WO2017152103A1 - Résines d'éther hydroxyle vinylique - Google Patents

Résines d'éther hydroxyle vinylique Download PDF

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Publication number
WO2017152103A1
WO2017152103A1 PCT/US2017/020747 US2017020747W WO2017152103A1 WO 2017152103 A1 WO2017152103 A1 WO 2017152103A1 US 2017020747 W US2017020747 W US 2017020747W WO 2017152103 A1 WO2017152103 A1 WO 2017152103A1
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WO
WIPO (PCT)
Prior art keywords
vher
bisphenol
epoxy
coatings
derakane
Prior art date
Application number
PCT/US2017/020747
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English (en)
Inventor
Akshay KOKIL
Yongwoo Lee
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University Of Massachusetts
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of WO2017152103A1 publication Critical patent/WO2017152103A1/fr

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Classifications

    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • Vinyl ester resins are high performance unsaturated resins with exceptional mechanical strength and corrosion resistance. In addition to their superior performance, these resins display lower viscosities than conventional epoxy resins resulting in significantly improved process ability. Due to their superior properties and excellent processability , VERs find use, either in pure form or as a matrix in fiber reinforced composites, in diverse industries, such as, ship building, automotive part construction, infrastructure polymer concrete reinforcements, corrosion resistance coatings (on chemical storage tanks, pipes and ducting fume extraction systems, gas cleaning units), top -coat materials (with excellent adhesion to plastics, steel and concrete), optical fiber coating UV curing inks and printed circuit board manufacture ⁇ Jaswal S.; Gaur, B. 'New trends in vinyl ester resins ' Rev. Chem. Eng. 2014, DOI 10.1515/revce-2014-0012). The versatility of these resins for diverse applications has resulted in a huge global market and ever increasing potential.
  • VERs are currently synthesized by addition reaction of epoxide resins with unsaturated carboxy lie acids.
  • a variety of chemical comp ounds containing the epoxy groups have been used for synthesis of VERs.
  • Particularly bisphenol-A (BP A) based VER resins are widely utilized due to their exceptional mechanical strength and chemical resistance.
  • the present invention provides a vinyl hydroxy! ether resin (VHER having the general structure:
  • R independently represents hydrogen, or mono-, di-, or tri-substitution of(Ci-Cio)hydrocarbyl.
  • the variable R represents O, S0 2 , or C(R 1 ) 2 .
  • Each occurrence of R 1 is independently chosen from hydrogen, phenyl, and substituted or unsubstituted (Ci-Cio)hydrocarbyl.
  • R 5 is (Ci- Cio)hy drocarby 1 substituted with one or more halogens selected from F, CI, and Br.
  • R is:
  • R' is CH 3 or CH(CH 3 )2.
  • the present invention p rovides a viny 1 hydroxy 1 ether resin (VHER) having the structure:
  • Some embodiments provide a polymerization product of a starting material composition that includes the VHER. Some embodiments provide a method of making the VHER including combining Bisphenol A:
  • VHER vinyl hydroxy 1 ether resin
  • Some embodiments provide a polymerization product of a starting material composition, the starting material composition including the VHER. Some embodiments provide a method of making the VHER including combining Bisphenol A:
  • Various embodiments include a new class of resins, vinyl hydroxy 1 ether resin
  • VHER VHER
  • Various embodiments including an environmentally benign "green” methodology for the synthesis of the VHERs.
  • Various embodiments provide a novel single-step synthetic protocol for the synthesis of the VHERs.
  • the retention of hydroxy! moieties in the structure of the VHERs would introduce stronger interactions with a variety of substrates and fiber reinforcements, as compared to other resins.
  • the elimination of ester moieties in the structure of the VHERs can provide imp roved stability towards chemical and thermal degradation of the resin.
  • the VHER can be cured to produce a thermoset polymer with reduced polar ester groups, compared to polymer made from VERs. This can advantageously reduce or minimize blistering-type defects, often observed in long term use of VER poly mers in aquatic environments.
