JP2019517599A - Polymers and other compounds functionalized with terminal 1,1-disubstituted alkene monomers and methods thereof - Google Patents

Abstract

Functionalized compounds comprising residues of one or more 1,1-disubstituted alkene compounds. Preferably, the functionalized compound comprises the residues of two or more 1,1-disubstituted alkene compounds spaced apart. Functionalized compounds may be produced by transesterification. Functionalized compounds may be employed in the polymerizable composition and may be used to prepare new polymers (eg, by reacting alkene groups).

Description

RELATED APPLICATIONS This application is based on Palsule et al. No. 62 / 421,754, filed Nov. 14, 2016, and Palsule et al. No. 62 / 345,334 filed on Jun. 3, 2016, and Palsule et al. No. 15 / 592,820, filed May 11, 2017, Palsule et al. U.S. Patent Application No. 15 / 437,164, filed February 20, 2017, and Palsule et al. No. 15 / 234,191, filed Aug. 11, 2016, which is hereby incorporated by reference in its entirety.

Field Disclosed are novel compounds and compositions containing polymers functionalized with one or more molecules having alkenyl groups. Also disclosed are methods of preparing the novel compounds and compositions, and crosslinked polymers and block copolymers comprising the novel compounds. The molecule (s) having an alkenyl group is preferably a 1,1-diester-1-alkene compound. Preferably, the polymer comprises a plurality of spaced apart alkenyl groups. For example, the polymer can have a central polymer portion, and at one or more ends of the central polymer portion are attached molecules having alkenyl groups. Preferred central polymer moieties comprise or consist essentially of or consist of one or more polyols.

  Polymers such as polyesters, polycarbonates and other polyols are generally linear or branched molecules that are typically devoid of unsaturated functional groups such as alkenyl groups.

  1,1-Diester-1-alkenes, such as methylene malonate, contain two diester groups, with an alkylene group disposed between the two diester groups. Advances in the synthesis of these compounds in recent years facilitate the synthesis of these compounds and their use in various applications (US Patent 8, of Malofsky, which is hereby incorporated by reference in its entirety for all purposes by reference). 609, 885, US 8, 884, 051 and US 9, 108, 914). Processes for transesterification of these compounds have also been recently developed. Malofsky et al., Which is incorporated herein by reference in its entirety for all purposes. WO 2013/059473, US 2014/0329980, disclose the preparation of multifunctional methylene malonates according to a number of synthetic schemes. One disclosed process involves reacting methylene malonate with a polyol to prepare a compound in the presence of a catalyst, where one of the ester groups of methylene malonate undergoes transesterification to obtain a polyol. React with to form a multifunctional compound (multifunctional means the presence of more than one methylene malonate core unit). The use of enzyme catalysts is disclosed. No. 14 / 814,961 filed on Jul. 31, 2015 in Sullivan, which is incorporated herein by reference in its entirety for all purposes, is 1,1-disubstituted -1- using specific acid catalysts. Transesterification of alkenes is disclosed.

  What is needed are compositions useful for the preparation of polyesters that can be skillfully crosslinked without the need for problematic catalysts and that use relatively mild conditions. There is a need for coatings exhibiting enhanced properties made from such compositions, such enhanced properties including flexibility, adhesion to substrates, pencil hardness, solvent resistance, abrasion resistance Properties, UV resistance, high temperature resistance, etc. are included. There is a need for processes of preparing components for such coatings, and the coatings.

U.S. Pat. No. 8,609,885 U.S. Patent No. 888,4051 U.S. Patent No. 9108914 International Publication No. 2013/059473 US Patent Application Publication No. 2014/0329980 U.S. Patent Application No. 14/814 961

  One aspect of the present invention is a functionalized multivalent compound comprising two or more of a central moiety (preferably isocyanurate trimer or central polymeric moiety) and a 1,1-disubstituted alkene compound (s) And one or both of the disubstituents contain ester groups, and each of the residues of the 1,1-disubstituted 1-alkene compound (s) is at a different end of the central portion The present invention relates to such functionalized polyvalent compounds which are attached to a moiety such that the functionalized polymer has at least two spaced alkene functional groups. The central portion is preferably formed of a multivalent compound. The central portion can be an isocyanurate trimer and the 1,1-disubstituted alkene compounds can be separated by an isocyanurate trimer. The central portion may comprise two or more ends separated by five or more atoms, where each of the residues of the 1,1-disubstituted 1-alkene compound (s) is different in the central portion Bonded to the end.

  The addition of alkenyl groups to the central polymer portion to form a functionalized polymer provides new sites for reacting the central polymer with other molecules. For example, an alkenyl group may be used to graft the central polymer moiety to another polymer. As another example, a plurality of spaced alkenyl groups may be attached to the central polymer moiety to form a multiblock structure such as a network structure in which the central polymer moiety is linked to multiple blocks of another polymer moiety. It is also good. The alkenyl group (s) can be copolymerized during polymerization of the alkenyl containing monomer. Such polymerization may be free radical polymerization, anionic polymerization or cationic polymerization. Anionic polymerization is described in International Patent Application No. PCT / US15 / 48846 (Sullivan et al., Filed on September 8, 2015, published March 17, 2016 as WO 2016/040261 A1), each of which is incorporated by reference in its entirety. U.S. Patent Application Publication No. 2016/0068616 A (Palsule et al., Published March 10, 2016), and U.S. Patent No. 9,249,265 B1 (Stevenson et al., Published February 2, 2016) One or more of the features described in 1.). As another example, a crosslinkable compound capable of forming a crosslink between two or more alkenyl groups (for example, a sulfur based crosslinkable compound or a non-sulfur based crosslinkable compound) and / or a crosslinker is used To crosslink the functionalized polymer.

  The central polymer portion may comprise or consist essentially of or consist of one or more polyols. The one or more polyols can be one or more polyether polyols, polysiloxane polyols, polycarbonate polyols, polyester polyols, polyethylene glycols, acrylic polyols, or polybutadiene polyols. The one or more polyols may be linear with 2 chain ends or branched with 3 or more chain ends. Preferably, one or more, two or more or all of the chain ends may have a hydroxyl group capable of reacting with the ester group. The hydroxyl groups may also be side groups on the backbone of the polyol. For example, the functional compound may be one containing an ester group and may be attached to the polyol by a transesterification reaction. Examples of transesterification reactions are: US Patent Application Publication No. 2016/0221922 A1 (Sullivan et al., Published August 4, 2016), and US Patent Application No. 15 / 234,191 (Palsule et al.) (Filed August 11, 2016), both of which are incorporated herein by reference in their entirety. The polyol may comprise one or more, two or more or three or more hydroxyl groups.

  Films or coatings can be made from the functionalized polymers disclosed herein. The thickness of the coating or film may be about 0.001 μm or more, about 0.1 μm or more, about 1 μm or more, or about 2 μm or more. The thickness of the coating or film is preferably about 200 μm or less, more preferably about 50 μm or less, and most preferably about 20 μm or less.

  The functional compound having an alkenyl group may be a 1,1-disubstituted alkene compound. As 1,1-disubstituted alkene compounds, monomers described, for example, in US Patent Application Publication No. 2016/0068616 A1 (see, eg, paragraph Nos. 0022 and 0030 to 0045), which is incorporated herein by reference. Can be mentioned. Such functional compounds may have a single alkenyl group or may be multifunctional (having more than one alkenyl group). Multifunctional compounds having a plurality of alkenyl groups include, for example, those described in US Patent Application Publication No. US 2016/0068616 Al (see, eg, paragraph number 0042), which is incorporated herein by reference. Preferably, some or all of the 1,1-disubstituted alkene compounds are those having a single alkenyl group.

  The functionalized polymer may be present in a solvent.

  The functionalized polymer may be concentrated (e.g., substantially or completely free of solvent). In the concentrated system, it is preferred that the amount of any solvent be less than or equal to about 10 weight percent, less than or equal to about 5 weight percent, less than or equal to about 2 weight percent, or less than or equal to about 1 weight percent. The amount of solvent may be about 0 weight percent or more, or about 0.1 weight percent or more.

  Disclosed are polymerizable compositions comprising i) a functionalized polymer having one or more alkenyl groups and ii) one or more monomers capable of polymerizing with the alkenyl groups of the functionalized polymer. Preferably, the one or more monomers comprise or consist essentially of or consist of one or more 1,1-diester-1-alkenes.

  Disclosed is a crosslinked network comprising a polymer block of a first polymer linked by a second block comprising or consisting of one or more 1,1-diester-1-alkenes. Preferably, the first polymer block is a polyol (eg, a polyol of the central polymer portion as described herein).

  Disclosed are functionalized multivalent compounds comprising a central portion of a polymeric polyol having two or more ends, one or more of the ends remaining of a 1,1-disubstituted alkene compound Blocked with groups, the functionalized multivalent compound is a functionalized polymer.

  Disclosed is a functionalized polyvalent compound by reacting a 1,1-disubstituted 1-alkene compound with a polyol polymer in a continuous reaction (e.g. using a tubular reactor) comprising the step of transesterification Is a method of forming Preferably, the tubular reactor is packed with or contains one or more catalysts.

  Disclosed are functionalized multivalent compounds comprising a central polymer portion having two or more ends separated by a plurality of monomer units comprising covalently linked adjacent monomer units; the central polymer portion being A homopolymer consisting essentially of identical monomer units or a copolymer comprising monomer units comprising a first monomer and one or more comonomers different from said first monomer; central polymer The monomer units of the moiety comprise terminal monomer units at each end of the central polymer moiety; additionally comprising one or more residues of the 1,1-disubstituted alkene compound (s), of the disubstituent One or both of them contain ester groups; each of the residues of the 1,1-disubstituted 1-alkene compound (s) is at a different end of the central polymer portion ( That is, they are linked to different terminal monomer units of the central polymer part or are side groups of the central polymer part; as a result, the functionalized polymer is a functionalized multivalent compound having at least one alkene functionality . Preferably, the functionalized multivalent compound is a functionalized polymer (preferably having four or more monomer units).

  Disclosed is a method of crosslinking polyols using monomeric 1,1-diester-1-alkenes.

  Disclosed are grafted polymers comprising or consisting essentially of one or more 1,1-diester-1-alkenes, and comprising one or more grafts. The graft may be a polyol. Preferred grafts include polyesters, polyethers, polybutadienes, polycarbonates, polyethylene glycols, acrylic containing polymers, or siloxane containing polymers.

  Disclosed is a method of grafting a polyol to a polymer comprising one or more 1,1-diester-1-alkene monomers. The grafting preferably takes place during the polymerization of the monomers. For example, grafting can occur during copolymerization of the alkenyl group attached to the polyol.

  Disclosed are articles comprising a coating formed by reacting one or more polymerizable monomers with a functionalized polymer having a polyol backbone and two or more terminal 1,1-disubstituted alkenes. is there. The polymerizable monomer preferably comprises or consists essentially of or consists of one or more 1,1-disubstituted alkenes. More preferably, the polymerizable monomer comprises one or more methylene malonate. The concentration of one or more polymerizable monomers can be about 1 weight percent or more, more preferably about 10 weight percent or more, and most preferably about 28 weight percent or more. The amount of one or more polymerizable monomers may be about 98 weight percent or less, preferably about 90 weight percent or less, and most preferably about 80 weight percent or less. The coating may be bonded to any substrate. For example, the substrate may be a metal substrate, a polymer substrate, a fiber substrate, a glass substrate or a ceramic substrate.

FIG. 1A is an example proton NMR spectrogram of a reaction mixture comprising DEMM and a terate polyol end-capped with DEMM. FIG. 1B is an enlarged region of the 6.5 ppm methylene region of the example proton NMR spectrogram of FIG. 1A. The amount of transesterified diethylmethylene malonate species (both mono and disubstituted) is about 29.92% and the amount of unreacted diethyl methylene malonate is about 70.08%. FIG. 1A is an example proton NMR spectrogram of a reaction mixture comprising DEMM and a terate polyol end-capped with DEMM. FIG. 1B is an enlarged region of the 6.5 ppm methylene region of the example proton NMR spectrogram of FIG. 1A. The amount of transesterified diethylmethylene malonate species (both mono and disubstituted) is about 29.92% and the amount of unreacted diethyl methylene malonate is about 70.08%. FIG. 7 is an example of a thermogravimetric analysis (TGA) curve of DEMM crosslinked by an end-capped aliphatic polyester polyol. Aliphatic polyester polyols can be end-capped with residues of DEMM. Example of proton NMR superposition of a polycarbonate polyol (top) and a transesterified polycarbonate polyol (bottom) end-capped with DEMM in excess DEMM. The disappearance / shift of 3.6 ppm of methylene protons in the polyol after the reaction indicates almost complete transesterification. A full scale proton NMR example of an end-capped polybutadiene in excess DEMM (eg, by residues of DEMM). Evidence for transesterification can be seen by the absence of a 4.1 ppm peak corresponding to the methylene group attached to the OH functionality of the polyol. FIG. 4B is a magnified example of the proton NMR spectrum from above FIG. 4A showing the consumption of methylene protons appearing at 4.1 ppm. FIG. 5A is an example of a full scale proton NMR of transesterification of DEMM with polyethylene glycol PEG300. The formation of new species can be supported in the 6.5 ppm methylene (double bond) region. FIG. 5B is an example proton NMR spectrogram of an end-capped polyethylene glycol PEG 300 polyol showing two species in the 6.5 ppm region of the spectrum of 5A. The amount of transesterified species is approximately 35 percent, and the amount of unreacted DEMM is about 65 percent. FIG. 6A is an example proton NMR spectrogram of transesterification of DEMM with glycerol ethoxylate. The formation of new species can be supported in the 6.5 ppm methylene (double bond) region. FIG. 6B is an example proton NMR spectrum showing the integration of two species found in the 6.5 ppm region of the spectrum of FIG. 6A. The amount of transesterified species is approximately 42% and the amount of unreacted DEMM is about 58 percent. 1 is an example proton NMR spectrogram of a reaction mixture containing end-capped isocyanurate. It is an example of < ¹³ > C-NMR spectrogram of an intermediate diol. (A) undiluted DEMM, (b) DEMM and urethane diol (without sulfuric acid), (c) DEMM and urethane diol and sulfuric acid, and (d) after reaction at 135 ° C. for 1 hour with DEMM, urethane diol and sulfuric acid It is an example of ¹³ C-NMR spectrogram.

