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Patent US5371151 - Curable composition comprising crosslinkable polymers prepared from ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA curable composition comprising a crosslinkable copolymer, wherein the copolymer is the free radical polymerization product of a mixture of monomers in the presence of a terminally unsaturated oligomeric chain transfer catalyst. Such compositions have advantageous properties when used in a variety of...http://www.google.com/patents/US5371151?utm_source=gb-gplus-sharePatent US5371151 - Curable composition comprising crosslinkable polymers prepared from oligomeric chain transfer agentsAdvanced Patent SearchPublication numberUS5371151 APublication typeGrantApplication numberUS 08/104,957Publication dateDec 6, 1994Filing dateAug 9, 1993Priority dateMay 1, 1992Fee statusPaidAlso published asCA2134870A1, CA2134870C, US5264530, US5362826, WO1993022351A1Publication number08104957, 104957, US 5371151 A, US 5371151A, US-A-5371151, US5371151 A, US5371151AInventorsJoseph A. Antonelli, Charles T. Berge, Michael J. DarmonOriginal AssigneeE. I. Du Pont De Nemours And CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (23), Non-Patent Citations (25), Referenced by (16), Classifications (19), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetCurable composition comprising crosslinkable polymers prepared from oligomeric chain transfer agentsUS 5371151 AAbstract A curable composition comprising a crosslinkable copolymer, wherein the copolymer is the free radical polymerization product of a mixture of monomers in the presence of a terminally unsaturated oligomeric chain transfer catalyst. Such compositions have advantageous properties when used in a variety of products including high performance coatings.
We claim: 1. A crosslinkable or curable composition comprising, by weight of (a) and (b) below, the following separate components:(a) 5 to 60 percent of a crosslinking agent; (b) 40 to 95 percent of a copolymer having crosslinkable groups, which copolymer is the reaction product of free radical polymerization of a reaction mixture comprising: (a) for chain transfer, an effective mount of an oligomeric chain transfer agent, or of a molecular weight distribution of oligomeric compounds having the following end group: ##STR9## wherein n is on average 2 to 100 and X.sup.1 to X.sup.n are independently X, wherein X is -CONR.sub.2, -COOR, OR.sup.1, -OCOR, -OCOOR.sup.1, -NRCOOR.sup.1, halo, cyano, or a substituted or unsubstituted phenyl or aryl, wherein each R is independently selected from the group consisting of hydrogen, silyl, or a substituted or unsubstituted alkyl, alkyl ether, phenyl, benzyl, and aryl, wherein substituted means with a substituent selected from the group consisting of epoxy, hydroxy, isocyanato, cyano, amino, silyl, acid, halo, or acyl; and wherein R.sup.1 is the same as R except not H; and wherein each alkyl is independently selected from the group consisting of branched, unbranched, or cyclical hydrocarbons having 1 to 12 carbon atoms; and halo or halogen is bromo, iodo, chloro or fluoro; except excluding the use of a pure dimer when X is substituted or unsubstituted phenyl or aryl; and (b) a mixture of monomers, the same or different, of which 2 to 100 percent by weight of the monomers have a reactive functionality which, on the polymerization product, is capable of crosslinking with itself or another polymer. 2. The composition of claim 1, wherein said monomers are ethylenically unsatured monomers 80-100% by weight of which are selected from the group consisting of methacrylates of the formula CH.sub.3 ═C(CH.sub.3)CO.sub.2 J wherein J is H, C.sub.1 -C.sub.12 alkyl, C.sub.2 -C.sub.12 alkenyl, glycidyl, C.sub.2 -C.sub.12 hydroxyalkyl, C.sub.x H(.sub.2x+1-y)F.sub.y where x is 1 to 16 and y is 0 to 2x+1; R.sub.6 R.sub.7 N(CH.sub.2).sub.z where R.sub.6 and R.sub.7 are independently C.sub.1 to C12 alkyl and z is 1 to 10, or R.sub.8 R.sub.9 R.sub.10 Si(CH.sub.2)z where R.sub.8, R.sub.9 and R.sub.10 are independently C.sub.1 to C.sub.12 alkyl or C.sub.1 to C.sub.12 alkoxy and z is 1 to10, and mixtures thereof.
6. The composition of claims 1, wherein polymerization is conducted in the presence of a said oligomeric compounds, or molecular weight distribution of said oligomeric compounds, in which X is -CONR.sub.2, COOR, or an unsubstituted or substituted phenyl or aryl, and R is as defined above.
