WO2016144415A1 - Copolymères séquencés de polyacrylates et de polyoléfines - Google Patents

Copolymères séquencés de polyacrylates et de polyoléfines Download PDF

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WO2016144415A1
WO2016144415A1 PCT/US2015/067267 US2015067267W WO2016144415A1 WO 2016144415 A1 WO2016144415 A1 WO 2016144415A1 US 2015067267 W US2015067267 W US 2015067267W WO 2016144415 A1 WO2016144415 A1 WO 2016144415A1
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Prior art keywords
polyacrylate
block copolymer
polyolefin
mole
group
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PCT/US2015/067267
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English (en)
Inventor
Wei Tang
Andy H. Tsou
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Exxonmobil Chemical Patents Inc.
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Publication of WO2016144415A1 publication Critical patent/WO2016144415A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F

Definitions

  • hydrophobic polyolefin components into acrylic polymers and acrylic networks to enhance the hydrophobicity of the acrylics, to lower their water uptake, to improve the crosslink stability of acrylic coatings and particles, to impact mechanical toughness, and to raise surface hydrophobicity.
  • One approach to achieve these ends is to use C 18-C22 fatty acid derivatives as di-acid chain extenders.
  • the hydrophobicity of acrylics can only be raised slightly in this manner due to the short alkyl length while the crosslink density is reduced.
  • Another method is to incorporate polyolefin latex into the acrylic coating formulation.
  • polyolefin latexes have been prepared by grinding polyolefin pellets into fine powders followed by dispersion in water with the aid of high concentrations of surfactant. These polyolefin latexes do not blend or mix well with polyacrylics or polymethacrylics (as used herein, "polyacrylics") and the surfactants made using these formulations could affect the coating coalescence and film formation.
  • controlled radical polymerization can only random-copolymerize or block-copolymerize styrenics, acrylics, and methacrylics.
  • styrenics acrylics
  • methacrylics methacrylics
  • polyacrylate-polyolefin block copolymer comprising (or consisting essentially of, or consisting of) compounds having the following structure:
  • PO is a polyolefin having a number average molecular weight of at least 300 g/mole
  • n and m are each an integer independently within a range from 1 to 20, or 100, or 500, or 1000, or 2000;
  • x is an integer from 1 to 3, or 4;
  • Ar is selected from the group consisting of C6 to CIO, or C20 aryls, a C7 to Cl l, or C32 alkylaryls, a C6 to CIO, or C20 aryloxys, and halogen substituted C6 to CIO, or C20 aryls and C7 to Cl l, or C32 alkylaryls (e.g., a benzyl group);
  • R is independently selected from the group consisting of hydrogen, hydroxyl, a CI to CIO alkyl, a CI to CIO alkoxy, a C6 to CIO, or C20 aryl, a C7 to Cl l, or C32 alkylaryl,
  • a method of forming a polyacrylate-polyolefin block copolymer comprising (or consisting essentially of) combining two or more acrylates selected from the group consisting of those having the following structures:
  • R is selected from the group consisting of hydrogen, hydroxyl, a CI to CIO alkyl, a CI to CIO alkoxy, a C6 to C20 aryl, a C6 to C20 aryloxy, halogen substituted C6 to C20 aryls, glycidyl, amine, and alkylamines, with the proviso that at least one acrylate is such that R is a C6 to C30 aryl or C6 to C30 aryloxy, or C7 to C32 alkylaryl, and/or halogen substituted C6 to C20 aryls;
  • R' is independently selected from hydrogen and CI to CIO alkyls, thus forming a polyacrylate; and combining the polyacrylate with a vinyl/vinylidene- terminated polyolefin having a number average molecular weight of at least 300 g/mole by alkylation to form the polyacrylate-poly olefin block copolymer
  • the inventors have found a way to incorporate hydrophobic polyolefin chains in a polyacrylate backbone to make compositions suitable for such end uses as solvent-free coatings. This is accomplished by incorporating a co-monomer of an aryl acrylate, such as benzyl acrylate, in the polyacrylate copolymers. Having the aryl groups as part of the polyacrylate, one can alkylate this pendant aromatic ring using vinyl or vinylidene terminated poly olefins through, for example, Friedel-Crafts alkylation. This will lead to the formation of polyolefin-grafted-polyacrylate (polyacrylate-polyolefin) block copolymers.
