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WO2001096291A1 - Polymercaptans a multireactivite, polymeres en forme d'etoiles et procedes de preparation - Google Patents

Polymercaptans a multireactivite, polymeres en forme d'etoiles et procedes de preparation Download PDF

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Publication number
WO2001096291A1
WO2001096291A1 PCT/US2000/015109 US0015109W WO0196291A1 WO 2001096291 A1 WO2001096291 A1 WO 2001096291A1 US 0015109 W US0015109 W US 0015109W WO 0196291 A1 WO0196291 A1 WO 0196291A1
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Prior art keywords
ethylenically unsaturated
acrylate
meth
polymer
residue
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PCT/US2000/015109
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English (en)
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Paul M. Petersen
Robert D. Harlan
Jules E. Schoenberg
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National Starch And Chemical Investment Holding Corporation
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Priority to PCT/US2000/015109 priority Critical patent/WO2001096291A1/fr
Priority to AU2000254565A priority patent/AU2000254565A1/en
Priority to EP00939486A priority patent/EP1289946A1/fr
Publication of WO2001096291A1 publication Critical patent/WO2001096291A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • Star-branched polymers also known as radial polymers, are characterized by having three or more polymeric arms emanating from a central core. These polymers can be prepared by various polymerization procedures such as anionic, cationic, and free radical mechanisms. The stars are usually formed by using either multifunctional initiators, multifunctional chain transfer agents, or multifunctional coupling agents.
  • the star-branched polymers have unique properties including: narrow molecular weight distributions; low viscosities at low molecular weights or in solution due to their compact structures; high viscosities at high molecular weights due to extensive entanglements.
  • Heteroarm star polymers have been prepared using free radical methods involving partially capping a polythiol, typically by acetylation, grafting from the uncapped SH groups, removing the blocking group by hydrolysis, and then grafting the second monomer off of the liberated SH groups.
  • U.S. Patent No. 5,679,762 discloses the preparation of heteroarm star copolymers by free radical polymerization using sequential addition of monomers. This process relies solely upon the order of addition of monomers for its selectivity.
  • the present invention improves over the methods of the prior art by using chain transfer agents containing thiol groups with multiple reactivities.
  • the selectivity is controlled by both the order of addition of the monomers and the composition of the polymercaptan core. Hence, greater control over the blockiness of the heteroarm star results.
  • the present invention is directed to multireactivity polymercaptan cores, star-shaped polymers and methods of preparing such polymers.
  • the star polymers of the present invention comprise a polyvalent mercaptan core and three or more polymeric arms which extend radially from the core.
  • the polyvalent mercaptan core comprises three or more thiol groups. In one embodiment at least two of the thiol groups are of different reactivities. Such cores will be referred to as cores of differential reactivity or heterocores.
  • the polymers of the present invention are prepared by a process which utilizes cores of differential reactivity having three or more SH groups, wherein at least two of the thiol groups have different chain transfer constants. These cores of differential reactivity, act as chain transfer agents in a free radical polymerization process to produce a star polymer.
  • Figure 1 is a graph of viscosity as a function of percent acrylic acid.
  • Figure 2 is a graph of 20 minute peel as a function of percent acrylic acid.
  • Figure 3 is a graph of 24 hour peel as a function of percent acrylic acid.
  • Figure 4 is a graph of loop tack as a function of percent acrylic acid.
  • Figure 5 is a graph of shear hold as a function of percent acrylic acid.
  • the star polymers of the present invention comprise a polyvalent mercaptan core and three or more polymeric arms which extend radially from the core.
  • the compositions of the arms themselves may be random, blocks or homopolymers.
  • the polyvalent mercaptan core of the present invention comprises three or more thiol groups, wherein at least two of the thiol groups are of different reactivities, such that the core is of differential reactivity or a heterocore. It is at the thiol groups that the monomers will react to create the polymeric arms of the star polymer. Cores comprising thiol groups, all of which are of the same composition and reactivity will be referred to as homocores.
  • the polyvalent mercaptan core comprises a central component, derived from a multifunctional alcohol which has been substituted with thiol derivatives.
  • the multifunctional alcohol can have any number of functional hydroxy units, preferably 3 to 8 functional units.
  • each of the OH functional units will be substituted with thiol units, preferably at least 2 of which are of different compositions.