FIELD OF THE INVENTION This invention relates to a curable composition comprising a crosslinkable polymer. The crosslinkable polymer is prepared using a ω-unsaturated oligomers as a chain transfer agent.
BACKGROUND OF THE INVENTION In preparing a film-foming polymer for a coating or other kind of curable composition, it is necessary to be able to control the molecular weight of the polymer so that it may be fitted to its particular use or needs. For example, in unperturbed polymerization systems which fundamentally tend to produce high molecular weight polymers, it may be desirable or necessary to limit the molecular weight of the polymers produced, and this must be done in a fairly predictable and controllable fashion. Such molecular weight limitation may be desirable or necessary in the preparation of polymer solutions for use in paints and finishes which require high solids content to assure reduced solvent emission during application and yet which require low viscosity to facilitate ready application.
SUMMARY OF THE INVENTION The present invention provides an improved composition which comprises a crosslinkable polymer prepared by polymerization in the presence of a chain transfer agent which is an m-unsaturated oligomer, as defined below. The compositions so produced have been found to have improved properties for use in coatings, especially finishes and paints. Such compositions may comprise, by weight of (a) and (b) below:
DETAILED DESCRIPTION OF THE INVENTION This invention is directed to a curable composition comprising at least one functional copolymer which is the polymerization product of a reaction mixture of comonomers at least a portion of which carry functional groups which can serve as crosslinking sites.
The polymer is the reaction product of a monomer mixture which is 80 to 100% by weight of methacrylates of the formula CH.sub.2 =C(CH.sub.3)CO.sub.2 J wherein J is H, C.sub.1 -C.sub.12 alkyl, C.sub.2 -C.sub.12 alkenyl, glycidyl, C.sub.2 -C.sub.12 hydroxyalkyl, allyloxyethyl, 2,4-hexadienyl, C.sub.x H(.sub.2x+1-y)F.sub.y where x is 1 to 16 and y is 0 to 2x+1, R.sub.6 R.sub.7 N(CH.sub.2).sub.z where R.sub.6 and R.sub.7 are independently C.sub.1 to C.sub.12 alkyl and z is 1 to 10, or R.sub.8 R.sub.9 R.sub.10 Si(CH.sub.2).sub.z where R.sub.8, R.sub.9 and R.sub.10 are independently C.sub.1 to C.sub.12 alkyl or C.sub.1 to C.sub.12 alkoxy and z is 1 to 10; methacrylonitrile, maleic anhydride, fumarate derivatives such as fumaronitrile, dialkylfumarate and fumaric acid; methacrylamide derivatives of the formula CH.sub.2 =C(CH.sub.3)CON(R).sub.2 wherein each R is independently H, C.sub.1 to C.sub.10 alkyl or (CH.sub.2).sub.n Z, n is an integer from 1 to 10, Z is COOY, OH, N(R.sub.1).sub.2, SO.sub.3 Y and Y is H, Li, Na, K, or N(R).sub.4 ; vinyl esters and acetates of the formula CH.sub.2 =CHOOCR, wherein R is C.sub.1 to C.sub.12 alkyl; and any and all monomer mixtures thereof. In the preferred embodiment, in which the monomer units of the polymer preferably is 80-100% by weight of methacrylate acid or alkyl esters or functional alkyl esters thereof, according to the above formula having J as a group, particularly preferred functional alkyl esters are those where J according to the above formula is hydrogen, glycidyl or hydroxy alkyl. In general herein, C.sub.1 to C.sub.10 moeities or groups are preferably C.sub.1 to C.sub.6 and usually most preferably C.sub.1 to C.sub.4.
