) 3.0:1   28.7      36.2         35.1(vi) 4.0:1   40.0      37.8         22.2______________________________________
As can be seen from Table I, more of the A.sub.2 B.sub.1 species, and less of A.sub.3 B.sub.2 and higher species are obtained with increase in the amount of unreacted starting diols.
In accordance with this invention, all or part of the unreacted starting diol can be subsequently removed. With the unreacted starting diol removed, the polyurethane polyol contains significantly higher proportions of the desired low molecular weight A.sub.2 B.sub.1 species as shown by the above table. The resultant polyurethane polyol is of low molecular weight and narrow molecular weight distribution.
In the process of preparing the instant polyurethane polyol, the starting polyol is reacted with a polyisocyanate. Typically, the urethane-forming reaction is conducted over a temperature range of 80 110 necessary, the reaction can be terminated before completion. The unreacted isocyanate groups can be removed from the reaction product preferably by chemical means. In accordance with this invention, the reaction product comprises a polyurethane polyol and an unreacted starting polyol. If desired, the polyurethane polyol can be subjected to "typical polyol" reactions with, say, an acid, isocyanate, lactone, and the like.
Illustratively, a diol which has a low boiling point and which does not crystallize at room temperature can be removed as follows. A reaction product comprising same is heated to a pot temperature of about 100 atmospheric pressure to about 300 to 0.01 torr. After the depressurization, heating of the pot is continued until the required amount of glycol is removed. Typically, heating is conducted over a pot temperature of 100 be employed if there is no further reaction of the resinous polyol. To facilitate the removal of the glycol, there may be introduced in the heating vessel a carrying means for the unreacted diol.
An unreacted diol which crystallizes at room temperature can be removed by employing a relatively high absolute reduced pressure of about 100 torr, a pot temperature of 150 temperature which will effect condensation of the diol. Said temperature is typically above the melting point of the unreacted diol in the distillation apparatus.
To determine molecular weight by gel permeation chromatography (GPC), the instrument is first calibrated using glycol standards. Glycol standards were purchased from Polymer Laboratories Ltd., Church Stretton, U.K. The weight average molecular weights of the glycol standards used were 998, 425 and 76 for polyethylene glycol, polyethylene glycol and propylene glycol, respectively. To obtain a calibration curve, a set of 2 percent by volume glycol solutions in tetrahydrofuran were prepared and a 75 microliters sample size was injected into the column and a GPC chromatogram was obtained. A linear least square fit of log.sub.10 (molecular weight) versus elution time of each standard was used as a calibration curve. The samples whose molecular weights are to be determined was prepared as a 1.0 percent per volume tetrahydrofuran solution. After filtration through a 0.5 micron filter, available from Gelman Corporation, Catalog No. 4219, a 75 microliters samples size was injected into the columns and a GPC chromatogram obtained under the same experimental conditions as the calibration. The chromatogram was divided into vertical segments of equal elution volume of approximately one milliliter and the height of each segment (Hi) and the corresponding molecular weight (Mi) obtained from the calibration curve were used to calculate the number average molecular weight (Mn) according to the equation: ##EQU3##
EXAMPLE 1 Part 1 This example illustrates the high solids compositions comprising a polyurethane polyol of the present invention, and the method of preparing same. The polyurethane polyol was prepared, as follows:
The above ingredients were charged to a 5-liter 4-necked flask equipped with a condenser, stirrer, thermometer and nitrogen inlet tube. The resultant mixture was heated to react in a nitrogen atmosphere to 60 rising to 130 to 115 indicated that the isocyanate group has been consumed. The reaction product was allowed to cool, discharged and analyzed. The determined solids content was 62.3 percent, estimated unreacted starting polyol based on solids content was 37.7, hydroxyl value was 503, Mn was 698, Mw was 754 and Mw/Mn was 1.081.
Part 2 Unreacted starting polyol was removed from the above reaction product comprising a polyurethane polyol by vacuum distillation.