  • the polyvalent mercaptan core is of the general formula:
  • X is derived from a tri- to octa- multi-functional alcohol such as glycerol, sorbitol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and inositol.
  • a tri- to octa- multi-functional alcohol such as glycerol, sorbitol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and inositol.
  • Variables Y 1? Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 are the same or different and each comprises C 2 . 10 alkanoic acids, preferably C 2 . 6 alkanoic acids.
  • Variables a and b are integers from 1 to 8 and variables c, d, e, f, g and h are integers from 0 to 8, provided that a+b+c+d+e+f+g+h ⁇ 8.
  • Each of the above identified (Y-SH) units are derived from, for example, 2- mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4- mercaptobutyric acid, 5-mercaptopentanoic acid, or 6-mercaptohexanoic acid. Preferred are 2-mercaptopropionic acid and 3-mercaptopropionic acid.
  • Examples of cores of differential reactivity within the scope of the present invention include pentaerythritol bis(3-mercaptopropionate) bis(2-mercaptopropionate); trimethylolpropane bis(3-mercaptopropionate)(2-mercaptopropionate); pentaerythritol tris(3-mercaptopropionate)(2-mercaptopropionate); and trimethylolpropane bis (2- mercaptopropionate) (3-mercaptopropionate).
  • cores of non-differential reactivity include pentaerythriol tetrakis(3-mercaptopropionate), trimethylolpropane trithiopropionate, tris(3- mercaptopropionate), pentaerythritol tetrakis(thioglycolate) and dipentaerythhtol hexakis(thioglycolate).
  • the polyvalent mercaptan core is prepared by reacting a multi-functional alcohol with the appropriate amount of mercapto acid to prepare the polyvalent mercaptan core.
  • the multifunctional alcohol is a tri-alcohol
  • three equivalents of mercapto acid are added to give three (HS-Y) units.
  • the three equivalents of mercapto acid can be made up of any combination of the preferred mercapto acids. For example, one equivalent of 2-mercaptopropionic acid (a secondary thiol-containing acid) and two equivalents of 3-mercaptopropionic acid (a primary thiol-containing acid) will provide a core of differential reactivity.
  • pentaerythritol can be used as the multifunctional alcohol, X, used to prepare the core.
  • X the multifunctional alcohol
  • To pentaerythritol is added 2 mole equivalents each of a primary thiol, 3-mercaptopropionic acid, and a secondary thiol, 2-mercaptopropionic acid.
  • the result will be a mixture of five compounds corresponding to molecules containing ratios of primary/secondary SH groups of 0/4, 1/3, 2/2, 3/1, and 4/0.
  • Those cores with ratios of 1/3, 2/2 and 3/1 are cores of differential reactivity and are within the scope of the present invention.
  • the cores with ratios of 0/4 and 4/0 are homocores.
  • the product mixture though a statistical mixture, has cores with an average of two primary thiol groups and two secondary thiol groups per core as shown by the following reaction:
  • dipentaerythritol seven possible compounds can be obtained corresponding to 0,1 ,2,3,4,5 and 6 primary SH groups per molecule. These differential thiols will be utilized to provide enhanced selectivity to generate heteroarm stars.
  • a homocore can be prepared by adding 4 mole equivalents of thiol to pentaerythritol to prepare a homocore:
  • the star polymers of the present invention are formed using the mercaptan core as a chain transfer agent in polymerization processes which include bulk, solution, emulsion, and suspension polymerization.
  • the process is a solution polymerization process employing a free radical initiator.
  • the polymerization reaction is typically conducted at temperatures in the range of 10 to 120°C, preferably 70 to 100°C.
  • the resulting polymer may comprise arms that are all different, or some different, or all the same after the S atom but with different Y connecting groups.
  • the preparation of the star polymers of the present invention is by the non-sequential addition of monomers to a core of differential reactivity. During the process of this embodiment, all of the monomers are added at the same time, i.e., a mixture of two or more monomers are added to the core. The monomers with the higher reactivity ratios in copolymerization will react with the most reactive thiol groups. The polymerization is initiated by a mercapto group on the polyvalent mercaptan core.
  • the preparation of the star polymers is by sequential addition of the monomer to the core of differential reactivity.
  • the monomer that is added first will tend to react with the more reactive SH groups. It is preferred that such monomers have a chain transfer constant close to one, i.e., acrylates and methacrylates.
