WO1993017062A1 - Polymeres fractals et copolymeres greffes formes a partir de ceux-ci - Google Patents

Polymeres fractals et copolymeres greffes formes a partir de ceux-ci Download PDF

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Publication number
WO1993017062A1
WO1993017062A1 PCT/US1993/001127 US9301127W WO9317062A1 WO 1993017062 A1 WO1993017062 A1 WO 1993017062A1 US 9301127 W US9301127 W US 9301127W WO 9317062 A1 WO9317062 A1 WO 9317062A1
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different
same
moieties
formula
polymer
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PCT/US1993/001127
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Shaul M. Aharoni
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Allied-Signal Inc.
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    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/003—Dendrimers
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • 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
    • 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
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • C08G85/004—Modification of polymers by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/005—Dendritic macromolecules

Definitions

  • This invention relates to a branched fractal three dimensional polymer species which comprises rigid aromatic recurring units having electrophilic or nucleophilic reactive moieties on the exterior thereof.
  • Another aspect of this invention relates to a star polymer comprising a polymeric core formed of the fractal polymers (FPS) of this invention having linear polymeric moieties grafted to the exterior thereof by way of residues formed by reaction between the reactive moieties on the exterior of the fractal polymer (FP) and complimentary reactive moieties on a linear
  • Yet another aspect of this invention relates to polymeric composites comprising a polymer matrix having dispersed therein the star polymers of this invention.
  • polymeric moieties grafted to the exterior of said at least two polymeric cores by way of residues formed by a reaction between reactive moieties on the exterior of the fractal polymer and complimentary reactive moieties on a linking polymer.
  • One aspect of this invention relates to a fractal polymer comprising a three dimensional or substantially three dimensional branched polymeric species
  • branching recurring monomeric units may be optionally linked by a plurality of linear or
  • substantially linear aromatic polymer segments having one or more recurring extension monomeric units of the formula: -B-R 3 -A- and a plurality of reactive pendant moieties on the exterior of said polymeric moiety and bonded thereto, said reactive pendant moieties of the formula:
  • a and b are different and are integers equal to 0, or equal to or greater than 3, with the proviso that a or b is 0;
  • R 1 is a polyvalent aromatic group such as phenyl, biphenyl, naphthyl or the like or is an aromatic moiety comprising two or more aromatic groups linked together by a linking moiety such as ester, urethane or amide linkage;
  • R 2 and R 3 are the same or different at each
  • Z 2 is the same or different at each occurrence and is a nucleophilic group such as -OH, -NH 2 , -N(R) 3 + ,
  • M ⁇ is a monovalent cation such as NH 1 ⁇ , Na ⁇ , K ⁇ , Cu ⁇ , Ni ⁇ and the like and R is as described above, which is capable of reaction i.e. displacement reaction or the like with a -Z 2 group to form a covalent bond;
  • A is the same or different at each occurrence the residue of a nucleophilic group such as -N(H)-, -O- and the like formed by a reaction between a nucleophilic group Z 2 and an electrophilic group Z 1 ;
  • B is the same or different at each occurrence and is the residue of an electrophilic group such as -C(O)-, -N(H) C(O)- and the like formed by reaction between a nucleophilic group -Z 2 and an electrophilic group -Z 1 ; and
  • c and d are different and are integers equal to or greater than 1, with the proviso that the sum of c and d is equal to or greater than 3, and with the further proviso that when a is equal to 0 then d is greater than c and that when b is equal to 0 then c is greater than d.
  • a three dimensional core comprising an aromatic nucleus of the formula: - (A) a -R 1 - (B) b - ; having a plurality of branching monomeric recurring units of the formula:
  • said branching monomeric units bonded to said nucleus and bonded to themselves, said core optionally
  • -Z 1 - is the residue formed by reaction of an exterior -Z 1 group of said core and a -Z 2 group substituted to a linear or substantially linear polymer precursor of said linear or substantially linear polymeric moieties
  • -Z 2 - is the residue formed by reaction of an exterior -Z 2 group of said core and a -Z 1 moiety substituted to a linear polymer.
  • Yet another embodiment of this invention relates to a copolymeric network comprising: a plurality of three dimensional cores each core comprising an aromatic nucleus of the formula:
  • a, b, c, d, R r , R 2 , R 3 are as described above, -A- and -B- are as described above and are nucleophilic or electrophilic residues formed by reaction of an exterior -Z 1 group and a -Z 2 moiety substituted to a linear polymer or is a
  • R 4 is linear polymer as for example a polyester, polyamide, polyurethane, polyalkylene, polyether and the like.
  • a molecular composite comprising a matrix which comprises one or more matrix polymers selected from the group consisting of crystalline polymers, amorphous polymers and combinations thereof having dispersed therein a star copolymer of this invention.
  • the molecular composite of this invention exhibits one or more advantages as compared to compositions formed from the matrix polymer alone. Such advantages include
  • copolymer of this invention exhibit higher heat deflection temperatures, and lower solution and melt viscosities than their linear analogues.
  • the AB-type fractal polymers of this invention are highly branched aromatic or substantially aromatic polymer entities.
  • the fractal polymer of this invention include one or more aromatic nuclei of the formula:
  • the number of aromatic nuclei include in the fractal polymer may vary widely.