  The explanations and illustrations provided herein are for the purpose of teaching those skilled in the art the present invention, its principles and its practical applications. The person skilled in the art can adapt and apply numerous forms of the present invention to the requirements of a particular application. Thus, the specified embodiments of the present invention are not intended to be exhaustive or to limit the teachings. Therefore, the scope of the teachings should not be determined with reference to the above description, but should be viewed in conjunction with the appended claims, along with the full scope of equivalents to which such claims are entitled. Should be determined. The disclosures of all articles and references, including patent applications and patent publications, are incorporated by reference for all purposes. Other combinations are possible as they may be gathered from the following claims, which are hereby incorporated by reference.

  Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of skill in the art to which this disclosure belongs. The following references provide the skilled artisan with a general definition of many of the terms used in this disclosure: Singleton et al. Dictionary of Microbiology and Molecular Biology (2nd ed. 1994), The Cambridge Dictionary of Science and Technology (Walker ed., 1988), The Glossary of Genetics, 5th Ed. , R. Rieger et al. (Eds.), Springer Verlag (1991), and Hale & Marham, The Harper Collins Dictionary of Biology (1991).

  As used herein, an acid catalyst is an acidic species that catalyzes a transesterification reaction with or without minimizing side reactions. As used herein, one or more means that at least one, or more than one of the listed components may be used as disclosed. The noun phrase used with regard to functionality refers to the theoretical functionality, which can usually be predicted from the stoichiometry of the raw materials used. Heteroatoms refer to atoms that are not carbon or hydrogen, such as nitrogen, oxygen, sulfur and phosphorus, and heteroatoms can include nitrogen and oxygen. As used herein, hydrocarbyl refers to a group containing one or more carbon backbone and hydrogen atoms, optionally it may contain one or more heteroatoms. When the hydrocarbyl group contains a heteroatom, the heteroatom can form one or more functional groups well known to those skilled in the art. The hydrocarbyl group may contain alicyclic moieties, aliphatic moieties, aromatic moieties or any combination of such moieties. The aliphatic moiety may be linear or branched. The aliphatic and cycloaliphatic moieties may contain one or more double bonds and / or triple bonds. Hydrocarbyl groups include alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl and aralkyl groups. Alicyclic groups may contain both cyclic and acyclic moieties. Hydrocarbylene refers to hydrocarbyl groups having a valence greater than 1 or any subset thereof as described, eg, alkylene, alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene, alkarylene and aralkylene. Weight percent or parts by weight, as used herein, refers to or is based on the weight of the described compound or composition, unless otherwise specified. Unless otherwise specified, parts by weight are based on 100 parts of the relevant composition.

  The functionalized multivalent compound comprises a central portion formed from the multivalent compound, wherein one or more hydroxyl groups are reacted with the functional compound to functionalize the multivalent compound. The polyvalent compound may be a monomer compound having two or more hydroxyl groups, or may be a polymer compound containing two or more hydroxyl groups. It is preferred that the functionalized multivalent compound comprises a functional group that differs from the structure along the length of the central portion. Preferably, the functionalized multivalent compound comprises an alkenyl group. For example, the functional compound can be a 1,1-disubstituted-1-alkene. The central portion usually has more than one end. Preferably at least one of the ends of the central part is linked to the functional compound. Preferably, two or more or all of the ends of the central portion are attached to the central compound. It will be appreciated that the residue of the polyvalent compound is attached to the functionalized compound when the hydroxyl group is reacted with the functional compound.

  When the multivalent compound is a polymer, the central portion is the central polymer portion.

  The functionalized polymer comprises a central polymer portion having two or more ends. At least one of the ends of the central polymer portion is attached to a functional compound having one or more functional groups. It is preferred that the functional compound comprises a functional group which differs from the structure along the length of the central polymer portion. Preferably, the functional compound comprises an alkenyl group. For example, the functional compound can be a 1,1-disubstituted-1-alkene.

  It is preferred that the functionalized multivalent compound (e.g., functionalized polymer) comprises two or more alkenyl groups. Preferably, the two or more alkenyl groups comprise a first alkenyl group separated from a second alkenyl group. For example, the alkenyl group can be located primarily on the terminal compound (e.g., terminal monomer) of the functionalized polymer.

  Functionalized multivalent compounds (eg, functionalized polymers) are prepared by reacting multivalent compounds (eg, polyols) having hydroxyl groups that are terminal or pendant groups with 1,1-disubstituted alkenes obtain. For example, the reaction may comprise a transesterification reaction. The reaction may be capped with one or more, two or more or all of the terminal parts of the polyvalent compound (e.g. polyol) with a 1,1-disubstituted alkene compound.

  The multivalent compound is preferably sufficiently long so that each hydroxyl group can readily react with the functional compound in accordance with the teachings herein. For example, the oxygen atoms of the hydroxyl group may be separated by about 5 or more additional atoms, more preferably about 7 or more additional atoms, more preferably about 9 or more additional atoms.

  In various embodiments, the multivalent compound is a mechanical or physical property requiring the presence of the multivalent compound as an oligomeric compound or polymer (eg, flexible, low temperature impact resistant, ductile or any of them) Combination) can be provided. As such, the spacing between hydroxyl groups on the multivalent compound may be about 12 or more, about 20 or more, about 50 or more, or about 100 or more.

  The multivalent compound is preferably short enough that the multivalent compound has a high concentration of functional groups. For example, the ratio of weight average molecular weight to the number of terminal hydroxyl groups per molecule (per polymer molecule) is about 200,000 or less, more preferably about 100,000 or less, still more preferably about 40,000. The following is even more preferably about 10,000 or less, and most preferably about 4,000 or less.

  Monomeric polyvalent compound

  The multivalent compound can be a monomeric compound having two or more spaced hydroxyl groups. The monomeric multivalent compound may be a linear compound or a branched compound.

  Examples of branched polyvalent compounds include neopentyl glycol, pentaerythritol, methyl-substituted propanediol, ethyl-substituted propanediol, methyl-substituted, ethyl-substituted, propyl-substituted butanediol, methyl-substituted, dimethyl-substituted, trimethyl-substituted, ethyl-substituted, Diethyl substituted, triethyl substituted, propyl substituted, dipropyl substituted hexanediol and the like can be mentioned. For example, as a branched polyvalent compound, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2 -Butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8- There may be mentioned octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanedimethanol, or any combination thereof. Other examples of branched multivalent compounds will be apparent to those skilled in the art.

  Linear multivalent compounds contain hydrocarbyl chains without branching. Examples of such compounds include 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol 1,12-dodecanediol, 1,13-tridecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-cyclohexanedimethanol, 1,5-decalindiol and the like. Preferred linear polyhydric alcohols are 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, tetraethylene glycol and combinations thereof.

  Additional examples of multivalent compounds include compounds having one or more nitrogen atoms. Preferred multivalent compounds containing nitrogen atoms contain one or more cyanurate groups, such as isocyanurate groups. Multivalent compounds include tris (hydroxyalkyl) isocyanurate, tris (hydroxybenzyl) cyanurate. For example, the polyvalent compound may comprise 1,3,5-tris (2-hydroxyethyl) isocyanurate.

  Central polymer part

  The central polymer portion may be a homopolymer consisting essentially of or consisting of only one monomeric compound, or may be a copolymer comprising two or more different monomeric compounds. Examples of copolymers include alternating copolymers, random copolymers and block copolymers.

  It is preferred that the central polymer portion have repeat units consisting of one or two monomers.

  It is preferred that the central polymer portion comprises or consists essentially of or consists of one or more polyols. Any polyol may be used as long as the polyol comprises one or more or two or more hydroxyl groups at the end of the polymer chain or along the length of the polymer chain. Preferred polyols include polyesters, polyethers, polybutadiene polyols, polycarbonates, polyacrylates (including, for example, acrylic acid and / or methacrylic acid).

  The central polymer portion may have a backbone, which is defined by the covalently attached atoms required to connect the ends of the central polymer portion. Usually, pendant groups are excluded from the atoms of the main chain unless pendant groups are connected with further monomer units, as in polymers with long chain branches comprising two or more monomer units.

  As used herein, a monomeric compound refers to the chemical structure of a molecule, and monomeric units refer to individual molecules. For example, the first monomer unit and the second monomer can refer to molecules having the same or different chemical structure. Similarly, a first monomeric compound and a second monomeric compound refer to molecules having different chemical structures.

Alternating comonomers are first monomer compound are alternately arranged (e.g., ^R1-M 1 -R2) and the second monomer compound (e.g., ^R3-M 2 -R4) can be essentially configured from a. Here, the central polymer portion (P ¹ ) comprises or consists essentially of recurring units (eg A) formed by one first monomeric compound and one second monomeric compound:
P ¹ = R 1-(A) _n -R 4
(Where A = -M ¹ -M ^2- , n is at least 3 and at least one of R 1 and R 4 is reacted with the functionalizing compound to form a functional group at the end of the central polymer portion ( Preferably, at least an alkenyl group can be added)
Can be expressed as R1 or R4 preferably undergoes transesterification, more preferably both R1 and R4 undergo transesterification.
The first monomer is a central polymer portion (P ² ):
P ² = R 1-(A) _n- M ^1- R 2
(Wherein A = -M ¹ -M ^2- , n is at least 3 and at least one of R 1 and R 2 is reacted with the functionalizing compound to form a functional group at the end of the central polymer portion ( Preferably, at least an alkenyl group can be added)
Terminal monomers at the two ends of. R1 or R2 preferably undergoes transesterification, more preferably both R1 and R2 undergo transesterification.

  The repeat units of the central polymer portion may have the same chemical structure or may have two or more different chemical structures.

  The monomer compound or repeating units of the central polymer portion may comprise aliphatic groups, aromatic groups or both. The aromatic group may be on the main chain or may be present as a pendant group. The aliphatic group may be on the main chain or may be present as a pendant group.

  The central polymer portion may be formed from one or more monomers using a condensation reaction (eg, a polycondensation reaction). For example, condensation is a reaction of an alcohol group of a first monomer unit and an acid group of a second monomer unit (eg, a carboxyl group, -CO (OH)) in which an ester bond is formed to join two monomer units. It can be.

  The central polymer moiety may comprise an ester bond linking adjacent repeat units, and the central polymer moiety may comprise an ester bond linking monomer units of the repeat unit, or both.

The central polymer portion is a monomer compound having an alcohol group and a carboxylic acid group:
(HO-M ³ -O (OH) C
And the central polymer portion comprises the repeating unit: M ³ . Central polymer portion may be configured or only then to or may comprise repeating units M ³ may consist essentially.

  The central polymer portion may be formed by ring opening polymerization of one or more monomeric compounds.

  The central polymer portion may be formed by a polycondensation reaction of at least a first monomeric compound which is a diol and a second monomeric compound which is a diacid. All of the diols may be the same, or two or more different monomeric compounds may be present, which are diols. All of the diacids may be the same or two or more different monomeric compounds may be present which are diacids. The polycondensation reaction preferably results in the formation of water molecules. The central polymer portion can be made using an excess of diol such that each end of the central polymer portion has hydroxyl groups. Preferably, each end of the central polymer portion has hydroxyl groups. More preferably, each end of the central polymer portion has a hydroxyl group (e.g. on the terminal monomer unit). Preferably, the hydroxyl group reacts with the functionalized compound to form an ester linkage.

Preferably, in the case of the central polymer part having two ends, the functionalized polymer is:
Z-C (O) -O-P-O-C (O) -Z
As shown in, it comprises one or more functional compounds (Z) which are each linked to the end of the central polymer part (P) by an ester linkage.

  Preferably, the central polymer portion is saturated. It is preferred that any alkenyl groups on the functionalized polymer be present only on one or more functional compounds each attached to a different end of the central polymer portion.

  Polyol

  The functionalized polymer is preferably formed by reacting a polyol (i.e., a compound having two or more functional hydroxyl groups (i.e., -OH groups)) that can be utilized for the reaction. Preferably, hydroxyl groups can be utilized in organic reactions. Preferably, the hydroxyl groups comprise or consist essentially of hydroxyl groups which are terminal or pendant.

  The polyol may be monomeric, oligomeric or polymeric.

  Monomeric polyols are typically low molecular weight compounds having about two or more hydroxyl groups. Preferred monomeric polyols have a molecular weight of about 400 g / mole or less, more preferably about 300 g / mole or less, and most preferably about 250 g / mole or less. It is preferred that the two or more hydroxyl groups of the monomeric diol be sufficiently separated such that they are neither geminal nor vicinal diol. Preferred monomeric polyols include, for example, glycerin, pentaerythritol, erythritol, ethylene glycol, sucrose, resorcinol, 1,4-butanediol, 1,6-hexanediol, propylene glycol, bisphenol A, 4,4'-dihydroxy Dicyclohexyl, 1,4-pentanediol, 1,5-pentanediol, mannitol, sorbitan, 2,5-tetrahydrofuran-dimethanol, and 1,2,6-hexanetriol.

  Polyester polyol

  The central polymer portion may comprise a polyester polyol, which may be a homopolymer or a copolymer. Examples of polyester homopolymers and copolymers, monomers for preparing the polyester, and methods of preparing the polyester that may be employed for the central polymer portion are described in Halmess et al. U.S. Pat. No. 4,725,664 (see, for example, column 3, line 15 to column 6, line 41), Kohler et al. No. 4,067,850, Muenster et al. No. 2,973,339, Hrach et al. No. 3,651,016, Ohguchi et al. No. 4,377,682, Inata et al. No. 3,972,852, Login et al. No. 4,263,370, Jones et al. No. 5,700,882, Hickey et al. No. 9,309,345, Hoshino et al. No. 8,318,893, each of which is incorporated herein by reference.

  The polyester polyol may comprise one or more repeating units characteristic of the following polymers: polyglycolide (ie poly (oxy (1-oxo-1,2-ethanediyl)), for example by condensation of glycolic acid Obtained), polylactic acid (eg, obtained by ring opening of lactide), polycaprolactone (eg, obtained by ring opening of caprolactone), polycaprole, polyhydroxyalkanoate (eg, polyhydroxybutyrate) Polyethylene adipate, PHBV (ie, a copolymer of 3-hydroxybutanoic acid and 3-hydroxypentanoic acid, butyrolactone and valerolactone), polybutylene succinate (eg, obtained by condensation of succinic acid and 1,4-butanediol) What is) Polyethylene terephthalate (eg, derived from terephthalic acid and ethylene glycol), polybutylene terephthalate (eg, derived from terephthalic acid and 1,4 butane diol), polytrimethylene terephthalate (PTT) (eg, terephthalate) Polyethylene naphthalate (PEN) (for example, those obtained by the condensation of at least one naphthalene dicarboxylic acid with ethylene glycol). Another polyester that may be employed is a polymer formed by the condensation of 4-hydroxybenzoic acid and 6-hydroxynaphthalene-2-carboxylic acid. The polyester may comprise aliphatic dicarboxylic acids and / or aliphatic diols.