  • the monomers added next will react with the less reactive SH groups.
  • the orders of reactivity of thiol groups are: SH groups attached to aromatic rings (i.e., thiophenols) are more reactive than SH groups attached to primary aliphatic carbon atoms which are more reactive than SH groups attached to secondary aliphatic carbon atoms, i.e., ArSH>RCH 2 SH> RR'CHSH.
  • the polyvalent mercaptan and a first polymerizable unsaturated monomer mixture are radically polymerized.
  • the first monomer mixture could be a single monomer or a mixture of two or more monomers.
  • This polymerization is initiated by a mercapto group on the polyvalent mercaptan core via a standard chain transfer reaction. Because the polyvalent mercaptan group comprises thiol groups of different reactivities, these first monomers will preferably react with the most reactive thiols.
  • the next step comprises the addition of a second polymerizable unsaturated monomer mixture to the product from the first radical polymerization.
  • the second monomer mixture which may or may not be different from the first unsaturated monomer mixture, is then radically polymerized with the polyvalent mercaptan core. Again because of the different reactivities of the thiol groups on the core, the second monomers will preferably react with the thiol groups of second order of reactivity. This process can be repeated with third, fourth, etc., monomers until all of the thiol groups are reacted. Because of the differences in reactivity of the thiol there is a great deal of control of the blockiness of the final polymer. As used herein, blockiness indicates that the arms of the polymer differ in composition from one arm to the next.
  • the first arms formed are those emanating from the most reactive thiols, the next arms from the next most reactive, etc. Hence greater selectivity, which translates into better control of the blockiness of the polymer, results as compared to the method of U.S. Patent No. 5,679,762.
  • the monomer mixtures can be added by any method familiar to the skilled artisan including dropwise or by slug dose.
  • Monomers which may be used to prepare the polymeric arms of the star polymers of the present invention include olefinically unsaturated monomers selected from the group consisting of acrylic and methacrylic acids, acrylamide and methacrylamide, acrylonitrile and methacrylonitrile, alkoxyalkyl acrylamides and methacrylamides, e.g., butoxymethyl acrylamide and methoxymethyl methacrylamide, hydroxyalkyl acrylamides and methacrylamides, e.g., N-methylol acrylamide and methacrylamide, the metal salts of acrylic and methacrylic acids, and the esters of acrylic and methacrylic acids with alcohols and phenols; the vinyl aromatic compounds, e.g., styrene, alpha-methylstyrene and substituted derivatives thereof such as the halogenated derivatives thereof and vinyl toluene; the vinyl esters; vinyl amides, e.g., vinyl acetate and vinyl pyrrol
  • Monomers may be selected from hydroxyalkyl esters of ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acids, ethylenically unsaturated epoxides, ethylenically unsaturated isocyanates and combinations thereof.
  • unsaturated monomers include hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, and the like; vinyl ethers which are represented by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like; fumaric acid, monoalkyl fumarates, dialkyl fumarates; maleic acid, monoalkyl maleates, dialkyl maleates; itaconic acid, monoalkyl itaconates, dialkyl itaconates; half esters of succinic anhydride or phthalic anhydride with hydroxyethyl (meth)acrylate; (meth)acrylonitrile, butadiene, isoprene, vinyl chloride, vinylidene chloride, vinyl ketones, vinyl pyridine, vinyl carbazo
  • the present invention also contemplates the use of multifunctional monomers such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acry!ate, diethylene glycol di(meth)acrylate trisacrylate, divinyl benzene, triallyl cyanurate, allyl acrylate, diallyl phthalate, diallyl sucrose.
  • multifunctional monomers such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acry!ate, diethylene glycol di(meth)acrylate trisacrylate, divinyl benzene, triallyl cyanurate, allyl acrylate, diallyl phthalate, diallyl sucrose.
  • the preferred monomers are acrylic acid and methacrylic acid and derivatives such as esters and amides which have chain transfer constants with thiols that are close to one.
  • Examples of such monomers include acrylic and methacrylic acid and esters of acrylic acid and methacrylic acid such as methyl acrylate (“MA”), ethyl acrylate (“EA”), n-butyl acrylate (“BA”), 2-ethylhexyl acrylate (“EHA”), 2- hydroxyethyl acrylate, hydroxy propyl acrylate, isobomyl acrylate, methyl methacrylate (“MMA”), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, isobomyl methacrylate, 2- ethylhexyl methacrylate, benzyl methacrylate, phenyl methacrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate (“HPMA”).