The Distillation Apparatus The vessel comprised of a 4-neck flask equipped with a stirrer addition funnel, a thermometer for measuring pot temperatures and a (CLAISEN type) adaptor. The adaptor was connected to a condenser (FRIEDRICH type, herein referred to as Condenser 1). The adaptor was equipped with two thermometers for measuring head temperatures at point (A) closer to the pot and point (B) closer to Condenser 1.
The Distillation Process 3800 grams of the reaction product of Part 1 was charged to the flask of the apparatus described herein. The contents of the flask were heated and the system was placed under vacuum. At a pot temperature of 122 C., applied reduced pressure was 50 mm. At a pot temperature of 160 into the system via a dropping funnel. At this stage, the head temperature at (A) was 30 and Condenser 1 was at 35 soon rose to 150 began to condense and was collected in Receivers 1 and 2.
The reaction mixture was heated to 176 (A) and (B) were 164 was added at a drop rate of 48 drops per minute, and the distillate came off at a drop rate of 260 drops per minute. The reaction temperature was maintained at 180 temperatures at (A) and (B) had fallen to 135 C., respectively. At the end of the distillation process, the amount of distillate collected in Receiver 1 and Receiver 2 were 1657 and 549, respectively. A total of 640 milliliters of water had been added. The reaction product remaining in the pot was thinned to 80 percent solids with methyl isobutyl ketone. Analysis gave a determined solids of 79.8 percent, a viscosity of 16.55 stokes, hydroxyl value of 155; Mn was 705, Mw was 781 and Mw/Mn was 1.11. Estimated unreacted starting glycol based on solids content was 0.25 percent.
EXAMPLE 2 Part 1 A polyurethane polyol was prepared, in essentially the same manner as described in Example 1, part 1. The following were used in the preparation.
Part 2 Unreacted 1,6-hexanediol was removed from the above reaction product by vacuum distillation in essentially the same manner as described in Example 1 and summarized hereinbelow.
3800 grams of the reaction product were charged to a properly equipped reaction vessel, heated and a vacuum was applied. At a pot temperature of 160 applied reduced vacuum pressure of 45 torr, addition of water into the reaction pot was started and distillation began. Heating was continued to 180 collected. The distillation was terminated after 640 grams of water had been introduced into the vessel.
EXAMPLE 3 This example shows the use of the polyurethane polyol in imparting hardness properties to coating compositions.
Part 1 A polyester polyol was prepared, as follows:
The above ingredients were charged to a properly equipped reaction vessel and the resultant mixture heated to react in a nitrogen atmosphere. At 170 reaction. With the continuous removal of the water, heating was continued to 200 for about 12 hours until an acid value of about 10.0 was attained. The resultant mixture was then cooled, discharged and analyzed.
Part 2 A polyester-urethane polyol was prepared with the above polyester polyol.
The above ingredients were charged to a properly equipped reaction vessel as described in Example 1 and the resultant mixture heated to react in a nitrogen atmosphere to a temperature of 90 was held at this temperature for about 2 hours until all the isocyanate had reacted. The resultant composition was discharged and analyzed.
Part 3 (Control) A coating composition was formulated with a polyester-urethane polyol of the same composition as the above. The polyester-urethane polyol was formulated with an aminoplast curing agent and other ingredients as listed below.
______________________________________                Parts by Weight                            ResinIngredients          (grams)     Solids______________________________________The above polyester-urethane polyol                88.9        80Melamine.sup.1       20          20Polymeric microparticles.sup.2                5.1         2.25Cellulose acetate butyrate                3           0.75U.V. absorber.sup.3  2           2Flow control agent   0.5         0.25U.V. stabilizer.sup.4                2           1Dodecylbenzene sulfonic acid                2           0.4Thinning solvent.sup.5                60.5______________________________________ .sup.1 RESIMINE 745 available from Monsanto Company. .sup.2 Prepared as described in Example II of U.S. Pat. 4,147,688. .sup.3 Available from CibaGeigy Company as TINUVIN. .sup.4 Available from CigaGeigy Company as TINUVIN. .sup.5 Isobutyl acetate/cellosolve acetate, in a 1:1 ratio.