  • the VHER has improved chemical stability compared to other resins, which can be used to produce thinner corrosion resistant coatings. Thinner coatings can help in lowering the environmental footprint of the materials.
  • a reactive diluent e.g., styrene
  • VHER viscosity can aid in efficient processing of the resin.
  • styrene is a carcinogenic compound, and hence a reduced amount in the formulations is desired for safer work environment.
  • VHER displays lower viscosity than vinyl epoxy resin (VER), which would reduce the amount of required reactive diluent (e.g., styrene) in the formulations, resulting in "greener" formulations.
  • VER vinyl epoxy resin
  • the VHER can be a more stable alternative to widely utilized resins used in diverse industries, such as, ship building automotive part constraction, infrastructure polymer concrete reinforcements, corrosion resistance coatings (e.g., on chemical storage tanks, pipes and ducting, fume extraction systems, gas cleaning units), topcoat materials (e.g, with excellent adhesion to plastics, steel and concrete), optical fiber coating, UV curing inks, printed circuit board manufacture, and fiber-reinforced composites.
  • resins used in diverse industries, such as, ship building automotive part constraction, infrastructure polymer concrete reinforcements, corrosion resistance coatings (e.g., on chemical storage tanks, pipes and ducting, fume extraction systems, gas cleaning units), topcoat materials (e.g, with excellent adhesion to plastics, steel and concrete), optical fiber coating, UV curing inks, printed circuit board manufacture, and fiber-reinforced composites.
  • FIG.1 is a reaction scheme for synthesis of model compound Bisphenol A bis(2-hy droxy p rop y l)ether (B ABHPE)
  • FIG. 2 is the p roton NMR spectrum of B ABHPE in DM SO-d 6 .
  • FIG. 3 is a reaction scheme for synthesis ofVHER by em loying vinyl ethylene carbonate.
  • FIG. 4 is the proton NMRof a VHER in DM SO-d 6
  • FIG. 5 is a reaction scheme for the synthesis of VHER by employing 3- butene-( i ,2-diol).
  • FIG. 6 is a reaction scheme for synthesis of VHER by employing l,2-epoxy-5- hexene.
  • FIG. 7 shows photographs of Derakane and VHER formulations (top row).
  • FIG. 8 is the protonNMRand FTIRspectra of a VHER.
  • FIG. 8A is the proton NMR of VHER in DM SO d 6 .
  • FIG. 8B is FT IR spectra for a VHER (upper line, red) and BPA (lower line, black).
  • FIG. 9 is a photograph of cured one pot synthesized VHER with 33% styrene.
  • FIG. 10 is a plot of Storage Modulus, Loss Modulus and Tan Delta traces obtained using the cured one pot synthesized VHER with 33% styrene.
  • FIG. 11 A is a plot of TGA traces for cured VHER.
  • FIG. 1 IB is a plot of TGA traces for cured Derakane 411-400.
  • FIG. 12 is photographs of cured coatings of VHER (left) and Derakane 411-
  • FIG. 13 is a plot ofwater uptake measurements for cured Derakane 41 1-400
  • FIG. 14 is photographs of VHER (left) and Derakane (right) coatings after the
  • FIG. 15 is photographs of the OT, IT, and 2T bend test results for VHER and Derakane 441-400 VER coatings after MEK double rub testing.
  • FIG. 16 is 0T bend test results for VHER (top) and Derakane (bottom) coatings after immersion in concentrated H2SO4 for 48 hours.
  • a range of "about 0.1 % to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range.
  • the statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise.
  • the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.
  • the acts can be carried out in any order without dep arting from the princip les of the invention, except when a temporal or operational sequence is explicitly recited.
  • specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately.
  • a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.
  • substantially refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%.
  • the term "polymer” refers to a molecule having at least one repeating unit and can include copolymers.
  • the polymers described herein can terminate in any suitable way.
  • thepolymers can terminate with an end group that is independently chosen from a suitable polymerization initiator, -H, -OH, a substituted or unsubstituted (Ci- C 2 o)hydrocarbyl(e.g., (Ci-Cio)alkyl or (C6-C 2 o)aryl) interrupted with 0, 1, 2, or 3 groups independently selected from -O-, substituted or unsubstituted -NH-, and -S-, a