  • aryl acrylate such as benzyl acrylate
  • Comb-blocks instead of linear di-, tri-, or multiblocks can provide enhanced processability due to the presence of long-chain comb branches.
  • These block copolymers could be useful in latex composition for coatings, especially those that are water-based and substantially free of volatile solvents.
  • the invention includes a polyacrylate-polyolefin block copolymer comprising (or consisting essentially of, or consisting of) compounds having the following structure (1):
  • PO is a polyolefin bound to the "Ar” and having a number average molecular weight of at least 300 g/mole;
  • Ar is an aryl group bound to the polyacrylate backbone and is selected from the group consisting of C6 to CIO or C20 aryls, a C7 to Cl l or C32 alkylaryls, a C6 to CIO or C20 aryloxys, and halogen substituted C6 to CIO or C20 aryls and C7 to CI 1 or C32 alkylaryls.
  • the other variables are as follows:
  • ⁇ n and m are each an integer independently within a range from 1 to 20, or 100, or 500, or 1000, or 2000;
  • x is an integer from 1 to 3, or 4;
  • R is independently selected from the group consisting of hydrogen, hydroxyl, a CI to C5 or CIO alkyl, a CI to C5 or CIO alkoxy, a C6 to CIO or C20 aryl, a C7 to Cl l or C32 alkylaryl, a C6 to CIO or C20 aryloxy, halogen substituted C6 to CIO or C20 aryls, glycidyl, amine, and alkylamines; and
  • each R' is independently selected from hydrogen and CI to C5 or CIO alkyls.
  • the polyacrylate-polyolefin block copolymer preferably comprises compounds having the following structure where the aryl ("Ar") group in (1) is a phenyl or benzyl group (2):
  • the polyacrylate-polyolefin block copolymer may be in the form of a comb structure wherein a number of pendant groups form a highly branched structure ("m" is larger than 10, or 20, or 30, or 40, or 50).
  • m is larger than 10, or 20, or 30, or 40, or 50.
  • each R is a hydroxy or methyloxy, or a combination thereof, and R' is a hydrogen or methyl, or combinations thereof.
  • the polyolefin or "PO" portion of the block copolymer derives from a vinyl/vinylidene-terminated polyolefin that is reacted through an alkylation reaction with the polyacrylic copolymer, preferably through an aryl group pendant to the polyacrylic copolymer.
  • the "PO" portion of the inventive block copolymer is of course a fragment of a polyolefin, but described herein as a "polyolefin” or "PO" and is preferably selected from the group consisting of ethylene homopolymer, copolymer of ethylene with one or more linear alpha olefins, propylene homopolymer, copolymer of propylene with one or more linear alpha olefins, isobutylene homopolymer, isobutylene copolymer with one or more conjugated dienes, and combinations thereof.
  • the PO is an isotactic or atactic polypropylene having a number average molecular weight within the range from 300 g/mole to 100,000 g/mole.
  • the vinyl/vinylidene-terminated polyolefins will be described further below.
  • the polyacrylate-polyolefin block copolymers described herein have certain desirable features that can be measured quantitatively. For instance, in any embodiment the inventive polyacrylate-polyolefin block copolymers having a branching, g' v i S avg (MALLS/3D) of less than 0.90, or 0.80, or 0.70, or 0.60, or 0.50.
  • MALLS/3D branching, g' v i S avg
  • the polyacrylate- poly olefin block copolymers a weight average molecular weight (Mw) (MALLS/3D) within a range from 20,000, or 50,000, or 90,000, or 100,000 g/mole to 150,000, or 175,000, or 200,000, or 500,000, or 1,000,000, or 2,000,000, or 3,000,000 g/mole.
  • Mw weight average molecular weight
  • inventive block copolymers have a MWD (weight average molecular weight/number average molecular weight) within the range from 1.1, or 1.3, or 1.5 to 8, or 9, or 10.
  • the MWD may largely be determined by the method in which the polyacrylate copolymer backbone is formed. It may be formed by any known method such as by free radical polymerization, or atom transfer radical polymerization.
  • the polyacrylate-polyolefin block copolymers may be useful alone or in combination with other ingredients in a coating composition, most preferably a water- based coating.
  • the coatings are substantially free of volatile solvents, meaning that if volatile solvents are present at all, they are present to less than 3, or 2, or 1 wt% by weight of the entire composition.