  The polyester may be an aromatic polyester. Aromatic polyesters can be formed by reacting an aromatic acid component with a hydroxylated component.

  The aromatic acid component of the aromatic polyester polyol composition includes, for example, phthalic acid materials, phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, pyromellitic anhydride, dimethyl terephthalate, polyethylene terephthalate, trimellitic anhydride , Their pot residues, derivatives, and combinations thereof. Phthalate-based material, as used herein, means phthalic acid or a derivative of phthalic acid. Examples of phthalic acid-based materials include, for example, various phthalic acids such as terephthalic acid and isophthalic acid, phthalic anhydride, dimethyl terephthalate, polyethylene terephthalate, trimellitic anhydride, derivatives thereof, and combinations thereof. Be Phthalic acid-based materials used to prepare polyester polyols include: (a) substantially pure phthalic acid or phthalic acid derivatives such as phthalic anhydride, terephthalic acid, dimethyl terephthalate, isophthalic acid and trimellitic anhydride Or (b) may be a rather complex mixture containing residues of phthalic acid, such as side streams, waste or waste products. In this context, the term "residue of phthalic acid" means any reacted or remaining pot residue remaining in the product after its preparation by a process starting from phthalic acid or a derivative thereof. It means unreacted phthalic acid. A complex mixture of phthalic acid residues is further described in US Pat. No. 5,922,779, which is incorporated herein by reference in its entirety.

  The preferred phthalic acid based material for use in the preparation of aromatic polyester polyols is phthalic anhydride. This component can be replaced by phthalic acid or phthalic anhydride residual composition, phthalic anhydride crude composition, or phthalic anhydride priming composition, such compositions are disclosed in US Pat. No. 4,529, It is defined in the 744 issue.

  The aromatic acid component of the aromatic polyester polyol composition may comprise, for example, about 20 wt% to about 50 wt%, alternatively about 20 wt% to about 40 wt% of the aromatic polyester polyol composition.

  The hydroxylated component of the aromatic polyester polyol composition of the present technology can be, for example, at least one aliphatic diol, at least one derivative thereof, or a combination thereof.

The hydroxylated component is represented by the general formula (1): HO-R ¹ -OH
And R ¹ is an alkylene radical each containing (a) 2 to 6 carbon atoms, and (b) Formula (2):-(R ² O) _n -R ^2-
(Wherein R ² is an alkylene radical containing 2 to 3 carbon atoms and n is an integer of 1 to 3)
And (c) a divalent radical selected from the group consisting of (c) mixtures thereof.

  Examples of suitable aliphatic diols of the formula (1) are ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, butylene glycol, 1,2-cyclohexanediol, ethylene oxide, propylene oxide or any combination thereof And poly (oxyalkylene) polyols each containing 2 to 4 alkylene radicals derived by condensation of As those skilled in the art will appreciate, when preparing mixed poly (oxyethylene-oxypropylene) polyols, ethylene oxide and propylene oxide can be added to the hydroxy-containing starting reactants in a mixed state or sequentially. It is also good. Mixtures of such diols can be employed as required. The currently most preferred aliphatic diol of formula (1) is diethylene glycol. In addition, amine based aliphatic hydroxylates (ie hydroxylated amines) such as monoethanolamine, diethanolamine and triethanolamine may be used as long as all of the amine functionality is completely consumed in the polyol.

  Mixtures of diols usually contain more than 0 percent and 100 percent of low molecular weight polyols (ie, compounds containing at least 3 hydroxyl groups per molecule while containing less than 7 carbon atoms per molecule) It can be incorporated in amounts ranging up to. Such polyols include, for example, glycerol, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, 2,2-dimethyl-1,3-propanediol, pentaerythritol, mixtures thereof And so on.

  The hydroxylated component of the aromatic polyester polyol composition is, for example, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, butylene glycol, 1,2-cyclohexanediol, hexane It may be a diol, pentanediol, polyoxyalkylene diols such as tri and tetra ethylene glycol, their derivatives and combinations thereof.

  The hydroxylated component of the aromatic polyester polyol composition may comprise, for example, about 30% to about 80% based on the total weight of the aromatic polyester polyol composition. Alternatively, the hydroxylated component of the aromatic polyester polyol may be about 30 to 65 wt% based on the total weight of the polyester polyol. Alternatively, the hydroxylated product in the polyester polyol is about 40-60% by weight based on the total weight of the aromatic polyester polyol.

  The polyester is one or more 1,4-arylenes that are reactive with linear and unbranched aliphatic diacids or diols with functionality that will react to the functionality of the arylene monomer Monomers such as terephthalic acid and hydroquinone or 2,6-arylene monomers such as 2,6-dihydroxynaphthalene may be included. The polyesters of the present invention may be made by transesterification, for example by condensation of a diacid and a diol by transesterification of hydroquinone diacetate or 2,6-naphthalene diacetate with an aliphatic diacid. The polyesters of the present invention are usually mostly transesterified with dialkyl terephthalates and linear saturated aliphatic diols, transesterification of hydroquinone diacetates with linear saturated aliphatic diacids, direct with linear saturated aliphatic diacids. Esterification, esterification of terephthaloyl chloride with linear unbranched saturated diol, transesterification of 2,6-naphthalenediacetate with linear saturated unbranched diol, and dicyclohexylcarbodiimide (DCC) as previously described By esterification using diacids and diols. Alkyl is lower alkyl having four or less carbons. In the latter reaction, any acid halide may be used instead of the acid chloride, and propionate or butyrate (lower alkyl having 4 or less carbons) may be used instead of acetate. In this aspect of the invention, the polyester may be defined as a reaction product of a polymeric vehicle, wherein the polyester is an arylene monomer selected from the group consisting of hydroquinone, 2,6-hydroxynaphthalene and mixtures thereof A reaction product with a linear saturated aliphatic diol or diacid having 6 to 17 carbon atoms that is reactive to an arylene monomer, and R is an alkyl or H having 1 to 4 carbon atoms And R ′ is alkyl having 1 to 4 carbon atoms, and X is halogen.

  The polyester polyol may regularly alternate between aromatic and linear unbranched substituents separating or separating arylene groups. Liquid crystalline properties of polyesters which will generally have a number average molecular weight in the range of about 350 to about 4,000, preferably about 400 to about 1800, as the spacing between arylene groups is increased to increase the overall molecular weight. Is reinforced by a smaller number of repeating units. The degree of polymerization can be controlled by the relative proportions of monomers in the reaction system.

  The polyhydroxy component may be selected for the production of polyester polyols based on the desired properties of the polyol composition. Any suitable polyhydroxy compound can be used, eg making the polyhydroxy compound a dihydroxy compound (diol), a trihydroxy compound (triol), a tetrahydroxy compound (tetraol) or a higher polyhydroxy compound Can. More specifically, the polyhydroxy compound may be ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, pentanediol, hexanediol, glycerin, trimethylolpropane, pentaerythritol or sorbitol or Can be a combination of

  The polycarboxylic acids may be diacids, triacids or higher functional polycarboxylic acids, or corresponding esters or anhydrides, including, but not limited to, polyfunctional aromatic acids, polyfunctional aromatic anhydrides And polyfunctional aromatic esters (eg, diol monoesters) and polyfunctional fatty acids, anhydrides and polyfunctional esters thereof, such as succinic acid, glutaric acid, adipic acid, phthalic acid, terephthalic acid, sebacic acid It may include azelaic acid, dodecanedioic acid, citric acid, succinic anhydride, phthalic anhydride, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl terephthalate and combinations thereof.

  The hydrophobic material may be vegetable oil (i.e. vegetable derived oil) or fatty acid or ester obtained therefrom; animal oil (i.e. animal derived oil) or fatty acid or ester derived therefrom; or synthetic oil, synthetic fatty acid or synthetic fatty acid ester . An oil is a hydrophobic compound regardless of the physical state at ambient temperature, ie the oil may be a solid at room temperature, eg a solid fat.

  The polyester polyol may be a multifunctional aromatic acid, or an anhydride thereof, or an active ester thereof, or a multifunctional ester thereof, or a mixture thereof. For example, the polyester polyol may comprise terephthalic acid, isophthalic acid, orthophthalic acid, trimellitic acid, pyromellitic acid or any combination thereof.

  Polycarbonate polyol

  The central polymer portion may be formed from a polycarbonate polyol. The polycarbonate polyol may be any polymer comprising, consisting essentially of, or consisting only of repeating units having a carbonate group (i.e. -O-C (= O) -O-) . Polycarbonate polyols contain two or more hydroxyl groups (eg, two or more terminal hydroxyl groups). The polycarbonate polyol may comprise polycarbonate diol, polycarbonate triol, polycarbonate polyol having 4 or more hydroxyl groups, or any combination thereof. The polycarbonate polyol may be linear. Preferred linear polycarbonate polyols have hydroxyl groups at both ends. The polycarbonate polyol may be a branched or hyperbranched polymer having three or more ends. Preferably, two or more, three or more, or even all of the terminal parts of the branched or hyperbranched polycarbonate polyol contain hydroxyl groups.

  As an example of polycarbonate polyols and methods of producing polycarbonate polyols, see US Pat. No. 3,689,462A (published on Sep. 5, 1972, by Maximovich, see eg column 1, line 25 to column 8, line 35). No. 4,533,729 (August 6, 1985, published by Newland et al., See, for example, column 54, line 4 to column 4, line 53), US 5,288, 839 A (1994 2). Published May 22nd, Greco, see, eg, column 2, line 12 to column 5, line 2, US 5, 527, 879 A (Nakae et al., Published June 18, 1996, eg, abstract and 2 Column 9 line 3 to column 48 line), US 6,872, 797 B2 (issued March 29, 2005, according to Ueno et al. See, for example, column 5, line 44 to column 16, line 19 and column 20, line 20 to column 24, line 55), and US 8,779,040 B2 (issued July 15, 2014, van der Weele et al. al., see, eg, column 5, line 12 to column 15, line 32), as well as US Patent Application Publication No. US 2003/01766222 A1 (published on September 18, 2013, by Konishi et al., eg, paragraph No. 8). ~ 74), US20040092699A1 (published May 13, 2004, according to Ueno et al., See eg paragraphs 2-8, 13-37 and 39-151), US2008 / 0146766A1 (June 2008) Published on 19th, according to Masubuchi et al., Eg abstract and paragraphs 13-5 4 and US20080167430A1 (published on July 10, 2008, Bruchmann et al. Et al., See, for example, paragraph Nos. 3 to 149), the contents of which are respectively described by reference. It is incorporated into the specification.

（ここで、Ｒ^１基は、脂肪族、脂環式、芳香族またはそれらの任意の組み合わせであることが好ましい）
の繰り返し構造カーボネート単位（同じであっても異なっていてもよい）を含み得るかまたはそれから本質的に構成され得るかまたはそれのみで構成され得る。好ましくは、Ｒ^１基の総数の少なくとも約６０パーセントは芳香族有機ラジカルであり、その残りは脂肪族、脂環式または芳香族ラジカルである。１つの態様において各Ｒ^１は、芳香族有機ラジカル、例えば式：−Ａ^１−Ｙ^１−Ａ^２−のラジカルであり、式中、Ａ^１及びＡ^２はそれぞれ単環式二価アリールラジカルであり、Ｙ’は、Ａ^１とＡ^２とを隔てる１つまたは２つの原子を有する架橋ラジカルである。例えば、１つの原子がＡ^１とＡ^２とを隔てている。この類のラジカルの例示としての非限定的な例は、−Ｏ−、−Ｓ−、−Ｓ（Ｏ）−、−Ｓ（Ｏ２）−、−Ｃ（Ｏ）−、メチレン、シクロヘキシルメチレン、２−［２．２．１］−ビシクロヘプチリデン、エチリデン、イソプロピリデン、ネオペンチリデン、シクロヘキシリデン、シクロペンタデシリデン、シクロドデシリデン及びアダマンチリデンである。架橋ラジカルＹ’は、メチレン、シクロヘキシリデンまたはイソプロピリデンなどの炭化水素基または飽和炭化水素基であり得る。 The polycarbonate polyols may be homopolymers or copolymers. Polycarbonate polyols have the formula:

(Here, the R ¹ group is preferably aliphatic, alicyclic, aromatic or any combination thereof)
The repeating structural carbonate unit (which may be the same or different) may be or consist essentially of or consist of it. Preferably, at least about 60 percent of the total number of R ¹ groups are aromatic organic radicals, with the remainder being aliphatic, alicyclic or aromatic radicals. In one embodiment, each R ¹ is an aromatic organic radical, such as a radical of the formula: -A ¹ -Y ¹ -A ^2- , wherein A ¹ and A ² are each monocyclic divalent aryl radicals And Y ′ is a bridging radical having one or two atoms separating A ¹ and A ² . For example, one atom separates A ¹ and A ² . Illustrative non-limiting examples of this class of radicals are: -O-, -S-, -S (O)-, -S (O2)-, -C (O)-, methylene, cyclohexylmethylene, 2 -[2.2.1] -bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene and adamantylidene. The bridging radical Y 'can be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene or isopropylidene.