  • Methyl methacrylate, 2-ethylhexyl acrylate, methyl acrylate, acrylic acid, butyl methacrylate, 2-hydroxyethyl acrylate and butyl acrylate are the most preferred monomers.
  • the polymer arm of the resulting polymer comprises 10 to 1500 monomer units, preferably 20 to 500.
  • the copolymer may be a block or random copolymer of such units.
  • the copolymer is a random copolymer as produced through conventional free radical polymerization.
  • Free radical initiators suitable for use in the polymerization process of the present invention include, for example: azo-based polymerization initiators such as 2,2'- azobisisobutyronitrile (“AIBN”) and 2,2'-azobis(cyclohexanecarbonitrile); peroxide-based polymerization initiators such as benzoyl peroxide; and the like.
  • azo-based polymerization initiators such as 2,2'- azobisisobutyronitrile (“AIBN”) and 2,2'-azobis(cyclohexanecarbonitrile)
  • peroxide-based polymerization initiators such as benzoyl peroxide
  • Suitable initiators include organic peroxides, hydroperoxides, persulfates and azo compounds such as methyl ethyl ketone peroxide, cumene hydroperoxide, potassium persulfate, lauroyl peroxide, 2,5- dimethyl-2,5-di(t-butylperoxy)hexane, diethyl peroxide, dipropyl peroxide, dilauryl peroxide, dioleyl peroxide, distearyl peroxide, di(tertiarybutyl) peroxide, di(tertiary amyl) peroxide, tertiary butyl hydroperoxide, tertiary amyl peroxide, acetyl peroxide, propionyl peroxide, lauroyl peroxide, stearoy' peroxi e, malonyl peroxide, succinyl peroxide, phthaloyl peroxide, acetyl benzoyl per
  • a solvent can be selected from the group consisting of organic solvents which are represented by: aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; cycloaliphatic hydrocarbons such as cyclohexane; aliphatic hydrocarbons such as hexane and pentane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aliphatic esters; alcohols; and the like.
  • organic solvents which are represented by: aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; cycloaliphatic hydrocarbons such as cyclohexane; aliphatic hydrocarbons such as hexane and pentane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl
  • Solution viscosities were determined on a Brookfield Model RVT viscometer operated at 25 rpm and 22°C.
  • the peel strength was measured from stainless steel panels in accordance with the Pressure Sensitive Tape Council ("PSTC"), Chicago, Illinois Test Method No. 1.
  • PSTC Pressure Sensitive Tape Council
  • "initial” peel represents a bonded time lapse of 20 minutes rather than the specified 1 minute.
  • "24 hrs OP" indicates a bonded time lapse of 24 hours and is indicative of the tendency for peel strength to increase with time after bonding.
  • the test strip backing is 0.002 inch thick PET (polyethylene terephthalate) film and the dry adhesive coating weight is 25 g/r ⁇ 2 .
  • the dry adhesive coatings are preconditioned overnight and then tested at 22°C and 50% R.H. The average test results are recorded in units of ounces per inch width.
  • the shear test is conducted in accordance with PSTC Test Method No. 7.
  • the coating preparation, preconditioning and test conditions are the same as for the peel test. Fifteen minutes elapsed time after bonding is allowed before attaching the load. A 1 kg weight is used on 1 square inch of bonded area giving 4.4 psi (nominally indicated as 4 psi in the Tables). The average time to failure is recorded in hours.
  • An octa-functional polymercaptan core with differential reactivity in accordance with the present invention was prepared in the following manner. To a one liter flask was added
  • a tetra-functional polymercaptan core with differential reactivity in accordance with the present invention was prepared in the following manner. To a two liter flask was added 68.1 grams of pentaerythritol (0.5 mol, 2 moles hydroxy groups), 116.8 grams of 2- mercaptopropionic acid (1.1 mol, 0.55 equivalents), 116.8 grams of 3-mercaptopropionic acid (1.1 mol, 0.55 equivalents) and 250 grams of toluene. A catalyst solution prepared from 1.5 grams of p-toluene sulfonic acid in 2 ml of water was added in a single shot. The mixture was stirred and heated to reflux, 115°C.