  • the number of nuclei is preferably from 1 to about 8, more preferably from 1 to about 4, and most preferably 1 or 2. Those embodiments in which the number of nuclei is 1 are the embodiments of choice.
  • the nuclei comprises a polyvalent aromatic moiety *R 1 -.
  • Useful polyvalent -R 1 - aromatic groups may vary widely. Illustrative of useful R 1 groups are
  • Other, small, fractal polymers may also serve as R 1 groups for larger fractal polymers.
  • R 1 groups are of the formula:
  • q is an integer from 0 to 4.
  • i is an integer from 0 to 6;
  • n 0 or 1;
  • U is the same or different at each occurrence and is -O-, -S-, -SO 2 , -N(R 5 )-,
  • R 4 is the same or different at each occurrence and are alkyl, aryl, alkoxyaryl, alkylaryl, arylalkyl, alkoxy, alkoxyalkyl, nitro, cycloalkenyl, halo, cyano, cycloalkyl or aryloxy; and
  • R 5 and R 6 are the same or different and are
  • R 1 groups are selected from the group consisting of those of the formula:
  • R 4 is the same or different at each occurrence and is alkyl, alkoxy, phenyl or halo;
  • q and i are the same or different and are 0 or 1; n is 0 or 1;
  • n 0 or 1
  • U is -O-, -S(O 2 )-, -N(H)C(O)N(H)-, [-C(R 5 R 6 )-], -C(O)-, -C(O)O- or -N(H)C(O)-;
  • R 5 and R 6 are the same or different at each
  • R 1 groups are the same or different and are phenylene, or an aromatic moiety formed by two or more phenylene groups connected by amide, ester or urethane linking groups (preferably amide or ester linking groups and more preferably amide linking groups).
  • the aromatic nuclei also includes divalent linking groups -A- and -B- which function to link various aromatic moieties.
  • Useful -A- and -B- are different and may vary widely.
  • -A- is the residue of a
  • nucleophilic group -Z 2 such as -N(H)-, -O- and the like
  • B is the residue of an electrophilic -Z 1 group such as -C(O)-, -N(H)C(O)- and the like.
  • electrophilic -Z 1 such as -C(O)-, -N(H)C(O)- and the like.
  • residues are formed by reaction between nucleophilic group -Z 2 and an electrophilic group -Z 1 which results in a covalent bond as for example a displacement reaction between a nucleophilic functional group and a electrophilic functional group, condensation reactions such as the reaction between a hydroxy or an amine function and a carboxylic acid or isocyanate group.
  • Preferred -A- groups are -O- or -N(H)- and preferred -B- groups is -C(O) or -N(H)C(O)-.
  • preferred -A- group is -C(O)- or -N(H)C(O)- and the more preferred -B- group is -N(H)- and the most
  • -A- is -N(H) and the most preferred group is -C(O)-.
  • the core As an second essential component, the core
  • embodiments are those in which -R 2 - is a polyvalent aromatic group such as phenylene, biphenylene,
  • alkylene group such as 2,2-biphenylene propane.
  • preferred embodiments of the inventions are those where the -B- group is -C(O) or -N(H)C(O)- and the
  • -A- group is -O- or -N(H)-.
  • the fractal polymer of this invention may also include one or more polymeric segments having one or more extension monomeric groups of the formula:
  • the mole % of branching monomer units and extension monomeric units and their relative proportions may vary widely depending on the desired properties. For example, the greater the amount of extension monomeric units, the greater the distance between branching points and the more expanded the fractal polymer particle. Conversely, the lesser the amount of
  • the mole % of branching monomeric units is from about 100 to about zero and the mole % of extension monomeric units is from 0 to about 95 based on the total moles of branching monomeric units and extension monomeric units.
  • the mole % of branching monomeric units is from about 100 to about 33 and the mole % of extension monomeric units is from about 10 to about 75; more preferably mole % of
  • branching monomeric units is from about 75 to about 40 and of extension monomeric units is from about 25 to about 60; and most preferred mole % of branching monomeric units is from about 70 to about 45 and the mole % of extension monomeric units is from about 30 to about 55.
  • a and b are different and are 0, or integers from 3 to about 20, with the proviso that one of a or b is 0, and c and d are different and are integers from 1 to about 5 with the proviso that the sum of c and d is from 3 to about 9.
  • a and b are different and are 0 or integers from 3 to about 12, with the proviso that one of a or b is 0, and c and d are different and are integers from 1 to about 5 with the proviso that the sum of c and d is from 3 to about 7.
  • a and b are different and are 0 or integers from 3 to 6 with the proviso that one of a or b is 0.
  • c and d are the same or different and are integers from 1 to about 4, with the proviso that the sum of c and d is from 3 to about 5.
  • the fractal polymer of this invention includes at least one electrophilic surface moiety -Z 1 or at least one nucleophilic surface moiety of -Z 2 .
  • moieties may vary widely and include nucleophilic moieties such as -NH 2 , -OH, and the like.
  • Preferred -Z 2 groups are -NH 2 , and -OH, and the more preferred -Z 2 group is -NH 2 .
