GB2242906A - Blends of fluorine-containing polymers and impact modifiers - Google Patents

Blends of fluorine-containing polymers and impact modifiers Download PDF

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Publication number
GB2242906A
GB2242906A GB9107595A GB9107595A GB2242906A GB 2242906 A GB2242906 A GB 2242906A GB 9107595 A GB9107595 A GB 9107595A GB 9107595 A GB9107595 A GB 9107595A GB 2242906 A GB2242906 A GB 2242906A
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United Kingdom
Prior art keywords
core
polymer
shell
fluorine
composition according
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Granted
Application number
GB9107595A
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GB2242906B (en
GB9107595D0 (en
Inventor
Louis Cornelis Sederel
Didier Michel Andre Leblanc
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Rohm and Haas Co
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Rohm and Haas Co
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Publication of GB9107595D0 publication Critical patent/GB9107595D0/en
Publication of GB2242906A publication Critical patent/GB2242906A/en
Application granted granted Critical
Publication of GB2242906B publication Critical patent/GB2242906B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of 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 halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of 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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of 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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of 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 halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of 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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of 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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Compositions comprise a blond of a fluorine-containing polymer such as poly (vinylidene fluoride), and a core-shell polymer in which the shell comprises mers of a vinyl aromatic monomer or an alkyl or cycloakly methacrylate monomer. The compositions have markedly improved impact modification properties.

