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
  • 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
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer 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
  • 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
  • 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
  • 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 graft copolymers of a function ⁇ alized polypropylene polymer and a novolak polymer as well as a process for producing said graft copolymers.
• the new graft copolymers are useful as compatibilizers, espe ⁇ cially in the production of polymer alloys of a polypropylene polymer with an alloying partner selected from polymers con ⁇ taining aromatic monomeric units as the repeating unit(s) in the polymer chain and/or having a functionality which is com ⁇ plementary to hydroxyl, including functionality allowing for secondary chemical bonds.
• 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 types of polymer materials.
• 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 type of polymer which it is desired to use.
• a compatibilization can be especially difficult in cases where the other type of polymer contains repeating aromatic monome ⁇ ric units in the polymer chain and is selected e.g. from poly- phenylene ethers (PPE), polyphenylene oxides (PPO), polybuty- lene terephthalates (PBT), polyethylene terephthalates (PET), polystyrenes (PS), polycarbonates (PC), and phenol-formalde ⁇ hyde thermoplastics and copolymers thereof (PF).
• PPE poly- phenylene ethers
• PPO polyphenylene oxides
• PBT polybuty- lene terephthalates
• PET polyethylene terephthalates
• PS polystyrenes
• PC polycarbonates
• PF phenol-formalde ⁇ hyde thermoplastics and copolymers thereof
• compatibilizers which increase the compatibility between the dissimilar polymers by directly participating in reactions with the polymers, or by entering into physical/chemical interactions with them.
• compatibilizers polyole- fins grafted with maleic anhydride, acrylic acid, allyl-2,3- epoxyalkyl ether, vinyl silanes and other vinyl monomers.
• GB 1463452 (UBE Ind. Ltd., 1971) teaches polyolefins modified s with ⁇ -metacryloyloxy-propyl-trimethoxy silane and glycidyl methacrylates and their use in the production of curable poly ⁇ mer compositions and as adhesives for use in the coating of metals, paper, glass, ceramics and plastics.
• These previously known modified polyolefins are not being used for compatibili- o zing polyoleifins with other polymers in a molten phase, and the patent is silent on blends or alloys of polypropylene polymers and polymers of the phenol-formaldehyde type (the novolak type) .
• 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 5 mention is made of polypropylene and compatibilization tech ⁇ nology.
• graft polymers of certain function ⁇ alized polypropylene polymers and certain novolak polymers are 5 very useful as compatibilizers in the production of polymer alloys of polypropylene polymers and alloying partners selec ⁇ ted from polymers containing aromatic monomeric units as the repeating unit(s) in the polymer chain and/or having a func ⁇ tionality which is complementary to hydroxyl.
• Said graft copo- o lymers are also useful as binders for the purpose of increa ⁇ sing the ability of polymers to adhere to metals.
• the graft copolymers are useful to increase the capacity of poly ⁇ mers to provide adhesion for varnishes and adhesives as a con ⁇ sequence of the increased functionality and polarity of the s graft copolymers compared to the starting polymer.
• the invention provides a graft copolymer of a functiona ⁇ lized polypropylene polymer and a novolak polymer, which graft copolymer is characterized in that: o it consists essentially 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, especially 5-200 5 g/10 min at 230 °C/2.16 kg, and a functionality of
• X is a group derived from e.g. maleic anhydride (MAH), glycidyl methacrylate (GMA), or acrylic acid
• Z is hydro ⁇ gen, Ci-Cs alkyl, hydroxyl, or C ⁇ -Cg alkoxy.
• MAH maleic anhydride
• GMA glycidyl methacrylate
• Z is hydro ⁇ gen, Ci-Cs alkyl, hydroxyl, or C ⁇ -Cg alkoxy.
• -CH-- groups may be present. The balance between -CH 2 -0-CH 2 - groups and -CH 2 - o groups depends on the synthesis conditions.
• the functionalized polypropylene polymer which is capable of reacting with hydroxyl groups is preferably produced from a polypropylene homopolymer or a copolymer of propylene with 5 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.
• the functionalized polypropylene polymer may advantage ⁇ ously be selected from the following materials: (1) Polypropylene polymers grafted with an epoxyalkyl acrylate compound using an organic peroxide as a radical former, and having a melt index MI in the range of 1-250 g/10 min at 230 °C/2.16 kg, especially in the range of 3-40 g/10 min at 230 °C/2.16 kg, and a graft ratio of 0.2-10 wt%, especially 0.8-2.5 wt%, and having been produced by:
• H 2 C C i-C-0-(CH 2 ) n -C AH-CH 2 (I)
• 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 graft copo ⁇ lymers of the invention have a molar ratio between phenol com ⁇ pound and formaldehyde in the range of 1:0.5 to 1:0.95, and a similar ratio when acetone is used in substitution of formal- dehyde.