  • cayley tree Accordingly, the number of reactive -Z 1 or -Z 2 groups each cayley tree is:
  • N 2 (a+b)(f-1) n
  • the number of exterior moieties -Z 1 or -Z 2 included in the fractal polymer of this invention may vary widely, and depends on the relative values of a, b, c and d.
  • the number of surface reactive groups -Z 1 or -Z 2 is usually at least about 6.
  • the number of -Z 1 or -Z 2 groups are preferably from about 6 to about 256, more preferably from about 8 to about 200 and most preferably from about 12 to about 128.
  • Fractal polymer average particle radius may very widely. In general, the average particle radius is equal to or less than about 50 nanometer (nm).
  • Preferred average particle radius is from about 20 nm to about 1 nm, more preferred average particle radius is from about 10 nm to about 1.5 nm, and most preferred average particle radius is from about 7.5 nm to about 1.5 nm.
  • the fractal polymer of this invention can be prepared by any suitable method.
  • the fractal polymer is formed by reacting one or more nuclei precursor
  • nuclei precursor monomers and branching precursor monomers may vary widely and include those which will provide the desired nuclei and branching monomeric units described above in the same preference.
  • more preferred precursor nuclei monomers and branching precursor monomers are those in which -Z 1 is -OH or -NH 2 (especially -NH 2 ), and -Z 2 is -C(O)OH.
  • branching monomers used may vary widely depending on a number of factors such as the desired number of
  • the amount of nuclei precursor monomers employed will usually depend on the total amount of branching precursor monomer and will vary from about 0.005 to about 10 mole % based on the total moles of reactive branching precursor monomer employed.
  • the preferred amount of nuclei precursor monomer is preferably from about 0.01 mole % to about 5 mole %, more preferably from about 0.05 mole % to about 3 mole % and most preferably from about 0.1 mole% to about 2 mole % in the aforementioned basis.
  • the manner in which the various reactive monomers are contacted is such that the branching precursor monomer preferentially reacts with the nuclei precursor monomer at the beginning of the reaction and with the growing fractal polymer and any remaining nuclei precursor monomer during the course of the reaction. Any procedure capable of accomplishing the foregoing may be employed. It is preferred to add the active branching precursor monomer in solution form having a concentration preferably of (from about 15% to about 1% and more preferably from about 10% to about 2% by wgt of the solution) to a solution of the nuclei precursor monomer (having a concentration preferably of from about 8% to about 2.5% and more preferably from about 6% to about 3% by wgt of the solution) dropwise
  • the addition should be at a rate sufficient to provide a reaction mixture in which the concentration of branching precursor monomer as a function of time is less than that of nuclei precursor monomer and growing fractal polymer.
  • aprotic solvent having a boiling point equal to or greater than about 115oC.
  • Useful aprotic solvents may vary widely, the only requirements are that they are solvents for the reactants, that they are inert under the reaction conditions and that they have the required boiling point.
  • Illustrative of such solvents are amides such as tetramethylurea, dimethyl formamide, dimethyl thioformamide, N,N-dimethyl acetamide, N-methyl-2-pyrrolidinone, and the like.
  • Preferred aprotic solvents may vary widely, the only requirements are that they are solvents for the reactants, that they are inert under the reaction conditions and that they have the required boiling point.
  • Illustrative of such solvents are amides such as tetramethylurea, dimethyl formamide, dimethyl thioformamide, N,N-dimethyl acetamide, N-methyl-2-pyrrolidinone, and the like.
  • solvents are N,N-dimethylacetamide and N-methyl-2-pyrrolidinone.
  • Reaction temperatures may vary widely, depending on the boiling point of the reactants and reagents.
  • the process is carried out at a temperature equal to or less than the boiling point of the solvent.
  • the reaction is preferably carried out at a temperature equal to or less than about 200oC.
  • phosphite esters compounds include aromatic or aliphatic
  • phosphite esters and phosphite esters containing more than one phosphite ester moiety linked by a divalent moiety, as for example an oxygen atom or an aliphatic or aromatic moiety.
  • a divalent moiety as for example an oxygen atom or an aliphatic or aromatic moiety.
  • triphenyl phosphite can be prepared by reacting three moles of phenol with one mole of phosphorous chloride
  • trisnonyl phenol phosphite can be prepared by reacting three moles of nonyl phenol with one mole of phosphorous chloride.
  • Mixed phosphite such as diphenyl isodecyl phosphite, diphenyl isooctyl phosphite and phenyl diisodecyl phosphite, can be prepared by
  • useful phosphite containing more than one phosphite ester moiety such as aryl phosphite
  • derivatives of pentaerythritol can be prepared by reacting aromatic and aliphatic alcohols at least one of which is pentaerythritol with phosphorus
  • usful phosphite ester compounds are of the formula:
  • R 6 , R 7 and R 8 are the same or different and are hydrogen, metal cations, ammonium radicals, or
  • substituted or unsubstituted phenyl, naphthyl or alkyl wherein permissible substituents are one or more of alkyl, alkoxy, cyano, nitro or halo groups, or any two or three of R 6 , R 7 and R 8 together may form a divalent alkylene, alkynylene or alkenylene chain (preferably alkylene) forming a monocyclic, bicyclic or tricyclic ring structure (preferably having from about five to about ten carbon atoms) which chain may be
  • R 6 , R 7 and R 8 individually may form a moiety of the formula:
  • n is 0 or a positive whole number
  • R 9 , R 10 , -R 11 and R 12 are the same or different and are R 6 , R 7 and R 8 and R 13 is -O- or a divalent organic moiety.
