WO2013071256A1 - Poly(lactone)s, method of manufacture, and uses thereof - Google Patents
Poly(lactone)s, method of manufacture, and uses thereof Download PDFInfo
- Publication number
- WO2013071256A1 WO2013071256A1 PCT/US2012/064709 US2012064709W WO2013071256A1 WO 2013071256 A1 WO2013071256 A1 WO 2013071256A1 US 2012064709 W US2012064709 W US 2012064709W WO 2013071256 A1 WO2013071256 A1 WO 2013071256A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lactone
- poly
- crosslinked
- repeat units
- post
- Prior art date
Links
- GSLDEZOOOSBFGP-UHFFFAOYSA-N C=C(CCO1)C1=O Chemical compound C=C(CCO1)C1=O GSLDEZOOOSBFGP-UHFFFAOYSA-N 0.000 description 1
- QGLBZNZGBLRJGS-UHFFFAOYSA-N CC(CCO1)C1=O Chemical compound CC(CCO1)C1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D137/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
Definitions
- This disclosure relates to biosourced poly(lactone)s, methods for the manufacture of the poly(lactone)s, and uses thereof.
- Poly(lactone)s as used herein are polymers that contain lactone groups where a carbon atom of the lactone ring is incorporated into the polymer backbone.
- poly(lactone)s can be distinguished from polymers containing lactone groups where the lactone is pendant from the polymer backbone, on the basis of their methods of manufacture, reactivity, properties, and uses.
- the invention is a poly(lactone) comprising units of formula I
- each b 0 or 1 ;
- w is the number of post-reacted and post-crosslinked a-methylene lactone repeat units
- r is the number of a-methylene lactone repeat units
- s is the number of comonomer repeat units
- t is the number of crosslinked repeat units
- w+s+t is at least 1 ;
- R 2 , and R 3 are each independently a hydrogen or Ci_ 4 alkyl
- R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, Ci_ 4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;
- X is a nucleophile residue
- Q " is a Ci-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I;
- G " is a single bond to an additional polymer backbone or G " is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I. Further, one or both of the following two sets of conditions applies:
- a crosslinked poly(lactone) comprises units of formula I-a
- each b 0 or 1 ;
- w is the number of post-reacted ⁇ -methylene lactone repeat units
- r is the number of ⁇ -methylene lactone repeat units
- s is the number of comonomer repeat units
- t is the number of crosslinked ⁇ -methylene lactone repeat units, provided that t is at least 1 ;
- R 2 , and R 3 are each independently a hydrogen or Ci_ 4 alkyl
- R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, Ci_ 4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-a, at least one and no more than two of R 4 , R 5 R 6 , and R 7 are F, and F is the same or different in each instance;
- X is a nucleophile residue;
- Q " is a Ci-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-a;
- G " is a single bond to an additional polymer backbone or G " is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-a;
- a crosslinked poly(lactone) comprises units of formula I-b
- each b 0 or 1 ;
- w is the number of post-reacted and post-crosslinked a-methylene lactone repeat units
- r is the number of ⁇ -methylene lactone repeat units
- s is the number of comonomer repeat units
- t is the number of crosslinked ⁇ -methylene lactone repeat units
- each value of w, r, s, and t are independent of any other value of w, r, s, and t;
- R 2 , and R 3 are each independently a hydrogen or Ci_ 4 alkyl;
- R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, Ci_ 4 alkyl or F, wherein F is a functional group that imparts a property to the poly(lactone) I-b and at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;
- X is a nucleophile residue
- Q " is a Ci-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones;
- G " is a single bond to an additional polymer backbone or G " is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones;
- G is a single bond or a Ci-30 hydrocarbyl group
- the invention is a crosslinked poly(lactone) comprising units of formula I-c
- each b 0 or 1 ;
- r is the number of a-methylene lactone repeat units
- s is the number of comonomer repeat units
- t is the number of crosslinked repeat units
- s+t is at least 1 ;
- R 2 , and R 3 are each independently a hydrogen or Ci_ 4 alkyl
- R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, Ci_ 4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-c, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;
- G is a single bond to an additional polymer backbone or G is a Ci-30 hydrocarbyl group optionally crosslinked with 0-5 additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-c;
- G " is a single bond to an additional polymer backbone or G " is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones;
- the total number of units (r+s+t) is 5,000 or greater;
- a poly(lactone) comprises units of formula I-d
- each b 0 or 1 ;
- r is the number of a-methylene lactone repeat units
- s is the number of comonomer repeat units
- t is the number of crosslinked repeat units
- s+t at least 1
- each value of r, s, and t are independent of any other value of r, s, and t;
- R 2 , and R 3 are each independently a hydrogen or Ci_ 4 alkyl;
- R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, Ci_ 4 alkyl or F, wherein F is a functional group that imparts a property to the poly(lactone) I-d and at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;
- G is a single bond or a Ci-30 hydrocarbyl group
- G " is a single bond to an additional polymer backbone or G " is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones,
- the total number of units (r+s+t) is 5,000 or greater;
- a poly( lactone) copolymer comprising units of formula I-e,
- each b 0 or 1 ;
- R 2 , and R 3 are each independently a hydrogen or Ci_ 4 alkyl
- G is a single bond or a Ci_3o hydrocarbyl group
- G " is a single bond to an additional polymer backbone or G " is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones;
- the total number of units (r+t) is 5,000 or greater;
- the invention is a poly(lactone) comprising units of formula I-f
- each b 0 or 1 ;
- w is the mole fraction of post-reacted and post-crosslinked a-methylene lactone repeat units
- r is the number of a-methylene lactone repeat units
- s is the number of comonomer repeat units
- t is the number of crosslinked a-methylene lacto repeat units
- each value of w, r, s, and t is independent of every other value of w, r s, and t;
- R 2 , and R 3 are each independently a hydrogen or Ci_ 4 alkyl;
- R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, Ci_ 4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-f, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;
- G " is a single bond to an additional polymer backbone or G " is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones;
- Q " is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-f;
- X is a nucleophile residue
- the total number of units (w+r+s+t) is 100 or greater; or second,
- the total of (wl+w2+w3+w4+r+s) is effective to provide a weight average molecular weight of 10,000 g/mol or greater prior to cross- linking.
- the invention is a crosslinked poly(lactone) comprising units of formula I-
- each b 0 or 1 ;
- r is the number of ⁇ -methylene lactone repeat units
- s is the number of comonomer repeat units
- t is the number of crosslinked repeat units, and each value of wl, w2, w4, r, s, and t are independent of any other value of wl, w2, w4, r, s, and t, and;
- Q " is a Ci-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-g;
- R 2 , and R 3 are each independently a hydrogen or Ci_ 4 alkyl
- R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, Ci_ 4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-g, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;
- G " is a single bond to an additional polymer backbone or G' is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones;
- Q is a Ci-30 hydrocarbyl group
- X is a nucleophile residue
- L is a leaving group
- the total number of units (wl+w2+w3+w4+r+s+t) is 100 or greater; or second,
- the invention is a poly( lactone) comprising units of formula I-h
- w:r:s (0.01-30):(99.99-2):(0-97.99), wherein w is the mole fraction of post-reacted and post-crosslinked ⁇ -methylene lactone repeat units, r is the number of a- methylene lactone repeat units, and s is the number of comonomer repeat units;
- R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, Ci_ 4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-h, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;
- X is a nucleophile residue
- Q " is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-h; and the total number of units (w+r+s) is 100 or greater, the total of (w+r+s) is effective to provide a weight average molecular weight of 10,000 g/mol or greater prior to cross-linking, or both.
- the invention is a post-crosslinked poly(lactone) compriing units of formula I-i
- each b 0 or 1 ;
- r is the number of ⁇ -methylene lactone repeat units
- s is the number of comonomer repeat units
- each value of wl, w2, w4, r, s, and t are independent of any other value of wl , w2, w4, r, s, and t;
- R 2 , and R 3 are each independently a hydrogen or Ci_ 4 alkyl
- R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, Ci_ 4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-i, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;
- Q " is a Ci-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones;
- Q is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones
- X is a nucleophile residue
- L is a leaving group
- the total number of units (wl+w2+w3+w4+r+s) is 100 or greater the total of
- (wl+w2+w3+w4+r+s) is effective to provide a weight average molecular weight of 10,000 g/mol or greater prior to cross-linking, or both.
- the invention is a crosslinked poly( lactone) comprising units of formula I-j
- each b 0 or 1 ;
- X is a nucleophile residue
- Q " is a Ci-30 hydrocarbyl group post-reacted with a crosslinking group wherein at least one Q " is crosslinked with one to five additional polymer backbones
- the total number of units (w+r) is 100 or greater, the total of (w+r) is effective to provide a weight average molecular weight of 10,000 g/mol or greater prior to cross-linking, or both.
- the invention is a crosslinked poly( lactone) comprising units of f rmula I-k
- each b 0 or 1 ;
- r is the number of ⁇ -methylene lactone repeat units
- each value of wl , w2, w4, and r are independent of any other value of wl , w2, w4, r, s, and t;
- Q " is a Ci-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones; Q is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones,
- X is a nucleophile residue
- L is a leaving group
- the total number of units (wl+w2+w3+w4+r) is 100 or greater, the total of
- (wl+w2+w3+w4+r) is effective to provide a weight average molecular weight of 10,000 g/mol or greater prior to cross-linking, or both.
- crosslinking monomer of formula III a crosslinking monomer of formula III, a comonomer of formula IV, or a combination comprising one or both of crosslinking monomer III and comonomer IV,
- R 2 , and R 3 are each independently hydrogen or Ci- 4 alkyl
- G is a single bond or a Ci-30 hydrocarbyl group
- R 4 , R 5 , R 6 and R 7 are each independently a hydrogen, Ci_ 4 alkyl or F, wherein F is a functional group that imparts a property to the poly(lactone), and at least one and no more than two of R 4 , R 5 , R 6 and R 7 are F, and F is the same or different in each instance, to form an optionally crosslinked polymer; and
- Q is a Ci-30 hydrocarbyl group
- X is a nucleophile reactive with a lactone group
- L is a leaving group
- compositions including the poly(lactone) of formula I, a poly(lactone) of any of formulas I-a to I-k, or a combination thereof.
- a poly(lactone) copolymer comprising units of formula I-m,
- each b 0 or 1 ;
- R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, Ci_ 4 alkyl or F, wherein at least one and no more than two of R 4 , R 5 , R 6 and R 7 are F and F is the same or different in each instance; and
- r and s are integers effective to provide a polymer having a weight average molecular weight of at least 500,000 g/mol.
- R 4 , R 5 , R 6 and R 7 are each independently a hydrogen, Ci_ 4 alkyl or F, wherein F is a functional group that imparts a property to the poly(lactone) I-m, and at least one and no more than two of R 4 , R 5 , R 6 and R 7 are F and F is the same or different in each instance.
- composition including the poly(lactone) I-m.
- each b 0 or 1 and n is a number effective to provide a molecular weight of 500,000 g/mol or greater.
- composition including the poly(lactone) I-n.
- a coating composition comprises a polymer binder; an aqueous phase; and the poly(lactone) I, specifically the poly(lactone) I-a to I-o, or a combination thereof.
- a method of preparing the coating composition comprises combining the polymer binder, the poly(lactone) I, specifically the poly(lactone) I-a to I-o, or a combination thereof, and the aqueous phase.
- a coated substrate comprises a substrate having a surface; and a coating disposed on the surface, wherein the coating comprises a polymer binder; optionally a pigment or a dye; and poly(lactone) I, specifically the poly(lactone) I-a to I-o, or a combination thereof.
- the coatings can be paints, inks, stains, caulks, and clear-coats, for example.
- a method of coating a substrate comprises contacting a coating composition comprising poly(lactone) I, specifically the poly(lactone) I-a to I-o, or a combination thereof, with a surface of the substrate to form a coating; and drying the coating.
- Poly(lactone)s are used in a variety of applications, including use as films and fillers. There remains a continuing need in the art for new types of poly(lactone)s, and in particular poly(lactone)s manufactured from biological, rather than petroleum feedstocks.
- the option to incorporate various types of functionality into the poly(lactone)s would further be useful, particularly if the type and amount of functional groups could be present in a selected mole percent.
- a still further advantage would be for such polymers to be crosslinked, or to have additional functionality for crosslinking.
- the production of poly(lactone)s of high molecular weights would also be advantageous.
- a new class of poly(lactone)s is described, wherein each poly(lactone) can contain a biosourced unit.
- the poly(lactone)s can be copolymerized with various monomer units and/or crosslinking agents to affect the functionality and/or properties of the poly(lactone)s.
- the percent of poly(lactone) units can be selected to provide the desired properties. It is possible to crosslink the poly(lactone)s using the hydroxyl groups, carboxyl groups, or both of the poly(lactone), with or without an added crosslinking agent.
- the poly(lactone)s can be crosslinked by the inclusion of a crosslinking monomer during polymerization of the poly(lactone).
- the functionality and/or properties of the poly(lactone)s can be modified by incorporation of a selected type and amount comonomer.
- the poly(lactone)s can be derived from biological feedstocks, in particular poly(lactone)s such as angelica poly( lactone).
- the poly(lactone)s can be derived from petroleum or renewable building blocks such as succinic acid, butanediol, gamma-butyropoly(lactone), gamma-valeropoly(lactone), or levulinic acid/esters.
- a poly( lactone) comprises units as shown in formula I.
- the methyl group can be located on the carbon gamma to the carbonyl group or beta to the carbonyl group. In an embodiment, the methyl group is located gamma to the carbonyl group.
