WO1995029955A1 - Polymer alloy compatibilized with a graft copolymer of functionalized polypropylene polymer and novolak polymer - Google Patents
Polymer alloy compatibilized with a graft copolymer of functionalized polypropylene polymer and novolak polymer Download PDFInfo
- Publication number
- WO1995029955A1 WO1995029955A1 PCT/NO1995/000069 NO9500069W WO9529955A1 WO 1995029955 A1 WO1995029955 A1 WO 1995029955A1 NO 9500069 W NO9500069 W NO 9500069W WO 9529955 A1 WO9529955 A1 WO 9529955A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- compatibilizer
- range
- produced
- polypropylene
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 222
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 79
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 77
- -1 polypropylene Polymers 0.000 title claims abstract description 64
- 239000000956 alloy Substances 0.000 title claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 51
- 229920003986 novolac Polymers 0.000 title claims abstract description 32
- 229920000578 graft copolymer Polymers 0.000 title description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 230000000295 complement effect Effects 0.000 claims abstract description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 150000002989 phenols Chemical class 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 28
- 239000000155 melt Substances 0.000 claims description 26
- 239000004793 Polystyrene Substances 0.000 claims description 16
- 229920000515 polycarbonate Polymers 0.000 claims description 16
- 239000004417 polycarbonate Substances 0.000 claims description 16
- 229920002223 polystyrene Polymers 0.000 claims description 14
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 229920001384 propylene homopolymer Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 26
- 229920005606 polypropylene copolymer Polymers 0.000 description 17
- 230000000694 effects Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 238000005275 alloying Methods 0.000 description 9
- 230000006870 function Effects 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 229910002056 binary alloy Inorganic materials 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229920000136 polysorbate Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 241000183024 Populus tremula Species 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical class O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000007518 monoprotic acids Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Chemical group 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- 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
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- 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
- C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; 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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
Definitions
- the invention relates to novel alloys between a polyolefin polymer and a polymer non-miscible therewith, in which alloys a graft copolymer is used as compatibilizer, as well as a pro ⁇ cess for producing such alloys.
- the invention relates to novel polymer alloys of a Polymer 1 consisting of a polypropylene polymer, a Polymer 2 containing aromatic monomeric units as repeating unit(s) in the polymer chain and/or functionality which is complementary to hydroxyl, and a compatibilizer consisting of a reaction product of a functionalized polypropylene polymer and a novolak polymer, as well as a process for producing such polymer alloys.
- the new polymer alloys combine properties which characterize polypropylene polymers with properties characterizing the Polymer 2 that has been utilized.
- polypropylene polymers exhibit a number of good properties which make them useful for many applications, there is a great demand for polymer materials combining the proper ⁇ ties of the polypropylene materials with the properties of other kinds of polymers.
- it is often desirable to pro ⁇ a blend or an alloy of a polypropylene polymer with such other kind of polymer so as to obtain a product having an optimal balance between the properties of the two components.
- to produce such blends or alloys wherein one of the components is a polypropylene polymer often presents problems, because the polypropylene polymer will often be incompatible with the other kind of polymer which it is desired to use.
- a compatibilization can be especially difficult in cases where the other kind of polymer contains repeating aromatic monome ⁇ ric units as repeating unit(s) in the polymer chain, and is selected from e.g. polyphenylene ethers (PPE), polyphenylene oxides (PPO), polybutylene terephthalates (PBT), polyethylene terephthalates (PET) , polystyrenes (PS), aromatic and •amor ⁇ phous polyamides, polycarbonates (PC), and phenol-formaldehyde thermoplastics and copolymers thereof (PF) .
- PPE polyphenylene ethers
- PPO polyphenylene oxides
- PBT polybutylene terephthalates
- PET polyethylene terephthalates
- PS polystyrenes
- aromatic and •amor ⁇ phous polyamides polycarbonates
- PC phenol-formaldehyde thermoplastics and copolymers thereof
- PF phenol-formaldehyde thermoplastics
- compatibilizers polyole- fins grafted with maleic anhydride, acrylic acid, allyl-2,3- epoxyalkyl ether, vinyl silanes and other vinyl monomers.