のビスフェノール化合物も挙げられ、式中、Ｒ^ａ及びＲ^ｂは、それぞれハロゲン原子または一価炭化水素基を表し、同じであっても異なっていてもよく；ｐ及びｑはそれぞれ独立して０〜４の整数であり；Ｘ^ａは、式：

（ここで、Ｒ^ｃ及びＲ^ｄはそれぞれ独立して水素原子または一価の直鎖もしくは環式の炭化水素基を表し、Ｒ^ｅは二価炭化水素基である）
の基のうちの一方を表す。 Polycarbonates can be prepared by the interfacial reaction of dihydroxy compounds having the formula HO-R ¹ -OH, where R ¹ is as defined above. Dihydroxy compounds suitable for interfacial reactions include dihydroxy compounds of formula (A) and dihydroxy compounds of formula HO-A ¹ -Y ¹ -A ² -OH, wherein Y 1, A ¹ and A ² are on top As defined. General formula:

Wherein R ^a and R ^b each represent a halogen atom or a monovalent hydrocarbon group, which may be the same or different; and p and q each independently represent 0 to 0. Is an integer of 4; X ^a is the formula:

(Wherein R ^c and R ^d each independently represent a hydrogen atom or a monovalent linear or cyclic hydrocarbon group, and R ^e is a divalent hydrocarbon group)
Represents one of the groups of

  Non-limiting examples illustrating suitable dihydroxy compounds include: resorcinol, hydroquinone, 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis (4-hydroxyphenyl) methane Bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-one Phenylethane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (hydroxyphenyl) cyclopentane, 1,1-bis ( 4-hydroxyphenyl) cyclohexane, 1,1-bi (4-hydroxyphenyl) isobutene, 1,1-bis (4-hydroxyphenyl) cyclododecane, trans-2,3-bis (4-hydroxyphenyl) -2-butene, 2,2-bis (4-hydroxyphenyl) Adamantine, (alpha, alpha'-bis (4-hydroxyphenyl) toluene, bis (4-hydroxyphenyl) acetonitrile, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis ( 3-ethyl-4-hydroxyphenyl) propane, 2,2-bis (3-n-propyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2 -Bis (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-t-butyl) 4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-methoxy -4-hydroxyphenyl) propane, 4,4'-dihydroxybenzophenone, 3,3-bis (4-hydroxyphenyl) -2-butanone, 1,6-bis (4-hydroxyphenyl) -1,6-hexanedione Ethylene glycol bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, 9, 9-Bis (4-hydroxyphenyl) fluorin, 2,7-diphenyl Droxypyrene, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethylspiro (bis) indane (“subilovindane bisphenol”), 3,3-bis (4-hydroxyphenyl) phthalide, 2- Phenyl-3,3-bis (4-hydroxyphenyl) phthalimide (PPPBP), 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathiin, 2,7- Examples include dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole and the like, and combinations comprising at least one of the above-mentioned dihydroxy compounds.

  Specific examples of the class of bisphenol compounds that may be represented by formula (3) include 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (2) 4-hydroxyphenyl) propane (hereinafter "bisphenol-A" or "BPA"), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) n-butane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, and 1,1-bis (4-hydroxy) And -t-butylphenyl) propane. Combinations comprising at least one of the above dihydroxy compounds may be used.

  The polycarbonate may be a linear polycarbonate or may be a branched polycarbonate. Branched polycarbonates can be prepared by adding a branching agent during polymerization. These branching agents include polyfunctional organic compounds containing at least three functional groups which are preferably selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl and mixtures of the above functional groups. The branching agent may be added at a level of about 0.05 weight percent or more, preferably about 0.10 weight percent or more, based on the total weight of the polycarbonate. The amount of branching agent (s) may be about 10 weight percent or less, preferably about 2 weight percent or less. All types of polycarbonate end groups are contemplated as useful in polycarbonate compositions, provided that such end groups do not significantly affect the desired properties of the thermoplastic agent.

  Suitable polycarbonates can be produced by processes such as interfacial polymerization and melt polymerization. Although the reaction conditions for interfacial polymerization can vary, typical processes typically involve dissolving or dispersing the dihydric phenol reactant in caustic soda or caustic potash water, and the resulting mixture in a suitable water immiscible solvent. With adding to the medium, and contacting the reactant with a carbonate precursor in the presence of a suitable catalyst such as triethylamine or a phase transfer catalyst under controlled pH conditions, such as a pH of about 8 to about 10. . The most commonly used water immiscible solvents include methylene chloride, 1,2-dichloroethane, chlorobenzene, toluene and the like. Suitable carbonate precursors include, for example, carbonyl halides, such as carbonyl bromide or carbonyl chloride, or haloformates, such as bishaloformates of dihydric phenols (eg, bis chloroformates such as bisphenol A, hydroquinone etc.) or glycols Bishaloformates such as ethylene glycol, neopentyl glycol, bishaloformates such as polyethylene glycol, etc. may be mentioned. Combinations comprising at least one of the foregoing types of carbonate precursors may be used.

（ここで、Ｄは、ジヒドロキシ化合物に由来する二価ラジカルであり、例えば、Ｃ_２−１０アルキレンラジカル、Ｃ_６−２０脂環式ラジカル、Ｃ_６−２０芳香族ラジカルまたは、２つ〜約６つの炭素原子、具体的には２つ、３つもしくは４つの炭素原子をアルキレン基が含有しているポリオキシアルキレンラジカルであり得；Ｔは、ジカルボン酸に由来する二価ラジカルであり、例えば、Ｃ_２−１０アルキレンラジカル、Ｃ_６−２０脂環式ラジカル、Ｃ_６−２０アルキル芳香族ラジカル、またはＣ_６−２０芳香族ラジカルであり得る）
の繰り返し単位を含み得る。 The polycarbonate diols and polycarbonate polyols used herein further include copolymers comprising carbonate chain units. The polycarbonate copolymer may comprise or consist essentially of carbonate chain units or may consist solely of it. The polycarbonate copolymer may further comprise one or more repeating units which are not carbonates. For example, the polycarbonate copolymer may comprise polyester, as in copolyester-polycarbonate. Such copolymers have the formula:

(Wherein D is a divalent radical derived from a dihydroxy compound, for example, a C _2-10 alkylene radical, a C _6-20 alicyclic radical, a C _6-20 aromatic radical or 2 to about 6 May be a polyoxyalkylene radical in which the alkylene group contains two carbon atoms, in particular two, three or four carbon atoms; T is a divalent radical derived from a dicarboxylic acid, for example It may be a C _2-10 alkylene radical, a C _6-20 alicyclic radical, a C _6-20 alkyl aromatic radical, or a C _6-20 aromatic radical)
May contain a repeat unit of

The diene polyol The polyol may comprise or consist essentially of or consist of one or more diene polyols. The diene polyol preferably comprises one or more dienes in an amount of at least about 40 weight percent, more preferably at least about 70 weight percent, and most preferably at least about 90 weight percent. The diene is preferably a diene having about 4 to about 20 carbon atoms, more preferably about 4 to about 8 carbon atoms, and most preferably 4 carbon atoms.

  Particularly preferred diene polyols are polybutadiene polyols. The polybutadiene polyol preferably contains about 40 weight percent or more butadiene repeat units. Butadiene may be represented as a 1-2 adduct, a cis 1-4 adduct, a 1-4 trans adduct, or any combination thereof. Preferably, the amount of 1-2 adducts is about 50 percent or less, more preferably about 40 percent or less, and most preferably about 30 percent or less based on the total number of butadiene repeating units in the polyol.

  Carbinol-terminated polyalkyl siloxane

The central polymer portion may comprise a carbinol-terminated polyalkyl siloxane. Preferred polyalkyl siloxanes have one or preferably two alkyl groups on each silicon atom. Preferred alkyl groups are C ₁ -C ₁₀ hydrocarbons. More preferably, the alkyl group comprises or consists of ethylene. Particularly preferred polyalkyl siloxanes are polydimethylsiloxanes. The polyalkyl siloxane may be linear or branched. Preferably, each chain end contains a hydroxyl group.

  Polyalkylene glycol

The central polymer portion may comprise a polyalkylene glycol. The polyalkylene glycol preferably comprises or consists essentially of or consists of one or more alkylene glycols having 2 to 10 carbon atoms. Preferably, C ₂ -C ₁₀ amount of alkylene glycol is about 50 percent by weight or more, more preferably about 80 percent by weight or more, even more preferably from about 90 weight percent, and most preferably about 95 weight percent. Polyalkylene glycols can include linear polymers, branched polymers, or both. Preferably, the polyalkylene glycol contains hydroxyl groups at each end of the polymer. Branched polymers may have three, four, five, six, seven or more chain ends. The hyperbranched polymer may have about 8 or more chain ends, about 15 or more chain ends, or about 20 or more chain ends.

  Preferred polyalkylene glycols include ethylene glycol, butylene glycol, propylene glycol or any combination thereof. The total amount of ethylene glycol, propylene glycol or butylene glycol is preferably at least about 50 weight percent, more preferably at least about 85 weight percent, still more preferably at least about 92 weight percent, most preferably about at least about 50 weight percent, based on the total weight of polyalkylene glycol. Is about 97 weight percent or more.

  The central portion may comprise an ethoxylate having more than one hydroxyl group. For example, the ethoxylate may be an aliphatic ethoxylate or an aromatic ethoxylate. The ethoxylate may contain any number of ethylene oxide groups. Preferably, the ethoxylate contains one or more ethylene oxide groups for each hydroxy group. The ethoxylate may be a straight chain compound or it may be branched. An example of a branched ethoxylate is glycerol ethoxylate.

  The central polymer portion may comprise a cyclic polyol. The cyclic polyol preferably comprises or consists essentially of an N—C = O ring structure as backbone and one or more hydroxyl groups, preferably three ethyl hydroxyl groups, or It consists only of them. An example of a cyclic polyol is 1,3,5-tris (2-hydroxyethyl) isocyanurate.

式中、Ｒは、１つ以上のヘテロ原子を含有していてもよいヒドロカルビル基であり、Ｘは酸素または直接結合（例えば、メチレンβ−ケトエステル）である。１，１−ジカルボニル置換エチレンの典型的な部類はメチレンマロネート、メチレンβ−ケトエステルまたはジケトンである。メチレンマロネートの例は式２である：

式中、Ｒは、出現毎に独立して、アルキル、アルケニル、Ｃ_３−Ｃ_９シクロアルキル、ヘテロシクリル、アルキルヘテロシクリル、アリール、アラルキル、アルカリール、ヘテロアリールもしくはアルキヘテロアリール、もしくはポリオキシアルキレンであり得るか、または両方のＲが５〜７員環の環式または複素環式の環を形成している。Ｒは、出現毎に独立して、Ｃ_１−Ｃ_１５アルキル、Ｃ_２−Ｃ_１５アルケニル、Ｃ_３−Ｃ_９シクロアルキル、Ｃ_２−２０ヘテロシクリル、Ｃ_３−２０アルキヘテロシクリル、Ｃ_６−Ｃ_１８アリール、Ｃ_７−Ｃ_２５アルカリール、Ｃ_７−２５アラルキル、Ｃ_５−１８ヘテロアリールもしくはＣ_６−２５アルキルヘテロアリール、もしくはポリオキシアルキレンであり得るか、または両方のＲ基が５〜７員環の環式または複素環式の環を形成している。列挙された基は、本明細書において開示される反応を妨害しない１つ以上の置換基で置換されていてもよい。好ましい置換基としては、ハロ アルキルチオ、アルコキシ、ヒドロキシル、ニトロ、アジド、シアノ、アシルオキシ、カルボキシまたはエステルが挙げられる。Ｒは、出現毎に独立して、Ｃ_１−Ｃ_１５アルキル、Ｃ_３−Ｃ_６シクロアルキル、Ｃ_４−Ｃ_１８ヘテロシクリル、Ｃ_４−Ｃ_１８アルキヘテロシクリル、Ｃ_６−Ｃ_１８アリール、Ｃ_７−Ｃ_２５アルカリール、Ｃ_７−２５アラルキル、Ｃ_５−Ｃ_１８ヘテロアリールまたはＣ_６−Ｃ_２５アルキルヘテロアリール、またはポリオキシアルキレンであり得る。Ｒは、出現毎に独立して、Ｃ_１−Ｃ_４アルキルであり得る。Ｒは、出現毎に独立して、メチルまたはエチルであり得る。Ｒは、１，１−ジカルボニル置換エチレンの各エステル基において同じであってもよい。典型的な化合物は、ジメチル、ジエチル、エチルメチル、ジプロピル、ジブチル、ジフェニル及びエチル−エチルグルコナートマロネート；または、ジメチル及びジエチルメチレンマロネートである（Ｒがメチルかエチルかのどちらかである）。 Functional Compounds The disclosed compositions comprise 1,1 disubstituted 1-alkene compounds which are preferably 1,1 dicarbonyl substituted alkene compounds. Preferred 1,1 dicarbonyl substituted alkene compounds are 1,1-dicarbonyl substituted ethylene compounds. A 1,1-dicarbonyl substituted ethylene compound refers to a compound having a double bond and a carbon further attached to two carbonyl carbon atoms. A typical compound is shown in Formula 1:

Wherein R is a hydrocarbyl group which may contain one or more heteroatoms, and X is oxygen or a direct bond (e.g. methylene beta-keto ester). A typical class of 1,1-dicarbonyl substituted ethylenes is methylene malonate, methylene beta-keto esters or diketones. An example of methylene malonate is Formula 2:

Wherein R is, independently at each occurrence, alkyl, alkenyl, C ₃ -C ₉ cycloalkyl, heterocyclyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl, heteroaryl or alkyl heteroaryl or polyoxyalkylene Or both R's form a 5- to 7-membered cyclic or heterocyclic ring. R is independently at each occurrence C ₁ -C ₁₅ alkyl, C ₂ -C ₁₅ alkenyl, C ₃ -C ₉ cycloalkyl, C _2-20 heterocyclyl, C _3-20 alkyl heterocyclyl, C ₆ -C _{18 aryl, C} 7- _{C 25 alkaryl, C 7-25 aralkyl, C 5-18} heteroaryl or _{C 6-25} alkylheteroaryl, or either can be a polyoxyalkylene, or both R groups are 5- to 7-membered The ring forms a cyclic or heterocyclic ring. The listed groups may be substituted with one or more substituents that do not interfere with the reactions disclosed herein. Preferred substituents include haloalkylthio, alkoxy, hydroxyl, nitro, azide, cyano, acyloxy, carboxy or ester. R is independently at each occurrence C ₁ -C ₁₅ alkyl, C ₃ -C ₆ cycloalkyl, C ₄ -C ₁₈ heterocyclyl, C ₄ -C ₁₈ alkyl heterocyclyl, C ₆ -C ₁₈ aryl, C _7- C _{25 alkaryl, C 7-25 aralkyl,} may be _{C 5-C 18} heteroaryl or _C 6- _{C 25} alkyl heteroaryl or polyoxyalkylene. R may be C ₁ -C ₄ alkyl independently at each occurrence. R may independently be methyl or ethyl on each occurrence. R may be the same in each ester group of 1,1-dicarbonyl substituted ethylene. Typical compounds are dimethyl, diethyl, ethylmethyl, dipropyl, dibutyl, diphenyl and ethyl-ethyl gluconate malonate; or dimethyl and diethylmethylene malonate (R is either methyl or ethyl) .