  • volatile solvents include such solvents as hexanes, toluene, xylenes, acetone, ketones, and other solvents well known in the art.
  • the polyacrylate portion of the polyacrylate-polyolefin block copolymer may be formed by any appropriate method such as by free radical polymerization, or atom transfer radical polymerization.
  • the invention disclosed herein also includes a method of forming a polyacrylate-polyolefin block copolymer comprising (or consisting essentially of) combining two or more acrylates selected from the group consisting of those having the following structures (3):
  • R is selected from the group consisting of hydrogen, hydroxyl, a CI to C IO alkyl, a CI to C IO alkoxy, a C6 to CI O, or C20 aryl, a C6 to CI O, or C20 aryloxy, halogen substituted C6 to CI O, or C20 aryls, glycidyl, amine, and alkylamines, with the proviso that at least one acrylate is such that R is a C6 to CI O, or C30 aryl or C6 to C IO, or C30 aryloxy, or C7 to Cl l, or C32 alkylaryl, and/or halogen substituted C6 to CI O, or C20 aryls; R' is independently selected from hydrogen and CI to C IO alkyls, thus forming a polyacrylate.
  • the polymer in structure (1) or (2) above should comprise at least 10, or 20, or 50, or 100, or 200, and up to 1000, or 2000 "mer” or monomer (3) units, where, preferably, within a range from 0.1, or 0.5, or 1, or 5 wt% to 10, or 20, or 40, or 50 wt% of the units comprise aryl groups as show in (2) above.
  • the inventive process further includes combining the polyacrylate with a vinyl/vinylidene- terminated polyolefin having a number average molecular weight of at least 300 g/mole alkylation conditions to form the polyacrylate-polyolefin block copolymer.
  • any method of alkylation may be used, but one desirable method is a Friedel Crafts-type alkylation process, which includes combining the vinyl/vinylidene-terminated polyolefin with the polyacrylate having at least one aryl pendant group under such conditions, preferably at elevated temperature and with a Lewis acid catalyst.
  • the combining (alkylation) of the polyacrylate with the vinyl or vinylidene terminated poly olefins takes place in an solvent at a temperature within the range from 40, or 50, or 90, or 100°C to 130, or 140, or 150, or 160, or 170, or 200°C.
  • the solvent is selected from the group consisting of benzene, toluene, xylene, C5 to C20 alkanes, or combinations thereof.
  • the thus formed block copolymer may be purified by separating the solvent, at least, and further by separating any unreacted components and forming a coating composition by addition (comprising combining) of the polyacrylate-polyolefin block copolymer to (with) an aqueous composition, wherein volatile compounds are substantially absent.
  • VTP vinyl/vinylidene-terminated polyolefins
  • VTP vinyl/vinylidene-terminated polyolefins
  • the polyolefin may be a mixture of both vinyl- and vinylidene-terminated polyolefins, or the polyolefin may be substantially all one form or the other.
  • the allyl chain ends are represented by the formula (5):
  • the amount of allyl chain ends is determined using X H NMR at 120°C using deuterated tetrachloroethane as the solvent on a 500 MHz machine, and in selected cases confirmed by 1 C NMR.
  • Resconi has reported proton and carbon assignments (neat perdeuterated tetrachloroethane used for proton spectra while a 50:50 mixture of normal and perdeuterated tetrachloroethane was used for carbon spectra; all spectra were recorded at 100°C on a Bruker AM 300 spectrometer operating at 300 MHz for proton and 75.43 MHz for carbon) for vinyl-terminated propylene polymers in Resconi et al, 114, J. AM. CHEM. SOC, pp. 1025-1032 (1992) that are useful herein.
  • the vinyl/vinylidene-terminated propylene-based polymers may also contain an isobutyl chain end.
  • "Isobutyl chain end” is defined to be an oligomer having at least one terminus represented by the formula (6):
  • the isobutyl chain end is represented by one of the following formulae (7):
  • the percentage of isobutyl end groups is determined using C NMR (as described in the example section) and the chemical shift assignments in Resconi for 100% propylene oligomers.
  • the vinyl/vinylidene-terminated polymers described herein have an ally lie terminus, and at the opposite end of the polymer an isobutyl terminus.