  • the reaction was driven by azeotropic removal of water using a Dean-Stark apparatus. Heating was discontinued once the theoretical amount of water had been removed. In this case, 38 ml of water was collected. After the reaction was complete, excess mercapto acid was neutralized with sodium bicarbonate. The solvent was then removed under vacuum to yield the multi-reactivity polymercaptan core.
  • a star polymer in accordance with the present invention was prepared in the following manner. Butyl methacrylate, 25 grams, and 6.5 grams bis(3-mercaptopropionate) bis(2-mercaptopropionate) pentaerythritol, prepared according to Example II, were added to
  • a star polymer was prepared from a non-multiple reactivity core in the following manner: Butyl methacrylate, 25 grams, and 6.5 grams pentaerythritol tetrakis(3-mercaptopropionate) were added to 200 grams ethanol, stirred and heated to reflux, approximately 80°C. To the mixture, half of an initiator solution (1.0 g azobisisobutyronitrile [AIBN] in 10 ml ethanol) was added. After approximately 90 minutes the heat was removed and 25 grams butyl acrylate and 150 grams acrylic acid along with the second half of the initiator solution were added. The mixture was stirred and heated for an additional two hours.
  • an initiator solution 1.0 azobisisobutyronitrile [AIBN] in 10 ml ethanol
  • control of the processing parameters are not so critical. This is because, on average, the multiple thiol cores have two thiol terminated arms that are relatively unreactive (secondary thiol) and two thiol terminated arms that are relatively reactive (primary thiol). The less reactive thiols will tend only to react when the second step monomer is added and the reaction allowed to proceed for the two hours. This ensures that all stars formed will contain both monomers in a blocky form.
  • the monomer mix was prepared and thoroughly mixed.
  • the initial charge was charged to a 3000 mL reaction flask, equipped with a condenser, paddle stirrer, thermometer, addition funnels and water bath.
  • the initial charge was heated to reflux and held for 5 minutes.
  • At reflux add very slowly 50% by volume of initiator solution to the flask contents.
  • monomer and initiator were slow added continuously and uniformly over 3 hours while maintaining reflux.
  • the flask contents were held at reflux for 2 hours.
  • the contents were then cooled to 25°C and analyzed for residual monomers, % solid, intrinsic viscosity and molecular weight, and the data shown below in Table I.
  • TYZOR GBA is a chelated titanium ester from DuPont.
  • Pentaerythritol tetrakis(3-mercaptopropionate) 1.25
  • the contents were cooled to 25°C and analyzed for residual 2-ethylhexyl acrylate ("2-EHA"), butyl acrylate (“BA”), methylacrylate (“MA”), hydroxypropyl methacrylate (“HPMA”), percent solid, intrinsic viscosity and molecular weight.
  • 2-EHA 2-ethylhexyl acrylate
  • BA butyl acrylate
  • MA methylacrylate
  • HPMA hydroxypropyl methacrylate
  • Stage-ll Urethane reaction and solvent strip: The reaction was carried out in the same flask with the same set-up with the addition of a CaCI 2 drying tube on top of the condenser.
  • the olefinic monomer 1-(1-isocyanato-1 -methyl ethyl)-3-(1 -methyl ethenyl)benzene (“m-TMI") 0.14 mmol/g of polymer was added to the base polymer solutions (1A, 1 B, 1C) and stirred for 10 minutes at 30°C.
  • Dibutyltin dilaurate catalyst 4.38x10 '4 g /g of polymer was added to the reaction mixture. The reaction mixture was stirred for an additional 10 minutes and heated to reflux for 12 hours. When the reaction was complete, the solvent was stripped under reduced pressure (10-30 mm Hg) at 95°C and the reaction product was discharged while still at approximately 80° to 90°C.
  • UV cure polymer Samples for UV curing polymers were prepared by adding 2% IRGACURE 184 (1 -hydroxycyclohexyl phenyl ketone) photoinitiator after the completion of the reaction and before vacuum stripping the solvent. Analytical properties for base polymers are listed in the following table:
  • EXAMPLE VII A mixture of acrylates in the ratio of 50 parts 2-ethylhexyl acrylate, 35 parts methyl acrylate and 10 parts butyl acrylate were polymerized with 5 parts hydroxypropyl methacrylate in the presence of different levels of (0.25 and 0.5 parts) tetrafunctional polymercaptan, pentaerythritol bis(2-mercaptopropionate) bis(3-mercaptopropionate) to give a polymer with 0.35 mmol hydroxy functionality per gram of polymer, base polymers 6A and 6B.