  • substituted as used herein in conjunction with a molecule or an organic group as defined herein refers to the state in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms.
  • the present invention provides a vinyl hydroxyl ether resin
  • R independently represents hydrogen, or mono-, di-, or tri-substitution of (Ci-Oo)hy drocarby 1.
  • the variable R represents O, SO2, or C(R 1 ) 2 .
  • Each occurrence of R 1 is independently chosen from hydrogen, phenyl, and substituted or unsubstituted (Ci-Cio)hy drocarby 1.
  • R 1 is (O- Cio)hy drocarby 1 substituted with one or more halogens selected from F, CI, and Br.
  • R is
  • the base can be any suitable base that is ca able of
  • Suitable bases include, but are not limited to, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydride, sodium hydride, and potassium hydride.
  • the reaction is typically conducted by heating the reagents neat (without solvent).
  • a suitable reaction temperature can be between 50-200 °C, or between 100-150 °C.
  • Suitable phenols for the reaction are not limited to Bisphenol A.
  • Other suitable phenols include, but are not limited to, bisphenol AP (l, l-bis(4-hydroxyphenyl)-l- phenyl-ethane), bisphenol AF (2,2-bis(4-hydroxyphenyl)hexafiuoropropane), bisphenolB (2,2-bis(4-hydroxyphenyl)butane), bisphenolBP (bis-(4-hydroxyphenyl)diphenylmethane), bisphenol C (2,2-bis(3-methyl-4-hydroxyphenyl)propane), bisphenol E (1,1 -bis(4- hydroxyphenyl)ethane), bisphenolF (bis(4-hydroxydiphenyl)methane), bisphenol G (2,2- bis(4 iydroxy-3-isopropyl-phenyl)propane), bisphenolPH (5,5'-(l-methylethyliden)- bis[l,l '-(bis(
  • the VHER can be made by a method including, combining Bisphenol A:
  • a method of making the VHER includes
  • epoxide starting materials under conditions sufficient to give the VHER.
  • an environmentally friendly solvent-free reaction single pot reaction can be conducted.
  • Other suitable epoxides include, but are not limited to, 2-epoxy-6-heptene, l,2-epoxy-7-octene, l,2-epoxy-8-nonene, l,2-epoxy-9-decene, or combinations thereof.
  • Suitable reaction conditions for reacting a phenol and an epoxide and a phenol are described in, for example, Lee et al. RSC Adv. 2015, 5, 38673-38679.
  • Example 1 One step protocol used for synthesis of a model compound bisphenol A bis(2- hv droxyp rop vDether (B ABHPE) .
  • Example 1 The model reaction procedure given in Example 1 establishes the synthetic procedure for VHER. As in-situ formation of the cyclic carbonate occurs, two different synthesis strategies can be used as presented below ( Figure 3 and 4). The reactions thus performed will be single step and single pot procedures. Investigations on these concepts are underway and the results will be included here. By changing the length of the alkyl segments (e.g., hexyl, octyletc.) used the viscosity and other properties ofthe final product can be tailored. The use of longer alkyl chains would also provide non-ally lie product.
  • the alkyl segments e.g., hexyl, octyletc.
  • a large scale synthesis of VHER can be also performed according to the following protocol as one embodiment of the invention.
  • VHER can also be synthesized using 3-butene-(l,2-diol) according to the reaction scheme presented in Figure 5.
  • VHER can be synthesized using cheap er commercially available starting materials (e.g. l,2-epoxy-5-hexene) through an environmentally benign solvent free single ot reaction methodology as conceptualized in Figure 6.
  • the reaction between an epoxy group and the BP A hydroxy 1 moiety has been reported (Lee et al. RSC Adv. 2015, 5, 38673-38679).
  • Example 3 Curing of VHER.
  • the synthesized VHER was mixed with 20, 33 and 40 wt % styrene to give formulations analogous to commercially available Derakane VERs. These mixtures were stored at room temperature in a dark location, and were stable under these conditions for over 6 months, with no gelation or precipitation.
  • the synthesized VHER was mixed with 33 wt% styrene, which is similar to the commercially available Derakane 441-400.
  • Derakane 441-400 1.5 phr methyl ethyl ketone peroxide ( EKP, Norox MEKP-925H) was used as the initiator and 0.2 phr cobalt naphthenate (6% in mineral spirits, Sigma Aldrich) was used as the accelerator.
  • EKP methyl ethyl ketone peroxide
  • cobalt naphthenate 6% in mineral spirits, Sigma Aldrich