  • triphenyl phosphite diphenyl phosphite
  • poly(dipropylene glycol) phenyl phosphite poly(4,4- isopropylidene glycol) phenyl phosphite, poly(4,4-isopropylidene diphenol neopentyl alcohol phosphite), bis-(2,4-di-t-butylphenyl)-pentaerythritol diphosphite, and tris- (2,4-di-t-butylphenyl)phosphite.
  • an effective amount of one or more phosphite ester compounds is employed.
  • an effective amount is an amount of the phosphite ester compounds which when added in accordance with this invention forms a mixture which when heated forms the desired fractal polymers.
  • the quantity of the one or more phosphite ester compound employed is at least equimolar to the amount of A and B groups to be formed in the
  • the weight percent of phosphite ester compound is in the range of from 0.1 to about 10 weight percent based on the total weight of the mixture.
  • the quantity of phosphite ester compound employed is from about 0.2 to about 2 weight percent based on the total weight of the mixture are most preferred.
  • the process of this invention is carried out in the presence of as little water as possible.
  • the conditions will be anhydrous, and this represents the most preferred embodiment of the invention.
  • good results can be obtained when as much as .165 weight percent water based on the total weight of the mixture is present therein.
  • the weight percent of water is less than about 0.1 weight percent, and in the particularly preferred embodiments, the weight percent of water is less than about 0.05 weight percent of the same basis.
  • the reaction is carried out in the presence of an organic base.
  • Useful organic bases may vary widely. Preferred bases are nitrogen bases such as pyridine, imidazole, and various alkylamines such as propylamine, triethylamine and the like, and the most preferred base is pyridine.
  • the base is employed in an amount which is
  • the amount of base employed is at least equimolar to the amount of branching monomer reactant. In the preferred embodiments of the invention, the amount of base is at least about 2 equivalents of base, based on the total moles of the branching monomer reactant. In the more preferred embodiments of the invention, the amount of base is from about 2
  • the reaction mixture may include an extension monomer reactant to control the distance between branchpoints formed from reaction of the branch point monomer reactants and therefore the size of the fractal polymer.
  • extension monomer reactants are of the formula:
  • the amount of extension monomer may vary widely and depends on the desired size and flexibility of the fractal polymer. In general, the greater the amount of extension monomer added to the reaction mixture, the larger the size and greater the flexibility of the fractal polymer. Conversely, the lower the amount of extension monomer added to the reaction mixture, the smaller the size of the fractal polymer and the lower the flexibility of the fractal polymer. The amount of extension monomer actually needed in any situation will be selected to provide fractal polymer of the desired size and flexibility.
  • the extension monomer is preferably added to the reaction mixture in the same manner as the branching precursor monomer, preferably at the same time or substantially at the same time.
  • the addition is in such a manner that the extension monomer may react with itself to form polymer segments, with the nucleus and with the growing fractal polymer so as to provide segments between the nucleus and branching monomeric units and/or between branching monomeric units.
  • Reaction pressures are not critical and can be varied widely.
  • the process can be any material that can be varied widely.
  • the process can be any material that can be varied widely.
  • the process can be any material that can be varied widely.
  • the process can be any material that can be varied widely.
  • the process can be any material that can be varied widely.
  • the process can be any material that can be varied widely.
  • the process can be any material that can be varied widely.
  • the process can be any reaction pressure
  • reaction times are influenced to a significant degree by the reactants; the reaction temperature; the concentration and choice of reactants and catalyst; the choice and concentration of reaction solvent; and by other factors known to those skilled in the art.
  • residence times can vary from about a few minutes to 24 hours or longer. In most instances, when employing preferred reaction conditions, residence times will be found to vary from a few minutes to about 3 hours.
  • the fractal polymeric product can be isolated from the reaction mixture and purified employing
  • the preferred isolation technique is precipitation of the fractal polymer in a non-solvent such as water, alcohol, acetone, etc.
  • the fractal polymers of this invention have a number of uses. For example, they can be reacted with linear polymers to form star copolymers. These star copolymers have relatively high molecular weight and are characterized by lower melt and solution viscosity than their linear analogues of the same or
  • the fractal polymers can be used for ion exchange purposes or as substrates for enzymatic or biomedical processes.
  • the fractal polymers can be reacted with flexible or stiff divalent or polyvalent linear polymer chains or monomers to form three
  • the networks may be especially useful as selective adsorbents (due to their swelling) for specific solvents.
  • the fractal polymers of this invention are:
  • the star copolymer of this invention comprises a fractal polymer having one or more linear graft polymeric moieties grafted to the exterior thereof by way of a linking group such as ester, amide or urethane moiety formed by way of reaction of the polymer precursor of the graft polymeric moieties with the exterior -Z 1 or -Z 2 moieties of the fractal
  • the polymeric networks of this invention comprise a plurality of fractal polymers covalently linked by a divalent linking moiety, grafted to two or more fractal polymers by way of a suitable linking group formed as described above.