The monomer (or comonomer) mixture may also comprise minor amounts of styrene and acrylates and derivatives thereof. In another embodiment, the monomer mixture may comprise up to 20% by weight of the following monomers: vinyl halides of the formula CH.sub.2 =CHX wherein X is Cl or F, vinylidene halides of the formula CH.sub.2 =C(X).sub.2 wherein each X is independently C1 or F, substituted butadienes of the formula CH.sub.2 =C(R)C(R)=CH.sub.2 wherein each R is independently H, C.sub.1 to C.sub.10 alkyl, Cl or F, ethylenesulfonic acid derivatives of the formula CH.sub.2 =CHSO.sub.3 X wherein X is Na, K, Li, N(R).sub.4, H, R or (CH.sub.2).sub.n Z where n is an integer from 1 to 10, Z is COOY, OH, N(R).sub.2, or SO.sub.3 Y, Y is H, Li, Na, K or N(R) and R is independently C.sub.1 to C.sub.10 alkyl, acrylamide derivatives of the formula CH.sub.2 =CHCON(R).sub.2 wherein each R is independently H, C.sub.1 to C.sub.10 alkyl, or (CH.sub.2).sub.n Z, n is an integer from 1 to 10, Z is COOY, OH, N(R.sub.1).sub.2 or SO.sub.3 Y and Y is H, Li, Na, K or N(R.sub.1).sub.4 where R is C.sub.1 to C.sub.10 alkyl. As indicated above, at least a portion of the monomers carry functional groups which can serve as crosslinking sites. Suitably, 2.0 to 100 percent by weight of the comonomers have a reactive functionality or a mixture of reactive functionalities, for example hydroxy plus silyl. Preferably, 5 to 60% of the monomers have a reactive functionality or a mixture of reactive functionalities, most preferably 20 to 40%. The functional monomer may be selected from the foregoing monomers which have functional groups. Preferred functional groups are hydroxy, epoxy, anhydride, carboxy (acid), acetoacetoxy, silyl, amide, and isocyanato. In certain preferred embodiments, the crosslinkable functional groups, in the copolymers according to the present invention, are hydroxy, epoxy, silyl, carboxy, or combinations thereof.
The methacrylates described above would thus include branched, unbranched, or cyclical alkyl or n-alkyl esters of C.sub.1 -C.sub.12, alcohols (for example, methyl and ethyl methacrylate), methacrylic acid, and allyl, glycidyl, hydroxyalkyl (for example, hydroxyethyl and hydroxypropyl), allyloxyethyl, 2,4-hexadienyl (sorbyl), dialkylaminoalkyl, fluoroalkyl, and trialkylsilylalkylene methacrylates. In general, preferred alkyls have 1 to 6 carbon atoms.
As one skilled in the art would recognize, however, each monome must have polymerizing compatibility with any adjacent monomers. "Polymerizing compatibility: as used herein, is determined by taking into account the steric and electronic properties of particular monomers. The polymerizing compatibility of various monomers is well-documented in the art. See, e.g., Young, L. H. "Copolymerization Reactivity Ratios" in Polymer Handbook, J. Brandrup and E. H. Immergut, eds., John Wiley & Sons, Inc. (1975). For example, α-methyl styrene does not have polymerizing compatibility with itself in free radical polymerizations above 60 C. and therefore cannot form homopolymers under these conditions. Thus, in the copolymer, α-methyl styrene may not occur adjacent to another α-methyl styrene under such reaction conditions. Also, maleic anhydride, fumaronitrile, dialkyl fumarate and fumaric acid do not have any polymerizing compatibility with themselves or with each other via free radical polymerization. Thus, for example, in the copolymer, maleic anhydride may not occur adjacent to another maleic anhydride, fumaronitrile, dialkyl fumarate or fumaric acid.
The present chain transfer agents (as well as the macromolecules or polymers produced thereby) include those having the following end group: ##STR1## where X is -CONR.sub.2, -COOR, OR.sup.1, -OCOR, -OCOOR.sup.1, -NRCOOR.sup.1, halo, cyano, or a substituted or unsubstituted phenyl or aryl, wherein each R is independently selected from the group of hydrogen, silyl, or a substituted or unsubstituted alkyl, alkyl ether, phenyl, benzyl, or aryl, wherein said groups may be substituted with epoxy, hydroxy, isocyanato, cyano, amino, silyl, acid (-COOH), halo, or acyl; and wherein R.sup.1 is the same as R except not H; wherein each alkyl is independently selected from the group consisting of branched, unbranched, or cyclical hydrocarbons having 1 to 12, preferably 1-6, and most preferably 1-4 carbon atoms; halo or halogen refers to bromo, iodo, chloro and fluoro, preferably chloro and fluoro, and silyl includes--SiR.sup.2 (R.sup.3)(R.sup.4) and the like, wherein R.sup.2,R.sup.3, and R4 are independently alkyl, phenyl, alkyl ether, or phenyl ether, preferably at least two of R.sup.2, R.sup.3, and R.sup.4 being a hydrolyzable group, more preferably two of which are alkyl ether, wherein alkyl is as defined above, preferably methyl or ethyl. A plurality of silyl groups may be condensed, for example, an organopolysiloxane such as -Si(R.sup.2).sub.2 -O-Si(R.sup.3).sub.2 R.sup.4, wherein R.sup.2, R.sup.3, and R.sup.4 are independently alkyl. See U.S. Pat. No. 4,5 18,726 for silyl groups in general.