  • the Derakane 411-400 formulations w r ere obtained using same procedure used for VHER, and contained the same amounts of initiator and accelerator.
  • the Derakane formulations were then cured at 60°C for 3 hours followed by post curing at 1 10°C for 1 hour.
  • Tg glass transition temperature
  • thermogravimetric analysis As seen in Figure 1 1 , the onset temperature for degradation cured VHER (T 0 ) was observed at 417 °C, and the highest rate of degradation (Tmax) was observed at 453 °C. In comparison for Derakane 441-400 the T 0 and T max were observed at 412 °C and 446 °C respectively. Without being bound by theory, this higher stability of VHER to thermal degradation can be attributed to the presence of ether moieties as opposed to ester groups in the case of Derakane. A higher char yield of 10 wt% was also observed for VHER as opposed to 3 w r t% for Derakane.
  • Barcol hardness measurements were performed according to ASTM D-2583 and a Barcol hardness of 32 was observed for the cured samples, which is comparable to the Barcol hardness of 35 reported for Derakane 441-400.
  • Example 5 Marine Applications of VHER.
  • Gardco wet film applicators (wire size 6, S6) were utilized for processing
  • VHER and Derakane 441-400 VER coatings on Q-panel uncoated 3" x 6" aluminum test panels were cleaned first by immersion in a pH 2 aqueous sulfuric acid bath for 5 minutes at 25°C. The panels were then washed with deionized water and dried at 110°C in a convection oven for 5 min.
  • VHER and Derakane 441-400 VER formulations with 1.5 phrMEKP (Norox MEKP-925H), 0.2 phr cobalt naphthenate (6% in mineral spirits, Sigma Aldrich), and in the case of VHER 0.15 phr of dimethyl aniline (DMA), were applied using the S6 wet film applicator.
  • DMA dimethyl aniline
  • the obtained coatings were characterized via theMEK double rub test (ASTM D5402) using cheese cloth and commercially available methyl ethyl ketone (Sigma Aldrich).
  • ASTM D5402 methyl ethyl ketone
  • a typical test a doubled-over piece of cheese cloth was placed in a beaker containing MEK and saturated until dripping wet. The MEK-wetted cheese cloth was then placed on the test sample and pressed firmly with the index finger at a 45° angle, and 100 double rubs were performed on the central area of each coating, after which they were visually inspected. No visual changes were observed in any of the coatings after the MEK double rub test.
  • a T-Bend tester was used to perform 0T, IT, and 2T coating flexibility bend tests (ASTM D4145) on all coated samples following MEK double rub testing (ASTM D5402). This test is important as it determines the flexibility and adhesion of the coatings on substrates that are deformed by bending.
  • coated samples were bent using a T- Bend tester procured from Qualtech Products Industry .0T, IT, and 2T bends were produced, after which the coatings were inspected for damage.
  • the pressure-sensitive tape provided in the ASTM D3359 Gardco Paint Adhesion Test Kit was used to determine the
  • Embodiment 1 provides a vinyl hydroxy 1 ether resin (VHER) having the structure: wherein
  • n is an integer ranging from 0 to 100
  • n is an integer ranging from 1 to 100
  • R' is independently a substituted or unsubstituted (O-
  • R is O, S0 2 , or C(R i ) 2 , and,
  • R 1 is independently hydrogen, phenyl, or substituted or unsubstituted (O- Cio)hydrocarbyl.
  • Embodiment 2 provides the vinyl hydroxy 1 ether resin (VHER) of embodiment 1 having the structure:
  • Embodiment 3 provides the vinyl hydroxyl ether resin (VHER) of embodiment 1 having the structure:
  • Embodiment 4 provides the vinyl hydroxy 1 ether resin (VHER) of embodiment 1, wherein m is 1, 2, 3, 4, or 5.
  • Embodiment 5 provides a p olymerization product of a starting material composition, the starting material composition including the VHER according to any one or combination of embodiments 1-4.
  • Embodiment 6 provides a method of making the VHER of embodiment 2, including:
  • Embodiment 7 provides a method of making the VHER of embodiment 2, including:
  • Embodiment 8 provides a method of making the VHER of embodiment 3, including:
  • Embodiment 9 provides a method of making the VHER of embodiment 1, including:
  • Embodiment 10 provides a polymerizationproduct of a starting material composition, the starting material composition including the VHER according to embodiment 3.