- compatibilizers a certain degree of compatibility has been achieved between polypropiiene polymers and polymers of the above-mentioned kind.
- alloys of polyolefin polymers are previously known for various applications, such alloys have not previously made use of graft copolymers of a functionalized polypropylene polymer and a novolak polymer as a compatibilizer.
- GB 1567375 (Du Pont, 1980) teaches blends of thermosetting resins with flexible copolymers of ethylene with various co- monomers. The aim is to produce a blend having a low thermal deformation and being useful especially for casting.
- Polypro ⁇ pylene is not mentioned in the patent and polymer alloying technology is not utilized.
- EP 416526 (Takeda Chem. Ind., 1989) discloses an addition of phenol-formaldehyde resols to thermoplastic resins to reduce the occurrence of cure shrinkage in the casting of sheets. No mention is made of polypropylene and compatibilization tech ⁇ nology.
- the invention provides a polymer alloy having a melt index in the range of 0.1-400 g/10 min at 230 °C/2.16 kg, especially 3-100 g/10 min at 230 °C/2.16 kg, which polymer alloy is essentially produced from:
- Polymer 1 consisting of a polypropylene polymer
- - a Polymer 2 used in an amount of 0.5-95 wt% of the amount of Polymer 1, and containing aromatic monome- ric units as repeating unit(s) in the polymer chain and/or having functionality which is complementary to hydroxyl, including functionality allowing for secon ⁇ dary chemical bonds, and - a compatibilizer consisting of a reaction product of:
- a functionalized polypropylene polymer having functional groups capable of reacting with hydroxyl groups, and having a melt index MI in the range of 0.1-450 g/10 min at 230°C/2.16 kg, and a functionality of 0.1-10 wt%, and
- a novolak polymer having a weight average molecular weight M., of 750-40.000 g/mole formed by reacting (a) phenol and/or one or more phenol derivatives with (b) formaldehyde or acetone, which reaction product contains 1-75 wt% of blocks of the novolak polymer and has a melt index in the range of 0.1-400 g/10 min at 230 °C/2.16 kg.
- the polymer alloy is produced by mixing Polymer 1, Polymer 2 and the compatibilizer with one another in a molten state under an inert atmosphere, e.g. in a nitrogen atmosphere, in a batch blender or an extruder, using melt temperatures of 160 to 340 °C, especially from 180 to 280 °C.
- the polymer alloy is produced by mixing and mel ⁇ ting the three components in an extruder, by either
- the polypropylene polymer which is used as Polymer 1 in the polymer alloy may advantageously consist of a propylene homo- polymer or a copolymer of propylene with ethylene and/or buta ⁇ diene.
- These preferred polypropylene polymers have a melt index MI in the range of 0.1-100 g/10 min at 230 "C/2.16 kg, especially in the range of 0.35-50 g/10 min at 230 "C/2.16 kg, and a weight average molecular weight in the range of 10.000-500.000 g/mole.
- the polymer containing aromatic monomeric units as repeating unit(s) in the polymer chain, and which is used as Polymer 2 in the polymer alloy, may advantageously be selected from polyphenylene ethers (PPE), polyphenylene oxides (PPO), poly- butylene terephthalates (PBT), polyethylene terephthalates (PET), polystyrenes (PS) , polycarbonates (PC) , aromatic and amorphous polyamides (PA), and phenol-formaldehyde thermoplas ⁇ tics and copolymers thereof (PF) .
- PPE polyphenylene ethers
- PPO polyphenylene oxides
- PBT poly- butylene terephthalates
- PET polyethylene terephthalates
- PS polystyrenes
- PC polycarbonates
- PA aromatic and amorphous polyamides
- PA aromatic and amorphous polyamides
- PF phenol-formaldehyde thermoplas ⁇ tics and copolymers
- the selected Polymer 2 should have viscosity properties such that its viscosity under the extrusion conditions is in the range of 0.1 to 10 times the viscosity of the polypropylene polymer used as Polymer 1.