A preferred class of oligomeric chain transfer agents for use in preparing compositions according to the present invention are those oligomers according to above structure in which X is -CONR.sub.2, -COOR, unsubstituted or substituted phenyl, aryl, halo, or cyano, and R is as defined above.
Preferably, the oligomers employed in the present invention, as well as the macromonomers and polymers produced thereby, are characterized by the following end group: ##STR3## wherein X.sup.1 and X.sup.2 are independently (the same or different) X as defined above.
The general chemical structure of suitable oligomers for use in the present invention is described below where n=2 to 100 on average. ##STR4## wherein X.sup.1 to X.sup.n is independently defined as above for X and n is on average 2 to 100, preferably 2 to 20.
For example, a general formula for a methacrylate oligomer is as follows: ##STR5## wherein R.sup.1 to R.sup.n are independently (the same or different) and defined as above for R and n is on average 2 to 20, preferably 2 to 7.
As a further very specific example, a methyl methacrylate trimer, wherein n equals 3 and R equals -CH.sub.3, is as follows. ##STR6##
When employing a cobalt chelate in the preparation of the present oligomers, it may be feasible to remove cobalt as well as any color from the reaction product by precipitation with a solvent and the subsequent use of activated charcoal. For example, the addition of ethyl acetate (Rhone-Poulenc AR grade, 99.5%, 0.005% acetic acid) in various proportions has been found to cause substantial precipitation of cobalt as a dark brown solid and therefore decreased color in the final solution. Other precipitating solvents include a mixture of acetone and ater and a mixture of acetonitrile and water. Color may be further removed by classical techniques, for example, simple treatment with activated charcoal for about 15 minutes followed by filtration though a short column packed with CELITE�545 filter aid.
The kind of reaction sequence which is preferably employed for preparing the oligomeric chain transfer agents, although with reference to the particular case where X is -GOOCH.sub.3 in the above formula, is illustrated as follows. ##STR8## wherein "M" is a metal chelate catalytic chain transfer agent such as one of the cobalt complexes known to those of skill in the art.
The polymerization process in which polymers or copolymers are produced for use in the present compositions, which process employs the above described oligomeric chain transfer agents, is suitably carried out at 20 200 50
For example, a hydroxy terminated polymer of methyl methacrylate, having a molecular weight (M.sub.n) of 2000 (DP=20), could be produced by polymerizing methyl methacrylate monomer with a hydroxyl containing radical initiator in the presence of an oligomer made from hydroxyethyl methacrylate having a DP equal to 2. The chain transfer process, by definition, terminates the growing radical chain. A specific end group is placed at the end of the polymer which in this case is a hydroxyethyl methacrylic group. In concert with this transfer, a hydroxymethacrylate radical is produced, which becomes the new propagating radical.
______________________________________           Parts by           Weight______________________________________Part 1Ethyl acetate     248.66Methyl methacrylate             499.07Part 2Ethyl acetate     87.25Catalyst*         0.3540Part 3Methyl methacrylate             1996.71Part 4VAZO 52           19.62Ethyl acetate     848.33______________________________________ *diaquobis (borondifluorodiphenylglyoximato) cobaltate (II) Part 1 was charged to the reactor and heated to 80 temperature stabilized at 80 as a single shot feed. Part 3 (the monomer feed) and Part 4 (the initiato feed) were added concurrently, except that Part 3 was added over 240 minutes and Part 4 was added over 300 minutes. When the initiator feed in complete, the reaction mixture is held for 30 minutes. The solvent and unreacted monomer are then distilled off.