- R 1 , R 2 and R 3 , at each occurrence in the poly(lactone) of formula I are each independently a hydrogen or Ci_ 4 alkyl.
- R 1 and R 2 are hydrogen and R 3 at each occurrence is the same or different and is a Ci_ 4 alkyl.
- each R 3 is the same, and is a Ci_ 4 alkyl, specifically methyl.
- R 1 , R 2 and R 3 are each hydrogen.
- R 4 , R 5 , R 6 and R 7 in the poly(lactone) of formula I are each independently a hydrogen, Ci_ 4 alkyl or a substituent F, wherein at least one and no more than two of R 4 , R 5 , R 6 and R 7 are F.
- Each F can be the same or different.
- F is a functional substituent that imparts a property to the poly(lactone) I.
- exemplary properties include solubility (for example hydrophobicity and/or hydrophilicity), charge, polarity, color, hygroscopicity, degradability (e.g., susceptibility to hydrolysis), detectability (e.g., via a fluorescent tag, radioactivity, luminosity, or the like).
- the property can affect the production and/or use of the compound.
- F is a charged group
- the presence of the charged group can affect an emulsion polymerization process used to manufacture the poly(lactone) and/or the final properties of the poly(lactone), and thus its use.
- F can be an alcohol, carboxy acid, carboxy acid salt, carboxy (Ci_ 24 alkyl) ester, carboxy (Ci_ 24 hydro xyalkyl) ester, -NR'R" (wherein each R' and R" is independently hydrogen or Ci_ 24 alkyl), thio, carbamyl, Ci_ 24 alkyl, C 2 _ 24 alkenyl, C 2 _ 24 alkynyl, C 3 -8 cycloalkyl, C 3 -7 heterocycloalkyl, C 6 -i 2 aryl, or C 3 - 1 1 heteroaryl, or two F groups on adjacent carbon atoms can form a 5- or 6-membered cycloalkyl or heterocycloalkyl ring including the carbon atoms, wherein the foregoing hydrocarbyl groups can be unsubstituted or substituted with one or more of a carboxy acid, carboxy acid salt, carboxy (Ci_ 24 alkyl) ester, carboxy (C
- R 4 and R 5 are hydrogen, R 6 is methyl or hydrogen, and R 7 is a carboxylic acid, ester, or salt, specifically a carboxylic acid.
- the group F is derived from reaction of acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, maleic anhydride, maleimide, itaconic anhydride, or a combination thereof as a comonomer as described below.
- G" in formula I is a single bond to an additional polymer backbone or G" is a Ci-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I. It will be understood that the additional polymer backbones crosslinked to G" can further contain units additional units containing Q " and/or G ⁇ but for simplicity, the additional polymer backbones have not been shown in formula I.
- Q " in formula I is a Ci-30 hydrocarbyl group post-reacted with a crosslinking group, where the crosslinking group may optionally be crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I. It will be understood that the additional polymer backbones crosslinked to Q " can further contain units additional units containing Q " or G ⁇ but for simplicity, the additional polymer backbones have not been shown in formula I.
- nucleophile residues containing a nucleophilic nitrogen atom include -NH- and -NR- wherein R is a Ci_io hydrocarbyl group, for example a Ci_ 3 alkyl group.
- R is a Ci_io hydrocarbyl group, for example a Ci_ 3 alkyl group.
- Other nucleophile residues are known in the art and can be used.
- each of the w r, s, and t units can be randomly or non-randomly arranged, or some units can be randomly arranged and some non- randomly arranged (e.g., in blocks).
- the values of w, r, s, and t can vary independently for each crosslinked polymer backbone, i.e., the values of w, r, s, and t in the main polymer fragment of I can be different from the values of r, s, and t in the additional polymer backbones crosslinked to Q " or G " .
- the values for the total of each of w i.e., all post-reacted and post-crosslinked a-methylene lactone repeat units, irrespective of location in the polymer backbone or additional polymer backbone
- r i.e., all a-methylene lactone repeat units, irrespective of location in the polymer backbone or additional polymer backbone
- s i.e., all comonomer repeat units, irrespective of location in the polymer backbone or additional polymer backbone
- t i.e., all crosslinked ⁇ -methylene lactone repeat units, irrespective of location in the polymer backbone or additional polymer backbone
- w i.e., all post-reacted and post-crosslinked a-methylene lactone repeat units, irrespective of location in the polymer backbone or additional polymer backbone
- s i.e., all comonomer repeat units, irrespective of location in the polymer backbone or additional polymer backbone
- t i.e.,
- the total number of units (w+r+s+t) as well as the molar ratio of the units is selected based on the desired properties, for example the desired degree of crosslinking, solubility, and other parameters.
- the total number of units is at least 100, at least 200, at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, or at least 1,000, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, or 2,000 or less.
- the total number of units is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the weight average molecular weight (Mw) of the poly( lactone) I can be 10,000, 20,000, 50,000, 100,000, 150,000, 200,000, 250,000, 300,000, 400,000, 500,000, 550,000, 600,000, 700,000, 750 ,000, 800,000 grams/mole (g/mole) or more.
- the weight average molecular weight can be 10,000 to 3,000,000 grams per mole; or 50,000 to 2,500,000 g/mol; or 100,000 to 2,000,000 g/mol, or 150,000 to 1,500,000 g/mol, or 200,000 to 1,000,000 g/mole or 250,000 to 950,000 g/mol.
- the weight average molecular weight is 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- At least one crosslinked a-methylene lactone repeat unit containin G " is present, such that a crosslinked poly(lactone) comprises units of formula I-a
- the total number of units (w+r+s+t) is at least 100, at least 200, at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, or at least 1,000, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, or 2,000 or less.
- the total number of units is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the weight average molecular weight (Mw) of the poly(lactone) I-a can be 10,000, 20,000, 50,000, 100,000, 150,000, 200,000, 250,000, 300,000, 400,000, 500,000, 550,000, 600,000, 700,000, 750,000, 800,000 grams/mole (g/mole) or more.
- the weight average molecular weight can be 10,000 to 3,000,000 grams per mole; or 50,000 to 2,500,000 g/mol; or 100,000 to 2,000,000 g/mol, or 150,000 to 1,500,000 g/mol, or 200,000 to 1,000,000 g/mole or 250,000 to 950,000 g/mol.
- the weight average molecular weight is 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1 ,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- a crosslinked poly(lactone) m rises units of formula I-b
- G in the poly(lactone)s of formula I is a single bond or a Ci-30 hydrocarbyl group having a valence c+d+1.
- G is a single bond or a residue of a crosslinking molecule having at least two (specifically, c+d+1) sites of ethylenic unsaturation, wherein crosslinking can occur upon polymerization as described below.
- a hydrocarbyl group as used herein means a group having the specified number of carbon atoms and the appropriate valence in view of the number of substitutions shown in the structure.
- Hydrocarbyl groups contain at least carbon and hydrogen, and can optionally contain 1 or more (e.g., 1-8) heteroatoms selected from N, O, S, Si, P, or a combination thereof. Hydrocarbyl groups can be substituted or unsubstituted.
- G can be a single bond or a Ci_i 2 alkyl substituted with 0-6 (Ci_ 6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination thereof, C 2 _i 2 alkenyl substituted with 0-6 (Ci_ 6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination thereof, C 2 _i 2 alkynyl substituted with 0-6 (Ci_ 6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6
- heterocycloalkyl substituted with 0-4 (Ci_6)alkoxycarbonyl groups, 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination thereof, C 6 -i 2 aryl substituted with 0-6 (Ci_ 6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination thereof, C 3-12 heteroaryl substituted with 0-4 (Ci_6)alkoxycarbonyl groups, 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination thereof, or C 2 -24 (C 1-4 alkyloxy)e(Ci_ 4 alkyl) groups wherein e 1 - 16 substituted with 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination thereof.
- Specific types of G groups include ethers, esters, amides, and isocyanurates.
- the total number of units is at least 100, at least 200, at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, or at least 1 ,000, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, or 2,000 or less.
- the total number of units is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the weight average molecular weight (Mw) of the poly(lactone) I-b can be 10,000, 20,000, 50,000, 100,000, 150,000, 200,000, 250,000, 300,000, 400,000, 500,000, 550,000, 600,000, 700,000, 750,000, 800,000 grams/mole (g/mole) or more.
- the weight average molecular weight can be 10,000 to 3,000,000 grams per mole; or 50,000 to 2,500,000 g/mol; or 100,000 to 2,000,000 g/mol, or 150,000 to 1,500,000 g/mol, or 200,000 to 1,000,000 g/mole or 250,000 to 950,000 g/mol.
- the weight average molecular weight is 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- poly(lactone s of this type comprise units of formula I-c
- the total number of units (r+s+t) is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the ratio of r:t is greater than 5000: 1, greater than 6,000: 1, greater than 8,000: 1, or greater than 10,000: 1, up to 80,000: 1.
- the weight average molecular weight (Mw) of the poly(lactone) I-c can be 500,000, 550,000, 600,000, 700,000, 750,000, 800,000 grams/mole (g/mole) or more, up to 3,000,000 grams per mole, up to 2,500,000 g/mol, up to 2,000,000 g/mol, up to 1,500,000 g/mol, or up to 1,000,000 g/mole or up to 950,000 g/mol.
- the weight average molecular weight is 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- Poly(lactone)s of this type can alternatively comprise units represented by f rmula I-d
- the total number of units (r+s+t) is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the total number of units (r+s+t) is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the ratio of r:t is greater than 5000: 1, greater than 6,000: 1, greater than 8,000: 1, or greater than 10,000: 1, up to 80,000: 1.
- the weight average molecular weight (Mw) of the poly( lactone) I-d can be 500,000, 550,000, 600,000, 700,000, 750,000, 800,000 grams/mole (g/mole) or more, up to 3,000,000 grams per mole, up to 2,500,000 g/mol, up to 2,000,000 g/mol, up to 1,500,000 g/mol, or up to 1,000,000 g/mole or up to 950,000 g/mol.
- the weight average molecular weight is 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- Poly(lactone)s of formula I-d when the comonomer is not present, comprise units of formula -e
- the molar ratio of the total of each r:t (99.99-70):(0.01-30), provided that t is at least 1.
- the total number of units (r+t) is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the ratio of r:t is greater than 5000: 1, greater than 6,000: 1, greater than 8,000: 1, or greater than 10,000: 1, up to 80,000: 1.
- the weight average molecular weight (Mw) of the poly(lactone) I-e can be 500,000, 550,000, 600,000, 700,000, 750,000, 800,000 grams/mole (g/mole) or more, up to 3,000,000 grams per mole, up to 2,500,000 g/mol, up to 2,000,000 g/mol, up to 1,500,000 g/mol, or up to 1,000,000 g/mole or up to 950,000 g/mol.
- the weight average molecular weight is 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- poly(lactone)s comprising post- crosslinked units comprise units of formula I-f
- the total number of units is at least 100, at least 200, at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, or at least 1,000, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, or 2,000 or less.
- the total number of units is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the ratio of (w+ r):t is greater than 100: 1, greater than 200: 1, greater than 300: 1, greater than 500:1 or greater than 700 : 1 , or greater than 1000: 1, greater than 5,000: 1, up to 50,000 to 1 or up to 80,000: 1. .
- the weight average molecular weight of the poly(lactone) I-f can be 10,000, 20,000, 50,000, 100,000, 150,000, 200,000, 250,000, 300,000, 400,000, 500,000, 550,000, 600,000, 700,000, 750,000, 800,000 g/mole or more, each prior to crosslinking.
- the weight average molecular weight can be 10,000 to 3,000,000 g/mol; or 50,000 to 2,500,000 g/mol; or 100,000 to 2,000,000 g/mol, or 150,000 to 1,500,000 g/mol, or 200,000 to 1,000,000 g/mole or 250,000 to 950,000 g/mol, each prior to crosslinking.
- the weight average molecular weight is 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol, each prior to crosslinking.
- the total of (w+r+s) is effective to provide a weight average molecular weight of 10,000 g/mol or greater, or 500,000 g/mol or greater prior to cross-linking.
- Such post-crosslinked poly(lactone)s can comprise repeat units of formula I-g
- Q in formula I-g is a Ci-30 hydrocarbyl group
- X is a nucleophile residue
- L is a leaving group.
- the moiety-X-Q(XL)f-X- is formed by post-reaction of a lactone functionality with the nucleophile -XL of a cross linking group having at least two (specifically, f) nucleophilic groups -XL, resulting in ring-opening. Subsequent reaction with the second nucleophilic group -XL with a lactone of another polymer chain results in the crosslink -X-Q(XL)f_ e -X-.
- Leaving groups for nucleophile X are known in the art, for example, hydrogen, a halogen, and the like, and depend on the nucleophile.
- Q can be a Ci_i 2 alkyl substituted with 0-6 (Ci_6)alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination thereof, C 2 _i 2 alkenyl substituted with 0-6 (Ci_ 6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6
- r is the number of ⁇ -methylene lactone repeat units
- s is the number of comonomer repeat units
- t is the number of crosslinked repeat units.
- each value of wl, w2, w4, r, s, and t are independent of any other value of wl, w2, w4, r, s, and t.
- the total number of units is at least 100, at least 200, at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, or at least 1 ,000, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, or 2,000 or less.
- the total number of units is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the ratio of (wl+w2+w3+w4+ r):t is greater than 100 : 1 , greater than 200: 1, greater than 300: 1, greater than 500: 1 or greater than 700: 1, or greater than 1000: 1, greater than 5,000: 1, up to 50,000 to 1 or up to 80,000:1.