  The 1,1-dicarbonyl substituted ethylene compounds disclosed herein exhibit a purity high enough to polymerize it. The purity of the 1,1-dicarbonyl-substituted ethylene is at least 70 mole percent, preferably at least 80 mole percent, more preferably at least 90 mole percent, still more preferably at least 95 mole percent of the 1,1-dicarbonyl-substituted ethylene. Most preferably, more than 99 mole percent may have a purity high enough to be converted to a polymer during the polymerization process. The purity of the 1,1-dicarbonyl-substituted ethylene is at least about 96 mole percent, at least about 97 mole percent, at least about 98 mole percent, at least about 99 mole percent, based on the total weight of the 1,1-dicarbonyl-substituted ethylene. Or about 99.5 mole percent or more. 1,1-dicarbonyl-substituted ethylene is not more than 4 mole percent 1,1-dicarbonyl-substituted-1,1-bis (hydroxymethyl) -methane, not more than 3 mole percent 1,1-dicarbonyl-substituted-1, 1-bis (hydroxymethyl) -methane, up to 2 mole percent 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl) -methane, up to 1 mole percent 1,1-dicarbonyl substituted-1,1, It contains 1-bis (hydroxymethyl) -methane or 0.5 mole percent or less of 1,1-dicarbonyl-substituted-1,1 (hydroxymethyl) -methane. The concentration of any impurities containing dioxane groups is preferably less than or equal to about 2 mole percent, more preferably less than or equal to about 1 mole percent, and even more preferably about 0 or less, based on the total weight of 1,1-dicarbonyl substituted ethylene. 2 mole percent or less, most preferably about 0.05 mole percent or less. The total concentration of any impurities in which the alkene group has been replaced by an analogue hydroxyalkyl group (eg by Michael addition of the alkene with water) is preferably about 3 mole percent based on the total number of moles of 1,1-dicarbonyl substituted ethylene. Or less, more preferably about 1 mole percent or less, still more preferably about 0.1 mole percent or less, and most preferably about 0.01 mole percent or less. Preferably, the 1,1-dicarbonyl substituted ethylene is one or more (eg two) distilling the reaction product or intermediate reaction product (eg reaction product or intermediate reaction product of formaldehyde source and malonic acid ester) Prepared by the process including the steps of

  The functional compounds may comprise one or more methylene malonates which may be the same or different.

  catalyst

  Transesterification reactions as taught herein are typically performed in the presence of one or more catalysts. The transesterification catalyst may be an acid, an ester of such an acid, or an enzyme. The transesterification catalyst may be an enzyme. The transesterification catalyst may be a lipase enzyme. A transesterification process utilizing enzymes is disclosed in US 2014/0329980, which is incorporated herein by reference in its entirety for all purposes.

  The transesterification catalyst can be one or more acids or esters of acids with a pKa of about -5 to about 14 in polar aprotic solvents. The acid or ester of the acid may be present in an amount such that the acid or ester of the acid does not exceed about 3.0 molar equivalents per molar equivalent of the ester containing the compound to be transesterified. When the catalyst is an acid or an ester of an acid, the process may be carried out at a temperature of about 20 ° C to about 160 ° C. The transesterification catalyst may be a lipase enzyme catalyst. When the catalyst is a lipase enzyme catalyst, the transesterification step is performed at an elevated temperature of about 20 ° C to 70 ° C. Volatile by-products may be formed during the transesterification reaction and may be removed from the reaction mixture. Volatile byproducts can be removed from the reaction mixture by applying a vacuum. Volatile by-products may be alcohols.

  The catalyst may be an acid or an ester thereof. Transesterification processes using acids or esters are disclosed in US patent application Ser. No. 14 / 814,961, filed Jul. 31, 2015, which is incorporated herein by reference in its entirety for all purposes. In the Any acid or ester thereof that catalyzes transesterification while minimizing side reactions may be used. In some embodiments, the acid, ie, the acid utilized to form the ester, is an acid having a pKa in a polar aprotic solvent, such as acetonitrile or dioxane, as disclosed below. In particular, the pKa is chosen to efficiently catalyze transesterification reactions while minimizing the concentration of catalyst in side reactions and reaction mixtures. The acid used may have a pKa of about -5 or more, about -3 or more, or about 1.0 or more. The acid used may have a pKa of about 14 or less, about 11 or less, or about 9 or less. The acid can be a Bronsted acid having a pKa as disclosed. The catalyst may be a super strong acid or an ester thereof. By superacid is meant an acid whose acid strength is greater than that of 100 percent sulfuric acid. The ester refers to a compound in which hydrogen in the acid has been replaced by a hydrocarbyl group, preferably an alkyl group, in the context of an acid catalyst. Super strong acids are acids having a strength greater than that of 100 percent sulfuric acid, a pKa less than 100 percent sulfuric acid, ie less than 8, more preferably less than about 5, and most preferably less than about 2. For the measurement of acid strength, Kutt et al., Published on the web on Dec. 17, 2010. It is based on "Equilibrium Acids of Super Acids," Journal of Organic Chemistry Vol 76 pages 391 to 395, 2011, which is incorporated herein by reference. Typical superacids include trifluoromethane sulfonic acid (triflic acid), sulfated tin oxide, triflated tin oxide, sulfated zirconia, triflated zirconia, and triflated HZSM-5. The most preferred superacids are triflic acid and fluorosulfonic acid.

  Typical acid catalysts include triflic acid, fluorosulfonic acid, and sulfuric acid. In the case of reactions where mono-substitution is required (it is going to replace only one hydroxyl group of the alcohol by transesterification), weaker acids with pKa values equal to or higher than sulfuric acid may be desirable. Examples of such acids include sulfuric acid or methanesulfonic acid. For reactions where disubstitution is required (where it is intended to replace the two hydroxyl groups of the alcohol by transesterification), stronger acids with pKa values equal to or lower than sulfuric acid may be desirable. Examples of such acids include sulfuric acid, fluorosulfonic acid and triflic acid. For reactions requiring multiple substitution (more than two hydroxyl groups on the alcohol), the choice of acid catalyst can be similar to that of the disubstitution reaction, but the reaction time may need to be extended. Acid esters useful as catalysts include alkyl triflates.

  The catalyst can be mixed with the reactants or can be supported on a substrate, such as a membrane, or an inert carrier, such as a porous support structure (making the catalyst heterogeneous) it can). Unsupported catalysts are generally referred to as homogeneous. The catalyst can be used at any concentration which catalyzes the transesterification reaction. The amount of catalyst utilized for the reaction depends on the type of catalyst selected. The concentration of the catalyst is about 3 molar equivalents or less; about 1 molar equivalent or less; about 0.5 molar equivalents or less; about 0.1 molar equivalents or less per equivalent of ester compound undergoing transesterification. The concentration of the catalyst is at least about 0.01 molar equivalent; most preferably at least about 0.1 molar equivalent per equivalent of ester compound undergoing transesterification. Higher concentrations of catalyst than those listed may be utilized. Malofsky et al. Nos. 8,609,885 and 8,884,051; and Malofsky et al. As disclosed in WO 2013/059473, the presence of the acid in the recovered 1,1-disubstituted alkene compound can be problematic with respect to the use of the compound, the concentration of acid in the product being at the time of use being Low is desirable. If the final product contains high levels of acid, further purification or removal steps may be required. The amounts listed achieve a balance between efficient catalysis and the need for low acid concentrations in the product for use. In embodiments where the catalyst is selected from sulfuric acid or an acid having a pKa value lower than that of sulfuric acid, the concentration of such catalyst in the reaction mixture is preferably at the upper end of the range recited herein. .

  The catalyst may comprise or consist of an enzyme catalyst. Any enzyme catalyst suitable to catalyze transesterification reactions may be used. Various enzyme catalysts are disclosed in U.S. Patent No. 7,972,822 B2 (Gross et al., Issued July 5, 2011, see, e.g., lines 8 to 4 and lines 7 to 35), U.S. Patent No. 5,416,927A (Zaks et al., May 31, 1994, for example, see column 2, line 64 to column 3, line 12), U.S. Patent 5,288,619 A (Brown) et al., published Feb. 22, 1994, eg, at column 4, line 18 to column 5, line 17), US Patent Application Publication No. 2016/177, 349 A1 (Addy et al., 2016). Published June 23, eg see paragraphs 0046-0048), US Patent Application Publication No. 2014/0017741 A1 (Nielsen et al., January 2014) 6 days published, for example, described in paragraph reference numbers 0026-0029), incorporated by reference contents of each by reference herein.

  A wide variety of enzymes can be employed in the enzyme-catalyzed transesterification of wax esters, such as those derived / obtained from biological organisms, synthetically produced and biologically and / or synthetically produced There are totally artificial ones whether they are or not. These may include, as enzymes that are lipases, one, several, any, or any combination of lipases from the following organisms: Aspergillus niger, Aspergillus oryzae, Bacillus subtilis, Bacillus thermocatenulatus , Burkholderia cepacia, Burkholderia glumae, Candida rugosa, Candida antarctica A, Candida antarctica B, Candida cylindracea, Candida parapsilosis, Chromobacterium viscosum, Geotrichum candidum, richum genus, Mucor miehei, Humicola lanuginose, Penicillium camembertii, Penicillium chrysogenum, Penicillium roquefortii, Pseudomonas cepacia, Pseudomonas aeruginosa, Pseudomonas fluorenscens, Pseudomonas fragi, Pseudomonas alcaligenes, Pseudomonas mendocina, Rhizopus arrhizus, Rhizomucor miehe, Staphylococcus hyicus, Staphylococcus aereus, Staphylococcu epidermidis, Staphylococcus warneria, Staphylococcus xylosus, Thermomyces lanuginosus, Aspergillus spp, Bacillus spp, Burkholderia genus, Candida genus, Chromobacterium genus, Geotrichum genus, Mucor genus, Humicola genus, Penicillium genus, Pseudomonas genus, Rhizopus genus, Staphylococcus genus and Thermomyces sp. The lipase may comprise or consist essentially of one or any combination of the following: Novozymes A / S, Bagsvaerd, marketed by Denmark under the trademark LIPOZYME TL IM or LIPEX And a lipase from Thermomyces lanuginosus, also immobilized on a substrate manufactured by Novozymes; the lipase being derived from Candida antarctica and marketed by Novozymes, A / S under the NOVOZYM trade name Also marketed by Novozymes under the trade names CALB L, NOVOZYME 435, NOVOCOR ADL, and LIPOLASE 100L Are those; c-LEcta, GMBH, Leipzig, those sold CALB, under the trademark CALA and CRL by Germany; Amano Enzyme Inc. , LIPASE A "AMANO" 12, LIPASE AY "AMANO" 30 SD, LIPASE G "AMANO" 50, LIPASE R "AMANO", LIPASE DF "AMANO" 15, LIPASE MER "AMANO", and NEWLASE F by N.A., Nagoya, Japan Commercially available under the name; Meito Sangyo Co. , Ltd. Commercially available under the tradenames LIPASE MY, LIPASE OF, LIPASE PL, LIPASE PLC / PLG, LIPASE QLM, LIPASE QLC / QLG, LIPASE SL, and LIPASE TL by N., Nagoya, Japan; derived from Candida antarctica A Lipase, a lipase derived from Candida antarctica B, and a lipase derived from Candida rugosa. In various embodiments, the lipase is preferably at least 60% of any lipase disclosed herein and in the patent applications disclosed herein (all of which are already incorporated by reference) It has at least 70%, at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, or even at least 99% identity.

  Polymerizable system

  One aspect according to the teachings herein relates to a polymerizable system comprising a functionalized polymer and one or more methylene malonate monomers. The methylene malonate monomer can be selected such that it will copolymerize with the alkenyl group of the functionalized polymer. A first polymer block wherein the copolymerization of the functionalized polymer and one or more methylene malonate monomers comprises or consists essentially of or consists of methylene malonate monomer (s) It will be appreciated that the block copolymer may comprise a central polymer portion (eg, a polyol containing polymer) and a second polymer block consisting essentially of or consisting only of it. Where the functionalized polymer comprises two or more spaced alkenyl groups (eg, spaced methylene malonate compounds, preferably at different ends of the central polymer portion), the functionalized polymer results in crosslinking of the methylene malonate monomers obtain.

  Any methylene malonate compound described herein with respect to functional compounds having alkenyl groups for the functionalized polymer may be employed as monomers in the polymerizable composition. Some or all of the methylene malonate monomers may be replaced by dimers, trimers or longer oligomers (eg having a degree of polymerization of about 4 to 50, about 4 to 15, or about 4 to 8) Will be understood.

  The second polymer block (eg, a block comprising a polyol containing polymer) may be more flexible than the first polymer block and may provide the block copolymer with flexibility and / or impact resistance.

  The polymerizable system may comprise a sufficient amount of a stabilizing agent to prevent or minimize polymerization of the heavy synthesis system. The process may include activating the polymerizable system to polymerize the methylene malonate monomer and the alkenyl group (s) attached to the central polymer moiety.

  The amount of one or more methylene malonate monomers in the first polymer block is preferably at least about 20 percent by weight, more preferably at least about 50 percent by weight, even more preferably about at least about 20 percent by weight based on the total weight of the first polymer block. It is at least 75 weight percent, most preferably at least about 85 weight percent. The amount of one or more methylene malonate monomers in the first polymer block is about 100 weight percent or less, about 99 weight percent or less, about 97 weight percent or less, about 93 weight percent based on the total weight of the first polymer block Or less or about 88 weight percent or less. The amount of polyol in the second polymer block is preferably at least about 25 weight percent, more preferably at least about 60 weight percent, even more preferably at least about 80 weight percent, most preferably about 25 weight percent based on the total weight of the second polymer block. Is about 90 weight percent or more. The amount of polyol in the second polymer block can be about 100 weight percent or less, about 98 weight percent or less, about 96 weight percent or less, or about 94 weight percent or less based on the total weight of the second polymer block. The ratio of the weight of one or more methylene malonate monomers to the weight of the functionalized polymer is about 0.05 or more, about 0.10 or more, about 0.20 or more, or about 0.45 or more, or about 0.60 or more It can be. The ratio of the weight of one or more methylene malonate monomers to the weight of the functionalized polymer is about 0.99 or less, about 0.96 or less, about 0.92 or less, about 0.88 or less, about 0.84 or less, or It may be about 0.80 or less.

  Functionalized polymers and / or polymerizable systems can be used for the films or coatings. The thickness of the film or coating may be about 0.001 μm or more, about 0.1 μm or more, about 1 μm or more, or about 2 μm or more. The thickness of the coating or film is preferably about 200 μm or less, more preferably about 50 μm or less, and most preferably about 20 μm or less.