  • Graft polymeric moieties may vary widely and essentially include any polymer which can be grafted onto the surface of the fractal polymer.
  • Illustrative of useful graft polymeric moieties are aliphatic polyamides such as poly(butyrolactam) (nylon-4), polycaprolactam (nylon 6), poly(undecanoamide) (nylon 11), and poly(dodecanamide) (polylaurolactam) (nylon 12) and copolymers thereof.
  • Another group of graft polymeric moieties for use in the practice of this invention are amorphous polyamides which are
  • Still other useful graft polymeric moieties include polyolefins such as poly(ethylene), poly(propylene), poly(4-methyl-1-pentene), poly(styrene) and the like; polyvinyls such as poly(vinyl alcohol) and the like; polyacrylics such as poly(acrylonitrile),
  • polycarbonates polyurethanes; poly(anilines);
  • polyetherpolyols and polyester polyols.
  • the nature of the reactable group on the graft polymer and linking polymer precursor is dictated by the reactive groups Z on the fractal polymer exterior, and may by amine, carboxylic acid, isocyanate, hydroxyl group, etc.
  • Preferred graft polymeric moieties are polyamides and polyesters. More preferred polyamides are poly(butyrolactam) (nylon-4), poly(caprolactam) (nylon 6), poly(undecanoamide) (nylon 11), and
  • poly(dodecanamide) polylaurolactam) (nylon 12) and copolymers thereof and more preferred polyesters are poly(ethylene terephthalate), poly(butylene
  • the most preferred polyamide is poly(caprolactam) (nylon 6), and the most preferred polyesters are poly(ethylene terephthalate) and
  • Linking moieties may vary widely and include polymeric, oligomeric or monomeric divalent moieties. Illustrative of useful linking moieties linking two or more cores of the polymer network are divalent forms of the graft polymeric moieties described above. Linking moieties also include aliphatic groups such as
  • alkenylene, alkynylene and alkylene groups having at least about 2 carbon atoms, preferably at least about 5 carbon atoms, arylene groups or a combination of arylene and aliphatic groups which may include one or more heteroatoms and functional groups such as -O-, -N(H)-, -C(O)- and the like.
  • the length of the graft polymeric moieties and the linking moieties may vary widely, and will depend on the desired uses of the star polymer or polymeric network. For example, in situations were relatively flexible materials are required longer and relatively flexible graft polymeric moieties and linking moieties are employed. Conversely, in situations were more rigid materials are employed shorter graft polymeric moieties and linking moieties are employed.
  • the star polymer and polymeric network of this invention can be conveniently prepared by reaction of a graft polymer precursor having a reactive group which is reactive with an exterior surface moiety of the fractal polymer or by reacting the fractal polymer with a linking moiety precursor having at least two
  • electrophilic or nucleophilic reactive groups one of which is reactive with a -Z 1 or -Z 2 exterior moiety of one fractal polymer and another of which is reactive with a -Z 1 or -Z 2 exterior surface moiety of another fractal polymer.
  • moieties include those that react in conventional polymerizations reactions such as addition polymerization and condensation
  • Illustrative electrophilic and nucleophilic groups include those described as useful for -Z 1 . and Z 2 moieties of useful nuclei precursor monomers, branching precursor moieties and extension precursor moieties as described above, in the same preferences.
  • the surface -Z 1 or -Z 2 moiety is a nucleophilic group such as -OH, -NH 2 or the like
  • the graft polymeric moiety precursor or linking moiety precursor may include a complimentary nucleophilic group such as a -OH or -NH 2 in the required number.
  • the star copolymer and the polymeric network are formed either by the solution process or melt process of this invention. Both processes preferably involve the formation of amide or ester groups by reaction of an amine or hydroxy group and a carboxyl group in the presence of phosphite esters.
  • one of the reactants is the monofunctional precursor polymer of the linear polymeric moieties of the star polymer or the polyfunctional precursor of the linking moieties of the polymeric network which has a reactive group as for example an amine group, hydroxy group, or carboxyl group, and the other is one or more fractal polymer of this invention having exterior -Z 1 or -Z 2 moieties which are reactive with the reactive groups of the precursor polymer of the linear moieties or linking polymeric moieties.
  • the precursor polymers of the graft polymeric moieties of the star polymer are AB terminated polymers. That is, each end of the precursor polymers is terminated with a
  • the most preferred precursor graft polymers are aliphatic polyamides or amorphous aromatic polyamides made exclusively or almost exclusively from AB monomers where A and B are different functional groups as for example an amine group and a carboxylic acid group such that each chain is terminated by a carboxyl group on one end and an amine group on the other such as nylon 6, nylon 7, nylon 4, nylon 3, nylon 8, nylon 11, nylon 12 and the like.
  • the linking moiety precursor must include two or more A functional groups, where the exterior
  • reactive -Z 1 or -Z 2 moieties of the fractal polymer are reactive with A functional groups or must include two or more B functional groups, where the exterior
  • polymers such as nylon 66, nylon 610, nylon 612 and the like; acid or hydroxy terminated polyesters; hydroxy and amine terminated polyethylene oxides or polyamines; polymers and copolymers having two or more pendant acid functions such as poly(acrylic acid), partly hydrolized polyacrylamide, poly(ethylene-co-acrylie acid),
  • terephthalic acid tetramethylene glycol, diamino xylylene and hexamethylene diamine; 4,4'-diamino benzanilide and the like are suitable for use.