- Useful kinds of Polymer 2 having "a functionality which is complementary to hydroxyl" are e.g. polybutylene tereph ⁇ thalate having free terminal carboxyl groups, polyamide having free terminal carboxyl groups and free terminal amine groups, and polyethylene terephthalate having free terminal carboxyl groups.
- the amount of Polymer 2 in relation to the amount of Polymer 1 is from 0.5 to 95 wt%. More par- ticularly, the amount of Polymer 2 is from 1 to 75 wt%.
- the compatibilizer is used in an amount of 1-40 wt%, preferably 5- 20 wt%, of the total composition.
- the produced polymer alloy of the invention is a product in which Polymer 1, Polymer 2 and the compatibilizer are physi ⁇ cally and/or chemically bonded to one another.
- the polymer alloy exhibits the following characteristics:
- E module 300-3500 MPa. Elongation at break: 0.5-600%.
- X is a group derived from e.g. maleic anhydride (MAH), glycidyl methacrylate (GMA), or acrylic acid
- Z is hydro ⁇ gen, C j ⁇ -Cs alkyl, hydroxyl, or C- ⁇ Cs alkoxy.
- -CH 2 -C—CH 2 - groups may be present. The balance between -CH 2 -0-CH 2 - groups and -CH 2 - groups depends on the synthesis conditions.
- the compatibilizers utilized in the invention can be produced as follows:
- the compatibilizers are produced at melt temperatures in the range of 160-275 °C, especially in the range of 180-240 °C.
- Catalyst is added as required.
- 0.01-2.5 wt%, espe ⁇ 0 cially 0.1-0.5 wt%, of a catalyst is added, and the catalyst may be selected e.g. from:
- R 6 , R 7 , R 8 , R 9 and R 10 are identical or non-identical and are selected from hydrogen and alkyl having 1 to 3 carbon atoms, and R X1 is alkyl having 1 to 3 carbon atoms,
- the compatibilizers are produced by the steps of: (i) reacting the functionalized polypropylene polymer in a molten state with the novolak polymer under an inert atmosphere in an extruder, by either (a) introducing the func ⁇ tionalized polypropylene polymer and the novolak polymer into the extruder through the hopper, in the form of a premixture s or separately, or (b) introducing the functionalized polypro ⁇ pylene polymer into the extruder through the hopper and intro ⁇ ducing the novolak polymer into the extruder through an aper ⁇ ture in the cylinder wall of the extruder at a position down ⁇ stream of the hopper, where the polypropylene polymer is in a o molten state,
- the functionalized polypropylene polymer which is capable of reacting with hydroxyl groups, and which is used in the pro ⁇ duction of the compatibilizer, is preferably produced from a polypropylene homopolymer or a copolymer of propylene with ethylene and/or butadiene.
- These preferred neat polypropylene polymers have a melt index MI in the range of 0.1-100 g/10 min at 230 "C/2.16 kg, especially in the range of 0.35-10 g/10 min at 230 "C/2.16 kg, and a weight average molecular weight in the range of 10.000-500.000 g/mole.
- the functionalization of the polypropylene polymer may be obtained by grafting with a compound selected from e.g. maleic anhydride, glycidylalkyl acrylates, acrylic acid, vinyl silanes and other vinyl mono ⁇ mers.
- the functionalized polypropylene polymer may advantage- ously be selected from the following materials:
- R is H or C _ 4 alkyl
- n is an integer of 1 to 6, having been introduced into the molten mixture, (iii) said mixture having been kneaded until the epoxyalkyl acrylate compound has reacted with the polypropylene polymer to a desired graft ratio, and (iv) the kneaded product having been cooled and gra ⁇ nulated.
- the novolak polymers used in the production of the compati ⁇ bilizer have a molar ratio of phenol compound to formaldehyde in the range of 1:0.5 to 1:0.95, and a similar ratio when ace ⁇ tone is used instead of formaldehyde.