The coating composition having a sprayable resin solids content of 57 percent by weight was sprayed on a 1/8-inch thick thermoplastic polyurethane commercially available from Mobay as TEXIN 355D. The coating was baked at 121 flexibility tests comprising a 1/4-inch mandrel bend at 20 (-7
Part 4 To improve the hardness while maintaining the flexibility of the above coating composition, it was reformulated with the above ingredients and a polyurethane polyol of Example 1.
______________________________________                Parts by Weight                            ResinIngredients          (grams)     Solids______________________________________The above polyester-urethane polyol                77.5        70The polyurethane polyol of Example 1                12.5        10Melamine.sup.1       20          20Polymeric microparticles.sup.2                5.1         2.25Cellulose acetate butyrate                3           0.75U.V. absorber.sup.3  2           2Flow control agent   0.5         0.25U.V. stabilizer.sup.4                2           1Dodecylbenzene sulfonic acid                2           0.4Thinning solvent.sup.5                60.5______________________________________ .sup.1 RESIMINE 745 available from Monsanto Company. .sup.2 Prepared as described in Example II of U.S. Pat. No. 4,147,688. .sup.3 Available from CibaGeigy Company as TINUVIN. .sup.4 Available from CigaGeigy Company as TINUVIN. .sup.5 Isobutyl acetate/cellosolve acetate, in a 1:1 ratio.
The coating composition having a sprayable resin solids content of 57 percent by weight was sprayed on a 1/8-inch thick thermoplastic polyurethane commercially available from Mobay as TEXIN 355D. The coating was baked at 121 flexibility and hardness tests as before.
SUMMARY OF THE INVENTION The present invention encompasses a polyurethane polyol having a number average molecular weight of up to about 1000 which is prepared by reacting a low molecular weight starting polyol with a polyisocyanate wherein the starting polyol is in an amount sufficient to produce a reaction product containing a significantly high amount, i.e., about 16 percent by weight or higher and preferably about 21 percent or higher of unreacted starting polyol. The percent by weight is based on weight of the reaction product. The low molecular weight starting polyols useful herein are simple polyols which are distinguishable from polymeric polyols.
The solids (i.e., the non-volatile) content of the resinous polyol is determined by ASTM D-2369 testing modified as follows: 0.5 grams of the resinous polyol (i.e., the reaction mixture which may comprise unreacted polyol) is mixed with 5 milliliters of 1:1 mixture of acetone and tetrahydrofuran and heated at 105 oven. The resinous polyol is then cooled in a desiccator, reweighed and the non-volatile content calculated. The percentage by weight of the resinous polyol remaining is reckoned as the solids content. By this method, unreacted starting polyol is usually volatile is not included in the determined solids.
The VOC is defined as any weight per volume of compound of carbon which evaporates from a paint or related coating material under the specific conditions for the determination of the non-volatile content of that material. This does not include water which is volatile under the test conditions. Thus, the water content of the material undergoing analysis must be determined. To obtain the VOC of a sample, the non-volatile content, water content and the density of the material are determined. The VOC number is calculated by correcting the total organic volatile content for the water content and dividing by the volume of the paint corrected for the water content. The determination of the VOC is by ASTM D-3960 testing which entails heating the paint or related coating material at 110
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A PA CORP.Oct 1, 1984ASAssignmentOwner name: PPG INDUSTRIES, INC., PITTSBURGH, PA. A PA CORP.Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:AMBROSE, RONALD R.;CHANG, WEN-HSUAN;MC KEOUGH, DAVID T.;AND OTHERS;REEL/FRAME:004319/0521Effective date: 19840928RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google