- the weight average molecular weight of the poly(lactone) I-g can be 10,000, 20,000, 50,000, 100,000, 150,000, 200,000, 250,000, 300,000, 400,000, 500,000, 550,000, 600,000, 700,000, 750,000, 800,000 g/mole or more.
- the weight average molecular weight can be 10,000 to 3,000,000 g/mol; or 50,000 to 2,500,000 g/mol; or 100,000 to 2,000,000 g/mol, or 150,000 to 1,500,000 g/mol, or 200,000 to 1,000,000 g/mole or 250,000 to 950,000 g/mol.
- the weight average molecular weight is 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- a specific poly(lactone) where the only crosslinking is provided by post- crosslinked lactone units comprises units of formula I-h
- the total number of units (w+r+s) is at least 100, at least 200, at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, or at least 1,000, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, or 2,000 or less.
- the total number of units is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the weight average molecular weight of the poly(lactone) I-h can be 10,000, 20,000, 50,000, 100,000, 150,000, 200,000, 250,000, 300,000, 400,000, 500,000, 550,000, 600,000, 700,000, 750,000, 800,000 g/mole or more.
- the weight average molecular weight can be 10,000 to 3,000,000 g/mol; or 50,000 to 2,500,000 g/mol; or 100,000 to 2,000,000 g/mol, or 150,000 to 1,500,000 g/mol, or 200,000 to 1,000,000 g/mole or 250,000 to 950,000 g/mol.
- the weight average molecular weight is 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- a post-crosslinked poly(lactone) of this type comprises units of formu -i
- the total number of units is at least 100, at least 200, at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, or at least 1,000, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, or 2,000 or less.
- the total number of units is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the weight average molecular weight of the poly(lactone) I-i can be 10,000, 20,000, 50,000, 100,000, 150,000, 200,000, 250,000, 300,000, 400,000, 500,000, 550,000, 600,000, 700,000, 750,000, 800,000 g/mole or more.
- the weight average molecular weight can be 10,000 to 3,000,000 g/mol; or 50,000 to 2,500,000 g/mol; or 100,000 to 2,000,000 g/mol, or 150,000 to 1,500,000 g/mol, or 200,000 to 1,000,000 g/mole or 250,000 to 950,000 g/mol.
- the weight average molecular weight is 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- the total number of units (w+r) is at least 100, at least 200, at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, or at least 1,000, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, or 2,000 or less.
- the total number of units is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the weight average molecular weight of the poly(lactone) I-i can be 10,000, 20,000, 50,000, 100,000, 150,000, 200,000, 250,000, 300,000, 400,000, 500,000, 550,000, 600,000, 700,000, 750,000, 800,000 g/mole or more.
- the weight average molecular weight can be 10,000 to 3,000,000 g/mol; or 50,000 to 2,500,000 g/mol; or 100,000 to 2,000,000 g/mol, or 150,000 to 1,500,000 g/mol, or 200,000 to 1,000,000 g/mole or 250,000 to 950,000 g/mol.
- the weight average molecular weight is 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- Poly(lactone)s of this type can be of formula I-k
- the total number of units is at least 100, at least 200, at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, or at least 1,000, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, or 2,000 or less.
- the total number of units is at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, or at least 9,500, up to, for example, 30,000 or less, 25,000 or less, 20,000 or less, 10,000 or less.
- the weight average molecular weight of the poly(lactone) I-k can be any weight average molecular weight of the poly(lactone) I-k.
- the weight average molecular weight can be 10,000 to 3,000,000 g/mol; or 50,000 to 2,500,000 g/mol; or 100,000 to 2,000,000 g/mol, or 150,000 to 1,500,000 g/mol, or 200,000 to 1,000,000 g/mole or 250,000 to 950,000 g/mol.
- the weight average molecular weight is 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- poly(lactone) I w and t are both 0 such that the poly(lactone) is of formula I-m
- r and s in the poly(lactone) I-m will vary depending on the overall length of the polymer, as well as the ratio of monomers used to form the polymer.
- the molar ratio of r:s (99.9-2):(0.1-98).
- the molar ratio of r:s (95-5):(5-95), (95-25):(5-75), (95-50):(5-50), (90-60):(10-40, or (90-70):(10-30).
- the weight average molecular weight (Mw) of poly(lactone) I-m can be 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- poly(lactone) I comprises units as shown in formula I-n.
- the weight average molecular weight (Mw) of the poly( lactone) can be 500,000 to 2,500,000 g/mol, specifically 500,000 to 2,000,000 g/mol, more specifically 500,000 to 1,000,000 g/mol, and more specifically 500,000 to 950,000 g/mol.
- F, G, c, d, r, s, and t are as defined in formula I and formula I-b.
- the c number of polymer fragments crosslinked to G can further contain units t (-CR 1 R 2 -CR 3 G-) derived from the crosslinking monomer as described below, but for simplicity, such units have not been shown in formula I-o.
- poly(lactone) of formula I specifically formulas I-a to I-k and I-o can be obtained by co -polymerization of appropriate amounts of the ethylenically unsaturated monomer of formula II,
- each b 0 or 1 , a crosslinking monomer, and a comonomer
- the crosslinking monomer is a monomer having at least two polymerizable ethylenically unsaturated groups.
- the groups can react such that the crosslinking comonomer is incorporated into a first polymer backbone via a first ethylenically unsaturated group and into a second polymer backbone via a second ethylenically unsaturated group as the monomers polymerize.
- the crosslinking monomer is of formula III.
- R 1 , R 2 , and R 3 are each independently hydrogen or Ci-
- R 1 and R 2 are hydrogen and R 3 is a Ci_ 4 alkyl, specifically methyl. In another embodiment, R 1 , R 2 , and R 3 are each hydrogen.
- G in formula III can be a Ci- 30 hydrocarbyl group having a valence c, for example a Ci_i 2 alkyl substituted with 0-6 (Ci_ 6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups , 0-6 aminocarbonyl groups, or a combination thereof, C 2 _i 2 alkenyl substituted with 0-6 (Ci_6)alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination thereof, C 2 _i 2 alkynyl substituted with 0-6 (Ci_6)alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6
- C 4 _i 2 heteroaryl substituted with 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination thereof, C 2 -24 (C 1-4 alkyloxy)e(Ci_ 4 alkyl)) groups wherein e 1 - 16 substituted with 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination thereof.
- Exemplary crosslinking monomers III include N,N'-(Ci_i 2 alkyl)bisacrylamide, N,N'-(Ci_i 2 alkyl)bismethacrylamide, a di-, tri-, tetra-, penta-, or hexa(meth)acrylic ester of a Ci_i 2 polyol, a di-, tri-, tetra-, penta- or hexa(meth) acrylic ester of a Ci_ 24 alkyleneoxide polyol, a mono-, di-, tri-, tetra-, or higher polyester of a mono- di-, tri-, tetra-, or higher carboxylic acid having 2-6 terminal unsaturations, a di-, tri-, tetra-, penta-, or
- hexa(meth)allyl(Ci_i2 alkane), and di-, tri-, and tetravinyl substituted C 6-12 aryl compounds A combination of different ethylenically unsaturated groups can be used, for example a combination of an allyl group and a (meth)acryloyl group.
- crosslinking monomers III include N,N-methylene bisacrylamide, N,N'-methylenebismethacrylamide, 1,2-, 1,3-, and 1,4-butanediol
- di(meth)acrylate ethyleneglycol diacrylate, ethyleneglycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, diethyleneglycol diacrylate, diethyleneglycol dimethacrylate, triethyleneglycol diacrylate, triethyleneglycol dimethacrylate,
- polyethyleneoxide glycol diacrylate polyethyleneoxide glycol dimethacrylate
- the comonomer can impart functionality, and is a comonomer of formula IV
- R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, Ci_ 4 alkyl or a substituent F, wherein at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F as described in Formula I, and F is the same or different in each instance.
- the substituent F is a functional group that imparts a property to the poly(lactone) I.
- monomer XIII examples include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, maleic anhydride, itaconic anhydride, styrene, n-butyl acrylate, N,N-dimethyl acrylamide, octadecyl acrylate, p-styrene sulfonate, butadiene, 2-vinylpyridine, 4-vinyl benzoic acid, N-vinyl pyrrolidone, methacrylic acid, divinyl benzene, or a combination thereof.
- poly(lactone)s I, IV, or I Such polymerization methods include anionic and free radical polymerization.
- the free radical polymerization can be initiated by that of those of redox initiation, thermally activated peroxide initiation, and the like transfer and can be a controlled polymerization via methods of reversible addition- fragmentation chain transfer (ATRP), atom transfer radical polymerization (ATRP), nitroxide mediated polymerization (NMP), and the like.
- ATRP reversible addition- fragmentation chain transfer
- ATRP atom transfer radical polymerization
- NMP nitroxide mediated polymerization
- high molecular weights can be obtained by purification of monomers II and/or III to remove any polymerization inhibitors.
- [001 15] Conversion of monomer to polymer can be effected by a large number of reaction parameters such as temperature, degree of dilution, reaction time, level of active catalyst, chain length distribution, choice of solvent, choice of catalyst, and other variables. Selection of an appropriate combination of such variables to achieve a high conversion can be accomplished by routine experimentation in view of the present disclosure.
- a solvent can be used during polymerization to maintain an acceptable viscosity, and is typically a polar or nonpolar aprotic solvent, for example, dimethyl formamide (DMF), benzene, tetrahydrofuran (THF), a halogenated hydrocarbon such as dichloromethane, and when emulsion polymerization is used, water.
- the solvent can be miscible with the polymer and other reactants, while not entering into unwanted side reactions.
- the amount of solvent used can vary widely and the optimum amount can be determined by routine experimentation. Too little solvent can result in excessive viscosity of the reaction mixture, sluggish reactions, and the like, while an excess can result in excessive reaction volume, excessive solvent recovery costs, and an undesirably low conversion of monomer to polymer during polymerization.
- Polymerization can be batch, semi-batch, or continuous, and can include emulsion polymerization, bulk polymerization, solution polymerization, core-shell polymerization, microemulsion polymerization, suspension polymerization, interpenetrating network polymerization (polymerization in the presence of a non-reacting monomer that is subsequently polymerized), for example.
- sufficient time is provided following mixing of the components and attainment of the final reaction temperature to allow the conversion of monomer to polymer to reach the desired level.
- the desired level would be near the equilibrium conversion corresponding to the final conditions. The time to reach equilibrium varies with such conditions as temperature, viscosity, and catalyst level.
- Emulsion polymerization can provide a polymer in water (e.g., polymer particles in water), and provide a high molecular weight polymer without the use of an organic solvent and in a process wherein isolation and recovery steps can be omitted if desired.
- an anionic, nonionic, or cationic surfactant specifically an anionic or nonionic surfactant can be included.
- Representative surfactants include, but are not limited to, alkyl sulfonates, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, ethylene oxide and/or propylene oxide adducts of long chain fatty acids or alcohols, ethylene oxide and/or propylene oxide adducts of alkyl phenols, mixed ethylene oxide/propylene oxide block polymers, diblock and triblock polymers based on polyester derivatives of fatty acids and poly(ethyleneoxide), diblock and triblock polymers based on poly(ethyleneoxide) and poly(propyleneoxide), diblock and triblock polymers based on polyisobutylene succinic anhydride and
- surfactants include sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monooleate, and surfactants sold by BASF under the PLURONIC trade name and surfactants by Uniqema under the ATLAS and ARLACEL trade names.
- Functional comonomers such as acrylic acid and others known to those of skill in the art can be used to stabilize or enable the emulsion.
- UV polymerization can be used, optionally in conjunction with a photo-initiator.
- photo -initiators can include, but are not limited to, benzophenone and substituted benzophenones, 1 -hydroxycyclohexyl phenyl ketone, thioxanthones such as iso- 45 propylthioxanthone, 2-hydroxy-2-methyl-l - phenylpropanl -one, 2-benzyl-2-dimethylamino-(4-morpholinophenyl) butan-l-one, benzil dimethylketal, bis (2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6- trimethylbenzoyldiphenylphosphine oxide, 2-methyl-l-[4-(meth-5-ylthio) phenyl]-2- morpholinopropan-l-one, 2,2-dimeth
- Suitable photo-initiators are disclosed in CRIVELLO, J. V., et al. VOLUME III: Photoinitiators for Free Radical Cation and Anion Photopolymerization, 2nd Edition, edited by BRADLEY, G., London, UK: John Wiley and Sons Ltd, 40 1998, pp. 287-294.
- the chain length can be controlled by various means known to one skilled in the art, for example by control of the level of polymerization initiator present in the system during polymerization, as the average chain length tends to decrease with increases in the amount of polymerization initiator present.
- the polymerization initiator can be an azo compound, an inorganic peroxide, or an organic peroxide, for example.
- Representative polymerization initiators include 2,2'-azobis (isobutyronitrile), 2,2'-azobis(2,4- dimethylvaleronitrile), ammonium persulfate, hydroxymethanesulfinic acid, potassium persulfate, sodium persulfate, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, di-tert- butyl peroxide, and others known to those of skill in the art.
- the polymerization initiator can be used singly or in a combination thereof.
- the polymerization initiator can be used in an amount of 0.001 to 10 wt%, specifically 0.001 to 5 wt%, or 0.01 to 1.0 wt%, based on the total weight of the ethylenically unsaturated monomer.
- the polymer chain lengths can be controlled by adding a chain transfer agent.