Description

BLENDS OF FLUORINE-CONTAINING POLYMERS AND IMPACT MODIFIERS This invention concerns polymers of fluorine-containing mers such as vinylidene fluoride (H2C=CF2), and the improvement of their impact properties by the addition of impact modifiers.
Poly(vinylidene fluoride) (PVDF), a polymer containing mers of the formula -CH2-CF2-, is employed mainly in applications where high chemical or heat resistance is required, but not where great strength is needed, as PVDF is a highly crystalline, brittle polymer which is not easy to modify. Whilst it might be expected that the strength of PVDF could be somewhat improved by the addition of impact modifiers in the known manner, we have surprisingly discovered that certain classes of impact modifiers improve the impact properties of PVDF and similar fluorine-containing polymers to a very much greater degree than could be anticipated.
Accordingly, therefore the invention provides a composition comprising a blend of (i) a fluorine-containing polymer comprising mers of the formula
wherein at least one of A, B, D, E, is H, at least one is F, and the remaining two are independently either H or F; (ii) a core-shell polymer having a shell comprising mers of a vinyl aromatic monomer or an alkyl or cycloalkyl methacrylate, wherein the amount of core-shell polymer is no more than that of the fluorinecontaining polymer.
The core-shell polymer, which acts as an impact modifier, is generally of the kind in which one or more stages of rubbery polymer are prepared by emulsion, and a final shell layer is polymerized in the presence of the core. The rubbery polymer is a polymer mainly of mers of one or more of butadiene or of an alkyl acrylate of from 3 to 8 carbon atoms, the alkyl acrylate preferably being nbutyl acrylate. The rubbery polymer may also contain a minor amount of mers of other alkyl (meth)acrylates, of vinyl aromatic monomers, such as styrene or acrylonitrile mers. The core polymer may be crosslinked by incorporation of polyunsaturated monomers such as divinylbenzene, polyol esters of (meth)acrylic acid, (meth)allyl esters of (meth)acrylic acid or maleic acid, and the like.The polyunsaturated monomers, if present, may be effectively used at levels from about 0.05 to about 5 percent by weight of the rubbery stage. The elastomer may be formed in one or more steps, and may be formed by polymerization in the presence of a "seed" polymer to control polymer particle size. The polymerizations are preferably conducted by emulsion polymerization.
Typical useful core polymers are copolymers of butadiene/styrene with greater than 75% butadiene, copolymers of butadiene/butyl acrylate, homopolymers of butadiene, copolymers of butadiene/acrylonitrile containing greater than 70% butadiene, copolymers of butyl acrylate with up to about 20% styrene, homopolymers of 2-ethylhexyl acrylate, and the like. Especially with polymers based mainly on alkyl acrylate mers, the presence of polyunsaturated monomers, preferably from about 0.5 to about 2%, is preferred. Especially preferred is a polyunsaturated monomer having two or more unlike unsaturated groups, such as diallyl maleate, allyl methacrylate, and the like.
One or more shell layers are polymerized in the presence of the core polymer, preferably with chemical grafting occurring due to the presence of residual double bonds in the core polymer. The shell layer may be any which is compatible with the ftuorine-containing polymer, and generally will be comprised predominantly of mers of a vinyl aromatic or alkyl or cycloalkyl methacrylate monomer, preferably styrene, particularly preferably methyl methacrylate. Other monomers, such as alkyl or cycloalkyl (meth)acrylates, (meth)acrylonitrile, styrene, and the like may also be present.
A preferred core-shell polymer is one in which the shell mainly comprises poly(methyl methacrylate) (PMMA); it is particularly preferred that the shell be composed substantially entirely of poly(methyl methacrylate).
The preferred fluorine-containing polymer is poly(vinylidene) fluoride, which comprises mers of the formula -CH2CF2-.
When blended with fluorine-containing polymers such as PVDF, the coreshell impact modifiers specified above provide a considerable increase in impact strength as measured by the 'V' notched Izod test (ASTM 256, 150 180/4A) and the 'U' notched Charpy test (DIN 53453). The amount of core/shell impact modifier added will obviously depend on the required properties of the final product. Whilst increasing the proportion of modifier will improve the impact strength of the polymer up to a certain level, it will also tend to make the polymer somewhat softer, and also possibly reduce its chemical and heat resistance. The amount of core/shell polymer based on the total weight core/shell polymer plus fluorine-containing polymer will not be more than 50%; preferably no more than 30% but at least 8%. The most preferred range is from 8 to 15%.The major advantage of the invention is that it is possible to achieve significant impact strength improvement by adding relatively little impact modifier, thereby minimising the deleterious effects of softness and reduced chemical and heat resistance outlined above, as well as reducing cost.
Typical particle sizes of the core-shell polymers employed in the invention are from 0.1 to 0.6 ,um; generally those with a butadiene/styrene core are from 0.1 to 0.2 Rm, and those which are all-acrylic are from 0.3 to 0.6 llm in size.
The following Table shows the results of notched Izod and notched Charpy impact strength tests performed on blends of poly(vinylidene)fluoride and core/shell impact modifiers according to the invention. The tests are standard and well known to those skilled in the art; reference should be made to ASTM 256 (Izod) and DIN 53453 (Charpy) for details.
The two core/shell polymers were each blended with PVDF and extruded before being injection moulded and tested. They were: A - a core-shell impact modifier having a PMMA shell and a styrene/butadiene core.
B- an all-acrylic core-shell impact modifier having a PMMA shell and a butyl acrylate core.
IZOD impact strength CHARPY impact strength %A %B T/M kI/m2 90 15 --5- - 110 21 5 - 110 21 10 - 530 43 15 - 1300 75 20 - 1200 70 25 - 1150 70 - 15 1400 75 - 20 1500 75 - 25 1500 70 - 25 1500 70 As can be seen from the table, the improvement in impact strength when these two core/shell polymers are added is considerable. As is customarily the case with impact modifiers, the increase in impact strength follows an 'S' curve, tailing off at higher levels of modifier.
Electron micrographs of the resulting blends show exceptionally good dispersion of the modifier in the polymer, and it is believed that this is the reason for the unusually good performance of these modifiers.