______________________________________          Parts by          Weight______________________________________Part 1Ethyl acetate    248.66Ethyl methacrylate            250.00Butyl methacrylate            250.00Part 2Ethyl acetate    87.25Catalyst*        0.3540Part 3Ethyl methacrylate            998.36Butyl methacrylate            998.36Part 4VAZO 52          19.62Ethyl acetate    648.33______________________________________ *diaquobis (borondifluorodiphenylglyoximato) cobaltate (II) Part 1 was charged to the reactor ahd heated to 80 temperature stabilized at 80 as a single shot feed. Part 3 (the monomer feed) and Part 4 (the initiato feed) were added concurrently, except that Part 3 was added over 240 minutes and Part 4 was added over 300 minutes. When the initiator feed in complete, the reaction mixture is held for 30 minutes. The solvent and unreacted monomer are then distilled off.
______________________________________              Wt. (g)______________________________________Part 1Ethyl acetate        248.66Glycidyl methacrylate (GMA)                499.07Part 2Ethyl acetate        87.25Catalyst*            2.50Part 3GMA                  1996.71Part 4VAZO � 52         19.62Ethyl acetate        648.33______________________________________ *diaquobis (borondifluorodiphenylglyoximato) cobaltate (II) Part 1 was introduced into reactor and heated to 80 charged to the reactor in a single shot. When temperature stabilized, Par 3 and 4 were charged to the reactor over 240 and 300 minutes, respectively. At the completion of adding Part 3, the reactor was held at temperature for 30 minutes before cooling.
______________________________________            Wt. (lb)______________________________________Monomer FeedMPTMS              636.74Co(II)(DPG-BF.sub.2).sub.2 2H.sub.2 O              0.26Initiator Feed 1VAZO 52            3.95Toluene solvent    80.74Initiator Feed 2VAZO � 52       3.95Toluene solvent    80.74______________________________________
The present continuous stirred tank acrylic polymerization process is comprised of three in-series 10 gallon reactors. Reactor 1 & 2 are filled with toluene solvent and brought up to reflux. Part 1 (monomer and cobalt complex) are fed into Reactor 1 at 0.79 lb/minute for 806 :minutes. Part 2 (Initiator Feed 1) and Part 3 (Initiator Feed 2) are delivered to Reactor 1 and 2, respectively, concurrently with the Part 1, each at 0.1.69 lb/minute for 500 minutes. Reactor 3 is held at 110 solvent.
______________________________________               Wt.______________________________________Monomer FeedHEMA                  59.05MMA                   1476.4Initiator Feed for Reactor 1VAZO � 52          49.2MEK (methyl ethyl ketone) solvent                 486.1Co(II)(DPG-BF.sub.2).sub.2 2H.sub.2 O                 1.2Initiator Feed for Reactor 2 and 3VAZO � 52          196.9MEK solvent           1944.3______________________________________
EXAMPLE 6 This example illustrates a method of preparing an epoxy resin consisting of GMA/STY/BMA/BA in the weight ratio of 30: 17.5: 35: 17.5 in which the aforesaid acronyms respectively respresent glyicidyl methacrylate, styrene, butyl methacrylate, and butyl acrylate. The chain transfer agent comprised glycidyl methacrylate, that is, the chain transfer agent was glycidyl (epoxy) functional. A one liter reactor was equipped with a stirrer, thermocouple, and condensor. The reactor was held under nitrogen positive pressure and the following components were introduced, as explained below.
Part I was charged into the reactor and heated to 120 minutes. The temperature was increased to 130 III were fed concurrently into the reactor over 300 and 240 minutes, respectively. After completing the addition of Part II, the reactor contents were held at 130 solids content was measured at 68.7%. The macromonomer product had an M.sub.n of 1736 and an M.sub.w of 5460. The Brookfield viscosity at 22.2.degree. C. was measured (at 20 RPM) at 4.0 poise and (at 50 RPM) at 3.9 poise.
EXAMPLE 7 This example illustrates a method of preparing a resin consisting of GMA/STY/BMA/BA in the weight ratio of 33: 17: 33: 17 in which the aforesaid acronyms respectively respresent glyicidyl methacrylate, styrene, butyl methacrylate, and butyl acrylate. The chain transfer agent comprised glycidyl methacrylate, that is, the chain transfer agent was glycidyl (epoxy) functional. A one liter reactor was equipped with a stirrer, thermocouple, and condensor. The reactor was held under nitrogen positive pressure and the following components were introduced, as explained below.
Part I was charged to the reactor and heated to 120 minutes. The temperature was then increased to 130 and III were fed concurrently to reactor over 300 and 240 minutes, respectively. After completing the addition of Part II, the reactor contents were held at 130 solids content was measured at 69.8%. The macromonomer product had a number average molecular weight (Mn) of 1967 and an weight average molecular weight (M.sub.w) of 5681.