  • both reactants are dissolved in an aprotic solvent such as N,N-dimethylacetamide (DMAc) or N-methyl-2-pyrrolidinone (NMP) optionally in the presence of LiCl at
  • phosphite compounds and an effective amount of an organic base are added, and the reaction is allowed to proceed for a time sufficient to form the desired star polymer or the polymeric network, usually up to about 5 hours.
  • the condensation is carried out in the presence of a base.
  • Useful bases may vary widely. Illustrative of useful bases are organic bases such as tertiary amines as for example, imidazole, pyridine or trialkylamines. Preferred bases are tertiary amines and the most preferred base is pyridine.
  • the base is employed in an amount which is
  • the molar amount of base employed is about equivalent to the molar amount of the phosphite ester in the reaction mixture.
  • the grafting reaction is conducted in the molten state at temperatures above the melting temperature of the linear precursor polymer of the graft polymeric moieties or the precursor of the linking moieties.
  • the reaction is carried out at temperatures much higher than in the solution process, and in the absence of the aprotic solvent, LiCl, and organic base.
  • the highest graft efficiency occurs at temperatures in the range of from about 225oC up to about 325oC.
  • the reaction is carried out at temperature equal to or greater than 115oC and lower than the boiling point of the solvent.
  • solution condensation process temperatures are from greater than about 115oC to about 185oC, and more preferred reaction temperatures are from about 120oC to about 155oC.
  • the preferred temperature at which to conduct the graft reaction for any particular linear polymer depends on the nature of the flexible polymer.
  • the linear polymer is an aliphatic polyamide such as
  • polycaprolactam nylon-6
  • the preferred temperature is from greater than 115°C to about 145oC
  • the most preferred temperature is from about 120oC to about 135oC.
  • the linear polymer is
  • PET poly(ethylene terephthalate)
  • the preferred temperature is from about 140oC to about 185oC, and the most preferred temperature is from about 165oC to about 180oC.
  • an appropriate reaction temperature may be used, usually dictated by the solubility of the linear polymer in the reaction solvent. In all cases, the reactions are conducted at temperatures higher than those prescribed by Yamazaki, Matsumoto and Higashi, J. Polymer Sci.: Polvm. Chem. Ed., 1975, 13, 1373. These authors found the
  • melt and solution processes are carried out under conditions substantially similar to those
  • the melt and solution processes are carried out in the presence of and effective amount of one or more phosphite esters.
  • Useful and preferred amounts of phosphite esters and reactants are as described below in the process for preparation of the fractal polymer.
  • the quantity of the one or more phosphite esters employed is about equimolar with the number of linking groups (preferably amide or ester groups) expected to be formed during the grafting procedure, and the process is carried out in the presence of no or substantially no water over a period of time sufficient to produce the star polymer or polymeric network in the desired yield.
  • the polymeric network of this invention has many uses.
  • the network can be used to absorb liquids by matching the polarity of the liquid with the polarity of the linking moiety.
  • the linking moiety is a polymeric moiety such as
  • the network can be used to absorb more polar liquids such as water, ethanol, acetone and the like.
  • the linking moieties are polymeric moieties such as poly(ethylene-co-methacrylic acid), poly(ethylene-co-acrylic acid), poly(acrylamide) or the like, then the network can be used to absorb less polar liquids.
  • the remaining -Z 1 and -Z 2 moieties and reactive sites can be used as prepared or after alteration for ion-exchange or selective
  • filtration resins and/or membranes for slow drug release where the drug is bound to either the fractal or the linking moiety and the release is effected by hydrolysis of the bonds by body fluids.
  • a multi-purpose exchange resin or drug release material can be prepared; e.g., a concurrent positive and negative ion-exchange resin or membrane.
  • the networks may be used as diagnostic substrates for proteins in medical and biochemical analyses.
  • the star polymer of this invention has many uses. For example, they are much more melt or solution processable than their linear analogues of the same molecular weight because of lower solution or melt viscosity. Because of their high molecular weight, the mechanical properties of the polymers in the solid state, such as ductility, tensile modules, strength and breaking strain are enhanced as compared with
  • star polymers to linear compatible polymers results in a composite blend having properties which are superior to those in the linear polymer.
  • the star copolymer of this invention is also useful as a compatibilizer to increase the homogeneity of a blend of two or more polymers.
  • the star copolymer may be substituted with two types of graft moieties one compatible with one component and the compatible with the other correspond.
  • the star polymer of this invention is especially useful as a precursor in the formation of the molecular composite of this invention which comprises a polymeric matrix which comprises a crystalline polymer, amorphous polymer or a combination thereof having dispersed therein at the nanometer scale (average radius equal to or less than about 1000 nm, preferably from about 500 to about 5 nm and more preferably from about 100 to about 10 nm) a star polymer of this invention.
  • the polymers that may serve in the polymeric matrix may vary widely.