  • polymers were prepared by equimolar replacement of tetrafunctional polymercaptan with linear methyl 3-mercaptopropionate, and polymers without any chain transfer agent were prepared, samples 6C, 6D, 6E.
  • the procedure used for base polymer preparation and urethane reaction was same as listed for Example VI.
  • Samples 6A, 6C, 6B, 6D, 6E were functionalized with m-TMI and designated 6A-1 , 6C-1 , 6B-1 , 6D-1 , 6E-1 , respectively. Solvent was not removed, and the samples analyzed in a solution form. The results are shown below in Table 3. Samples 6A-1 and 6C-1 where cured at different energy levels, and the results shown in Table 4.
  • star polymer 6A-1 which has a lower apparent molecular weight, has better adhesive properties than the linear version of the same polymer.
  • star polymer 6A-1 has better pressure sensitive properties, peel adhesion and tack, than linear polymer 6C-1 which has the highest molecular weight among the series tested.
  • a mixture of acrylates in the ratio of 50 parts 2-ethylhexyl acrylate, 35 parts methyl acrylate and 10 parts butyl acrylate were polymerized with 5 parts hydroxypropyl methacrylate in the presence of different levels of (0.25 and 0.5 parts) tetrafunctional polymercaptan with dual reactivity, pentaerythritol bis(2-mercaptopropionate) bis(3- mercaptopropionate), to give a polymer with 0.35 mmol hydroxy functionality per gram of polymer.
  • Samples 7A and 7B respectively. The procedure used to make the polymer, by sequential addition of monomers, is described below.
  • Ethyl acetate, 2-EHA, HPMA and VAZO 67 an azo initiator available from DuPont were charged as an initial charge to the flask and heated to reflux. After 10 minutes of the reflux, started monomer slow add-1 containing 2-EHA, HPMA and polymercaptan over 1hour. Simultaneously initiator slow add-3 containing ethyl acetate ("EtOAc”) and VAZO 67 started over 4h. At the end of monomer slow add-1 , wait for 1 hour. Started monomer slow add-2 over 2 hour. At the end of slow adds, hold for 2 hour. The contents were cooled to 25°C and analyzed for residual 2-EHA, BA, MA, HPMA, percent solid, intrinsic viscosity and molecular weight.
  • EXAMPLE IX A mixture of acrylates in the ratio of 70 parts 2-ethylhexyl acrylate, 27.5 parts t- octyl acrylamide and 2.5 parts acrylic acid were polymerized in the presence of 0.65 parts tetrafunctional polymercaptan pentaerythritol bis(2-mercaptopropionate) bis(3- mercaptopropionate), to yield a heterocore star polymer.
  • the same monomer composition was polymerized in the presence of equimolarly substituted linear methyl 3-mercaptopropionate to provide a linear control polymer.
  • the reagents and procedure for preparation of each sample were as described below. Materials Weight (g) Monomer Mix: 2-Ethylhexyl acrylate 700 t-Octyl acrylamide 275 Acrylic acid 25 Polymercaptan 6.5
  • the monomer mix was prepared and thoroughly mixed.
  • the initial charge was charged to a 3000 mL reaction flask, equipped with a condenser, paddle stirrer, thermometer, addition funnels and water bath.
  • the initial charge was heated to reflux and held for five minutes.
  • At reflux very slowly add 50% by volume of initiator solution to the flask contents.
  • monomer and initiator were slow added continuously and uniformly over three hours while maintaining reflux.
  • the flask contents were held at reflux for two hours.
  • the contents were cooled to 25°C and analyzed for residual monomers, percent solid, intrinsic viscosity and molecular weight, and the results shown below.
  • a mixture of acrylates in the ratio of 70 parts 2-ethylhexyl acrylate, 27.5 parts t- octyl acrylamide and 2.5 parts acrylic acid were polymerized in the presence of 0.65 parts tetrafunctional polymercaptan, pentaerythritol tetrakis(3-mercaptopropionate) to yield a star polymer.
  • the reagents and procedure for preparation of each sample were as described below.
  • the monomer mix was prepared and thoroughly mixed.