EXAMPLE 8 This example illustrates the use of the epoxy resin, according to Examples 6 and 7, in a clearcoat composition. The following components were thoroughly mixed:
______________________________________Epoxy   Film                      SolventResin   Build   Bake       Hardness                             ResistanceExample (mils)  (                      (Knoop)                             (MEK rubs)______________________________________6       2.7     265/30     7.2    7 @ 100 rubs   2.1     285/30     7.1    8 @ 100 rubs7       3.1     265/30     9.1    5 @ 100 rubs   2.3     285/30     8.1    8 @ 100 rubs______________________________________
EXAMPLE 9 This example demonstrates the use of acrylosilane oligomer comprising trimethoxysilypropyl methacrylate (MPTMS) monomeric units to make acrylosilane functional polymer. This copolymer is than formulated into a coating finish which utilizes the hybrid crosslinking chemistry of an acrylosilane polymer and a hydroxy-melamine. The acrylosilane copolymer was the polymerization reaction of the a monomer mixture consisting of STY/MPTMS/MMA/BMA/2-EHA in the ratio of 35.2: 36.5: 17: 5.67 5.67, respectively, as described below.
Part I was charged to a glass reactor equipped with a stirrer, thermocouple, nitrogen positive pressure and a condenser. The mixture was heated to 120 80 reactor over 360 and 240 minutes, respectively. Upon completing the addition of Part II, the reactor was held at 80 additional 60 minutes and cooled to ambient temperature.
COMPARATIVE EXAMPLE 10 This example illustrates the synthesis of a typical acrylosilane resin without the use of the present oligomeric chain transfer agents. This copolymer was then formulated into a coating finish which utilized the hybrid crosslinking chemistry of acrylosilane and hydroxy-melamine components. The acrylosilane copolymer was synthesized as the polymerization product of the monomers STY/MPTMS/MMA/BMA/2-EHA in the ratio of 20:52: 16:6:6.
______________________________________                   Wt.______________________________________Part IXylene                    65.1Hydrocarbon solvent (b. p. range = 150-160                     97.6Part IIStyrene (STY)             119.0n-Butyl methacrylate (BMA)                     35.62-Ethyl hexylacrylate (2-EHA)                     35.6Methy methacrylate (MMA)  95.2Trimethoxysilypropyl methacrylate (MPTMS)                     309.3Hydrocarbon solvent (b. p. range = 150-160                     9.2Xylene                    15.3Part IIIt-Butylperoxyacetate (70% in mineral spirits)                     31.3Hydrocarbon solvent (b. p. range = 150 = 160                     22.3Xylene                    22.3______________________________________
Part I was charged to a glass reactor equipped with stirrer, thermocouple, nitrogen positive pressure and condenser and heated to 148 reactor over 360 and 420 minutes, respectively. Upon completion of the introduction of Part III, the reactor was held at reflux for an additional 60 minutes and cooled to ambient temperature.
EXAMPLES 11-12 This example illustrates a coating formulation 11 and a comparative coating formulation 12 prepared using the acrylosilane polymers of previous Example 9 and comparative Example 10, respectively. The formulations contained the following thoroughly mixed components:
______________________________________                Example  ComparativeComponent            11       Example 12______________________________________Acrylosilane resin solutionExample 9            192.42   --Comparative Example 10                --       192.42NAD Resin Solution (70% solids)                25.51    25.51Tinuvin � 123 stabilizer                4.63     4.63Tinuvin � 1130 stabilizer                4.63     4.63Acrylic polyol resin soln. (71.5% solids)                109.04   109.04NAD resin soln. (65.5% solids)                104.05   104.05DDBSA/AMP soln. (33.8%)                8.12     8.12TMOA                 15.68    15.68Methyl alcohol       14.25    14.25Cymel � 1168 melamine formaldehyde                19.53    19.53resinResiflow � S (flow control agent)                1.43     1.43(50% in hydrocarbon solvent)Dibutyl tin dilaurate                0.71     0.71______________________________________
______________________________________    Bake       Hardness Acid Etch*Example  (               (Knoop)  Spot Free Temp.______________________________________11       265/30     7-8      11712       265/30     7-8      118______________________________________ *Spot Free Temperature is the temperature ( sulfuric acid will not etch the fully cured film.