  • the VTPs can be made by any suitable means, but most preferably the VTPs are made using conventional slurry or solution polymerization processes using a combination of bridged metallocene catalyst compounds (especially bridged bis-indenyl or bridged 4- substituted bis-indenyl metallocenes) with a high-molecular volume (at least a total volume of 1000 A 3 ) perfluorinated boron activator, for example, as described in US 2012/0245299.
  • bridged metallocene catalyst compounds especially bridged bis-indenyl or bridged 4- substituted bis-indenyl metallocenes
  • a high-molecular volume at least a total volume of 1000 A 3
  • perfluorinated boron activator for example, as described in US 2012/0245299.
  • the vinyl/vinylidene-terminated polyolefin can be any polyolefin having a vinyl/vinylidene-terminal group, and is preferably selected from the group consisting of vinyl/vinylidene-terminated isotactic polypropylenes, atactic polypropylenes, syndiotactic polypropylenes, propylene-butene copolymers, propylene-hexene copolymers, and propylene-ethylene copolymers (wherein the copolymers may be random, elastomeric, impact and/or block), and combinations thereof, each having a number-average molecular weight (Mn) of at least 3000 g/mole.
  • Mn number-average molecular weight
  • the VTP may be a copolymer or terpolymer wherein the C2 content (ethylene derived units) of the vinyl/vinylidene- terminated polyolefin is from 3 to 50 wt%, the C3 content (propylene derived units) is from 50 to 97 wt%; in yet another embodiment, the VTP may contain a third comonomer, thus, the C4 through C14 content (units derived from C4 to C14 a-olefins or dienes) is from 5 to 30 wt% in those embodiments, while the C2 content is from 5 to 50 wt% and the C3 content is from 20 to 90 wt%.
  • the VTP is a polyethylene, especially a high density polyethylene, wherein the high density polyethylene preferably has a density of at least 0.940, or 0.945, or 0.950 g/cm 3 .
  • greater than 70, or 80, or 90, or 94, or 96% of the VTP comprises terminal vinyl groups; or within the range of from 50, or 60 wt% to 70, or 80, or 90, or 95, or 98 or 99%.
  • the vinyl/vinylidene-terminated polyolefins preferably have a number average molecular weight (Mn) value of at least 300, or 400, or 500, or 1000 g/mole, or within the range of from 300, or 400, or 500, or 1,000, or 10,000, or 20,000 g/mole to 20,000, or 30,000, or 40,000, 50,000, or 100,000 g/mole.
  • the vinyl/vinylidene-terminated polyolefins preferably have a weight-average molecular weight (Mw) value within the range from 3,000, or 4,000, or 5,000, or 10,000 g/mole to 25,000, or 30,000, or 40,000, or 50,000, or 100,000, or 200,000, or 250,000 g/mole.
  • Mw weight-average molecular weight
  • the VTPs most useful herein have a molecular weight distribution (Mw/Mn) of less than 3.0 or 4.0 or 5.0, or within a range of from 1.8, or 2.0 to 3.0, or 4.0, or 4.5, or 5.0.
  • the VTP useful herein is amorphous polypropylene, and desirably has a glass transition temperature (Tg) of less than 10 or 5 or 0°C, more preferably less than -10°C; or within the range of from 0, or -5, or -10°C to -30, or -40, or -50°C or as described herein.
  • Tg glass transition temperature
  • the VTPs are preferably linear, meaning that there is no polymeric or oligomeric branching from the polymer backbone, or described quantitatively, having a branching index "g" (or g'( V is avg)) °f at l east 0-90 or 0.96 or 0.97 or 0.98, wherein the "branching index" is well known in the art and measurable by published means, and the value of such branching index referred to herein is within 10 or 20% of the value as measured by any common method of measuring the branching index for poly olefins as is known in the art such as in US 2013/0090433.
  • VTP is one wherein the vinyl terminated polyolefin is a compound or mixture of compounds represented by the formula (8):
  • each "R” is selected from hydrogen and C I to C4 or CI O alkyls, preferably hydrogen or methyl, or a mixture thereof; and n is an integer from 20, or 40 to 100, or 200, or 500, or 800, or 1000, or 1500, or 2000. It is these VTPs that are reacted, under suitable conditions, with an alkylating agent to form the poly acrylate-poly olefins structures shown in (1) or (2) above.
  • the inventive block copolymers herein are highly branched and thus quantifying the branching must take into account some factors.