  • Useful polymers include thermoplastic polymers such as poly(esters), poly(amides),
  • thermoplastic polymers are polyesters such as
  • polyamides such as the aliphatic polyamides and the amorphorus polyamides described below as precursor for the graft polymeric moieties of the star copolymer.
  • Polyamides are more preferred and nylon polyamides, especially nylon 6, nylon 4, nylon 12, nylon 11 and nylon 66, nylon 610 and nylon 64 are most preferred.
  • the amount of matrix polymer contained in the molecular composite may vary widely, depending on the uses, but is usually at least about 50 weight percent based on the total weight of the composite.
  • the amount of matrix polymer contained in the molecular composite is preferably from about -50 to about 99% by weight, more preferably from about 70 to about 98% by weight and most preferably about 80 to about 95% by weight based on the total weight of the molecular composite.
  • the molecular weight of the polymer forming the polymeric matrix of the composite may vary widely. In general, the molecular weight of the matrix polymer is sufficiently high such that such polymer can form a solid molecular composite. In the preferred
  • the matrix polymer is a polyamide
  • its number average molecular weight is preferably at least about 5000.
  • the star copolymer is selected such that the graft polymeric moieties are generally "compatible" with the polymer or polymers forming the matrix.
  • compatible refers to the extent to which the polymer of polymers of the matrix and the graft polymeric moieties of component have a favorable interaction which promotes the intermingling of the polymer or polymers forming the matrix and the flexible polymeric moieties of the star copolymer.
  • Compatibility derives from one or more of the following criteria: similar, cohesive energy densities for the polymer or polymers of the matrix and the graft polymeric moieties of the star copolymer, similar or complimentary capacities for dispersive, polar, ionic or hydrogen bonding interactions, or other specific interactions, such as acid/base or Lewis-acid/Lewis-base interactions.
  • the graft polymeric moieties preferably include the same or substantially the same recurring monomeric units as the polymer (s) or copolymer(s) of forming the matrix.
  • graft polymeric moieties of the star copolymer include the same or substantially the same recurring monomeric units as the polymer (s) of the matrix described above.
  • the number average molecular weight or number of repeating units in the graft polymeric moieties of the star polymer included in the molecular composite of this invention is critical.
  • precursor polymers used to form the graft polymeric moieties of the star copolymer are preferably sufficiently long to co-crystallize with the matrix polymer where the matrix polymer and the graft
  • the graft polymeric moieties of the star copolymer are of polyamides, typified by poly(caprolactam)
  • the graft polymeric moieties of the star copolymer preferably include at least about 20 repeat units; that is for poly(caprolactam), have a number average molecular weight M n preferably of at least about 2500.
  • the graft polymeric moieties of the star copolymer are polyesters such as
  • PET polyethyleneterephthalate
  • polymeric moieties of the star copolymer is not less than about 4000.
  • the M n is equal to or greater than about 2000.
  • the respective minimal M n is preferably about 2000 for polyethylene and preferably about 3000 for
  • the amount of the star copolymer in the molecular composite may vary widely. It is limited from below by the magnitude of the desired property enhancement, and from above by processing limitations such as
  • the amount of the star copolymer contained in the molecular composite is at least about 0.5% by weight, and may reach up to 100% by weight of the molecular composite. Preferred amounts are from about 0.5% to about 50% by weight, more preferred amounts are from about 2% to about 30% and most preferred amounts are from about 5% to about 20% by weight of the molecular composite.
  • the molecular composite of this invention may include various optional ingredients known for use in molecular composites.
  • Such optional components include fibrillar and non-fibrillar fillers, plasticizers, impact modifiers, colorants, mold release agents, antioxidants, ultraviolet light stabilizers,
  • the molecular composite of this invention can be obtained by conventional melt blending the matrix polymer and graft star copolymer of this invention, and various optional components to the extent necessary to obtain the desired dispersion.
  • the manner in which the melt is formed is not critical and conventional methods can be employed.
  • the melt can be formed through use of conventional polymer and additive blending means, in which the polymeric components are heated to a temperature equal to or greater than the melting point of at least one of the polymers, and below the degradation temperature of each of the polymers.
  • the polymers are heated above the melting point of the matrix polymer and the graft polymeric moieties of the star copolymers. The melt is then vigorously stirred until the desired dispersion of the graft copolymers in the matrix is obtained.
  • the various essential and optional components can be granulated, and the granulated compounds mixed dry in a suitable mixer, as for example, a tumbler or a Branbury Mixer, or the like, as uniformly as possible. Thereafter, the composition is heated in an extruder or melt blender until the graft polymeric moieties of the star
  • copolymer and the matrix are melted.
  • the mixture is maintained at that temperature and vigorously mixed until the desired dispersion of the star copolymer in the matrix is obtained.
  • the molecular composite is thereafter ejected with cooling.
  • the molecular composite of this invention can be used for conventional purposes.
  • the molecular composite of this invention can be used to form injection molded elements, melt-spun fibers of high modules and tenacity, unoriented or oriented films with high strength, and the like.
  • a 48-amine AB-type fractal polyamide was prepared as described above using trifunctional nuclei (prepared from 0.5g 1,3,5-benzenetricarboxylic acid and 1.4g 1,4-phenylenediamine) and 0.1 mol (15.25g) 3,5-diaminobenzoic acid and 0.1 mol (13.71g) 4-aminobenzoic acid.