  • the initial charge was charged to a 3000 mL reaction flask, equipped with a condenser, paddle stirrer, thermometer, addition funnels and water bath.
  • the initial charge was heated to reflux and held for 5 minutes.
  • At reflux add very slowly 50% by volume of initiator solution to the flask contents.
  • monomer and initiator were slow added continuously and uniformly over three hours while maintaining reflux.
  • the flask contents were held at reflux for two hours.
  • the contents were cooled to 25°C and analyzed, and the results shown below.
  • Other monomers and reagents were also prepared by the above method and these results also shown in Table 7 below. Table 7
  • AIAcAc aluminum acetylacetonate
  • 2PD 2,4 pentanedione
  • Viscosity, peel, shear and loop tack were plotted against percent acrylic acid, and the results shown in Figures 1-5.
  • Figure 1 indicates that tOA gives the lowest viscosity and that in general, viscosity increases with an increase in acrylic acid content.
  • Figure 2 shows 20 minute peel as a function of acrylic acid content. In general, peel decreases with increase in acrylic acid content, although sometimes a maximum is seen such as with the 106 series containing methyl methacrylate. The steepest decline in peel is seen in the 111 series which contains tOA. However in all cases, peel values are in the range of 20 to 60 oz/inch.
  • Figure 3 shows 24 hour peel, and the tends are exactly the same as in Figure 2, however the peel values are all higher indicating a build up with time.
  • Figure 4 shows loop tack values for all the samples.
  • Figure 5 shows the shear holds for the same polymer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des polymercaptans à multiréactivité, des copolymères en forme d'étoiles et des procédés de préparation dans lesquels le polymère comprend un noyau de mercaptan polyvalent et trois bras polymérisés ou plus qui se déploient radialement à partir du noyau. Ledit noyau comprend trois groupes thiol ou plus, dont au moins deux sont de réactivités différentielles, de telle sorte que le noyau présente une réactivité différentielle. Ces thiols multi-fonctionnels, qui seront répertoriés comme noyaux de réactivité différentielle, agissent en tant qu'agents de transfert de chaîne dans un procédé de polymérisation radicalaire.
PCT/US2000/015109 2000-06-02 2000-06-02 Polymercaptans a multireactivite, polymeres en forme d'etoiles et procedes de preparation WO2001096291A1 (fr)

Priority Applications (3)

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PCT/US2000/015109 WO2001096291A1 (fr) 2000-06-02 2000-06-02 Polymercaptans a multireactivite, polymeres en forme d'etoiles et procedes de preparation
AU2000254565A AU2000254565A1 (en) 2000-06-02 2000-06-02 Multireactivity polymercaptans, star polymers and methods of preparation
EP00939486A EP1289946A1 (fr) 2000-06-02 2000-06-02 Polymercaptans a multireactivite, polymeres en forme d'etoiles et procedes de preparation

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003064502A1 (fr) * 2002-01-31 2003-08-07 University Of Jyväskylä Dendrimeres de polyester, procede de fabrication de ces dendrimeres et utilisation correspondante

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0448224A1 (fr) * 1990-03-23 1991-09-25 Imperial Chemical Industries Plc Polymères
US5399642A (en) * 1991-11-04 1995-03-21 Rohm & Haas Company Latent thiol mercaptan chain transfer agents and their use in the synthesis of polymers
WO1996037520A1 (fr) * 1995-05-25 1996-11-28 Imperial Chemical Industries Plc Composition a base de polymere acrylique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0448224A1 (fr) * 1990-03-23 1991-09-25 Imperial Chemical Industries Plc Polymères
US5399642A (en) * 1991-11-04 1995-03-21 Rohm & Haas Company Latent thiol mercaptan chain transfer agents and their use in the synthesis of polymers
US5492965A (en) * 1991-11-04 1996-02-20 Rohm And Haas Company Compositions containing block copolymers composed of latent thiol mercaptan chain transfer agents
WO1996037520A1 (fr) * 1995-05-25 1996-11-28 Imperial Chemical Industries Plc Composition a base de polymere acrylique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003064502A1 (fr) * 2002-01-31 2003-08-07 University Of Jyväskylä Dendrimeres de polyester, procede de fabrication de ces dendrimeres et utilisation correspondante

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AU2000254565A1 (en) 2001-12-24

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