- chain transfer agents include alcohols such as methanol, ethanol, 1- propanol, 2-propanol, butyl alcohol, glycerol, or polyethyleneglycol, sulfur compounds such as alkylthiols, thioureas, sulfites, or disulfides, carboxylic acids such as formic or malic acid, or their salts or phosphites such as sodium hypophosphite or sodium formate.
- alcohols such as methanol, ethanol, 1- propanol, 2-propanol, butyl alcohol, glycerol, or polyethyleneglycol
- sulfur compounds such as alkylthiols, thioureas, sulfites, or disulfides
- carboxylic acids such as formic or malic acid
- phosphites such as sodium hypophosphite or sodium formate.
- the chain length can be controlled, for example, by the surfactant concentration, monomer concentration, the initiator, or chain transfer agent, if present.
- poly(lactone)s i.e., poly(lactone)s of formula I-c, I-d, or I-e
- the poly(lactone)s can be obtained in yields of greater than 50% of theory, greater than 75% of theory, greater than 80% of theory, greater than 85% of theory, or greater than 90% of theory, up to 100% of theory.
- the architecture of the poly(lactone)s can be linear or branched.
- the poly(lactone) I can be random, alternating, graft, or block copolymers including diblocks, triblock, tetrablocks, and pentablocks.
- poly(lactone) containing ring-opened poly(lactone) units can be contacted with an acid to reform the poly(lactone) units of the poly(lactone) I.
- the acid can be a carboxylic acid, such as formic acid, acetic acid, or oxalic acid, or a diacid such as citric acid or malic acid, for example.
- the acid can also be a strong acid such as H 2 SO 4 , HC1, HF, HI, and the like.
- Poly(lactone)s produced after polymerization can be the crosslinked products of formula I-c, I-d, or I-e described above wherein the crosslinking occurs during
- crosslinking group containing G e.g., unit "t” in formula I-c
- further crosslinking can occur via oxidative crosslinking of residual double bonds.
- post-crosslinking occurs via use of a crosslinking agent.
- the crosslinking agent can be a two-pot system (i.e. poured together just before use) for an ambient or heated cure.
- the crosslinking agent can be a protected crosslinking agent in the case of a one -pot system wherein the crosslinking is initiated when either the crosslinking agent is deprotected with heat (e.g. blocked isocyanates), when a component evaporates, or the crosslinking agent is contained in a separate phase.
- the crosslinking agent can be any substance that promotes or regulates intermolecular covalent bonding between the polymer chains.
- the crosslinking agent can be a monomer or an oligomer that reacts with the functional groups derived from units containing F, when present.
- poly(lactone)s can be post-crosslinked via lactone ring-opening by a post-crosslinking monomer containing group Q, i.e., a post-crosslinking monomer of formula V
- Q in formula III can be a Ci-30 hydrocarbyl group having a valence z+1 , for example a Ci_i 2 alkyl substituted with 0-6 (Ci_ 6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups , 0-6 aminocarbonyl groups, or a combination thereof, C 2 _i 2 alkenyl substituted with 0-6 (Ci_ 6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination thereof, C 2 _i 2 alkynyl substituted with 0-6 (Ci_ 6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6
- C 4 _i 2 heteroaryl substituted with 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination thereof, C 2 _ 24 (Ci_ 4 alkyloxy) e (Ci_ 4 alkyl)) groups wherein e 1 - 16 substituted with 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination thereof.
- the group -XL in formula V is a nucleophile X and a leaving group L, for example a hydroxyl or activated hydro xyl, amine or activated amine, carboxylic acid halide, and the like.
- a leaving group L for example a hydroxyl or activated hydro xyl, amine or activated amine, carboxylic acid halide, and the like.
- post-crosslinking monomers include a diol, triol, tetrol, pentol, or hexol, a diamine, triamine, tetramine, pentamine, or hexamine, or a combination comprising at least one of the forgoing the post-crosslinking monomers
- Exemplary crosslinking agents include polyisocyanates, including polyisocyanate oligomers, various diols and higher polyols, diamines and higher amines, di- or polymeric epoxides, and aminoalcohols, compounds having at least two sites of ethylenic unsaturation, as well as dicarboxyl and higher carboxylic acids and their Ci_3alkyl esters and acid halides.
- Such crosslinking produces crosslinked ionic polymers that can have crosslinks in the r or s units. The crosslinks can accordingly form between the F groups of the comonomer units or the lactone groups.
- the crosslinks are the crosslink residues of the polyisocyanates, including polyisocyanate oligomers, various diols and higher polyols, diamines and higher amines, di- or polymeric epoxides, and aminoalcohols, compounds having at least two sites of ethylenic unsaturation as well as dicarboxyl and higher carboxylic acids and their Ci_3alkyl esters and acid halides.
- Conditions for reaction of poly(lactone)s with diisocyanates and higher isocyanates are known, and can be effected by contacting polymer I and optionally another polyol and the appropriate stoichiometry of a di- or polyisocyanate and causing a reaction to occur by heating and/or with a catalyst to accelerate the reaction.
- catalysts for making the polyurethanes and polyisocyanate compounds include tin catalysts such as dibutyl tin dilaurate, and tertiary amines such as l,4-diazabicyclo[2.2.2]octane (DABCOTM, TED), and the like.
- the reaction can be carried out in the presence of an inert solvent, which can optionally be removed at the end of the reaction by distillation or extraction.
- organic polyisocyanates include 1 ,4-tetramethylene diisocyanate, 1 ,6-hexamethylene diisocyanate, 2,2,4-trimethyl-l,6-hexamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, cyclohexane-1 ,3- diisocyanate, cyclohexane-l ,4-diisocyanate, l-isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanato- 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4- isocyanatocyclohexyl) methane, 2,4'-dicyclohexyl-methane diiso
- polyisocyanate adducts include those containing isocyanurate, uretdione, biuret, urethane, allophanate, carbodiimide and/or oxadiazinetrione groups.
- polyisocyanate cross-linkers used in coatings and adhesives for outdoor applications where exterior durability is required are bis(4-isocyanatocyclohexyl)methane, the isocyanurate trimers of 1,6-hexanediisocyanate and isophorone diisocyanate, the biuret of 1,6-hexanediisocyanate, and the uretdione of 1,6-hexanediisocyanate.
- Specific polyisocyanates include
- diphenylmethane-4,4'-diisocyanate the reaction product of trimethylolpropane with toluene diisocyanate, and the isocyanurate trimer of toluene diisocyanate.
- Non- limiting examples ofpolyols include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3 -propanediol, 2,2-dimethyl-l,3-propanediol (neopentyl glycol), 2- butyl-2-ethyl- 1,3 -propanediol, 3-mercaptopropane-l,2-diol (thioglycerol), dithiothreitol, 1,2- butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- butanediol, 1,5-pentanediol, 3-methyl-l,5- pentanediol, 1,6-hex
- Polyether or polyester diols or polyols can be used, for example polyalkylene ethers such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethylene polypropylene glycol, the oligomeric and polymeric ethers available under the trade name VORANOL from Dow, and the like.
- polyalkylene ethers such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethylene polypropylene glycol, the oligomeric and polymeric ethers available under the trade name VORANOL from Dow, and the like.
- poly(lactone)s are contacted with the diamine or higher amine to crosslink at the carboxyl group, to form water as a byproduct by amidation methods known in the art.
- polyamine crosslinking agents include primary or secondary diamine or polyamines in which the radicals attached to the nitrogen atoms can be saturated or unsaturated, aliphatic, alicyclic, aromatic, aromatic- substituted-aliphatic, aliphatic-substituted-aromatic, or heterocyclic.
- Nonlimiting examples of aliphatic and alicyclic diamines include 1 ,2-ethylene diamine, 1 ,2-propylene diamine, 1 ,8- octane diamine, isophorone diamine, or propane-2,2-cyclohexyl amine.
- Nonlimiting examples of aromatic diamines include the phenylene diamines and toluene diamines, for example o-phenylene diamine and p-toluene diamine.
- Representative commercially available polyamines include those available Huntsman Corp., of Houston, Texas under the designation JEFFAMINE.
- Representative diamines and polyamines e.g., tri-, tetra-, and pentamines
- Representative diamines and polyamines useful in crosslinking include JEFFAMINE D-230 (molecular weight 230), JEFFAMINE D- 400 (molecular weight 400), and JEFFAMINE D-2000 (molecular weight 2000),
- JEFFAMINE XTJ-510 (D-4000) (molecular weight 4000), JEFFAMINE XTJ-50 (ED-600) (molecular 60 weight 600), and JEFFAMINE XTJ-501 (ED900) (molecular weight 900), for example.
- an aminoalcohol can be used to crosslink the poly(lactone)s.
- exemplary aminoalcohols are include a primary or secondary amino groups and a primary or secondary hydro xyl group linked by a saturated or unsaturated, aliphatic, alicyclic, aromatic, aromatic-substituted-aliphatic, aliphatic-substituted-aromatic, or heterocyclic CI -18 radical.
- the poly( lactone) can be contacted with the dicarboxyl or higher carboxylic acid (or the Ci_ 3 alkyl ester or carboxylic halide thereof) to react at the hydroxyl group, to form water, a Ci_ 3 alcohol, or hydrogen halide as a byproduct.
- Conditions are selected to avoid hydrolysis of the lactone, and condition for such esterification, trans-esterification, or nucleophilic addition are known.
- Exemplary dicarboxylic acids include C 4 _ 32 linear or branched saturated or unsaturated aliphatic dicarboxylic acids, Cs- 2 o aromatic dicarboxylic acids, polyether dicarboxylic acids, dimethyl terephthalate, or the like, as well as the corresponding Ci_ 3 alkyl esters and carboxylic halides, or a combination comprising at least one of the foregoing.
- Exemplary aliphatic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, decane dicarboxylic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, brassylic acid, a, ⁇ -diethylsuccinic acid, a-butyl-a-ethyl glutaric acid, and the like as well as the corresponding Ci_ 3 alkyl esters and carboxylic halides.
- Exemplary aromatic dicarboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, and the like, as well as the corresponding Ci_ 3 alkyl esters and carboxylic halides.
- Exemplary polyether dicarboxylic acids can include polyalkylene ethers such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethylene polypropylene glycol, and the like, as well as the corresponding Ci_ 3 alkyl ester carboxylic halides.
- the group F includes a site of unsaturation
- compounds having at least two sites of ethylenic unsaturation can be used for crosslinking, including compounds of formula III, the crosslinking monomer.
- Conditions for crosslinking include those used for polymerization as described above.
- the degree of crosslinking can be controlled by use of a combination of mono functional, difunctional, or poly functional compounds to provide the crosslinked poly(lactone), the relative amounts of the crosslinking agent, reaction conditions, and like considerations.
- the crosslinking agent can be present in the crosslinking composition in an amount of 0.25-80 weight percent (wt.%), specifically 0.5-60 wt.%, 1 to 40 wt.%), or 1-30 wt.%), or 1-15 wt.%, based on a total weight of the poly(lactone) and the crosslinking agent.
- the residue of the crosslinking agent can be present in the crosslinked poly(lactone) in an amount of 0.01-60 wt.%, specifically 0.01 to 10 wt.%, 0.05-5 wt.%), or more specifically 0.1- 1 wt.%, based on the total weight of the crosslinked poly(lactone).
- the poly(lactone) is more heavily crosslinked, such that the residue of the crosslinking agent is present in an amount 10-60 wt.%, or 20-40 wt.% based on the total weight of the crosslinked poly(lactone).
- a number of methods can be used to recover the poly(lactone)s I, specifically poly(lactone)s I-a to I-k and I-o, including precipitation in a nonsolvent, evaporation, sedimentation, coagulation, and the like. Unless desired, such conditions should not expose the poly(lactone) to conditions that cause depolymerization, such as excessively high temperatures for extended periods of time. Accordingly, the pH can be maintained to be 6 to 9.5, or 8 to 9, above 9.5, or above 10.0.
- the product can be recovered as a solution, slurry, gel, wet cake, or dry solid, depending upon its intended use. If the product is dried, excessive exposure to high temperature is avoided to prevent degradation and/or excess crosslinking.
- R 4 , R 5 , R 6 and R 7 are each independently a hydrogen, Ci_ 4 alkyl or F, wherein F is a functional group that imparts a property to the poly(lactone) la, and at least one and no more than two of R 4 , R 5 , R 6 and R 7 are F and F is the same or different in each instance.
- the above-described polymerization conditions can be used.
- the poly(lactone) I-n can be obtained by a process comprising polymerization of polymerization of the corresponding ethylenically unsaturated monomer II,
- Poly(lactone)s I specifically poly(lactone)s I-a to I-o, have a wide variety of uses, depending on their properties, such as molecular weight, identity of any comonomers, degree of crosslinking and crosslinking agent if used.
- poly(lactone)s I can be formulated with a variety of other materials, such as a compatible polymer, curing agent, catalyst, coalescing agent, surfactant, plasticizer, fragrance, defoamer, wetting agent, pigment/colorant, desiccant, preservative, filler, superabsorbent polymer, an antioxidant, an antiozonant, a thermal stabilizer, a mold release agent, a dye, a pigment, an antibacterial, a flavorant, a fragrance molecule, an aroma compound, an alkalizing agent, a pH buffer, a conditioning agent, a chelant, a solvent, a surfactant, an emulsifying agent, a blowing agent, a foam stabilizer, a hydrotrope, a solubilizing agent, a suspending agents, a humectant, an accelerator, a ultraviolet light absorber, or the like, or a combination comprising at least one of the for
- the poly(lactone) I can be formulated with a filler such as fibers, including glass fibers, carbon fibers, polymer fibers, and the like; functional additives including flame retardants, blowing agents, antioxidants, impact modifiers, compatibilizers, mold-release agents, and the like; talc; carbon black; metal; clay; ceramic; and the like.