- a novolak polymer is used which is produced by reaction of (a) one or more phenol compounds having the general formula: wherein R lr R 2 , R 3 , R 4 and R 5 are identical or non-identical and are selected from hydrogen, alkyl having 1 to 3 carbon atoms, and hydroxyl, with (b) a compound selected from formaldehyde and acetone.
- Statoil P 410 which is a copolymer of propylene with ethylene, having a melt index MI of 2.0 g/10 min at 230 "C/2.16 kg, premixed with standard stabilizers,
- Statoil P 401 which is a copolymer of propylene with ethylene, having a melt index MI of 0.35 g/10 min at 230 "C/2.16 kg, premixed with standard stabilizers, and
- Statoil P 330 which is a copolymer of propylene with ethylene, having a melt index MI of 5.0 g/10 min at 230 "C/2.16 kg, premixed with standard stabilizers.
- Graft copolymer of MAH-qrafted PP and novolak polymer (PF) A maleic acid-grafted polypropylene (PP) containing 1.2 wt% of grafted MAH (maleic anhydride) and having a melt index MI of 50 g/10 min at 230 "C/2.16 kg was reacted with a novolak poly- mer consisting of a phenol-formaldehyde polymer (PF) having a molar ratio of formaldehyde to phenol of 0.9 and a molecular weight of 7500 g/mole, in an extruder with no catalyst pre ⁇ sent.
- the novolak polymer was introduced in an amount of 17 s wt% based on the total mixture.
- the extruder was a twin screw extruder of the type "Clextral BC 21" having 25 mm co-rotating screws.
- the hopper was flushed with nitrogen gas in order that the preparation should be carried out in an essentially inert atmosphere.
- the screw speed was 200 r.p.m. and the extrusion o speed was 3 kg/h. All raw materials were introduced gravimet- rically into hopper 1.
- the temperature profile of the extruder was maintained in the range of 195 to 210 °C. A graft copoly ⁇ mer with 2.5 wt% grafted PF was obtained.
- graft copolymer of GMA-qrafted PP and novolak polymer (PF) was followed, except that the maleic acid- grafted polypropylene was replaced by a glycidyl methacrylate- grafted polypropylene having a content of grafted glycidyl methacrylate (GMA) of 1.25 wt%, having a melt index MI of 28 g/10 min at 230 "C/2.16 kg, produced in accordance with Nor ⁇ wegian Patent Application No. 924746.
- the novolak polymer (PF) was added in an amount of 17 wt%, based on the total mixture. A graft copolymer with 8.0 wt% grafted PF was obtained.
- a polypropylene polymer (Polymer 1) is reacted/mixed with an alloying partner (Polymer 2), with or without addition of a compatibilizer.
- Polymer 1 is introduced into hopper 1
- Polymer 2 is introduced into hopper 2 ( ownstream of hopper 1) .
- the hoppers are flushed with nitro ⁇ gen gas in order that the mixing and kneading should take place in an essentially inert atmosphere. All raw materials are introduced gravimetrically into the respective hoppers.
- the screw speed of the extruder is 200 r.p.m. and the extru- sion speed is 3 kg/h.
- Polymer 1 was a polypropy- lene copolymer of the grade Statoil P 401 having a melt index MI of 0.35 g/10 min at 230 "C/2.16 kg, premixed with standard stabilizers.
- Polymer 2 was a polyphenylene ether having a vis ⁇ cosity of 1000 Pa.s at 1000 s" x /265 “C. Polymer 2 was added in amounts of 5, 25, 50, 75 and 95 wt°-, respectively, based on the total mixture. No compatibilizer was used. The temperature profile of the extruder was maintained in the range of 225 to 275 "C. The components added, the amounts thereof, and the results are given in Table 1 below.
- Examples 1.1-1.5 were repeated, except that 2.5 wt% of the above described Compatibilizer I, based on the total mixture, were introduced into hopper 1 together with the polypropylene copolymer, with adjustments of the amounts of Polymer 1 and Polymer 2 as required, maintaining the same weight ratio be ⁇ tween them. Otherwise, the operation conditions were as indi ⁇ cated in Examples 1.1-1.5. The components added, the amounts thereof, and the results are given in Table 1 below.