• a novolak polymer is used, which novolak polymer is a polymer produced by reaction of (a) one or more phenol compounds having the general formula:
• R-_, 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. 5
• novolak polymers and the production thereof are described i.a. in L.H. Baekeland, "The Synthesis, Constitution and Uses of Bakelite", J. Ind. Eng. Chem. 1 (1909), p.p. 149-161; E. Manegold & W. Petzold, Kolloid-Z, 94 (1941), p. 284; and D.N. o Khana, D.L. Durham, F. Seyedi, P.H. Lu & T. Perera, "Novolak Resins With High Thermal Stability, High Resolution, Improved Photospeed and Etch Characteristics for Advanced Photoresist Applications", Polymer Engineering and Science 32 (1992), p.p. 1500-1508. 5
• the invention also provides a process for producing a graft copolymer of a functionalized polypropylene polymer and a novolak polymer, which graft copolymer contains 1-75 wt%, especially 1-40 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, especially 3-100 g/10 min at 230 °C/2.16 kg.
• the process is characterized in that:
• the graft copolymer is produced by the steps of (i) reacting the functionalized polypropylene polymer in a molten state with the novolak polymer under an inert atmos ⁇ phere in an extruder, by either (a) introducing the functiona- lized polypropylene polymer and the novolak polymer into the extruder through the hopper, in the form of a premixture or separately, or (b) introducing the functionalized polypropy ⁇ lene 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 molten state, (ii) processing the mixture in the extruder un ⁇ til the novolak polymer has reacted with the functionalized polypropylene polymer to the desired degree of conversion, and (iii) extru
• the graft copolymer of the invention is produced at melt tem ⁇ peratures in the range of 160-275 C C, especially in the range of 180-240 °C.
• Catalyst is added as required.
• 0.01-2.5 wt%, especially 0.1-0.5 wt%, of 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 is alkyl having 1 to 3 carbon atoms,
• organic and inorganic mono- and diprotic acids such as formic acid, oxalic acid and sulphuric acid.
• E module 1000-3500 MPa.
• the new compatibilizers consisting of graft copo ⁇ lymers of a functionalized polypropylene polymer and a novolak polymer it is possible - through an appropriate selection of alloying partners and alloying conditions, to produce polymer alloys exhibiting a reproducible broad range of desired pro- perties, especially alloys having improved E module and impact strength, thus making the alloys useful for many applications.
• the above polymer alloys are produced essentially from: s - a Polymer 1 consisting of a polypropylene polymer,
• 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 a functionality which is complementary o to hydroxyl, including a functionality allowing for secondary chemical bonds, and a compatibilizer consisting of a graft copolymer of the present invention.
• the new polymer alloys 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, are produced by mixing Polymer 1, Polymer 2 and the compatibilizer with one another in a molten state o 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 polypropylene polymer which is used as Polymer 1 in the 5 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, o 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 5 in the polymer alloy, may advantageously be selected from polyphenylene ethers (PPE), polyphenylene oxides (PPO), poly- butylene terephthalates (PB ), polyethylene terephthalates (PET), polystyrenes (PS), polycarbonates (PC), and phenol-for ⁇ maldehyde thermoplastics and copolymers thereof (PF) .
• PPE polyphenylene ethers
• PPO polyphenylene oxides
• PB poly- butylene terephthalates
• PET polyethylene terephthalates
• PS polystyrenes
• PC polycarbonates
• PF phenol-for ⁇ maldehyde thermoplastics and copolymers thereof
• Polymer 2 having "a functionality which is complementary to hydroxyl” are e.g. polybutylene terephtha- late having free terminal carboxyl groups, polyamide having free terminal carboxyl groups, and polyethylene terephthalate o 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%. Especially, the amount of Polymer 2 is from 1 to 75 wt%.
• the compatibilizer is s used in an amount of 1-40 wt%, preferably 5-20 wt%, of the total composition.
• a maleic acid-grafted polypropylene (PP) containing 0.4 wt% of MAH (maleic anhydride) and having a melt index MI of 50 g/10 min at 230 "C/2.16 kg was reacted in an extruder with a novo ⁇ lak polymer consisting of a phenol-formaldehyde polymer (PF) 5 having a molar ratio of formaldehyde to phenol of 0.9 and a molecular weight of 7500 g/mole, with no catalyst present.
• the novolak polymer was introduced in amounts of 10, 25, 40 and 20 wt%, respectively, 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 runs should be carried out in an essentially inert atmosphere.
• the screw speed was 200 r.p.m. and the extrusion 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.
• the components added, the amounts thereof, and the results are given in Table 1 below.