- a filler such as fibers, including glass fibers, carbon fibers, polymer fibers, and the like; functional additives including flame retardants, blowing agents, antioxidants, impact modifiers, compatibilizers, mold-release agents, and the like; talc; carbon black; metal; clay; ceramic; and the like.
- poly(lactone)s I can be combined, e.g., blended, with various other polymers to form a polymer composition, for example with poly( vinyl chloride) (PVC); styrene butadiene rubber (SBR); polystyrene including atactic, isotactic, and syndiotactic; poly(alkyl methacrylates) including poly(methyl methacrylate) (PMMA); polyamide including those made from hexane-l,6-diamine and hexanedioic acid, hexane-l,6-diamine and dodecanedioic acid, butane- 1,4-diamine and hexanedioic acid, capro lactam, and caprolactam; polyethylene including high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and copolyethylene including
- the polymers to be blended with the poly(lactone)s I can be in the form of a copolymer (e.g. added as compatibilizing agents); polymer particles (e.g. SAN, SBS, PMMA, SBR); and the like.
- Other polymers include a polylactic acid, a polyvinylchloride, a polyacetal, a polyolefin, a polysiloxane, a polyacrylic, a polycarbonate, a polystyrene, a polyester, a polyamide, a polyamideimide, a polyarylate, a polyarylsulfone, a
- polyethersulfone a polyphenylene sulfide, a polyvinyl chloride, a polysulfone, a polyimide, a polyetherimide, a polytetrafluoroethylene, a polyetherketone, a polyether etherketone, a polyether ketone ketone, a polybenzoxazole, a polyphthalide, a polyacetal, a polyanhydride, a polyvinyl ether, a polyvinyl thioether, a polyvinyl alcohol, a polyvinyl ketone, a polyvinyl halide, a polyvinyl nitrile, a polyvinyl ester, a polysulfonate, a polysulfide, a polythioester, a polysulfone, a polysulfonamide, a polyurea, a polyphosphazene, a polysilazane, or a combination comprising
- the polymer compositions can be homogeneous or heterogeneous.
- the polyketal adduct can be added to the organic polymer in amounts of about 0.1 wt% to about 90 wt%, specifically about 4 wt% to about 70 wt%, and more specifically about 40 to 60 wt%, based on the total weight of the polymer composition.
- the poly(lactone)s I can be processed via continuous melt processing including the methods of extrusion (e.g. twin screw, single screw, disk extruder, co-extrusion with another polymer for stratified structures),
- extrusion e.g. twin screw, single screw, disk extruder, co-extrusion with another polymer for stratified structures
- thermoforming single shaft mixer, double shaft mixer, dynamic melt mixer, cavity transfer mixers, calendaring, melt spun fibers, airlaid, and the like.
- the poly(lactone)s I, or the corresponding crosslinked polymers can be processed via semi-continuous melt process via injection molding, transfer molding, and the like.
- the poly(lactone)s I, or the corresponding crosslinked polymers can be processed via batch melt processing via the methods of roll milling, kinetic energy mixing, compression molding, blow molding, and the like.
- the poly(lactone)s I can be processed from solids via compacting, compressing, sifting, grinding, tearing, pulverizing, sieving, powder coating, electrostatic coating, electrostatic spraying, centrifugational casting, rotational molding, compression molding, thermoforming, vacuum forming, pressure forming, matched mold forming, forging or cold forming, ablation, lithography, mechanical forces, sintering, and the like.
- poly(lactone)s I are used in coating compositions to form films.
- the coating compositions comprise a liquid carrier, poly(lactone)s I, and optionally other functional components, such as a pigment.
- a method of use, coating a substrate with a poly(lactone) coating composition is described. The method comprises contacting a surface of the substrate with the poly(lactone) coating composition to form a film; drying the film to harden the film, and optionally curing the film.
- the film can be transparent.
- the film is a roofing film, a composite film, a film for laminated safety glass, or a packaging film.
- the packaging container is a food or drink container.
- the film can also be a paint an ink, a stain, a clear-coat, and the like.
- the film can be applied through any known technique including those of casting, from solvent, from water, or from mixed solvent systems; dispensing (e.g. as in nozzle sprays); knife over roll coating, or roll coating, for example, to provide either a continuous coverage or a patterned coverage; shush molding; spray-drying; phase inversion; dip coating; curtain coating; spin coating; pouring, brush, rollers, mops, air-assisted or airless spray, electrostatic spray, foam; anilox; and the like to provide a continuous or patterned coating.
- a composition comprising the poly(lactone) or crosslinked
- poly(lactone) can be applied to a side of a substrate by roll, pond, or fountain application and metering with a roll, rod, blade, bar, or air knife.
- Printing methods are other suitable application techniques, including gravure, jet printing, screen printing, or screen coating, or by rotary screen printing or rotary screen coating, which is a combination of roll printing or coating and screen printing or coating.
- the coating compositions can be applied to fibrous or non- fibrous substrates.
- substrates include paper; paperboard; textiles; non-wovens; wood; ceramic; masonry; concrete; a woven web; fabric including knitted fabric, woven fabric, and nonwoven fabric; cellulose tissue; plastic film; laminate; glass a stranded composite; an elastomer net composite; metal; glass; or fiber including glass fiber, natural fiber, or synthetic fiber; or a combination comprising at least one of the foregoing substrates.
- the coating composition can further be deposited onto filter cartridges or substrates for use in filtration systems for allergen removal, blood filtration, water purification, and the like.
- plastic film substrates include those made of polypropylene, polyurethane, and polyolefin including modified and surface-treated polyolefins.
- the polyolefin can be low density polyethylene, high density polyethylene ("HDPE,” a polyethylene having a density of about 0.95 g/cm 3 or greater), linear low density polyethylene (“LLDPE,” polymers of ethylene and a higher alpha-olefin comonomer such as a C 3 _i 2 comonomer, or a combination thereof, having a density of about 0. 900-0.935 g/cm 3 ), and ultra-low density polyethylene
- ULDPE polymers of ethylene and a higher alpha-olefin comonomer such as a C 3 _i 2 comonomer, or a combination thereof, having a density of about 0.860 to less than 0.900 g/cm 3 ).
- drying can be performed without crosslinking the film. Drying conditions can be selected to provide for removal of a solvent or water from the poly(lactone) without crosslinking as described in further detail below.
- the poly(lactone) can be coated onto a substrate and subsequently dried and cured.
- the poly(lactone) can be partially cured, to provide a poly(lactone) that is insoluble but swells when contacted by a selected solvent, or the poly(lactone) can be highly crosslinked, to provide a poly(lactone) that does not significantly swell when contacted by a variety of solvents. Drying can be accomplished through any known technique including those of freezing or via dryers (e.g. as in yankee drum dryer or belt dryer) and the like.
- the curing is by the post-cross linking methods described above.
- curing is a single bond or achieved by evaporation in ambient conditions or in heated conditions to accelerate the process or because the solvent has a higher boiling point, or by reaction curing.
- Reaction curing can be achieved by an oxidative cure in the case of drier, catalysts, and radiation cures; by a blocking curing agent wherein deblocking occurs either thermally by some transformative process (e.g.
- curing is a single bond or achieved by chemical reaction with a crosslinking agent and can occur in ambient conditions, wherein the components are mixed just before use, or in heated conditions.
- the film can be factory applied, wherein the equipment, such as ovens or radiation via UV, e-beam, and the like, is used to assist curing or drying or in the field, wherein the curing is a single bond or achieved at ambient conditions.
- the poly(lactone) I can also be used as an additive in a coating for a variety of purposes, for example to alter the viscosity of a coating composition, or enhance the plasticity or durability of the coating.
- a relatively low concentration of the poly(lactone) e.g., less than 10 wt.%, specifically less than 5 wt.%, less than 2 wt.%, or less than 1 wt.%>
- a relatively low concentration of the poly(lactone) e.g., less than 10 wt.%, specifically less than 5 wt.%, less than 2 wt.%, or less than 1 wt.%>
- the poly(lactone) can act as a binder in the coating composition.
- the poly(lactone) I can act as an additive or binder in a variety of coating compositions, for example paints, inks, solvent borne, or coating compositions.
- the ketal adducts can function as a polymer binder, a solvent, or a condensation reactive product.
- the ketal adducts can have more than one function, including one or more of solubilization, solvent coupling, surface tension reduction, viscosity reduction, and the like.
- the poly(lactone) I can also function as a plasticizer, increasing the flexibility of the compositions.
- selection of the specific G ⁇ Q ⁇ R 1 , R 2 , R 3 , R 4 , R 6 , and R 7 groups, and b in the poly(lactone) I allows the chemical and physical properties of the poly(lactone) I to be adjusted to achieve the desired combination of properties, for example, solubilizing activity and volatility.
- a coating composition comprises the poly(lactone) I, specifically poly(lactone)s I-a to I-o, as a binder and a carrier, such as water or an organic solvent.
- the poly(lactone) I can be present in carrier completely dissolved, i.e., in the form of a solution, in the form of aggregates, or an aqueous dispersion, and can include about 5 to about 85 weight percent (wt.%>) solids, specifically about 10 to about 75 wt.% solids (i.e., the weight percentage of the poly(lactone) I based on the total weight of the coating composition).
- solids refers to the 100% binder in whatever form, such as a solid or liquid.
- the polymer binder can be present in a wide variety of particle sizes, for example a mean polymer binder particle size from about 10 to about 1,000 nanometers (nm), specifically about 50 to about 800 nm.
- the particle size distribution can be mono-modal or multimodal, for example bimodal.
- a method of preparing coating composition comprises combining the poly(lactone) I, , specifically poly(lactone)s I-a to I-o, carrier (e.g., organic or aqueous phase (i.e., water and any cosolvents if present)), and any additives, if present, to form a coating composition.
- carrier e.g., organic or aqueous phase (i.e., water and any cosolvents if present)
- any additives if present
- the poly(lactone) I is used in a water-borne paint compositions, stain composition, or clear-coat
- a water-borne paint, stain, or clear-coat composition comprises water, optionally a pigment, and the poly(lactone) I, specifically poly(lactone)s I-a to I-o.
- the coating compositions comprise the uncured polymer and one or more of a curing agent, catalyst, initiator, or promoter, if used.
- a pigment can be present in the paint or stain composition.
- pigment as used herein includes non- film- forming solids such as extenders and fillers, for example an inorganic pigment aluminum oxide, barites (barium sulfate), CaC03 (in both ground and precipitated forms), clay (aluminum silicate), chromium oxide, cobalt oxide, iron oxides, magnesium oxide, potassium oxide, silicon dioxide, talc (magnesium silicate), Ti02 (in both anastase and rutile forms), zinc oxide, zinc sulfite, an organic pigment such as solid (high Tg) organic latex particles added to modify hardness or (as in the case of hollow latex particles) to replace Ti02, carbon black, and a combination comprising at least one of the foregoing.
- inorganic pigment aluminum oxide, barites (barium sulfate), CaC03 (in both ground and precipitated forms), clay (aluminum silicate), chromium oxide, cobalt oxide, iron oxides, magnesium oxide, potassium oxide, silicon dioxide, talc (magnesium silicate),
- Representative combinations include blends of metal oxides such as those sold under the marks Minex® (oxides of silicon, aluminum, sodium and potassium commercially available from Unimin Specialty Minerals), Celites® (aluminum oxide and silicon dioxide commercially available from Celite Company), Atomites® (commercially available from English China Clay International), and Attagels® (commercially available from Engelhard).
- the pigment includes Ti0 2 , CaC0 3 , or clay.
- the mean particle sizes of the pigments are about 0.01 to about 50 micrometers.
- the Ti0 2 particles used in the aqueous coating composition typically have a mean particle size from about 0.15 to about 0.40 micrometers.
- the pigment can be added to the aqueous coating composition as a powder or in slurry form.
- a dye can be present in the paint or stain composition, in addition to or instead of a pigment.
- the term "dye” as used herein includes organic compounds generally soluble in the compositions, and that impart color to the compositions.
- the paint, stain, or clear-coat composition can contain additional additives, as known in the art, to modify the characteristics of the composition, provided that the additives do not significantly adversely affect the desired properties of the paint, stain, or clear-coat, for example, viscosity, drying time, or other characteristic.
- additives can include a plasticizer, drying retarder, dispersant, surfactant or wetting agent, rheology modifier, defoamer, thickener, biocide, mildewcide, colorant, wax, perfume, pH adjuster, or cosolvent.
- the additives are present in the amount ordinarily used in paint, stain, or clear-coat compositions.
- the paint, stain, or clear-coat composition consists essentially of water, an optional pigment, an optional dye, and a poly(lactone) I, specifically poly(lactone)s I-a to I-k.
- the poly(lactone) I can be present in the paint composition in an amount from about 2 to about 60 wt.%, and more specifically about 4 to about 40 wt.% of the paint composition, based on the dry weight of the polymer binder.
- the pigment can be used in the paint composition in an amount from about 2 to about 50 wt.%, specifically about 5 to about 40 wt.% of the total solids in the paint composition.
- the poly(lactone) I can be present in the stain composition in an amount from about 0.1 to about 50 wt.%, and more specifically about 0.5 30 wt.%) of the stain composition, based on the dry weight of the poly(lactone) I, specifically poly(lactone)s I-a to I-o.