- Examples 1.1-1.3 were repeated, except that 7.5 wt% of the above described Compatibilizer I, based on the total mixture, were introduced into hopper 1 together with the polypropylene copolymer, with adjustments of the amounts of Polymer 1 and Polymer 2 as required, maintaining the same weight ratio be ⁇ tween them. Otherwise, the operation conditions were as given in Examples 1.1-1.3. The components added, the amounts there ⁇ of, and the results are given in Table 1 below.
- Example 1.12 was repeated, except that 7.5 wt% of the above described Compatibilizer II, based on the total mixture, were introduced into hopper 1 together with the polypropylene copo ⁇ lymer, with adjustments of the amounts of Polymer 1 and Poly- mer 2 as required, maintaining the same weight ratio between them. Otherwise, the operation conditions were as given in Examples 1.12. The components added, the amounts thereof, and the results are given in Table 1 below.
- Polymer 1 there was used a polypropylene copolymer of the grade Statoil P 410 having a melt index MI of 2.0 g/10 min at 230 "C/2.16 kg, premixed with standard stabilizers.
- Polymer 2 there was used a polybutyl- ene terephthalate having a melt index MI of 34 g/10 min at 250 "C/21.2 N. Polymer 2 was added in amounts of 5, 25, 50, 75 and 95 wt%, respectively, based on the total mixture. No com ⁇ patibilizer was used. The temperature profile of the extruder was maintained in the range of 225 to 265 °C. The components added, the amounts thereof, and the results are given in Table 2 below.
- Examples 2.6 - 2.10 Examples 2.1-2.5 were repeated, except that 2.5 wt% of the above described Compatibilizer I, based on the total mixture, were introduced into hopper 1 together with the polypropylene copolymer, with adjustments of the amounts of Polymer 1 and Polymer 2 as required, maintaining the same weight ratio be- tween them. Otherwise, the operation conditions were as given in Examples 2.1-2.5. The components added, the amounts there ⁇ of, and the results are given in Table 2 below.
- Examples 2.11 - 2.13. Examples 2.1-2.3 were repeated, except that 7.5 wt% of the above described Compatibilizer I, based on the total mixture, were introduced into hopper 1 together with the polypropylene copolymer, with adjustments of the amounts of Polymer 1 and Polymer 2 as required, maintaining the same weight ratio be- tween them. Otherwise, the operation conditions were as given in Examples 2.1-2.3. The components added, the amounts thereof, and the results are given in Table 2 below. Example 2 . 14 .
- Example 2.12 The procedure of Example 2.12 was followed, except that 7.5 wt% of the above described Compatibilizer II, based on the total mixture, were introduced into hopper 1 together with the s polypropylene copolymer, with adjustments of the amounts of Polymer 1 and Polymer 2 as required, maintaining the same weight ratio between them. Otherwise, the operation conditions were as given in Example 2.12. The components added, the amounts thereof, and the results are given in Table 2 below. 0
- polymer 1 there was used a polypropylene copolymer of the grade Statoil P 401 having a melt index MI of 0.35 g/10 min at 230 "C/2.16 kg, premixed s with standard stabilizers.
- Polymer 2 a low-viscous poly ⁇ carbonate having a melt index MI of 15 ml/600 s at 260 "C/1.2 kg was used.
- Polymer 2 was added in an amount of 1 part by weight to 3 parts by weight of polymer 1.
- Example 3.1 (com ⁇ parison example), no compatibilizer was used, whereas 5 wt% of 0 the above described Compatibilizer I, based on the total mix ⁇ ture, were used in Example 3.2, and 10 wt% of the same Compa ⁇ tibilizer I were used in Example 3.3.
- the temperature profile was maintained in the range of of 250 to 295 °C.
- the com ⁇ ponents added, the amounts thereof, and the results are given 5 in Table 3 below.