EXAMPLE 13 These examples illustrate acrylic polymerization of a reaction mixture of STY/nBA/HPA/pMMA oligomer, in the respective ratio of 15:30-X: 17:38: X, where STY is styrene monomer, nBA is n-butyl acrylate, HPA is hydroxypropylacrylate, and pMMA is a poly(methyl methacrylate) ω-unsaturated oligomeric chain transfer agent. The following components were used:
Part 1 is charged to a reactor equipped with a stirrer, thermocouple, nitrogen positive pressure and a condensor. The reaction mixture is heated to 110 reactor over 360 minutes. Part 3 is charged to an initiated feed vessel, premixed, and added to the reactor over 375 minutes concurrenly with the monomer feed. Following completion of the initiator feed, the reaction mixture is held for 60 minutes. The results are shown in Table 1 below.
EXAMPLE 14-16 These examples illustrate the preparation of a copolymer made from a mixture of STY/HEMA/IBMA/MMA/pMMA oligomer in the respective ratio of 15:20: 45:20-X: X, wherein STY is styrene, HEMA is hydroxyethyl methacrylate, IBMA is isobutyl methacrylate, and MMA is methyl methacrylate monomer. The oligomer pMMA is poly(methyl methacrylate) which is a ω-unsaturated oligomeric chain transfer agent.
EXAMPLES 17-18 This example illustrates the preparation of a hydroxy functional polymer employing an ethyl methacrylate oligomer as a chain transfer agent. For the control, the following components were used:
In the above list, LMA stands for lauryl methacrylate, MAK stands for methyl amyl ketone, and TBPA stands for t-butyl peroxyacetate (75% in mineral spirits). Part I is charged to a 5 liter flask and heated to reflux at 149 constant rate over 300 minutes with Part 3. Part 3 is also premixed and added with Part 2 at a constant rate over 310 minutes. After completing the addition of Parts 2 and 3, the reaction mixture is held under reflux 30 minutes at 145 mixture cooled to 55
Part 1 is charged to a 5 liter flask and heated to reflux at 149 over 300 minutes with Part 3. Part 3 is premixed and added with Part 2 at a constant rate over 310 minutes. After the completion of addition of Pans 2 and 3, the reaction mixture is held under reflux for 30 minutes at 145 55
EXAMPLE 19 This example illustrates the preparation of an acrylic polyol for use in a composition according to the present invention and a comparative acrylic polyol. The polyol is prepared with or without an oligomeric chain transfer agent which consists of hydroxy, ethyl methacrylate/methyl methacrylate (HEMA/MMA) monomeric units in the weight ratio of 80: 20. The acrylic polyol had an overall composition of isobornyl methacrylate (IBOMA)/hydroxyethyl methacrylate (2-HEMA)/2-ethylhexyl methacrylate (2-EHMA)/styrerie (STYRlEE)/isobutylmethacrylate (IBMA)/methylmethacrylate (MMA) in the weight ratio, respectively, of 50.0/27.5/16.38/2.05/2.03/2.05. The polyol was prepared by continuous polymerization employing the following reactants, inititiator, and solvents.
The continuous stirred tank acrylic polymerization process is comprised on three 1000 ml in-series reactors. Reactor 1, 2 and 3 are filled with MAK (methyl amyl ketone) solvent. Reactors 1 and 2 are brought to 165 C. and Reactor 3 Reactor 1 at a rate of 199.76 g/min. The initiator feed for Reactor 1 is delivered, concurrently with the monomer fee, at a rate of 24.05 g/min. Initiator Feed 2 is delivered to Reactor 2 at a rate of 3.07 g/min. Initiator Feed 3 is delivered to Reactor 2 at a rate of 18.20 g/min. The product is collected as it flows out Reactor 3.