- the pigment or dye can be used in the stain composition in an amount from about 0.1 to about 40 wt.%, specifically about 0.5 to about 30 wt.%) of the total solids in the stain composition.
- the dye can be used in the paint or stain composition in an amount from about 0.001 to about 10 wt.%, specifically about 0.005 to about 5 wt.% of the total solids in the paint or stain composition.
- the paint composition can include about 5 to about 85 wt.% and more specifically about 35 to about 80 wt.% water, i.e., the total solids content of the paint composition can be about 15 to about 95 wt.%, more specifically, about 20 to about 65 wt.% of the total composition.
- compositions can be formulated such that the hardened (dried) coatings comprise at least about 2 to about 98 volume % (vol.%) polymer solids and about 2 to about 98 vol.% of non-polymeric solids in the form of pigments or a combination of a pigment and a dye, together with other additives (if present).
- the stain composition can includes about 10 to about 95 wt.% and more specifically about 25 to about 90 wt.% water, i.e., the total solids content of the stain composition can be about 5 to about 75 wt.%, more specifically, about 10 to about 75 wt.% of the total composition.
- the stain compositions are typically formulated such that the hardened (dried) coatings comprise at least about 1 vol. %, for example about 5 to about 98 vol.%) poly(lactone) I, specifically poly(lactone)s I-a to I-o, and about 0.1 to about 99 vol.% of non-polymeric solids in the form of pigments and/or dyes, and other additives (if present).
- a wood stain coating can penetrate the wood substrate to some degree.
- the clear-coating composition can include about 10 to about 95 wt.% and more specifically about 25 to about 90 wt.% water, i.e., the total solids content of the clear- coating composition can be about 5 to about 75 wt.%, more specifically, about 10 to about 75 wt.% of the total composition.
- the compositions are typically formulated such that the hardened (dried) clear-coatings comprise at least about 1 vol.% polymer solids, for example about 1 to about 100 vol.% polymer solids, if present, the poly(lactone) I, specifically poly(lactone)s I-a to I-o, and 0 to about 10 vol.% of non-polymeric solids.
- certain additives e.g., calcium carbonate, talc, or silica
- a method of preparing a paint, stain, or clear-coating composition comprises combining the poly(lactone) I, specifically poly(lactone)s I-a to I-o, the pigment (if used), carrier such as water, and any optional additives to form a composition.
- the components can be added in any suitable order to provide the composition.
- the components of the coating composition e.g., a paint, stain, or clear-coat composition
- a first part of includes poly(lactone) I, specifically poly(lactone)s I-a to I-o
- a second part includes crosslinker.
- the parts are mixed in a predetermined ratio to provide the system.
- a method of use that is, coating a substrate with the paint, stain, or clear-coat composition is described. The method comprises contacting a surface of the substrate with the paint, stain, or clear-coat composition to form a film; and drying the film to harden the film.
- the composition can at least partially
- the film can further optionally be cured.
- the substrate can be a wide variety of materials, including but not limited to, paper, wood, concrete, metal, glass, textiles, ceramics, plastics, plaster, roofing substrates such as asphaltic coatings, roofing felts, foamed polyurethane insulation, polymer roof membranes, and masonry substrates such as brick, cinderblock, and cementitious layers, including EIFS systems (synthetic stucco made from engineered layers of polystyrene insulation with a cement- like mud called a topcoat or basecoat, and which is applied with a trowel).
- the substrates include previously painted, primed, undercoated, worn, or weathered substrates.
- the coating composition can be applied to the materials by a variety of techniques well known in the art such as, for example, curtain coating, brush, rollers, mops, air-assisted or airless spray, electrostatic spray, and the like. Paints and clear-coats may or may not partially penetrate, i.e., partially impregnate the substrate upon coating. In an embodiment, a paint composition does not substantially penetrate or impregnate the substrate. In another embodiment, a clear-coat composition does not substantially penetrate or impregnate the substrate. Stains are generally designed to partially or fully impregnate the substrate upon coating. In embodiment, the substrate is fully impregnated by the stain composition, such that the film formed conforms to the interior of the coated substrate, and may be continuous or discontinuous.
- Hardening can be by drying, for example storage under atmospheric conditions at room temperature. Drying can also include solvent wicking, for example by the substrate itself (e.g., wood or paper). Heat can be used as an aid to drying. Curing can be used to further harden the film. Curing may be carried out before drying, during drying, or after drying, or any combination thereof.
- the dried coating can be disposed on a surface of the substrate, in the form of a film that can partially or completely cover the surface.
- the coating can be disposed directly on the surface, or one or more intermediate layers (e.g., a primer) can be present between the coating and the surface of the substrate.
- the coating can be partially or fully impregnated into the substrate and conform to interior surfaces of the substrate.
- the poly(lactone)s I specifically poly(lactone)s I-a to I-o, have a wide variety of other uses, depending on their properties, such as molecular weight, degree of
- the poly(lactone)s I can be used in paper manufacturing, textile finishes, oil production, plastics, coatings, personal care compositions aqueous ink compositions, food packaging, construction materials (e.g., masonry, grout, concrete formulations, and the like, for example to retard drying time) and biomedical applications, among others.
- the poly(lactone)s I, specifically poly(lactone)s I-a to I-o can function as coatings, horticultural additives, rheology modifiers and grease thickeners, adhesives, or binders.
- the poly(lactone)s I can function as parts including films; laminates; sheets (e.g. artificial glass); shaped articles including automotive parts (e.g. head lamps, bumpers, body panels, doors, dashboards, trunk or trunk liners, tailgates, display panels, roof racks, door handles, and the like), housings and casings (e.g. for electronics, medical equipment, and the like), pipes, beams, protective articles (e.g. eye wear, splash shields, and the like), furniture, containers (e.g. trays (e.g. food, surgical, and the like), bottles, boxes, drums, and the like); decorative items; cable sheathing; wire sheathing; and the like.
- automotive parts e.g. head lamps, bumpers, body panels, doors, dashboards, trunk or trunk liners, tailgates, display panels, roof racks, door handles, and the like
- housings and casings e.g. for electronics, medical equipment, and the like
- pipes, beams, protective articles e.g. eye
- the poly(lactone)s I can function as mechanical property modifiers as incorporated as a blend, as a particulate (e.g. rubber particles in high impact polystyrene (HIPS)), as a fiber and can function as an adhesive (e.g. when polymerized with rubbery comonomers), or as an poly(lactone) (e.g. when polymerized with ionic comonomers).
- a particulate e.g. rubber particles in high impact polystyrene (HIPS)
- HIPS high impact polystyrene
- an adhesive e.g. when polymerized with rubbery comonomers
- poly(lactone) e.g. when polymerized with ionic comonomers
- the poly(lactone)s I can be used in specific applications such as gel mouse pads, air fresheners, or as thickening agents for example for water based paints and coatings.
- the poly(lactone) I specifically poly(lactone)s I-a to I-o
- the total number of units can be 20 to 200, or 50 to 100.
- Mn Number average molecular weight average (Mn), weight average molecular weight (Mw), and polydispersity were determined by gel permeation chromatography using a dimethylformamide mobile phase containing 1 wt.% LiBr relative to a poly(methyl methacrylate) (PMMA) standard, unless otherwise indicated.
- PMMA poly(methyl methacrylate)
- AUL absorption under load
- the total weight of piston and cylinder is 106.8 g to give a 2.1 kilopascals (kPa) (0.3 pounds per square inch (psi)) load.
- the metal plate with the product in the cylinder on top was immersed into a 0.9 % saline solution.
- the level of the saline solution had the same level as the nylon screen so that the filter paper and the particles could absorb water.
- a soak time of 1 hour was applied.
- the plate was then removed from the saline solution and the excess water in the holes of the plate was removed with a tissue.
- the weight was removed from the swollen gel and the gel was weighed.
- the ratio of absorbed saline solution to polymer particles was reported as the absorption under load.
- Free Absorbency was measured as follows. Approximately 0.25 g of dried, crushed polymer was placed in a tea bag (small Press 'N Brew tea bag from Mountain Rose Herbs of Eugene, OR), which was then heat-sealed with a hot iron. The masses of the empty bag and the polymer were recorded before the start of the experiment. Beakers of the test solutions were prepared by taring the beakers, rinsing them with the test liquid (either DI water, 0.9% NaCl solution in water, or 8% NaCl solution in water), and filling with 125 g of the test liquid. A single sealed tea bag was then placed in each of the test solutions.
- the test liquid either DI water, 0.9% NaCl solution in water, or 8% NaCl solution in water
- the tea bags were periodically pulled from the test solutions by tweezers, allowed to drain until liquid no longer freely dripped, and then weighed on a tared balance.
- the total mass (bag + polymer + absorbed liquid) was recorded as a function of time.
- the amount of absorbed liquid was calculated by subtracting the starting masses of the dried bag and the dried polymer. Blank bags were soaked in separate containers of the test liquids to estimate how much liquid was absorbed by the bag.
- the mass uptake per gram of polymer (free absorbency capacity) was calculated according to the following equation, where rnuunk is the average absorbency of an empty tea bag in the test liquid: m m
- Water solubility was visually assessed by dissolving 0.1 g of polymer in 1 g of water and visually assessing whether a clear solution formed or whether a gel formed.
- Glass transition temperature was determined by differential scanning calorimetry (DSC) at a heating/cooling rate of 10°C/min. The sample was initially heated to 250 °C and cooled to -60 °C after a 2-minute hold at 250 °C. The Tg was measured on the second scan to 250 °C.
- Example 1 Synthesis of 191 kDa poly(a-methylene-Y-butyrolactone-acrylic acid).
- Example 6 Addition of caustic solution to 191 kDa poly(a-methylene-Y-butyrolactone- acrylic acid).
- Example 7 Addition of KOH to 191 kDa poly(a-methylene-Y-butyrolactone-acrylic acid).
- Example 8 Addition of 0.1 molar equivalents based on the number of lactone groups of NaOH to 191 kDa poly(a-methylene-Y-butyrolactone-acrylic acid).
- Example 9 Addition of 0.3 molar equivalents based on the number of lactone groups of NaOH to 191 kDa poly(a-methylene-Y-butyrolactone-acrylic acid).
- Example 10 Addition of DMF to 191 kDa poly(a-methylene-Y-butyrolactone-acrylic acid).
- Example 13 Prophetic- Addition of CsOH to poly(a-methylene-Y-butyrolactone-acrylic acid).
- Example 14 Addition of a caustic solution to 507 kDa poly(a-methylene-Y-butyrolactone- acrylic acid).
- polydispersity of 1.75 was added to a scintillation vial, along with 3.40 g (0.189 mol) of water and homogenized in a sonication bath to create a stable suspension of polymer particles in water.
- the suspension was then exposed to 24 kHz ultrasonic oscillations in 0.5-second bursts via a 14 mm titanium ultrasonic horn placed just below the liquid surface in the scintillation vial.
- 1.38 g of a 20% caustic solution was added to the vial and the reaction mixture was loosely capped and placed in a 90°C oven for 125 minutes.
- the reaction cooled to room temperature under vacuum before 1H NMR analysis. Comparison of the protons corresponding to the ring opened lactone with those of the ring close lactone showed 86%> of the original lactone groups had been successfully saponified.
- Example 15 Addition of a 20% NaOH solution to 507 kDa poly(a-methylene-Y- butyrolactone-acrylic acid).
- a scintillation vial charged with 0.6321 g of the 507 kDa poly(a- methylene-Y-butyrolactone-acrylic acid) prepared in Example 2 was added 4.988 g water and 1.1802 g of a 20% NaOH(aq) solution.
- the vial was capped and placed in a 90°C oven for 120 minutes before removing the vial and adjusting the pH of the reaction mixture to 7 using a 5% aqueous citric acid solution before drying.
- the resulting dry polymer was completely soluble in water, as determined optically as a homogenous solution.
- Example 16 Addition of a 50% NaOH solution to 507 kDa poly(a-methylene-y- butyrolactone-acrylic acid).
- Example 17 Formation of a clear poly(a-methylene-Y-valerolactone-acrylic acid) film.
- Examples 18-22 Degree of ring opening of 191 kDa poly(a-methylene-Y-butyrolactone- acrylic acid).
- Examples 23-24 were prepared according to the following procedure.
- Example 1 1 Approximately 50 mg of the 507 kDa poly(a-methylene-Y-butyrolactone-acrylic acid) prepared in Example 1 1 that had been dried, ground, and sieved to a particle size between 297 and 595 ⁇ (30 and 50 mesh sieves, respectively) was added to a vial with
- polymer sample to be crosslinked is a poly(a-methylene-y-valerolactone-acrylic acid) sample similar to that prepared in Example 4.
- Example 28 is reacted with 1,6-hexanediol in the presence of a NaOH catalyst to yield a cross-linked, insoluble network
- Example 29 is reacted with 1,6-Hexanediamine without a catalyst also yielding a cross-linked, insoluble network.
- Insolubility as in the above examples, is determined by eye as the presence of either a homogenous solution or two -phase mixture.
- Examples 30-32 and Comparative Examples 33-34 Post-synthesis crosslinking of 507 kDa poly(a-methylene-Y-butyrolactone-acrylic acid) using dielectrophilic reagents.
- post-synthesis crosslinking of the saponified poly(a-methylene-Y-butyrolactone-acrylic acid) can be accomplished using dielectrophilic reagents.