  Functionalized polymers and / or polymerizable systems according to the teachings herein may be employed in crosslinked polymers. The cross-linked polymer may comprise or consist essentially of or consist of a functionalized polymer and a polymerized 1,1-disubstituted alkene monomer (e.g. methylene malonate monomer). In the crosslinked polymer, the total of the functionalized polymer and the polymerized 1,1-disubstituted alkene monomer is at least about 5 weight percent, at least about 20 weight percent, at least about 45 weight percent, based on the total weight of the crosslinked polymer. It may be about 70 weight percent or more, or about 90 weight percent or more. The total amount of functionalized polymer and polymerized 1,1-disubstituted alkene monomer in the crosslinked polymer can be up to about 100 weight percent, or up to about 98 weight percent, based on the total weight of the crosslinked polymer.

  process

によって反応するエステル基を含み得る。 Functionalized polymers can be prepared by reacting a polymer comprising a polyol and having one, two, three or more hydroxyl groups with one or more functional compounds containing alkenyl groups. Functional compounds are transesterification reactions:

May contain an ester group to be reacted.

  The process may employ a catalyst that accelerates the transesterification reaction. Preferred catalysts for reacting polyol-based polymers with functional compounds comprising esters include enzyme catalysts or acid catalysts.

  The process may be a batch process, a continuous process, or a combination thereof. For example, the continuous process may include the step of providing one or more reactants (e.g., a 1,1-disubstituted compound and a compound that forms the central portion) into a continuous reactor. The catalyst may be fed into the reactor, or the reactor may be equipped with a catalyst. For example, at least a portion of the reactor may include a filler with a catalyst, or the catalyst is present at a surface within the reactor (eg, the surface of the reactor or the surface of a component within the reactor) It may be A continuous reactor is a tubular reactor or any other reactor suitable for inserting at least one reactant at one end and removing at least one reaction product at the opposite end. obtain. Preferably, the continuous reactor is a tubular reactor in which a catalyst is packed in the reactor. The continuous process is preferably at a temperature of about 10 ° C. or more, more preferably about 15 ° C. or more, and most preferably about 20 ° C. or more. The reaction temperature is preferably about 150 ° C. or less. When an acid catalyst is employed, the reaction temperature is preferably about 40 ° C to about 150 ° C, more preferably about 60 ° C to about 150 ° C. If an enzyme catalyst is employed, the reaction temperature is preferably about 80 ° C. or less, more preferably about 70 ° C. or less, and most preferably about 60 ° C. or less.

  The process of polymerizing one or more methylene malonate monomers with one or more functionalized polymers (including, for example, a polyol) to form a block copolymer is any polymerization suitable for polymerizing methylene malonate monomers. A method may be adopted. It is preferred that the functional groups on the functionalized polyol comprise alkenyl groups suitable to be anionically polymerizable. Preferably, the functional group comprises methylene malonate that is the same as or different from the methylene malonate monomer. More preferably, the functional group comprises methylene malonate which is also employed as a monomer of the polymerization process to form the block copolymer.

  A transesterification process may be employed to react each hydroxyl group (ie, each terminal hydroxyl group) of the polyol polymer with the 1,1-disubstituted alkene compound to form a functionalized polymer. When a 1,1-disubstituted alkene is reacted with two different polyol polymers, it can extend the length of the polyol polymer and add an alkenyl group to the central polymer portion of the functionalized polymer. It may be beneficial to avoid such chain extension reactions. The chain extension reaction during formation of the functionalized polymer is mitigated, substantially eliminated or completely eliminated by the choice of 1,1-disubstituted alkene compounds, the use of excess 1,1-disubstituted alkene compounds, or both It can be done. For example, a 1,1-disubstituted alkene compound may comprise or consist essentially of a compound having a single ester group capable of transesterification. As another example, the 1,1-disubstituted alkene compound may contain two or more ester groups and is in excess such that an unreacted 1,1-disubstituted alkene compound is present after transesterification Can be present at various concentrations. The amount of excess 1,1-disubstituted alkene compound is determined by the molecular weight of the polyol polymer, the mobility of the polyol polymer, the compatibility of the polyol polymer with the 1,1-disubstituted alkene compound, and the hydroxyl groups in the polyol polymer (e.g. It may depend on the number of terminal hydroxyl groups). Preferably, an excess of 1,1-disubstituted alkene compound is present (ie, the number of terminal hydroxyl groups of the polyol polymer that can be used for the transesterification reaction can be used for the transesterification reaction1 , The number of molecules of the 1-disubstituted alkene compound must be smaller). Preferably, the molar ratio of the 1,1-disubstituted alkene compound to the weight of the polyol polymer is about 1.5 or more, more preferably about 1.9 or more, even more preferably about 2.3 or more, still more preferably It is about 3 or more, more preferably about 4 or more, and most preferably about 4 or more. When the molecular weight of the polyol polymer is relatively high (eg, the ratio of the molecular weight of the polyol polymer to the molecular weight of the 1,1-disubstituted alkene compound is about 6 or more, or about 15 or more), an excess of 1,1-di Substituted alkene compounds may be employed to reduce the viscosity of the mixture and / or to accelerate the end capping reaction. Thus, the molar ratio of 1,1-disubstituted alkene compound to polyol polymer may be much greater than 4 (e.g., about 10 or more, about 30 or more, or about 100 or more).

  The process may include the step of separating some or all of the unreacted 1,1-disubstituted alkene compound from the end-capped polyol. It may also be desirable to minimize the amount of unreacted 1,1-disubstituted alkene compound. For these reasons, the weight ratio of 1,1-disubstituted alkene compounds is generally (eg, excess 1,1-disubstituted alkene compounds can be reduced and / or easily removed by separation or other techniques Moderately low may be desirable. The ratio of the weight of the 1,1-disubstituted alkene compound to the weight of the polyol polymer is preferably about 40 or less, more preferably about 20 or less, still more preferably about 10 or less, most preferably about 5 or less. However, weight ratios higher than 40 may be employed. That some unreacted 1,1-disubstituted alkene compounds may be used in the polymerizable composition for copolymerizing the 1,1-disubstituted alkene compounds and the alkenyl group attached to the polyol polymer Will be understood. The transesterification reaction may substantially or completely avoid the reaction of one 1,1-disubstituted alkene compound with a large number of hydroxyl groups.

Test Methods Assuming that any lower limit and any upper limit are separated by at least 2 units from any numerical value listed in this specification, any value from the lower limit to the upper limit in increments of 1 unit. Contains the value. For example, if it is stated that the amount of component or process variable such as temperature, pressure, time etc. is, for example, 1 to 90, preferably 20 to 80, more preferably 30 to 70 Values such as ~ 85, 22-68, 43-51, 30-32 etc. are intended to be explicitly listed herein. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are merely examples of what is specifically intended, and that possible combinations of numerical values between the lower and upper limits listed are likewise explicitly mentioned in the present application. It should be considered. It will be appreciated that the teaching of the amounts expressed as "parts by weight" herein also contemplates the same range expressed by weight percent. Thus, in the detailed description of the invention, the recitation of the range “by weight“ x ”of the resulting polymer blend composition” is the same amount of “resulting polymer blend composition” as listed. Also contemplated are teachings on the range of "x" in weight percent.

  Unless otherwise specified, all ranges include both endpoints and all numbers between the endpoints. The use of “about” or “approximately” in the context of a range applies to the endpoints of the range. Thus, "about 20-30" is intended to encompass "about 20 to about 30", including at least the stated endpoints.

  The disclosures of all articles and references, including patent applications and patent publications, are incorporated by reference for all purposes. The term “consisting essentially of” to describe a combination does not substantially affect the identified elements, components, components or steps and the basic and novel characteristics of the combination. Such elements, components, components or steps of As used herein, the use of the term "comprising" or "including" to describe a combination of elements, components, components or steps consists essentially of the elements, components, components or steps Embodiments are also contemplated.

  Multiple elements, components, components or steps can be provided by a single integral element, component, component or step. Alternatively, a single integral element, component, component or step may be divided into separate plural elements, components, components or steps. The disclosure of "a" or "one" to describe an element, ingredient, component or step is not intended to exclude an additional element, ingredient, component or step.

  It is understood that the above description is intended to be illustrative and not restrictive. After reading the above description, many embodiments and many applications other than the provided examples will become apparent to those skilled in the art. Accordingly, the scope of the present invention should not be determined with reference to the above description but with reference to the appended claims, with reference to the full scope of equivalents which can be found for such claims. It should be decided. The disclosures of all articles and references, including patent applications and patent publications, are incorporated by reference for all purposes. The omission of any aspect of the subject matter disclosed herein in the claims that follow is not a waiver of such subject matter, and we do not disclose such subject matter. It should not be regarded as not considered as part of the subject matter of the present invention.

  Example

  Example 1 and Example 2

  Example 1 is a reaction mixture comprising a linear aromatic polyester polyol that is capped at both ends with methylene malonate monomer and the remaining monomer. Example 2 is the filtrate of Example 1 after removal of residual methylene malonate monomer.

In a round bottom flask, about 6 grams of aromatic polyester polyol and about 30 grams of diethyl methylene malonate monomer are mixed until the polyol is dissolved or dispersed in the monomer. Aromatic polyesters are commercially available from INVISTA and have an average of about 2.2 hydroxyl groups per molecule, a hydroxyl number of about 295 mg KOH / g, and a viscosity of about 6,000 cps at 25 ° C. TERATE® HT 5100 It is a polyol. The aromatic polyester polyol contains a repeating unit having an aromatic group (for example, a residue of bisphenol) and an ester group along the main chain.

  About 3 g of enzyme catalyst (about 10% by weight of diethyl methylene malonate monomer) is added to the reaction mixture. The enzyme catalyst is a NOVOZYM 435 immobilized lipase enzyme commercially available from NOVOZYMES (Denmark). Attach a round bottom flask to a rotary evaporator maintained at a temperature of about 45 ° C. and rotate at 100 rpm for 2 hours under 200 mm Hg vacuum. At the end of the reaction, a small amount is taken for NMR analysis, and the remaining mixture is filtered using a cotton plug packed into a 100 ml syringe to remove the enzyme. The filtrate (i.e., the reaction mixture) is a blend of about 70 percent by weight of diethyl methylene malonate monomer (i.e., DEMM) and about 30 percent by weight of an end-capped aromatic polyester polymer. FIG. 1A is a proton NMR spectrogram of a reaction mixture containing DEMM. As can be seen in FIG. 1B, the formation of new species with methylene double bonds is confirmed in the 6.535-6.583 ppm region of the spectrum, and the residual DEMM is confirmed in the 6.51-6.535 ppm region of the spectrum. .

に示す特徴のうちの１つ以上を有し得る。 End-capped aromatic polyesters are as follows:

Can have one or more of the features shown in FIG.

  A lap shear sample is made on a cold rolled sheet using a reaction mixture containing residual DEMM and an end-capped aromatic polyester polymer, using 0.1 wt% Na benzoate as the activator in ethanol . The lap shear strength after room temperature curing for 24 hours is measured on at least three samples. The average lap shear strength is about 5.7 MPa. Another lap shear sample is allowed to cure at room temperature for 24 hours and then aged in an oven at 120 ° C. for 2 days. After aging, the lap shear strength increased to over 10 MPa. The increase in lap shear strength is believed to be the result of thermal crosslinking. The aromatic nature of the polyol results in an adhesive system having a bulky backbone structure with high stiffness.

  A sample of the reaction mixture containing unreacted DEMM is cured using tetramethyl guanidine (i.e. TMG) in bulk in an aluminum pan. The resulting polymer is not soluble in dichloromethane (ie DCM). This indicates a high degree of crosslinking.

  Example 2

  Hexane is added to a sample of the reaction mixture of Example 1 containing unreacted DEMM. Hexane is a good solvent for residual DEMM, and a poor solvent for polyols and end-capped polyols. The end-capped polyol is separated from excess DEMM of the reaction mixture. The end-capped polyol is then dried in vacuo to remove residual hexane. The adhesion of the isolated end-capped aromatic polyester is then tested by making a lap shear sample using the same cure time as for the lap shear test of the reaction mixture. The lap shear strength of the isolated end-blocked polyester is about 4 MPa after 24 hours of cure at room temperature cure and 6.6 MPa after 2 days of cure at 120 ° C. The bulky structure of the central polymer portion and the low concentration of alkenyl groups are believed to make anionic polymerization of the isolated end-capped polyol difficult. The use of methylene malonate monomers such as DEMM can improve adhesion, as demonstrated by the higher adhesion of Example 1 compared to Example 2.

  Example 3

  Example 3 is a reaction mixture comprising an end-capped aliphatic polyester polyol and residual methylene malonate monomer.

The examples are prepared by reacting TERRIN® 168 polyol with DEMM to seal the end of the polyol. TERRIN (TM) 168 aliphatic polyester polyol is commercially available from INVISTA, glycols (including glycol _{HO-C 2 H 4 -O-} C 2 H 4 -OH) and the carboxylic acid functional monomer (mainly, adipic Acid and 6-hydroxycaproic acid).

  In a round bottom flask, about 30 g of DEMM and about 6 g of TERRIN® 168 (about 5: 1 weight ratio) are mixed until the polyol dissolves or disperses in the DEMM monomer. About 3 g of NOVOZYM® 435 enzyme catalyst (about 10 wt% DEMM) is added to the flask. Attach the flask to a rotary evaporator maintained at 45 ° C. and rotate at 100 rpm for 2 hours under a vacuum of 200 mm Hg. At the end of the reaction, a small amount is taken for NMR analysis, and the remaining mixture is filtered using a cotton plug packed into a 100 ml syringe to remove the enzyme. The reaction mixture (i.e., the filtrate) is a blend comprising unreacted DEMM and end-capped aliphatic polyester polymer in a weight ratio of about 75:25.

  A sample of the reaction mixture is cured using tetramethyl guanidine (TMG) in bulk in an aluminum pan. The resulting polymer was not soluble in DCM, indicating a high degree of crosslinking. After washing with DCM, the polymer is tested using thermogravimetric analysis (TGA) at a heating rate of about 10 ° C./min. The TGA scan is shown in FIG. Degradation leading to weight loss begins at a temperature of about 250 ° C. There is a 50% weight loss at temperatures above about 300 ° C. (eg, about 335-365 ° C.). In comparison, the temperature (measured by TGA) corresponding to a 50 weight percent weight loss of DEMM homopolymer is typically about 210 ° C., and crosslinked DEMM (about prepared by transesterifying DEMM with hexanediol The temperature corresponding to a weight loss of 50 weight percent of the one prepared by polymerizing 70 weight percent DEMM in the presence of 30 weight percent crosslinker is greater than about 300 ° C. These TGA results are believed to demonstrate that the end-capped aliphatic polyester polyols copolymerize with DEMM to result in cross-linking of DEMM.