Claims (10)

CLAIMS:
1 Composition comprising a blend of (i) a fluorine-containing polymer comprising mers of the formula
wherein at least one of A, B, D and E is hydrogen, at least one is fluorine, and the remaining two are each independently either hydrogen or fluorine; (ii) a core-shell polymer having a shell comprising mers of a vinyl aromatic monomer or an alkyl or cycloalky methacrylate monomer; wherein the amount of core-shell polymer is no more than that of the fluorine-containing polymer.
2 Composition according to claim 1 wherein the proportion of core-shell polymer based on the total of core/shell polymer plus fluorine-containing polymer is no more than 50% by weight.
3 Composition according to claim 2 wherein the proporition of core-shell polymer based on the total of core/shell polymer plus fluorine-containing polymer is from 8 to 30% by weight.
4 Composition according to claim 3 wherein the proportion of core-shell polymer based on the total of core/shell polymer plus fluorine-containing polymer is from 8 to 15% by weight.
5 Composition according to any preceding claim wherein the fluorine containing polymer is poly (vinylidene) fluoride.
6 Composition according to any preceding claim wherein the shell of the core/shell polymer is substantially entirely comprised of mers of an acrylic monomer.
7 Composition according to claim 6 wherein said acrylic monomer is poly (methyl methacrylate).
8 Composition according to any preceding claim wherein the core of said core/shell polymer is a rubbery polymer.
9 Composition according to claim 8 wherein said rubbery polymer comprises butyl acrylate or styrene/butadiene.
10 Composition substantially as hereinbefore described.
GB9107595A 1990-04-11 1991-04-10 Blends of fluorine containing polymers and impact modifiers Expired - Fee Related GB2242906B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB909008294A GB9008294D0 (en) 1990-04-11 1990-04-11 Blends of fluorine-containing polymers and impact modifiers

Publications (3)

Publication Number Publication Date
GB9107595D0 GB9107595D0 (en) 1991-05-29
GB2242906A true GB2242906A (en) 1991-10-16
GB2242906B GB2242906B (en) 1993-02-24

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GB9107595A Expired - Fee Related GB2242906B (en) 1990-04-11 1991-04-10 Blends of fluorine containing polymers and impact modifiers

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JP (1) JPH04227652A (en)
GB (2) GB9008294D0 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2727422A1 (en) * 1994-11-28 1996-05-31 Atochem Elf Sa THERMOPLASTIC COMPOSITIONS BASED ON VINYLIDENE POLYFLUORIDE
FR2876697A1 (en) * 2004-10-19 2006-04-21 Arkema Sa Composition, useful in structure and device, comprises: mixture comprising polyethylene carrying epoxy group and impact modifier; and a mixture comprising fluorinated polymer and functionalized fluorinated polymer
FR2876698A1 (en) * 2004-10-19 2006-04-21 Arkema Sa Composition, useful in structure and device for storage and transfer of fluids, comprises: a mixture comprising polyethylene and impact modifier; and a mixture comprising fluorinated polymer and functionalized fluorinated polymer
WO2006045637A1 (en) * 2004-10-19 2006-05-04 Arkema France Fluoropolymer-based impact-resistant barrier composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3004714B1 (en) * 2013-04-23 2015-12-18 Arkema France FLUORESCENT FILM

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2727422A1 (en) * 1994-11-28 1996-05-31 Atochem Elf Sa THERMOPLASTIC COMPOSITIONS BASED ON VINYLIDENE POLYFLUORIDE
EP0714944A1 (en) * 1994-11-28 1996-06-05 Elf Atochem S.A. Thermoplastic compositions based on polyvinylidene fluoride
FR2876697A1 (en) * 2004-10-19 2006-04-21 Arkema Sa Composition, useful in structure and device, comprises: mixture comprising polyethylene carrying epoxy group and impact modifier; and a mixture comprising fluorinated polymer and functionalized fluorinated polymer
FR2876698A1 (en) * 2004-10-19 2006-04-21 Arkema Sa Composition, useful in structure and device for storage and transfer of fluids, comprises: a mixture comprising polyethylene and impact modifier; and a mixture comprising fluorinated polymer and functionalized fluorinated polymer
WO2006045637A1 (en) * 2004-10-19 2006-05-04 Arkema France Fluoropolymer-based impact-resistant barrier composition

Also Published As

Publication number Publication date
JPH04227652A (en) 1992-08-17
GB9008294D0 (en) 1990-06-13
GB2242906B (en) 1993-02-24
GB9107595D0 (en) 1991-05-29

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 20030410