- polymer 1 there was used a polypropylene copolymer of the 0 grade Statoil P 410 having a melt index MI of 2.0 g/10 min at 230 "C/2.16 kg, premixed with standard stabilizers.
- Polymer 2 a polystyrene having a melt index MI of 3.5 g/10 min at 205 "C/2.16 kg was used.
- Polymer 2 was added in an amount of 1 part by weight to 3 parts by weight of polymer 1.
- Example 5 3.4 comparativ example
- no compatibilizer was used, whereas 5 wt% of the above described Compatibilizer I, based on the total mixture, were used in Example 3.5.
- the temperature pro ⁇ file was maintained in the range of of 210-225 "C.
- the com ⁇ ponents added, the amounts thereof, and the results are given in Table 3 below.
- polymer 1 there was used a polypropylene copolymer of the grade Statoil P 330, having a melt index MI of 5.0 g/10 min at 230 "C/2.16 kg, premixed with standard stabilizers.
- polymer 2 a novolak polymer consisting of a phenol-formaldehyde poly ⁇ mer (PF) having a viscosity of 150 Pa.s at 10 Hz/210 "C was used. Polymer 2 was added in an amount of 1 part by weight to 3 parts by weight of polymer 1.
- PF phenol-formaldehyde poly ⁇ mer
- Example 3.6 comparative example
- 5 wt% of the above described Compatibilizer I based on the total mixture
- the temperature profile of the ex- truder was maintained in the range of of 200-225 "C.
- the com ⁇ ponents added, the amounts thereof, and the results are given in Table 3 below.
- Fig. 1 shows the E module and the impact strength as a function of the content of polyphenylene ether (PPE) in the polymers of the series of examples 1.1-1.14;
- Fig. 2 shows the E module and the impact strength as a function of the content of polybutylene terephthalate (PBT) in the polymers of the series of examples 2.1-2.14;
- Fig. 3 shows the impact strength, plotted as a func ⁇ tion of the E module, of the polymers of the series of exampl- es 1.1-1.14;
- Fig. 4 shows the impact strength, plotted as a func ⁇ tion of the E module, of the polymers of the series of examp ⁇ les 2.1-2.14;
- Fig. 5 shows the impact strength, plotted as a func- tion of the E module, of the polymers of the series of Examp ⁇ les 3.1-3.7. Assessment of the results obtained in Examples 1.1-1.14.
- Example 1.1-1.14 The results obtained in Example 1.1-1.14 are shown in Table 1 and the appended Figures 1 and 3. It can ben seen from Fig. 1 that the E module increases significantly with increased addi ⁇ tion of compatibilizer when the alloying partner (Polymer 2), which in this case is a polyphenylene ether (PPE), is used in amounts of 5 to 50 wt%, based on the polymer alloy. When PPE is used in amounts exceeding 50 wt%, the effect of the com- patibilizer decreases and becomes small and negligible. The effect of the amount of the compatibilizer on the E module is highest in the range of 5 to 40 wt% PPE.
- the alloying partner which in this case is a polyphenylene ether (PPE)
- PPE polyphenylene ether
- the impact strength values that can be seen from Fig. 1 also show that the compatibilizer is effective in the range of up to 50 wt% PPE and has a maximum of effectiveness in the range of up to 35-40 wt% PPE. Addition of the compatibilizer in amounts exceeding 2.5 wt% has no great effect on the impact strength values in this range. With amounts of PPE exceeding 50 wt% the effect of the compatibilizer on the impact strength is small or negligible.
- Fig. 3 shows the impact strength as a function of the E module. It can be seen that the E module of the polymer blends/alloys (1.1-1.14) increases substantially in relation to that of the non-modified polypropylene polymers Statoil P 401, P 410 and P 330. With a compatibilizer present, the im ⁇ pact strength is improved for the majority of the alloys, as compared with a binary system of polymer PP and PPE (Examples 1.1-1.5).