  Example 4 and Example 5

  Example 4 is a reaction mixture comprising a polycarbonate polyol end-capped with methylene malonate monomer and the remaining monomer. Example 5 is an end-capped polycarbonate polyol after removal of residual monomers.

  Example 4 mixes about 30 g of DEMM and about 6 g of PACAPOLTM F250 polycarbonate polyol (weight ratio of about 5: 1) in a round bottom flask until the polyol is dissolved or dispersed in the DEMM monomer Prepared by PACAPOLTM F250 is an aliphatic polycarbonate polyol commercially available from INSTRUMENTAL POLYMER TECHNOLOGIES. PACAPOLTM F260 is slightly branched, 100% solids, and has hydroxyl functionality at an equivalent weight of about 225 g / eq. A solvent (eg, toluene) may be used to facilitate mixing of the polycarbonate polyol and the methylene malonate monomer. About 3 g of CLEA 102B4 candida antarctica isoform B / powder (about 10% by weight DEMM), which is a crosslinked enzyme aggregate, is added to the flask as a reaction catalyst. CLEA 102B4 is a product of CLEA TECHNOLOGIES B.2. V. It is commercially available from (Delft, The Netherlands). The flask is attached to a rotary evaporator, and the reaction is performed at 45 ° C. for 2 hours under a vacuum of about 200 mmHg with a rotation speed of about 100 rpm. At the end of the reaction, a small amount is taken for NMR analysis, and the remaining material is filtered using a cotton plug packed into a 100 ml syringe to remove the enzyme. The reaction mixture (i.e., the filtrate) comprises a blend of DEMM and end-capped polycarbonate polyol in a weight ratio of about 75:25.

の構造において示される特徴のうちの１つ以上を有し得る。 The end-capped polycarbonate polyols are as follows:

Can have one or more of the features shown in the structure of

  The reaction mixture is cured using TMG in an aluminum pan. The resulting polymer was not soluble in DCM, indicating a high degree of crosslinking.

  Example 5 is prepared by removing unreacted methylene malonate monomer from Example 4. Example 5 is prepared by adding hexane to the reaction mixture of Example 4. Hexane is a poor solvent for polycarbonate polyols and end-capped polycarbonate polyols. After removing the DEMM, the end-capped polyol is dried at room temperature under vacuum to remove residual hexane.

  The isolated blocked polycarbonate polyol is cured using TMG in an aluminum pan. The resulting polymer was not soluble in DCM, indicating a high degree of crosslinking.

  FIG. 3 is a proton NMR spectrogram of the isolated end-capped polycarbonate polyol.

  A coating of the reaction mixture (containing end-capped polycarbonate polyol and unreacted DEMM) of Example 4 is spread on a treated cold rolled sheet. The cold rolled sheet is treated with 0.1% Na benzoate in BUTYL CELLOSOLVETM solvent (commercially available DOW CHEMICAL COMPANY) to initiate polymerization of DEMM. The reaction mixture is spread using a Meyer Rod 10 and allowed to cure for about 24 hours at room temperature. The resulting coating has a thickness of about 25 μm. The coating has a high degree of flexibility observed from the coating maintaining adhesion when the plate is folded about 180 ° with a mandrel according to ASTM D522-93. In a similar bending test on a sample prepared using only DEMM monomer on a treated cold rolled sheet (i.e., DEMM homopolymer), the film peels off the surface of the sheet during bending. Thus, the addition of end-capped polycarbonate improves the flexibility of the product of polymerizing DEMM.

  Example 6

  Example 6 is a reaction mixture comprising a polybutadiene polyol end-capped with methylene malonate monomer and the monomer.

  An example of a polybutadiene polyol is shown below.

  Example 6 DEMM Monomer in a round bottom flask with about 40 g of DEMM and about 10 g of POLY BD® R-20 LM hydroxyl terminated polybutadiene resin (ie HTPB) (ie, a weight ratio of about 4: 1). It is prepared by mixing until the polyol dissolves or disperses. POLY BD® resin is commercially available from CRAY VALLEY HYDROCARBON SPECIALTY CHEMICALS and has a number average molecular weight of about 1200, a glass transition temperature of about -70 ° C, and an average of about 2.5 hydroxyl groups per chain. Have. Of the monomer units in HTPB, about 20% are 1,2 adducts and about 80% are 1-4 adducts. Then, about 4 g of CLEA 102B4 enzyme catalyst (about 10% by weight of DEMM) is added to the flask. Attach the flask to a rotary evaporator maintained at about 45 ° C. and rotate at about 100 rpm for 2 hours under a vacuum of about 200 mm Hg. At the end of the reaction, a small amount is taken for NMR analysis. The remaining material is filtered using a cotton plug packed into a 100 ml syringe to remove the enzyme. The reaction mixture (ie, the filtrate) is a blend comprising unreacted DEMM and end-capped polybutadiene in a weight ratio of about 75:25.

の構造において示される特徴のうちの１つ以上を有し得る。 The end-blocked polybutadiene is as follows:

Can have one or more of the features shown in the structure of

  FIG. 4 shows the H-NMR of the reaction mixture. The methylene protons next to the OH group in HTPB typically appear at 4.1 ppm and 4.3 ppm in the H-NMR spectrum. They are significantly reduced (e.g. disappear or appear very weak) in the reaction mixture after the transesterification reaction.

  The reaction mixture is cured using TMG in an aluminum pan. The resulting polymer was not soluble in DCM, indicating a high degree of crosslinking.

  These results confirm that the end closure of the polybutadiene has been achieved.

  Example 7

  Example 7 is a reaction mixture comprising end-capped polybutadiene and unreacted methylene malonate monomer.

  Example 7 is prepared in a continuous column reactor at a temperature of about 30 ° C., a pressure of about 150 mm Hg, a feed flow rate of about 100 mL / hr, and a weight ratio of about 5: 1 DEMM to HTPB. Heat the stainless steel supply container with heat tape and place on a stir plate to keep the mixture of DEMM and HTPB homogeneous. Apply heat tape to the feed line leading to the bottom of the reactor and insulate. The reactor is covered, heated with an oil heater and insulated to reduce heat loss. A temperature probe is placed in the reactor, feed line and feed vessel to maintain 30 ° C. Pump the DEMM / HTPB mixture at about 100 mL / hr using a peristaltic pump. The mixture is fed from the bottom into the reactor, contacted with the CLEA 102B4 enzyme and pumped out from the top of the reactor. The reactor is charged with about 25 g of CLEA 102B4 enzyme. A vacuum is drawn from the top of the reactor above the outlet from which the product is removed. The product (i.e., the reaction mixture) is pumped into the collection vessel using a peristaltic pump and analyzed by H-NMR every hour after the start of product collection. Transesterification is confirmed by H-NMR as described above for Example 6.

  The reaction mixture is cured using TMG in an aluminum pan. The resulting polymer was not soluble in DCM, indicating a high degree of crosslinking.

  Example 8:

  Example 8 is a reaction mixture comprising carbinol-terminated polydimethylsiloxane end-capped with methylene malonate monomer and unreacted methylene malonate monomer.

  Example 8 was prepared by dissolving about 60 g of DEMM and about 12 g of GELEST DMS C-21 carbinol-terminated poly (dimethylsiloxane) (5: 1 weight ratio) in a round bottom flask, the polyol dissolved in the DEMM monomer or Prepared by mixing until dispersed. GELEST DMS C-21 is manufactured by GELEST, INC. (Morrisville, PA), which has a number average molecular weight of about 4,500 to 5,000, a specific gravity of about 0.98, and a viscosity of about 110 to 140 cSt. The CAS number is 156327-07-0. About 6 g of CLEA 102B4 enzyme catalyst (about 10 wt% DEMM) is added to the flask. Attach the flask to a rotary evaporator maintained at 45 ° C. and rotate at 100 rpm for 2 hours under a vacuum of 200 mm Hg. At the end of the reaction, the mixture is filtered using a cotton plug filled into a 100 ml syringe to remove the enzyme. The resulting reaction mixture (i.e., the filtrate) is a blend of DEMM and end-capped siloxane polyol in a weight ratio of about 75 to 25.

の構造において示される特徴のうちの１つまたは任意の組み合わせを有し得る。 The end-capped siloxane polyols are as follows:

It may have one or any combination of the features shown in the structure of

  The reaction mixture is cured using TMG in an aluminum pan. The resulting polymer was not soluble in DCM, indicating a high degree of crosslinking.

  Coat the reaction mixture of end-capped siloxane with unreacted DEMM using Meyer Rod 10 on a cold-rolled plate that has been pre-initiated (0.1% Na benzoate in butyl cellosolve), Cure for about 24 hours at room temperature followed by heating at 82 ° C. for 1 hour. The coating has a thickness of 25 μm. The coating remains adhesive to the board which has been bent about 180 ° with a mandrel in accordance with ASTM D522-93. This points to the high flexibility of the coating.

  The coating exhibits hydrophobic properties. For example, the contact angle of water on the coating is about 70 °. In comparison, the coating of DEMM monomer only, which has been spread on a cold-rolled plate that has been pretreated, has a contact angle of water on the coating of about 55-55 ° (ie, about 15-20 ° lower). . As exemplified by Example 8, end-capped polysiloxane polyols may be used to impart hydrophobicity to coatings based on methylene malonate (e.g., DEMM).

  Example 9

  Example 9 is a reaction mixture comprising a polyalkylene glycol end-capped with methylene malonate monomer and unreacted methylene malonate monomer. End capping of polyalkylene glycols is performed using a pegylation process.

  CARBOWAXTM PEG 300 polyethylene glycol (commercially available from DOW CHEMICAL COMPANY) is purified through an alumina column for residual base catalyst. The polyethylene glycol has a number average molecular weight of about 285 to 300 g / mole, a hydroxyl number of about 340 to 394 mg KOH / g, a melting range of about -15 ° C to about -8 ° C, and a heat of fusion of about 37 cal / g. Charge about 30 g (0.17 mol) of DEMM, about 3 g (10 wt% of DEMM) of CLEA 102B4 enzyme, and about 16.6 g (0.083 mol) of PEG 300 in a 250 mL round bottom flask (alumina Passed through). The flask is connected to a rotary evaporator evacuated to about 200 mm Hg and heated to about 45 ° C. for 2 hours. The vacuum removes ethanol as a reaction by-product. The enzyme is then filtered off from the reaction mixture using a cotton plug packed into a 20 ml syringe. NMR results indicate that about 35 percent of the DEMM react with PEG and about 65 percent of the DEMM remain in the reaction mixture as unreacted monomer. FIG. 5 shows the NMR of the reaction mixture.

において示される特徴のうちの１つ以上（または全て）を有する、ポリアルコキシドを含む中央ポリマー部分と末端メチレンマロネート基とを含んだ構造を有し得る。 End-capped polymers are as follows:

The polymer may have a structure including a central polymer portion including a polyalkoxide and a terminal methylene malonate group having one or more (or all) of the features shown in 1.

  The reaction mixture of end-capped PEG and DEMM is coated on a cold rolled plate previously primed (0.1% Na benzoate in butyl cellosolve) using Meyer Rod 10 at room temperature After about 24 hours of complete cure and subsequent heating at 82 ° C. for 1 hour, a 25 micron thick film is obtained. The coating exhibits hydrophilic properties, water easily wets the surface, and finally penetrates the coating layer by a series of exposures. Similar coatings applied using only DEMM monomer do not demonstrate hydrophilic properties. This demonstrates that polyethylene glycol imparts hydrophilicity to the DEMM-based coating.

  Example 10

  Example 10 is a reaction mixture comprising a polyalkylene glycol end-capped with methylene malonate monomer and unreacted methylene malonate monomer. End capping of polyalkylene glycols is performed using an acid catalyzed transesterification process.

Assemble a three-neck (250 mL) round bottom flask equipped with a distillation head, thermometer, vacuum adapter and recovery flask using high vacuum grade grease with a mantle heater (and thermocouple) and a magnetic stirrer. In this round bottom flask apparatus, about 20 g (about 0.12 mol) of DEMM, about 4.6 g (about 0.023 mol) of CARBOWAXTM PEG 200 polyethylene glycol (commercially available from DOW CHEMICAL COMPANY), about 0.02 g Charge (about 1000 ppm) MeHQ and about 0.3 ml (about 0.0058 mol) H ₂ SO ₄ . CARBOW AX® PEG 200 polyethylene glycol has a weight average molecular weight of about 190 to 210 g / mole, an average hydroxyl number of about 535 to about 590 mg KOH / g, and a melting point of about -65 ° C. or less. A vacuum pump is used to maintain a reduced pressure of about 400 mm Hg during the reaction. The reaction mixture is then heated to about 130 ° C. and stirred for about 2 hours. Ethanol is recovered as a reaction by-product. The amount of end blockage of PEG is calculated using NMR. About 45 percent of the DEMMs react with PEG, and about 55 percent of the DEMMs remain as monomers.

において示される特徴のうちの１つ以上（または全て）を有する、ポリアルコキシドを含む中央ポリマー部分と末端メチレンマロネート基とを含んだ構造を有し得る。 The end-capped polymers are as follows:

The polymer may have a structure including a central polymer portion including a polyalkoxide and a terminal methylene malonate group having one or more (or all) of the features shown in 1.

  Example 11

  Example 11 is a reaction mixture comprising glycerol ethoxylate end-capped with methylene malonate monomer and unreacted methylene malonate monomer. End capping of the glycerol ethoxylate can be performed using a transesterification process.

About 30 g (about 0.17 moles) of DEMM and about 3 g (about 10 parts per 100 parts of DEMM) of the enzyme NOVOZYME 435 candida antarctica isoform B (commercially available from NOVOZYME) in a 250 mL round bottom flask, about 56 g (0.056) Mol) glycerol ethoxylate (number average molecular weight about 1000, obtained from Sigma Aldrich) is charged. The flask is connected to a rotary evaporator at a reduced pressure of about 200 mm Hg and heated to about 55 ° C. for about 8 hours. Ethanol is removed as a reaction by-product. The enzyme is then filtered from the product using a cotton plug packed in a 20 ml syringe to isolate the reaction mixture. NMR results are obtained from the reaction mixture and used to calculate the conversion of glycerol ethoxylate to end-capped product. About 40% of the desired transesterification product (ie end-capped product) is observed. The NMR spectrum of the reaction mixture is shown in FIG. The reaction mixture is believed to contain disubstituted and trisubstituted glycerol ethoxylate reaction products. The resulting reaction mixture comprises an end-capped glycerol ethoxylate having one or more of the features shown in the following structure.