• a maleic acid-grafted polypropylene (PP) having a content of grafted MAH of 0.15 wt%, and having a melt index MI of 7 g/10 min at 230 "C/2.16 kg was reacted with a novolak polymer consisting of a phenol-formaldehyde polymer having a molar ratio of formaldehyde to phenol of 0.9, and having a molecular weight of 7500 g/mole, in the extruder used in Exam ⁇ ples 1 to 4.
• the novolak polymer was added in an amount of 20 wt% of the total mixture. No catalyst was added. Otherwise, the conditions were as indicated in Examples 1 to 4.
• the com ⁇ ponents added, the amounts thereof, and the results are given in Table 1 below.
• Example 7 Comparison Example
• a polypropylene (PP) with no content of grafted MAH, and with a melt index MI of 7 g/10 min at 230 "C/2.16 kg was reacted with a novolak polymer consisting of a phenol-formaldehyde polymer having a molar ratio of formaldehyde to phenol of 0.9, and having a molecular weight of 7500 g/mole, in the extruder used in Examples 1 to 4.
• the novolak polymer was added in an amount of 20 wt% of the total mixture. No catalyst was added. Otherwisw, the conditions were as indicated in Examples 1 to 4. In this comparison example, no reaction was expected.
• the components added, the amounts thereof, and the results are given in Table 1 below.
• Example 8 A maleic acid-grafted polypropylene (PP) having a content of grafted MAH of 0.4 wt%, and having a melt index MI of 50 g/10 min at 230 "C/2.16 kg was reacted with a novolak polymer con ⁇ sisting of a phenol-formaldehyde polymer having a molar ratio of formaldehyde to phenol of 0.9, and having a molecular weight of 7500 g/mole, in the extruder used in Examples 1 to 4, in the presence of a catalyst. As catalyst 0.5 wt% of oxalic acid dihydrate was used. The novolak polymer was added in an amount of 40 wt%, based on the total mixture. Otherwise, the reaction conditions were otherwise as stated in Examples 1 to 4. The components added, the amounts thereof, and the re ⁇ sults are given in Table 1 below.
• Example 5 The process of Example 5 was repeated, except that the reac- tion was carried out in the presence of 0.5 wt% of triethyl- amine (TEA) as a catalyst, based on the total mixture.
• TAA triethyl- amine
• Non-grafted PP having a viscosity similar to that of the maleic acid-grafted PP with a low (0.15 wt%) maleic acid content.
• a GMA-functionalized PP provides a higher content of grafted PF (8.8 wt%) than a MAH-functio- nalized PP having a high MAH content (3 wt%) and/or a MAH- functionalized PP having a low MAH content (1.0 wt%) .
• Example 7 (comparison example), wherein a non- functionalized PP was used.
• Example 3 shows that the degree of conversion of the novolak polymer (PF) increased, and that the amount of PF grafted on the poly ⁇ mer increased from 7.0 wt% to 7.5 wt%.
• Example 5 shows that the degree of conversion of PF increased from 44.1% to 45.8%, and that the amount of grafted PF increased from 8.8 wt% to 9.2 weigh%.
• a polypropylene polymer (Polymer 1) is reacted/mixed with an alloying partner (Polymer 2), with or without addition of compatibilizer.
• Polymer 1 is introduced into hopper 1
• Polymer 2 is introduced into hopper 2 (downstream 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.
• a polypropylene copolymer of the type Statoil P 401 having a melt index MI of 0.35 g/10 min at 230 "C/2.16 kg was used as Polymer 1, pre- mixed with standard stabilizers.
• a polyphenylene ether having a viscosity of 1000 Pa.s at 1000 s _1 /265 "C was used as Polymer 2.
• Polymer 1 and Polymer 2 were added in amounts of 69.4 wt% and 23.1 wt%, respectively, based on the total mixture.
• the temperature profile of the extruder was maintained in the range of 225 to 275 °C.
• a polymer alloy was obtained, the pro ⁇ perties of which are compared in Table 2 below with the prope ⁇ rties of the corresponding binary polymer blend containing o 75 wt% of Polymer 1 and 25 wt% of Polymer 2, i.e. a polymer blend having the same weight ratio between the two Polymers 1 and 2.
• Example 11 5 The above described procedure was followed.
• a polypropylene copolymer of the type Statoil P 401 having a melt index MI of 0.35 g/10 min at 230 "C/2.16 kg was used as Polymer 1, pre- mixed with standard stabilizers.
• Polymer 2 there was used a polybutylene terephthalate having a melt index MI of 34 g/10 0 min at 250 "C/21.2 N.
• Polymer 1 and Polymer 2 were added in amounts of 69.4 wt% and 23.1 wt%, respectively, based on the total mixture.
• the temperature profile of the extruder was maintained in the range of 225 to 265 °C.
• a polymer alloy was obtained, the properties of which are compared in Table 2 below with the properties of the corresponding binary polymer blend containing 75 wt% of Polymer 1 and 25 wt% of Polymer 2, i.e. a polymer blend having the same weight ratio between the two Polymers 1 and 2.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=19897049

Family Applications (1)

Country Status (3)

Citations (3)

• 1994
  • 1994-04-28 NO NO941558A patent/NO179839C/no not_active IP Right Cessation
• 1995
  • 1995-04-26 AU AU24213/95A patent/AU2421395A/en not_active Abandoned
  • 1995-04-26 WO PCT/NO1995/000068 patent/WO1995029949A1/en active Application Filing

Patent Citations (3)

Also Published As

Similar Documents

Legal Events