  • the calculated g' v i S av g values herein were not corrected for the acrylate coil dimensional changes, and were based on polyolefin coil dimension references, hence, this g' number can vary greatly depending on the reference used.
  • the values herein are an estimate ( ⁇ 30%).
  • the g' values can be determined as described in US 2013/0090433.
  • Polymer molecular weight (weight-average molecular weight, Mw, number- average molecular weight, Mn, and z-averaged molecular weight, Mz) and molecular weight distribution (Mw/Mn) are determined using Size-Exclusion Chromatography.
  • Equipment consists of a High Temperature Size Exclusion Chromatograph (either from Waters Corporation or Polymer Laboratories), with a differential refractive index detector (DRI), an online light scattering detector, and a viscometer (SEC-DRI-LS-VIS), and also a Multi-Angle Light Scattering detector (MALLS), and mono-dispersed polystyrene is the standard.
  • DRI differential refractive index detector
  • SEC-DRI-LS-VIS viscometer
  • MALLS Multi-Angle Light Scattering detector
  • mono-dispersed polystyrene is the standard.
  • SEC-DRI-LS-VIS shall be used.
  • Solvent for the SEC experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of reagent grade 1 ,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 ⁇ glass pre-filter and subsequently through a 0.1 ⁇ Teflon filter. The TCB is then degassed with an online degasser before entering the SEC.
  • TCB reagent grade 1 ,2,4-trichlorobenzene
  • MALLS analysis is relied upon for Mw and Mz when calculating, for example, Mw/Mn, or Mz/Mn, which is a better method for measuring highly branched polymers, while DRI values are used for Mn, which is more sensitive and detects smaller molecules.
  • Example 1 Synthesis of p(MMA-r-BzMA)-b-iPP block copolymer.
  • the obtained polymer (5 g) was added to a round bottom flask, along with 0.3 g vinyl/vinylidene-terminated isotactic polypropylene (VTiPP) (Mn is 23,000 g/mole), 10 mg methane sulfonic acid and 20 g xylene.
  • VTiPP vinyl/vinylidene-terminated isotactic polypropylene
  • the mixture was purged with N 2 and heated to 120°C for 2 hours.
  • the reaction mixture was precipitated into methanol and the obtained white powder of poly(MMA-r-BzMA)-b-iPP or polymethacrylate and polyolefin block copolymer was dried in a vacuum oven.
  • the reaction scheme is shown in Figure 1.
  • Atom transfer radical polymerization was carried out for the synthesis of the backbone polymer of polymethacrylates (p(MMA-r-BzMA)).
  • the VTiPP was then grafted onto the phenyl or benzyl groups in the backbone polymer through Friedel-Crafts alkylation using a Lewis-acid catalyst (methane sulfonic acid, in this example).
  • Scheme (1) depicts this reaction, where the iPP can be in para or ortho position):
  • the obtained polymer (5 g) was added to a round bottom flask, along with 0.6 g vinyl/vinylidene-terminated atactic polypropylene (Mn is 1 ,000 g/mole), 60 mg methane sulfonic acid and 30 g xylene. The mixture was purged with N 2 and heated to 120°C for 2 hours. The reaction mixture was precipitated into methanol and the obtained white powder of a polymethacrylic and polyolefin block copolymer was dried a vacuum oven.
  • Mn vinyl/vinylidene-terminated atactic polypropylene
  • the GPC traces of the final block copolymer product yield a p(DMAA-GMA- BzMA)-b-aPP block copolymer having a Mn of 45,500 g/mole, a Mw of 78,000 g/mole, and a Mz of 123,400 g/mole, and a g' v i S wg of about 0.3 (long chain branch index based on viscometric radius ratio).
  • the polymethacrylic and polyolefin copolymer can be dispersed in water to form a stable dispersion.
  • the polymer can be further cured with addition of polyamines (such as tetraethylenepentaamine) to form a crosslinked methacrylic film.