- the vials were charged with approximately 0.50 g of the poly(a-methylene-Y-butyrolactone-acrylic acid) prepared in Example 2 in which 67% of the lactone rings had been saponified by aqueous caustic solution at 90°C for 120 minutes.
- To each vial was added approximately 40 of a crosslinker and the reaction mixtures were heated at 90°C for 120 minutes.
- Comparative Examples 33 and 34 were prepared in the same manor except no crosslinker solution was added.
- Example 35 is cross-linked with diethyl sebacate in the presence of a NaOH catalyst to yield a cross-linked, insoluble network.
- Example 36 is reacted with butanediol diglycidyl ether in the presence of a NaOH catalyst, to yield a cross-linked, insoluble network.
- Example 37 is reacted with isophorone diisocyanate without a catalyst to yield a cross-linked, insoluble network.
- Insolubility is determined by eye as the presence of either a homogenous solution or two-phase mixture.
- Examples 38-40 Sol-Gel determination of poly(a-methylene-y-valerolactone-acrylic acid).
- an aqueous mixture consisting of 22.270 g (1.237 mol) water, 0.355 g (1.23 x 10 ⁇ 3 mol) sodium dodecyl sulfate (20% aqueous solution), 0.039 g (1.63 10 " 4 mol) sodium persulfate, and 0.053 g of a 20% aqueous sodium hydroxide solution was also added dropwise over 110 minutes.
- the emulsion was allowed to stir for an additional 60 minutes, after which the reaction was cooled to room temperature and dried for 16 hours at 90°C under vacuum.
- Example 41 Prophetic-Synthesis of poly(a-methylene-Y-valerolactone-triallyl amine-acrylic acid) copolymer.
- an aqueous mixture consisting of 18.937 g (1.05 mol) water, 0.300 g (1.04 x 10 ⁇ 3 mol) sodium dodecyl sulfate (20%) aqueous solution), 0.033 g (1.39 x 10 "4 mol) sodium persulfate, and 0.037 g of a 20%) aqueous sodium hydroxide solution is also added dropwise over 120 minutes.
- the emulsion stirs for an additional 60 minutes, after which the reaction is cooled to room temperature and the polymer can be dried under vacuum for isolation.
- the resulting polymer can be saponified as described above.
- Example 42 Prophetic-Synthesis of poly(a-methylene-Y-butyrolactone-triallyl amine-acrylic acid) copolymer.
- the resulting polymer can be saponified as described above.
- Example 42 Synthesis of poly(a-methylene-Y-butyrolactone-n-butyl acrylate-acrylic acid) copolymer.
- an aqueous mixture consisting of 16.711 g (0.928 mol) water, 0.267 g (9.26 x 10 "4 mol) sodium dodecyl sulfate (20% aqueous solution), 0.026 g (1.09 x 10 "4 mol) sodium persulfate, and 0.033 g of a 20%) aqueous sodium hydroxide solution was added via syringe pump over 115 minutes. After both the monomer and aqueous mixtures were added completely, the emulsion was allowed to stir for an additional 60 minutes, after which the reaction was cooled to room temperature and dried under vacuum under vacuum at 90°C overnight.
- Size exclusion chromatography yielded a monomodal peak with a weight average molecular weight of 296 kDa and a polydispersity of 2.84, relative to polystyrene standards.
- Differential scanning calorimetry showed a single first order transition at approximately 21°C.
- the resulting polymer can be saponified as described above.
- Example 44 Synthesis of poly(a-methylene-Y-butyrolactone-n-butyl acrylate-acrylic acid) copolymer.
- the resulting polymer can be saponified as described above.
- Example 45a and b Prophetic-Synthesis of poly(a-methylene-y-valerolactone-n-butyl acrylate- acrylic acid) copolymer.
- Example 35 Similar to Example 35 and Example 36, except a-methylene-y-valero lactone is used in place of a-methylene-y-butyro lactone.
- the resulting polymer can be saponified as described above.
- Example 46 Synthesis of poly(a-methylene-Y-butyrolactone-styrene-acrylic acid) copolymer.
- an aqueous mixture consisting of 16.694 g (0.927 mol) water, 0.269 g (9.33 x 10 "4 mol) sodium dodecyl sulfate (20% aqueous solution), 0.033 g (1.39 10 "4 mol) sodium persulfate, and 0.041 g of a 20% aqueous sodium hydroxide solution was added via syringe pump over 130 minutes. After both the monomer and aqueous mixtures were added completely, the emulsion was allowed to stir for an additional 60 minutes, after which the reaction was cooled to room temperature and dried under vacuum under vacuum at 90°C overnight.
- Size exclusion chromatography yielded a monomodal peak with a weight average molecular weight of 104 kDa and a polydispersity of 1.96, relative to polystyrene standards.
- Differential scanning calorimetry showed a single first order transition at approximately 167°C.
- the resulting polymer can be saponified as described above.
- Example 47 Prophetic-Synthesis of poly(a-methylene-Y-valerolactone-styrene-acrylic acid) copolymer.
- the resulting polymer can be saponified as described above.
- Example 48 Synthesis of poly(a-methylene-Y-butyrolactone-acrylic acid) copolymer.
- an aqueous mixture consisting of 16.661 g (0.926 mol) water, 0.282 g (9.78 x 10 "4 mol) sodium dodecyl sulfate (20% aqueous solution), 0.034 g (1.43 x 10 "4 mol) sodium persulfate, and 0.032 g of a 20% aqueous sodium hydroxide solution was added via syringe pump over 135 minutes. After both the monomer and aqueous mixtures were added completely, the emulsion was allowed to stir for an additional 60 minutes, after which the reaction was cooled to room temperature and dried under vacuum under vacuum at 90°C overnight.
- Size exclusion chromatography yielded a monomodal peak with a weight average molecular weight of 126 kDa and a polydispersity of 2.12, relative to polystyrene standards.
- Differential scanning calorimetry showed a single first order transition at approximately 174°C.
- the resulting polymer can be saponified as described above.
- Example 49 Prophetic-Synthesis of poly(a-methylene-y-valerolactone-acrylic acid) copolymer.
- Example 44 Similar to Example 44, except a-methylene-y-valerolactone is used in place of a-methylene-y-butyro lactone.
- the resulting polymer can be saponified as described above.
- Example 50 Synthesis of poly(a-methylene-Y-butyrolactone-N,N-dimethyl acrylamide) copolymer.
- an aqueous mixture consisting of 16.658 g (0.925 mol) water, 0.264 g (9.15 10 "4 mol) sodium dodecyl sulfate (20% aqueous solution), 0.029 g (1.22 x 10 "4 mol) sodium persulfate, and 0.028 g of a 20% aqueous sodium hydroxide solution was added via syringe pump over 120 minutes. After both the monomer and aqueous mixtures were added completely, the emulsion was allowed to stir for an additional 60 minutes, after which the reaction was cooled to room temperature and dried under vacuum under vacuum at 90°C overnight.
- Size exclusion chromatography yielded a mo no modal peak with a weight average molecular weight of 200 kDa and a polydispersity of 3.32, relative to polystyrene standards.
- Differential scanning calorimetry showed a first order transition at approximately 162°C.
- the resulting polymer can be saponified as described above.
- Example 51 Prophetic-Synthesis of poly(a-methylene-Y-valerolactone-N,N-dimethyl acrylamide) copolymer.
- the resulting polymer can be saponified as described above.
- Example 52 Prophetic - Synthesis of poly(a-methylene-Y-butyrolactone-itaconic acid-acrylic acid).
- an aqueous mixture consisting of 18.015 g (1.00 mol) water, 1.42 g (5.97 x 10 "3 mol) sodium persulfate, and 1.32 g (3.33 x 10 ⁇ 2 mol) sodium hydroxide is added via syringe pump over 300 minutes at reflux. After both the monomer and aqueous mixtures are added completely, the emulsion is allowed to stir for an additional 60 minutes before cooling to room temperature and drying under vacuum at elevated temperature for isolation.
- the resulting polymer can be saponified as described above.
- Example 53 Prophetic-Synthesis of poly(a-methylene-y-valerolactone-acrylic acid).
- the resulting polymer can be saponified as described above.
- Example 54 Prophetic - Synthesis of poly(a-methylene-Y-butyrolactone-octadecyl acrylate) copolymer.
- the resulting polymer can be saponified as described above.
- Example 55 Prophetic-Synthesis of poly(a-methylene-y-valerolactone-octadecyl acrylate) copolymer.
- the resulting polymer can be saponified as described above.
- Example 56 Prophetic - Synthesis of poly(a-methylene-Y-butyrolactone-acrylonitrile-p- styrene sulfonate) copolymer.
- the resulting polymer can be saponified as described above.
- Example 57 Prophetic-Synthesis of poly(a-methylene-Y-valerolactone-acrylonitrile-p- styrene sulfonate) copolymer.
- the resulting polymer can be saponified as described above.
- Example 58 Prophetic - Synthesis of poly(a-methylene-Y-butyrolactone-butadiene-acrylic acid) copolymer.
- a 150 mL round bottom flask with a magnetic stir bar is charged with 17 g (0.943 mol) of water, 0.01 g (6.49 x 10 "5 mol) of sodium hydro xymethylsulfinate and 0.001 g (2.63 x 10 ⁇ 6 mol) of tetrasodium ethylene diamine tetraacetate.
- the reactor is heated to 80°C under nitrogen.
- aqueous mixture consisting of 0.25 g (4.20 x 10 "3 mol) of sodium persulfate and 7 g (0.389 mol) of water is added over 2 minutes. After stirring for 20 minutes at 80°C, the remainder of the monomer pre-emulsion and aqueous mixture is added uniformly over 300 minutes. When all additions were completed, the polymerization is allowed to stir for an additional 7 hours at 80°C. Upon completion, steam is passed through the mixture under reduced pressure and a solution of 0.25 g (1.62 x 10 "3 mol) of sodium hydro xymethylsulfmate in 1 g (5.55 x 10 ⁇ 2 mol) of water is added slowly, with stirring. The pH of the dispersion is brought to 7 with 10%> strength aqueous ammonia before the dispersion is dried under vacuum at elevated temperature for isolation.
- the resulting polymer can be saponified as described above.
- Example 59 Prophetic-Synthesis of poly(a-methylene-Y-butyrolactone-butadiene-acrylic acid) copolymer.
- the resulting polymer can be saponified as described above.
- Example 60 Prophetic - Synthesis of core-shell particles of poly(a-methylene-y- butyro lactone-butadiene) .
- a 250 mL flask with stirring is charged with 42.3 g (2.35 mol) water, 0.06 g (2.83 x 10 "4 mol) tripotassium phosphate, 6.53 g of a 10%> C 14 -C 18 unsaturated potassium salt solution, 0.54 g of a 20%> solution of a disproportionate rosin acid potassium salt, 0.12 g of a 47.5% sodium naphthalene sulfonate formaldehyde active dispersion.
- the pH of the solution is adjusted with a 20%> aqueous potash solution to between 10.5-11.
- an activator stock solution (containing 10 g (0.555 mol) water, 0.1 g (6.49 x 10 "4 mol) hydroxymethane-sulfinic acid monosodium salt dihydrate, and 0.03 g (8.17 x 10 "5 mol) EDTA ferric sodium complex) and 23.75 g (0.242 mol) of a-methylene-y-butyro lactone.
- the reactor is purged with nitrogen before the addition of 1.25 g (2.31 x 10 "2 mol) of 1,3- butadiene.
- the reactor is sealed and heated at 23°C with stirring before the addition of 0.02 g of a 44% active pinane hydroperoxide solution. The seed polymerization is deemed complete when solids content reached a plateau.
- Polymerization of the shell begins with the addition of 23.3 g of the above emulsion, 46.7 g (2.59 mol) water and 1.01 g of the activator stock solution from above to a 250 mL flask with stirring. The mixture is purged with nitrogen before the addition of 7.5 g (0.139 mol) 1,3-butadiene is added and the reactor is sealed and heated to 23°C with stirring. Polymerization is initiated with the addition of 0.02 g of a 44% active pinane hydroperoxide solution. The polymerization is deemed complete when the solids content reached a plateau, at which point the core shell particles are isolated via drying at elevated temperature.
- the resulting polymer can be saponified as described above.
- Example 61 Prophetic-Synthesis of core-shell particles of poly(a-methylene-y- valero lactone-butadiene) .
- the resulting polymer can be saponified as described above.
- Example 62 Prophetic - Synthesis of particles with poly(a-methylene-Y-butyro lactone) core and polystyrene shell.
- a reactor is charged with water (2358 g), seed latex (0.39 g), and sodium persulfate (3.1 g) and heated to 80°C.
- a monomer mixture of 382.8 g a-methylene- ⁇ - butyrolactone, 277.2 g methacrylic acid, and 2.8 g sodium alkyl benzene sulfonate are added over 120 minutes to the initial charge.
- the emulsion is allowed to stir for an additional 60 minutes, after which the reactor is cooled to room temperature and the polymer core is removed
- a reactor is charged with 1713 g water, 192.2 g the core latex, and 3.27 g sodium persulfate and heated to 92°C.
- a monomer mixture of 733.6 g styrene and 8.5 g acrylic acid are added over the course of 100 minutes while simultaneously feeding an aqueous mixture of 112.3 g water and 0.71 g sodium alkylbenzene sulfonate.
- the emulsion is allowed to stir for an additional 60 minutes, after which the reactor is cooled to room temperature and the core/shell latex is removed.
- Example 63 Prophetic - Synthesis of particles with poly(of a-methylene-y-valerolactone) core and polystyrene shell
- Example 64 Synthesis of poly(a-methylene-Y-butyrolactone-2-vinylpyridine) copolymer.