EXAMPLE 20 This experiment shows the comparative results for the use of an acrylic polymer prepared according to Example 19 above, which polymer was made with a HEMA/MMA oligomeric chain transfer agent (CTA), as compared to a control in which the acrylic polyer was made without the use of the chain transfer agent. The comparative results are as follows:
______________________________________                   Parts by                   Weight______________________________________Part I (Enamel)Acrylic Resin             47.27Propylene glycol monomethyl ether acetate                     3.08Methyl amyl ketone        3.70Tinuvin 292 HALS (Ciba-Geigy)                     .70Tinuvin 328 UV Absorber (Ciba-Geigy)                     .70Resiflow                      .17Siloxane solution         .86Dibutyl tin dilaurate solution                     1.66Butyl acetate             .03BYK                      .03Black tint (dispersion)   41.68                     100.00Part II (Isocyanate Activator)Polyisocyanate (Desmodur                      23.37Butyl acetate             7.05Hydrocarbon solvent (Hydrosol                      1.30Diisobutyl ketone         1.77Ethyl acetate             2.31                     35.80Part III (Reducer)Methyl ethyl ketone       1.65Butyl acetate             5.17Butyl cellosolve acetate  .83Methyl amyl ketone        .62                     8.27______________________________________
______________________________________  Time  Zahn #2 Sec______________________________________  Initial        25  1 Hour        31  2 Hour          3 Hour        ______________________________________
______________________________________Part I (Enamel)Acrylic Resin (prepared in Example 3 above)                     47.27Propylene glycol monomethyl ether acetate                     3.08Methyl amyl ketone        3.70Tinuvin 292 HALS (Ciba-Geigy)                     .70Tinuvin 328 UV absorber (Ciba-Geigy)                     .70Resiflow Siloxane solution         .86Dibutyl tin dilaurate solution                     1.66Butyl acetate             .03BYK Black tint (dispersion)   41.68                     100.00Part II (Isocyanate Activator)Polyisocyanate (Desmodur                      23.37Butyl acetate             7.05Hydrocarbon solvent (Hydrosol                      1.30Diiobutyl ketone          1.77Ethyl acetate             2.31                     35.80Part III (Reducer)Methyl ethyl ketone       1.65Butyl acetate             5.17Butyl cellosolve acetate  .83Methy amyl ketone         .62                     8.27______________________________________
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Du Pont De Nemours And CompanyCoatings that contain reactive silicon oligomersUS6121364 *Apr 24, 1996Sep 19, 2000Zeneca LimitedBinder resin, process for its manufacture and composition containing itUS6174953Jan 29, 1999Jan 16, 2001E. I. Du Pont De Nemours And CompanyLow molecular weight (meth) acrylate copolymer emulsionsUS6329489Dec 20, 1999Dec 11, 2001E. I. Du Pont De Nemours And CompanyProcess for producing reactive silane oligomersUS6399731Dec 2, 1998Jun 4, 2002The University Of AkronChain transfer agents and its use in polymer synthesisUS6503975Mar 29, 2000Jan 7, 2003E. I Du Pont De Nemours And CompanySurfactant free aqueous emulsionsUS6872789Nov 7, 2002Mar 29, 2005Akzo Nobel N.V.Cross-linkable polymer compositionUS7034085Jul 15, 2003Apr 25, 2006Nuplex Resins, B.V.Method for polymerizing ethylenically unsaturated monomers by degenerative iodine transferUS7998115 *Feb 15, 2007Aug 16, 2011Baxter International Inc.Dialysis system having optical flowrate detectionEP1211269A1 *Feb 28, 2000Jun 5, 2002Sekisui Chemical Co., Ltd.Acrylic copolymer, acrylic pressure-sensitive adhesive composition, acrylic pressure-sensitive adhesive tape or sheet, and acrylic adhesive compositionWO2003040192A2 *Nov 5, 2002May 15, 2003Akzo Nobel NvCross-linkable polymer compositionWO2004009648A2 *Jul 8, 2003Jan 29, 2004Akzo Nobel NvMethod for polymerizing ethylenically unsaturated monomers by degenerative iodine transfer* Cited by examinerClassifications U.S. Classification525/377, 526/217, 526/213, 526/204, 526/209, 526/207, 526/194, 526/206, 526/215, 526/201International ClassificationC08F2/42, C08F220/10, C09D157/00, C08F2/16, C08F2/38, C08F2/18, C08F20/18Cooperative ClassificationC08F2/38European ClassificationC08F2/38Legal EventsDateCodeEventDescriptionMay 12, 2006FPAYFee paymentYear of fee payment: 12May 16, 2002FPAYFee paymentYear of fee payment: 8May 19, 1998FPAYFee paymentYear of fee payment: 4Jan 7, 1994ASAssignmentOwner name: E. I. DU PONT DE NEMOURS AND COMPANY, DELAWAREFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BERGE, CHARLES T.;DARMON, MICHAEL J.;ANTONELLI, JOSEPH A.;REEL/FRAME:006822/0559Effective date: 19931020RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google