  • a polyacrylate-polyolefin block copolymer comprising (or consisting essentially of, or consisting of) compounds having the following structure:
  • PO is a poly olefin having a number average molecular weight of at least 300 g/mole
  • n and m are each an integer independently within a range from 1 to 20, or 100, or 500, or 1000, or 2000;
  • x is an integer from 1 to 3, or 4;
  • Ar is selected from the group consisting of C6 to C20 aryls, a C7 to C32 alkylaryls, a C6 to C20 aryloxys, and halogen substituted C6 to C20 aryls and C7 to C32 alkylaryls;
  • R is independently selected from the group consisting of hydrogen, hydroxyl, a CI to CIO alkyl, a CI to CIO alkoxy, a C6 to C20 aryl, a C7 to C32 alkylaryl, a C6 to C20 aryloxy, halogen substituted C6 to C20 aryls, glycidyl, amine, and alkylamines; and
  • R' is independently selected from hydrogen and CI to CIO alkyls.
  • PO is selected from the group consisting of ethylene homopolymer, copolymer of ethylene with one or more linear alpha olefins, propylene homopolymer, copolymer of propylene with one or more linear alpha olefins, isobutylene homopolymer, isobutylene copolymer with one or more conjugated dienes, and combinations thereof.
  • P5. The poly acrylate-poly olefin block copolymer of any one of the previous numbered paragraphs, wherein PO is an isotactic or atactic polypropylene having a number average molecular weight within the range from 300 g/mole to 100,000 g/mole.
  • P6 The polyacrylate-polyolefin block copolymer of any one of the previous numbered paragraphs, having a branching, g' v i S avg (MALLS/3D) of less than 0.90, or 0.80, or 0.70, or 0.60, or 0.50.
  • MALLS/3D branching, g' v i S avg
  • MALLS/3D weight average molecular weight
  • polyacrylate-polyolefin block copolymer of any one of the previous numbered paragraphs having a MWD (weight average molecular weight/number average molecular weight) within the range from 1.1 , or 1.3, or 1.5 to 8, or 9, or 10.
  • a coating composition comprising the polyacrylate-polyolefin block copolymer of any one of the previous numbered paragraphs.
  • PI 1 The coating composition of numbered paragraph 10, wherein volatile organic compounds are substantially absent.
  • a method of forming a polyacrylate-polyolefin block copolymer of any one of the previous numbered paragraphs 1 to 10 comprising (or consisting essentially of) combining two or more acrylates selected from the group consisting of those having the following structures:
  • R is selected from the group consisting of hydrogen, hydroxyl, a C I to C IO alkyl, a CI to CI O alkoxy, a C6 to C20 aryl, a C6 to C20 aryloxy, halogen substituted C6 to C20 aryls, glycidyl, amine, and alkylamines, with the proviso that at least one acrylate is such that R is a C6 to C30 aryl or C6 to C30 aryloxy, or C7 to C32 alkylaryl, and/or halogen substituted C6 to C20 aryls; R' is independently selected from hydrogen and CI to CIO alky Is, thus forming a polyacrylate; and
  • polyacrylate-poly olefin block copolymer combining the polyacrylate with a vinyl/vinylidene-terminated polyolefin having a number average molecular weight of at least 300 g/mole alkylation conditions to form the polyacrylate-poly olefin block copolymer.
  • the phrase “consisting essentially of what is meant is that the claimed compound or composition does not include any components that influence its overall usefulness and/or properties; alternatively, it the phrase means that any other components are present to a level of less than 3, or 2, or 1 wt% by weight of the composition or compound being claimed. With reference to a method or process, the phrase means that no other step is involved that alters/adds/removes any chemical bonds in the polyacrylate copolymer and/or polyacrylate-poly olefin block copolymer.
  • Also disclosed herein is the use of a polyacrylate-polyolefin block copolymer as described in a coating composition that is substantially free of volatile solvents.

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Abstract

L'invention concerne un copolymère séquencé de polyacrylate-polyoléfine et une composition pour un revêtement, exempt de solvant volatil, comprenant des composés présentant la structure suivante : dans laquelle "PO" est une polyoléfine présentant un poids moléculaire numérique moyen d'au moins 300 g/mole et "Ar" est choisi dans le groupe constitué par les C6-C20-aryles, les C7-C32-alkylaryles, les C6-C20-aryloxys et les C6-C20-aryles et C7-C32-alkylaryles substitués par halogène alors que les autres variables sont décrites dans la description. Les copolymères séquencés peuvent être produits dans une réaction d'alkylation entre le polyacrylate souhaité et une polyoléfine à terminaison vinyle/vinylidène.
PCT/US2015/067267 2015-03-06 2015-12-22 Copolymères séquencés de polyacrylates et de polyoléfines WO2016144415A1 (fr)

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