Abstract

Divers modes de réalisation de l'invention concernent des résines d'éther hydroxyle vinylique, des produits de polymérisation de celles-ci, et des procédés de fabrication de celles-ci.
PCT/US2017/020747 2016-03-04 2017-03-03 Résines d'éther hydroxyle vinylique WO2017152103A1 (fr)

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US62/303,724 2016-03-04

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5710211A (en) * 1995-08-01 1998-01-20 Kuraray Co., Ltd. Process for producing vinyl alcohol polymer
US6646102B2 (en) * 2001-07-05 2003-11-11 Dow Global Technologies Inc. Process for manufacturing an alpha-dihydroxy derivative and epoxy resins prepared therefrom
US20080051488A1 (en) * 2004-07-14 2008-02-28 Eckert Adrian S Dental Composition Containing Unsaturated Halogenated Aryl Alkyl Ether Components
US20100068470A1 (en) * 2008-09-17 2010-03-18 Fujifilm Corporation Resin composition for laser engraving, relief printing plate precursor for laser engraving, relief printing plate and method of producing the same
US8067085B2 (en) * 2007-09-14 2011-11-29 Fujifilm Corporation Gas barrier film, and display device comprising the same
WO2014197797A1 (fr) * 2013-06-07 2014-12-11 Wang Tongxin Compositions et procédés pour composites dentaires bio-actifs

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5710211A (en) * 1995-08-01 1998-01-20 Kuraray Co., Ltd. Process for producing vinyl alcohol polymer
US6646102B2 (en) * 2001-07-05 2003-11-11 Dow Global Technologies Inc. Process for manufacturing an alpha-dihydroxy derivative and epoxy resins prepared therefrom
US20080051488A1 (en) * 2004-07-14 2008-02-28 Eckert Adrian S Dental Composition Containing Unsaturated Halogenated Aryl Alkyl Ether Components
US8067085B2 (en) * 2007-09-14 2011-11-29 Fujifilm Corporation Gas barrier film, and display device comprising the same
US20100068470A1 (en) * 2008-09-17 2010-03-18 Fujifilm Corporation Resin composition for laser engraving, relief printing plate precursor for laser engraving, relief printing plate and method of producing the same
WO2014197797A1 (fr) * 2013-06-07 2014-12-11 Wang Tongxin Compositions et procédés pour composites dentaires bio-actifs

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TOPCZEWSKI ET AL.: "Iridium-Catalyzed Allylic Fluorination of Trichloroacetimidates", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 133, no. 48, 7 November 2011 (2011-11-07), pages 1 - 27, XP055037601 *

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