  • trifunctional nuclei prepared from 0.5g 1,3,5-benzenetricarboxylic acid and 1.4g 1,4-phenylenediamine
  • 0.1 mol 15.25g
  • 3,5-diaminobenzoic acid and 0.1 mol (13.71g) 4-aminobenzoic acid was added.
  • Work up was as before.
  • NMR analysis indicated that all the free amines were reacted to produce exclusively methyl ester-terminated FPs. From the ratio of methyl to aromatic carbons in the NMR scans, it was found that each polymer molecule is associated with close to 48 ester
  • the carboxyl-terminated FP A2105-78B was dissolved in DMAc at over 80oC. To this solution a slight molar excess of KOH in methanol was added, resulting in gradual precipitation. After workup in methanol and acetone, the dried polymer contained over 16.0% by weight potassium. This product was coded A2105-82G.
  • the low temperature of the reaction was set in order to prevent the aliphatic amines at the chain-ends of the nylon from reacting, and to limit the reaction to only the aromatic amines of A2105-72B and the carboxyl groups at the other end of the nylon chains.
  • Work up was conducted as usual: precipitation in methanol, followed by filtration and wash in methanol, tap water, boiling water and methanol again.
  • the product of this procedure, coded A2105-73B, was found by light
  • PET Poly(ethylene terephthalate) (PET) (60g) is ground and then dried under dynamic vacuum at ca. 130°C overnight.
  • A2105-82G (0.6g, 1.0% by weight of the PET) are mixed with 0.91g triphenylphosphite (1.5% TPP). This mixture is added to the PET and thoroughly mixed in a sealed vessel by shaking and tumbling. The well mixed mixture is then melt blended at a nominal
  • the networks were first obtained as their swollen gels. After careful washing several times over in liquids such as methanol, water, etc., the gels were dried and the dry networks obtained.
  • the procedure or Yamazaki et al. J. Polymer Sci. Polym. Chem. Ed. 13, 1373 (1975) was employed in most instances to prepare the networks. Otherwise, our modification where the condensation takes place at 130oC and higher was used.
  • Networks A2105-74B and A2105-77 demonstrate that networks consisting mostly of fractal polyamides can be prepared. Importantly, these and the other networks contain a large number of accessible amine groups capable of serving in various functions such as
  • Networks A2105-74C and A2105-75B are highly swellable in appropriate fluids.
  • the long nylon-6 network segments were found to be swellable in fluids such as DMAc/5% LiCl, cone, sulfuric acid and formic acid. All these are solvents for uncrosslinked nylon-6.
  • the long poly(acrylic acid) network segments were swellable in fluids which are common solvents for normal
  • the star polymer is useful as a compatibilizer for blends of nylon 6 and the amorphous linear aromatic polyamide coded A2105-61E or similar amorphous polyamides.

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Abstract

L'invention concerne une espèce de polymère tridimensionnel fractal ramifié comprenant des unités récurrentes aromatiques rigides présentant des fractions réactives électrophiles ou nucléophiles sur leur extérieur. Un autre aspect de l'invention concerne un polymère en étoile comprenant un noyau polymère formé sur les polymères fractals (PF) de l'invention, ayant des fractions polymères linéaires greffées sur son extérieur au moyen de résidus formés par réaction entre les fractions réactives sur l'extérieur du polymère fractal (PF), et des fractions réactives complémentaires sur un polymère linéaire. Un autre aspect de cette invention concerne des composites polymères comprenant une matrice polymère dans laquelle sont dispersés les polymères en étoile de cette invention. En outre, l'invention concerne des réseaux polymères comprenant au moins deux noyaux polymères formés à partir des polymères fractals de l'invention, lesquels sont liés ensemble par liaison de fractions polymères greffées à l'extérieur desdits au moins deux noyaux polymères, au moyen de résidus formés par une réaction de variation entre des fractions réactives, sur l'extérieur du polymère fractal, et des fractions réactives complémentaires sur un polymère de liaison.
PCT/US1993/001127 1992-02-21 1993-02-09 Polymeres fractals et copolymeres greffes formes a partir de ceux-ci WO1993017062A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000022030A1 (fr) * 1998-10-14 2000-04-20 Epox Ltd. Oligomeres hautement ramifies, leur procede de preparation et applications mettant en oeuvre de tels oligomeres

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Macromolecules, vol. 23, no. 9, 30 April 1990, American Chemical Society, S.M. AHARONI et al.: "Fractal nature of one-step highly branched rigid rodlike macromolecules and their gelled-network progenies", pages 2533-2549 (cited in the application) *
Macromolecules, vol. 24, no. 1, 7 January 1991, American Chemical Society, S.M. AHARONI: "Gelled networks prepared from rigid fractal polymers", pages 235-239 (cited in the application) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000022030A1 (fr) * 1998-10-14 2000-04-20 Epox Ltd. Oligomeres hautement ramifies, leur procede de preparation et applications mettant en oeuvre de tels oligomeres
US6288208B1 (en) 1998-10-14 2001-09-11 Epox, Ltd. Highly branched oligomers, process for their preparation and applications thereof

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