- the resulting polymer can be saponified as described above.
- Example 65 Prophetic-Synthesis of poly(a-methylene-Y-valerolactone-2-vinylpyridine) copolymer.
- the resulting polymer can be saponified as described above.
- Example 66 Prophetic - Synthesis of poly(a-methylene-Y-butyrolactone-hydroxyethyl methacrylate-4-vinyl benzoic acid) copolymer.
- the resulting polymer can be saponified as described above.
- Example 67 Prophetic-Synthesis of poly(a-methylene-y-valerolactone-hydroxyethyl methacrylate-4-vinyl benzoic acid) copolymer.
- the resulting polymer can be saponified as described above.
- the resulting polymer can be saponified as described above.
- Example 69 Prophetic-Synthesis of poly(a-methylene-Y-valerolactone-N-vinyl pyrrolidone- methacrylic acid) copolymer.
- the resulting polymer can be saponified as described above.
- Example 70 Synthesis of poly(a-methylene-Y-valerolactone-divinyl benzene) copolymer.
- the resulting polymer can be saponified as described above.
- Example 71 Prophetic-Ring opening of poly(a-methylene-Y-butyrolactone-styrene) copolymer.
- Example 72 Formation of a clear film of poly(methylene-butyro lactone -n-butyl acrylate) copolymer.
- Crosslinked refers to a covalent or bond that links one polymer or polymer chain to another polymer or polymer chain.
- a “hydrocarbyl group” as used herein means a group having the specified number of carbon atoms and the appropriate valence in view of the number of substitutions shown in the structure. Hydrocarbyl groups contain at least carbon and hydrogen, and can optionally contain 1 or more (e.g., 1-8) heteroatoms selected from N, O, S, Si, P, or a combination thereof.
- Hydrocarbyl groups can be unsubstituted or substituted with one or more substituent groups up to the valence allowed by the hydrocarbyl group independently selected from a CI -30 alkyl, C2-30 alkenyl, C2-30 alkynyl, C6-30 aryl, C7-30 arylalkyl, Cl- 12 alkoxy, Cl-30 heteroalkyl, C3-30 heteroarylalkyl, C3-30 cycloalkyl, C3-15 cycloalkenyl, C6-30 cycloalkynyl, C2-30 heterocycloalkyl, halogen (F, CI, Br, or I), hydroxy, nitro, cyano, amino, azido, amidino, hydrazino, hydrazono, carbonyl, carbamyl, thiol, carboxy (Cl-6alkyl) ester, carboxylic acid, carboxylic acid salt, sulfonic acid or a salt thereof, and phosphoric acid or
- Alkyl refers to a straight or branched chain saturated aliphatic hydrocarbyl group having the specified number of carbon atoms and the appropriate valence in view of the structure.
- Alkenyl refers to a straight or branched chain hydrocarbyl group that comprises at least one carbon-carbon double bond and the appropriate valence in view of the structure.
- Cycloalkyl refers to a groups having the indicated number of carbon atoms in the ring of the valence dictated by the structure, and that comprises one or more saturated and/or partially saturated rings in which all ring members are carbon, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
- Cycloalkenyl refers to a cycloalkyl group that is at least partially unsaturated.
- Aryl refers to a cyclic moiety having the appropriate valence in view of the structure, in which all ring members are carbon and at least one ring is a single bond or aromatic, the moiety having the specified number of carbon atoms. More than one ring can be present, and any additional rings can be independently aromatic, saturated or partially unsaturated, and can be fused, pendant, spirocyclic or a combination thereof.
- Alkoxy refers to an alkyl moiety that is linked via an oxygen (i.e., -O-alkyl).
- Nonlimiting examples of CI to C30 alkoxy groups include methoxy groups, ethoxy groups, propoxy groups, isobutyloxy groups, sec-butyloxy groups, pentyloxy groups, iso-amyloxy groups, and hexyloxy groups.
- Hetero means a group or compound including at least one heteroatom (e.g., 1 to 4 heteroatoms) each independently N, O, S, Si, or P. (Meth)acryl is inclusive of both acryl and methacryl groups.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12846937.6A EP2776491A4 (en) | 2011-11-11 | 2012-11-12 | Poly(lactone)s, method of manufacture, and uses thereof |
JP2014541380A JP2014533322A (en) | 2011-11-11 | 2012-11-12 | Poly (lactones), production methods, and uses thereof |
US14/357,670 US20140343222A1 (en) | 2011-11-11 | 2012-11-12 | Poly(lactone)s, method of manufacture, and uses thereof |
KR1020147015611A KR20140126291A (en) | 2011-11-11 | 2012-11-12 | Poly(lactone)s, method of manufacture, and uses thereof |
CA2857094A CA2857094A1 (en) | 2011-11-11 | 2012-11-12 | Poly(lactone)s, method of manufacture, and uses thereof |
CN201280066778.1A CN104245788A (en) | 2011-11-11 | 2012-11-12 | Poly(lactone)s, method of manufacture, and uses thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161558983P | 2011-11-11 | 2011-11-11 | |
US61/558,983 | 2011-11-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013071256A1 true WO2013071256A1 (en) | 2013-05-16 |
Family
ID=48290667
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2012/064709 WO2013071256A1 (en) | 2011-11-11 | 2012-11-12 | Poly(lactone)s, method of manufacture, and uses thereof |
Country Status (7)
Country | Link |
---|---|
US (1) | US20140343222A1 (en) |
EP (1) | EP2776491A4 (en) |
JP (1) | JP2014533322A (en) |
KR (1) | KR20140126291A (en) |
CN (1) | CN104245788A (en) |
CA (1) | CA2857094A1 (en) |
WO (1) | WO2013071256A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105373244A (en) * | 2015-12-16 | 2016-03-02 | 苏州天擎电子通讯有限公司 | Mouse pad with fluorescent effect |
CN107868189B (en) * | 2016-09-28 | 2020-06-09 | 中国石油化工股份有限公司 | Acrylamide copolymer and preparation method and application thereof |
CN110628187B (en) * | 2019-09-30 | 2021-09-07 | 中国科学院理化技术研究所 | Water-collecting degradable mulching film and preparation method thereof |
CN111253556B (en) * | 2020-03-20 | 2022-02-18 | 南京工业大学 | Functionalized recyclable high-molecular homopolymer and preparation method and application thereof |
CN111961207B (en) * | 2020-07-08 | 2022-08-02 | 大连大学 | Method for synthesizing caprolactone and dimethyl siloxane triblock copolymer by using citric acid as catalyst |
CN114276524B (en) * | 2021-12-27 | 2023-04-21 | 青岛科技大学 | Preparation method of high molecular weight degradable recyclable polyester containing double bond side group |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5028667A (en) * | 1989-09-29 | 1991-07-02 | E.I. Du Pont De Nemours And Company | Yttrium and rare earth compounds catalyzed lactone polymerization |
JPH0912644A (en) * | 1995-06-29 | 1997-01-14 | Mitsubishi Rayon Co Ltd | Clear heat-resistant resin |
US6388036B1 (en) * | 1998-12-16 | 2002-05-14 | E. I. Du Pont De Nemours And Company | Oligomerization, polymerization and copolymerization of substituted and unsubstituted α-methylene-γ-butyrolactones and products thereof |
KR20070108394A (en) * | 2005-02-10 | 2007-11-09 | 다이셀 가가꾸 고교 가부시끼가이샤 | Ring-opening polymerization process for lactone compound and active carbon catalyst for ring-opening polymerization |
WO2011038337A1 (en) * | 2009-09-26 | 2011-03-31 | Segetis, Inc. | Ketal lactones and stereospecific adducts of oxocarboxylic ketals with trimethylol compounds, polymers containing the same, methods of manufacture, and uses thereof |
US20120118832A1 (en) * | 2010-11-11 | 2012-05-17 | Segetis, Inc. | Ionic polymers, method of manufacture, and uses thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3580909B2 (en) * | 1995-06-30 | 2004-10-27 | 三菱レイヨン株式会社 | Heat resistant resin |
US6642346B2 (en) * | 2000-02-28 | 2003-11-04 | E. I. Du Pont De Nemours And Company | Coating compositions containing substituted and unsubstituted exomethylene lactone or lactam monomers |
WO2001098410A2 (en) * | 2000-06-21 | 2001-12-27 | E.I. Dupont De Nemours And Company | BLENDS OF POLY[α-METHYLENELACT(ONE)(AM)] HOMO- AND COPOLYMERS |
DE10154030A1 (en) * | 2001-11-02 | 2003-05-22 | Basf Coatings Ag | Effect generator, aqueous coating material, process for its preparation and its use |
BR0214442A (en) * | 2001-11-30 | 2004-09-14 | Du Pont | Acrylic Copolymer, Process for Production of Acrylic Copolymer, Process for Production of Copolymer, Methods for Polymerization, Method for Copolymerization and Composition of Thermoplastic Polymer |
JP4240204B2 (en) * | 2003-03-07 | 2009-03-18 | 日産化学工業株式会社 | Positive photosensitive resin composition |
US7512309B2 (en) * | 2004-12-27 | 2009-03-31 | Mitsubishi Rayon Co, Ltd. | Polymer composition, plastic optical fiber, plastic optical fiber cable, and method for manufacturing plastic optical fiber |
US20080293901A1 (en) * | 2007-05-25 | 2008-11-27 | Basf Corporation | Polymers and compounds prepared with alpha-methylene lactones, methods therefor, and coatings |
EP2691426B1 (en) * | 2011-03-30 | 2014-12-24 | DSM IP Assets B.V. | Process for radically curing a composition |
-
2012
- 2012-11-12 US US14/357,670 patent/US20140343222A1/en not_active Abandoned
- 2012-11-12 CN CN201280066778.1A patent/CN104245788A/en active Pending
- 2012-11-12 CA CA2857094A patent/CA2857094A1/en not_active Abandoned
- 2012-11-12 EP EP12846937.6A patent/EP2776491A4/en not_active Withdrawn
- 2012-11-12 WO PCT/US2012/064709 patent/WO2013071256A1/en active Application Filing
- 2012-11-12 KR KR1020147015611A patent/KR20140126291A/en not_active Application Discontinuation
- 2012-11-12 JP JP2014541380A patent/JP2014533322A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5028667A (en) * | 1989-09-29 | 1991-07-02 | E.I. Du Pont De Nemours And Company | Yttrium and rare earth compounds catalyzed lactone polymerization |
US5028667B1 (en) * | 1989-09-29 | 1993-02-09 | Du Pont | |
JPH0912644A (en) * | 1995-06-29 | 1997-01-14 | Mitsubishi Rayon Co Ltd | Clear heat-resistant resin |
US6388036B1 (en) * | 1998-12-16 | 2002-05-14 | E. I. Du Pont De Nemours And Company | Oligomerization, polymerization and copolymerization of substituted and unsubstituted α-methylene-γ-butyrolactones and products thereof |
KR20070108394A (en) * | 2005-02-10 | 2007-11-09 | 다이셀 가가꾸 고교 가부시끼가이샤 | Ring-opening polymerization process for lactone compound and active carbon catalyst for ring-opening polymerization |
WO2011038337A1 (en) * | 2009-09-26 | 2011-03-31 | Segetis, Inc. | Ketal lactones and stereospecific adducts of oxocarboxylic ketals with trimethylol compounds, polymers containing the same, methods of manufacture, and uses thereof |
US20120118832A1 (en) * | 2010-11-11 | 2012-05-17 | Segetis, Inc. | Ionic polymers, method of manufacture, and uses thereof |
Non-Patent Citations (1)
Title |
---|
See also references of EP2776491A4 * |
Also Published As
Publication number | Publication date |
---|---|
CA2857094A1 (en) | 2013-05-16 |
EP2776491A4 (en) | 2015-10-21 |
JP2014533322A (en) | 2014-12-11 |
KR20140126291A (en) | 2014-10-30 |
EP2776491A1 (en) | 2014-09-17 |
US20140343222A1 (en) | 2014-11-20 |
CN104245788A (en) | 2014-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2638094B1 (en) | Ionic polymers, method of manufacture, and uses thereof | |
EP2776491A1 (en) | Poly(lactone)s, method of manufacture, and uses thereof | |
US10336853B2 (en) | Polymer, process and composition | |
TWI816652B (en) | Polycarbonate polyols and polyurethanes | |
CN105829381B (en) | Aqueous coating composition and preparation of multicoat paint system using said coating composition | |
CN105026055A (en) | Methods and compositions for coating substrates | |
Fertier et al. | New biosourced UV curable coatings based on isosorbide | |
US20040198903A1 (en) | Ambient curable polymer | |
US9796873B2 (en) | Linear polyglycidyl amine additives for controlled crosslinking of latex polymers | |
CN106366277B (en) | A kind of preparation method and application of ultraviolet light cross-linking solidfication water polyurethane | |
WO2017135925A1 (en) | Linear polyglycidyl amine additives for controlled crosslinking of latex polymers | |
CN103403050B (en) | Method for producing a colour and/or effect-producing multi-layered coating | |
CN103347918A (en) | Use of aqueous dispersions as primers | |
Van den Dungen | Self-healing coatings based on thiol-ene chemistry | |
ŞABANİ | ISTANBUL TECHNICAL UNIVERSITY★ INSTITUTE OF SCIENCE AND TECHNOLOGY |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12846937 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014541380 Country of ref document: JP Kind code of ref document: A Ref document number: 2857094 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20147015611 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012846937 Country of ref document: EP |