- a compatibilizer (II) based on GMA-functionalized PP and novolak polymer (PF) in a polymer alloy containing 23.1 wt% PPE results in a higher stiffness (E module) but a lower impact strength than the corresponding values exhibited by a similar polymer alloy using a compatibilizer (I) based on MAH-functionalized PP and novolak polymer (PF) (Example 1.12).
- the PPE that was used did not contain terminal groups comple ⁇ mentary to hydroxyl and no reaction between the functionalized polypropylene polymer and the PPE could therefore be expected.
- the effect of the compatibilizer could be explained s by an orbital overlapping of the phenyl rings in the phenol groups and the repeating unit in the PPE and any secondary bonding forces between the compatibilizer and the PPE.
- Fig. 2 shows the E module and the impact strength of the polymers as a function of the con ⁇ tent of PBT in the alloy
- Fig. 4 shows the impact strength s of the polymers plotted as a function of the E module.
- the E module increases signi ⁇ ficantly with increasing addition of compatibilizer for con ⁇ tents of polybutylene terephthalate (PBT) in the range of o about 20 wt% to up to 100 wt% of the polymer alloy.
- PBT polybutylene terephthalate
- Fig. 2 shows that an addition of 2.5 wt% of compatibilizer results in a positive effect on the impact strength when 50 wt% of PBT or more is used.
- Fig. 2 also shows that addition of 5 the compatiblizer in an amount of 7.5 wt% gives a positive effect on the impact strength in the range of up to about 50 wt% of PBT.
- Fig. 4 shows the impact strength of the polymer alloy plotted o as a function of the E module. It can be seen that the E module of the polymer alloys is substantially improved com ⁇ pared to that of the non-modified polypropylene polymers (Statoil P 401, P 410, P 330). For the majority of the polymer alloys the impact strength values are increased with com- 5 patibilizers present, as compared to a binary system of poly ⁇ mer PP and PBT without compatibilizer (Examples 2.1-2.5). In particular, polymer alloys having a low content of PBT exhibit a substantially increased E module compared to a neat polypro ⁇ pylene copolymer, while the impact strength is maintained or increased. Even with higher contents of PBT the compatibilizer gives a significant increase in the E module and the impact strength.
- Polybutylene terephthalate contains terminal groups that are complementary to hydroxyl, and a reaction between the functionalized polypropylene polymer and the PBT was therefore to be expected.
- the effect of the compatibilizer could be explained by an orbit?1 overlapping between the phe- ⁇ o nyl rings in the phenol groups of the compatibilizer and the repeating unit of the PBT, as well as by secondary linkages.
- a compatibili ⁇ zer based on GMA-functionalized PP and novolak polymer (PF) gives a somewhat lower stiffness (E module) but an improved impact strength than a compatibilizer based on a 25 MAH-functionalized PP and a novolak polymer (PF) (Example 2.12).
- Examples 1.6-1.14 to Examples 2.6-2.14 show that the compatibilizer provides an effect for PP/PPE o polymer alloys as well as for PP/PBT alloy systems, but it shows that the effect of the compatibilizer is higher in a system in which the secondary polymer has a complementary che ⁇ mistry (which is the case for PBT), and any additional secon ⁇ dary bonding forces such as ⁇ - ⁇ orbital overlapping, hydrogen
- Polymer 2 Polycarbonate (PC) , polystyrene (PS) . novolak polymer (PF) .
- Example 3.1 A comparison of Example 3.1 with Examples 3.2 and 3.3 in Table 3 that the E module is not noticeably altered in a system of PP + PC (polycarbonate) when a compatibilizer is used, but that the impact strength is increased somewhat in relation to that of the binary system, viz. from 3.2 J to 4.5-4.6 J at 0 "C.
- PP + PC polycarbonate
- Fig. 5 shows that the E module increases substantially in re ⁇ lation to the non-modified polypropylene copolymers Statoil P 401, P 410, P 330.
- the impact strength of the polymer alloys containing a compatibilizer is higher than for the correspon- ding binary systems of PP + PC, but it is lower than for the neat polypropylene copolymer (Statoil P 401, P 410, P 330).