  The reaction mixture is spread using a Meyer Rod 10 on a cold-rolled plate that has been pre-initiated (0.1% Na benzoate in butyl cellosolve), and fully cured for about 24 hours at room temperature After heating for about 1 hour at about 82 ° C., a 25 micron thick film is obtained. The coating exhibits hydrophilic properties, water easily wets the surface, and finally penetrates the coating layer by a series of exposures. In contrast, samples prepared using a reaction mixture replaced with DEMM only and cured under the same conditions (eg, resulting in DEMM homopolymer) do not demonstrate hydrophilic properties. Thus, it is demonstrated that end-capped glycerol ethoxylates can be used to impart hydrophilicity to coatings (eg, methylene malonate coatings, such as DEMM-based coatings).

  Example 12

The polymerizable composition may be prepared by combining the reaction mixture of diol and methylene malonate with one or more additional monomers and / or one or more crosslinkers. As an example, Example 12 is prepared by mixing the reaction mixture of Example 11 with the amounts of dimethylmethylene malonate (ie D3M), additional DEMM, and 1,5 pentanediol DEMM crosslinker shown in the table below. Be prepared.

  The polymerizable composition is spread using a Meyer Rod 10 onto a cold-rolled plate which has been pretreated (0.1% Na benzoate in butyl cellosolve) and completely cured at room temperature for about 24 hours and After a subsequent heating at about 82 ° C. for about 1 hour, a 25 micron thick film is obtained. The coating does not exhibit the hydrophilic behavior seen in Example 11 above. This is believed to be due to the large amount of crosslinking provided by the pentanediol crosslinking agent. By adjusting the amount of polyol moiety (eg, glycerol ethoxylate) in the final coating by formulation, it may be possible to obtain anti-soiling properties while maintaining a durable water resistant coating.

  Urethane / carbamate bond

  End-capped compounds may contain urethane or carbamate linkages. Such structures may be prepared using reactions involving isocyanurate. Such structures may be prepared by methods that avoid the need for any isocyanurate or isocyanate. For example, the carbamate bond may be obtained by reacting a cyclic carbonate with an amine (eg, a compound having one or more, two or more, or three or more amine groups) to form a carbamate bond and a terminal alcohol. Good. The terminal alcohol can then be used to endblock the carbamate containing compound with the 1,1-disubstituted alkene compound (eg, by transesterification). Preferably each amine group provides a carbamate group and is endcapped with a 1,1-disubstituted alkene compound.

  Example 13

  Example 13 is a reaction mixture comprising an isocyanurate ethoxylate end-capped with methylene malonate monomer and unreacted methylene malonate monomer. End capping of the isocyanurate can be performed using a transesterification process.

About 200 g (about 1.16 moles) of DEMM and about 0.4 g (about 2000 ppm) of BHT (ie, about 2000 ppm) in a 250 mL round bottom flask equipped with a distillation head, thermometer, vacuum adapter, recovery flask and mechanical stirrer , Butylated hydroxytoluene)). The mixture is heated and about 0.6 ml of 1 mole% sulfonic acid is added to the round bottom flask using a syringe when the temperature reaches about 40 ° C. Next, about 1.0 equivalents (50.6 grams equivalent to about 1.94 moles) of 1,3,5-tris (2-hydroxyethyl) isocyanurate are added in portions to the flask. The reactants, and one of the desired products are shown in the following formula:

  The reaction is carried out at a temperature of about 110 ° C. under a reduced pressure of about 500 mmHg for about 3 hours with vigorous stirring. Ethanol is recovered as a reaction by-product. After the reaction, the reaction mixture is analyzed using 1 H NMR as shown in FIG. The conversion of isocyanurate to end-capped analog is about 30 percent.

  Example 14

において示される特徴のうちの１つまたは任意の組み合わせを含み得る。 Compounds containing carbamate linkages are prepared without isocyanate by first reacting the cyclic carbonate with one or more amine groups to obtain a compound with one or more carbamate groups and one or more hydroxy groups. obtain. The hydroxyl group is then reacted to form a 1,1-disubstituted alkene compound. For example, the process may include the first step of reacting a cyclic carbonate with a diamine using a ring opening reaction to obtain a diurethane diol. Preferred cyclic carbonates include ethylene carbonate and propylene carbonate. The reaction is as follows:

Can include one or any combination of the features set forth in

に挙げる特徴のうちの１つまたは任意の組み合わせを含み得る。 The reaction of the carbamate containing polyol with the 1,1-disubstituted alkene compound is as follows:

Can include one or any combination of the features recited in.

  The resulting end-capped compound preferably comprises a plurality of carbamate linkages and spaced alkene groups. It will be appreciated that the spacing between alkene groups can be controlled by the length of the amine starting material. For example, two amine groups may be separated by 4 or more, 6 or more, 10 or more, 15 or more or 20 or more carbon atoms.

Example 14 can be prepared by dissolving ethylene carbonate (eg, about 26.5 g, 0.30 mole, 2.0 equivalents) in dichloromethane (about 150 ml). An initial endotherm is observed during dissolution, and the temperature drops from about 23 ° C to about 0.2 ° C. Thereafter, hexamethylenediamine (about 17.51 g, 0.15 mol, 1.0 equivalent) is added to the solution. A slight exotherm of about 10-12 ° C. is observed. The solution is allowed to react and stir for 3 hours, during which time the temperature rises to about 27 ° C. and the solution becomes cloudy. The reaction is then continued with stirring at about 30 ° C. for an additional hour. The reaction product is insoluble in the solvent and precipitates out of solution. The suspension is then filtered and washed multiple times to remove unreacted starting material. FIG. 8 shows ¹³ C NMR spectrograms of diol intermediates.

The solid diurethane diol filtrate is then reacted with DEMM as described below. DEMM (31 g, 0.18 mol, 5.96 equivalents) and BHT (0.05 g) are placed in a three-necked round bottom flask fitted with a thermocouple and a vacuum adapter. Solid diurethane diol (8.8 g, 0.030 mol, 1.0 eq.) Is then added to the flask. The flask is then heated to about 130-135 ° C. Sulfuric acid (0.1 mL) is added via syringe while the flask is heated. The reaction is then stirred under reduced pressure (about 190 mm Hg) to efficiently remove the ethanol by-product. At temperatures above about 70 ° C., the suspension (ie, diurethane diol) dissolves to form a pale yellow to dark yellow clear solution. The solution is then stirred for about 1 to 1.5 hours and then cooled under reduced pressure. Solid particulates are observed, which are filtered off. The reaction is followed using ¹³ C NMR as shown in FIG. FIG. 9A shows a 13 C NMR spectrogram of undiluted DEMM. FIG. 9B shows a mixture of DEMM and urethane diol prior to the addition of sulfuric acid. FIG. 9C shows the mixture after sulfuric acid addition. FIG. 9D shows the spectrogram of the mixture after reacting at 135 ° C. for 1 hour.

Claims (27)

A functionalized multivalent compound,
A central portion comprising isocyanurate trimers or having two or more ends separated by five or more atoms;
And two or more residues of a 1,1-disubstituted alkene compound (s) (preferably, a 1,1 dicarbonyl substituted alkene compound (s)), one or both of the disubstituents Contains an ester group,
Each of said residues of said 1,1-disubstituted 1-alkene compound (s) is attached to different ends of said central portion, such that said functionalized polymer comprises at least two spaced alkene functional groups Said functionalized multivalent compound. A functionalized multivalent compound,
A homopolymer comprising a central polymer portion having two or more ends separated by a plurality of monomer units comprising adjacent monomer units covalently linked, said central polymer portion consisting essentially of identical monomer units Or a copolymer having monomer units comprising a first monomer and one or more comonomers different from said first monomer, said monomer units of said central polymer portion being each of said central polymer portions Comprising terminal monomer units at the ends, comprising one or more residues of the 1,1-disubstituted alkene compound (s), one or both of said disubstituents comprising an ester group,
Each of said residues of said 1,1-disubstituted 1-alkene compound (s) is attached to different ends of said central polymer part (ie different terminal monomer units of said central polymer part), As a result, said functionalized polymer has at least one alkene functionality,
The functionalized polyvalent compound, wherein the functionalized polyvalent compound is a functionalized polymer. A functionalized multivalent compound,
A polymeric polyol having two or more ends, wherein one or more of the ends are capped with a residue of a 1,1-disubstituted alkene compound, and the functionalized multivalent compound is functionalized The functionalized multivalent compound which is a polymer.   4. The method according to claim 1, wherein the number of said residues of said 1,1-disubstituted alkene compound is 2 or more and said functionalized multivalent compound comprises a plurality of alkene groups separated by said central polymer moiety. Functionalized multivalent compound as described in any of the above.   Said central portion being the central polymer portion and comprising the residue of a polyol having two or more primary OH groups, of said residue of said 1,1-disubstituted 1-alkene compound (s) 5. The functionalized multivalent compound according to any of claims 1 to 4, wherein each is linked to the residue of the polyol by an ester bond.   6. A functionalized multivalent compound according to any of the preceding claims, wherein the central part is a central polymer part and comprises ether or ester linkages.   7. A functionalized multivalent compound according to any of the preceding claims, wherein the central part is an isocyanurate trimer.   8. The functionalized multivalent polymer according to any of claims 1 to 7, wherein said central part is a central polymer part comprising polyester, polyether, polybutadiene, polycarbonate, acrylic containing polymer, siloxane containing polymer or any combination thereof. Compound.   9. The functionalized multivalent compound of any of the preceding claims, wherein at least about 50 weight percent of the central portion is polyester, polyether, polybutadiene, polycarbonate, an acrylic containing polymer or a siloxane containing polymer.   10. The functionalized multivalent compound of claim 9, wherein the central polymer portion has a weight average molecular weight of about 300 or more.   5. A functionalized multivalent compound according to any of the preceding claims, wherein the central part is a monomeric compound.   The 1,1-disubstituted alkene is a 1,1-disubstituted ethylene having a central carbon atom double bonded to another carbon atom, wherein the central carbon atom is further bonded to two carbonyl groups 12. A functionalized multivalent compound according to any of the preceding claims. The 1,1-disubstituted alkene is
Containing one or more additional central carbon atoms, each double bonded to another carbon atom and further bonded to two carbonyl groups (eg, dimers or trimers or longer oligomers) 13. The functionalized multivalent compound according to any one of claims 1 to 12.   13. The functionalized multivalent compound of any of claims 1-12, wherein the 1,1-disubstituted alkene compound is methylene malonate.   15. The functionalized multivalent compound of any of claims 1-14, wherein the central portion comprises aliphatic polyester, aromatic polyester, polyether, carbinol terminated siloxane, polybutadiene, isocyanurate or polyethylene glycol. The residue of the 1,1-disubstituted alkene monomer has the structure:

(Wherein R ¹ is a hydrocarbyl group which may contain one or more heteroatoms, independently at each occurrence)
16. A functionalized multivalent compound according to any of claims 1 to 15 (e.g. said functionalized polymer), which is a residue of a 1,1-disubstituted ester having.   The functionalized multivalent compound according to any of claims 1 to 15, wherein the central part is a residue of an aromatic polyester polyol or a residue of an aliphatic polyester polyol.   18. The functionalized multivalent compound of any of claims 1-17, wherein the central portion is a residue of a polycarbonate polyol or a residue of a polybutadiene polyol. The central polymer portion is
1-2 arrangement (ie,

)
1-4 cis arrangement,
1-4 transformer arrangement,
Or butadiene repeat units of any combination thereof,
18. A functionalized multivalent compound according to claim 17, wherein the number of butadiene repeat units in the central polymer part is about 3 or more (preferably about 5 or more).   16. A functional group according to any one of the preceding claims, wherein said central part is a central polymer part which is a residue of carbinol-terminated siloxane and the number of siloxane units along said central polymer part is about 3 or more Multivalent compounds.   A polyalkylene glycol wherein said central portion is a central polymeric portion and comprises one or more ethylene glycol repeat units, one or more propylene glycol repeat units, one or more butylene glycol repeat units, or any combination thereof 16. A functionalized multivalent compound according to any of claims 1 to 15, wherein the number of alkylene glycol repeat units is about 3 or more.   23. A functionalized polyvalent compound according to any of the preceding claims, wherein the functionalized polyvalent compound comprises a carbamate bond linking a 1,1, disubstituted alkene compound (s) to the central moiety. . A transesterification method,
Mixing the polymer intermediate having at least a terminal OH group with a 1,1-disubstituted alkene compound, and reacting the polymer intermediate with the 1,1-disubstituted alkene compound, the disubstituted The process wherein at least one of the groups is an ester so that the 1,1-disubstituted alkene compound is at the end of the polymer.   24. A method comprising crosslinking the functionalized multivalent compound according to any of the preceding claims.   24. Prepared by polymerizing a composition comprising one or more 1,1-disubstituted alkene compounds and a functionalized multivalent compound according to any of claims 3-23 (e.g. said functionalized polymer) A polymer, said composition (eg from said functionalized polymer) having two different (preferably more than about 20 ° C. different) glass transition temperatures and / or two different (preferably more than about 20 ° C. different) The polymer may have a melting temperature (eg, one glass transition temperature and / or melting temperature associated with the polyol, and one glass transition temperature and / or melting temperature associated with polymethylene malonate) (eg, the 1, 1 A sufficient amount of said polyol and a sufficient amount of said 1,1-disubstituted alky Compound (s) (e.g., malonate, such as malonate) containing the polymer.   24. The functional group according to any of the preceding claims, wherein the functionalized multivalent compound comprises a carbamate bond (e.g. for linking the 1,1, disubstituted alkene compound (s) to the central moiety). A modified multivalent compound (e.g. said functionalized polymer). 24. A method of forming a functionalized multivalent compound according to any of claims 1 to 23, comprising
Continuously feeding the 1,1-disubstituted compound into the reactor,
Continuously feeding a polymeric polyol (e.g. a polyhydroxyl terminated polybutadiene polymer) into the reactor;
The process comprising the step of continuous flow reaction of the 1,1-disubstituted compound with the polymeric polyol in the presence of a catalyst such that the functionalized multivalent compound is formed by transesterification.

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