- Table 3 shows that the E module increases noticeably in a sys- tem of PP + PS (polystyrene) when a compatibilizer is used, viz. from 1666 MPa to 1880 MPa, whereas the impact strength is not altered or is slightly reduced in relation to that of the binary system PP + PS, viz. from 1.6 J to 1.5 J at 0 "C. This can also be seen from Fig. 5, where the impact strength of the polymers is plotted as a function of the E module.
- PP + PS polystyrene
- Table 3 shows that the E module increases noticeably in a sys ⁇ tem of PP + PF (novolak polymer) when the system also contains 5 wt% of compatibilizer, viz. from 1775 MPa to 1950 MPa.
- the impact strength increases in relation to that of the binary system PP + PF, viz. from 1.5 J to 2.2 J at 0 °C. This can also be seen from Fig. 5.
- Neither the polycarbonate (PC) , the polystyrene (PS) nor the novolak polymer (PF) has groups complementary to the hydroxyl groups of the compatibilizer and it was therefore expected that the effect of the compatibilizer would be less than in a reactive system such as the system PP + PBT.
- the compatibilizer had an effect on the E module of all the three alloying systems PP + PC, PP + PS, and PP + PF, and also on the impact strength of the systems PP + PC and PP + PF.
- the fact that the compatibilizer has no effect on the E module of the system PP + PS can be explained by the fact that PF is relatively non-polar compared to both PC and PF, and that it cannot be expected, therefore, that any other secondary bon ⁇ ding forces than ⁇ - ⁇ orbital overlapping would occur between the compatibilizer and the PS.
- other secon- dary linkages such as hydrogen bonds, etc. could be expected between the compatibilizer and PC and PF, respectively.
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Priority Applications (1)
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AU24214/95A AU2421495A (en) | 1994-04-28 | 1995-04-26 | Polymer alloy compatibilized with a graft copolymer of functionalized polypropylene polymer and novolak polymer |
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NO941559 | 1994-04-28 | ||
NO941559A NO179840C (no) | 1994-04-28 | 1994-04-28 | Polymerlegering hvor det som kompatibilisator er anvendt en podet kopolymer av en funksjonalisert polypropylenpolymer og en novolakpolymer |
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AU (1) | AU2421495A (enrdf_load_stackoverflow) |
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Cited By (1)
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WO2001005858A1 (en) * | 1999-07-16 | 2001-01-25 | Borealis Technology Oy | A method for the modification of polyolefins |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1990012054A1 (en) * | 1989-04-12 | 1990-10-18 | Tonen Corporation | Polypropylene-polyester graft copolymer and production method thereof |
WO1991014248A1 (en) * | 1990-03-08 | 1991-09-19 | Exxon Chemical Patents Inc. | Crystalline polyolefin graft copolymers |
EP0577208A1 (en) * | 1992-07-02 | 1994-01-05 | ENICHEM S.p.A. | Thermoplastic composition based on polyphenylene ether and polyamide |
-
1994
- 1994-04-28 NO NO941559A patent/NO179840C/no not_active IP Right Cessation
-
1995
- 1995-04-26 AU AU24214/95A patent/AU2421495A/en not_active Abandoned
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1990012054A1 (en) * | 1989-04-12 | 1990-10-18 | Tonen Corporation | Polypropylene-polyester graft copolymer and production method thereof |
WO1991014248A1 (en) * | 1990-03-08 | 1991-09-19 | Exxon Chemical Patents Inc. | Crystalline polyolefin graft copolymers |
EP0577208A1 (en) * | 1992-07-02 | 1994-01-05 | ENICHEM S.p.A. | Thermoplastic composition based on polyphenylene ether and polyamide |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001005858A1 (en) * | 1999-07-16 | 2001-01-25 | Borealis Technology Oy | A method for the modification of polyolefins |
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NO941559D0 (enrdf_load_stackoverflow) | 1994-04-28 |
NO179840C (no) | 1996-12-27 |
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