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    The energy and feedstock crisis has resulted in a serious strain on the prospects for petrochemicals in polymers? Many petrochemicals and petroleum-derived polymers have become less competitive due to the high price of oil or petroleum fractions. As the availability of oil and petroleum fractions has become very uncertain, this has resulted in a severe competition for oil between uses as fuel for energy and as feedstock for petrochemicals. Although the entire petrochemical industry (including fertilizers and synthetic polymers) consumes less than 10% of the supply of crude oil, the greater demand for fuel for energy makes uncertain the future supply of feedstocks for petrochemicals at a reasonable price. The cost advantage of polymer materials in general over the other conventional materials has already been eroded considerably by the price rise of crude oil. Never before have plastics been faced with such tough competition from traditional materials like metals, alloys, glass, etc.

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    The energy and feedstock crisis has resulted in a serious strain on the prospects for petrochemicals in polymers? Many petrochemicals and petroleum-derived polymers have become less competitive due to the high price of oil or petroleum fractions. As the availability of oil and petroleum fractions has become very uncertain, this has resulted in a severe competition for oil between uses as fuel for energy and as feedstock for petrochemicals. Although the entire petrochemical industry (including fertilizers and synthetic polymers) consumes less than 10% of the supply of crude oil, the greater demand for fuel for energy makes uncertain the future supply of feedstocks for petrochemicals at a reasonable price. The cost advantage of polymer materials in general over the other conventional materials has already been eroded considerably by the price rise of crude oil. Never before have plastics been faced with such tough competition from traditional materials like metals, alloys, glass, etc.

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    © All Rights Reserved
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    144 views42 pages

    Rosin

    Uploaded by

    Vingiu Katre
    The energy and feedstock crisis has resulted in a serious strain on the prospects for petrochemicals in polymers? Many petrochemicals and petroleum-derived polymers have become less competitive due to the high price of oil or petroleum fractions. As the availability of oil and petroleum fractions has become very uncertain, this has resulted in a severe competition for oil between uses as fuel for energy and as feedstock for petrochemicals. Although the entire petrochemical industry (including fertilizers and synthetic polymers) consumes less than 10% of the supply of crude oil, the greater demand for fuel for energy makes uncertain the future supply of feedstocks for petrochemicals at a reasonable price. The cost advantage of polymer materials in general over the other conventional materials has already been eroded considerably by the price rise of crude oil. Never before have plastics been faced with such tough competition from traditional materials like metals, alloys, glass, etc.

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    © All Rights Reserved
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    of 42

    Prog. Polym. Sci., Vol. 14, 297-338, 1989 0079-6700/89 $0.00 + .

    50
    Printed in Great Britain. All rights reserved. Copyright © 1989 Pergamon Press plc

    ROSIN: A RENEWABLE RESOURCE FOR POLYMERS


    AND POLYMER CHEMICALS

    SUKUMAR MAITI,* SABYASACHIS1NHA RAY and ACHINTYA K. KUNDU


    Polymer Materials Division, Materials Science Centre, Indian Institute of Technology,
    Kharagpur 721302, India

    CONTENTS

    I. Introduction 297
    I.l. Source of rosin 299
    1.2. Chemistry of rosin 299
    2. Rosins as polymer chemicals 301
    2.1. Rosin in paint, varnish and coatings 301
    2.1.1. Antifouling paint formulations 302
    2.1.2. Traffic paint 302
    2.2. Rosin in printing ink formulations 304
    2.3. Rosin in adhesive formulations 304
    2.4. Miscellaneous uses of rosin and rosin derivatives 305
    3. Rosins as polymer feedstocks 305
    3.1. Polymerization of rosin 306
    3.2. Copolymerization of rosin and rosin derivatives 307
    3.3. Alkyd resins 308
    3.4. Polyurethanes 310
    3.5. Epoxy resins 311
    3.6. Polyesters 313
    3.7. Polyamides 316
    3.8. Polyesterimides 316
    3.9. Polyamideimides 318
    3.10. Miscellaneous rosin polymers 323
    4. Properties of polymers 323
    5. Thermal behavior 324
    6. Polymer modification 327
    6.1. Crosslinking 327
    7. Polymer blends 328
    8. Rosin-maleic anhydride adduct vs trimellitic anhydride 332
    9. Conclusion 334
    Acknowledgements 334
    References 334

    I. I N T R O D U C T I O N

    The energy and feedstock crisis has resulted in a serious strain on the prospects
    for petrochemicals in polymers? Many petrochemicals and petroleum-derived
    *To whom all correspondence should be mailed.

    297
    298 S. MAITI et al.

    polymers have become less competitive due to the high price of oil or petroleum
    fractions. As the availability of oil and petroleum fractions has become very
    uncertain, this has resulted in a severe competition for oil between uses as fuel
    for energy and as feedstock for petrochemicals. Although the entire petro-
    chemical industry (including fertilizers and synthetic polymers) consumes less
    than 10% of the supply of crude oil, the greater demand for fuel for energy
    makes uncertain the future supply of feedstocks for petrochemicals at a reason-
    able price. The cost advantage of polymer materials in general over the other
    conventional materials has already been eroded considerably by the price rise of
    crude oil. Never before have plastics been faced with such tough competition
    from traditional materials like metals, alloys, glass, etc.
    This scarcity and high price of crude oil has led to research and development
    activities worldwide for the use of alternative, preferably renewable, resource
    materials as feedstocks for polymers and petrochemicals. Trimellitic anhydride
    (TMA), benzophenonetetracarboxylic dianhydride (BTDA), and pyromellitic
    dianhydride (PMDA) are the key chemicals for the manufacture of a number of
    industrially important chemicals and polymers such as high temperature resist-
    ant polyamideimides, polyimides, polyesterimides and other copolyimides, high
    temperature plasticizers, paint additives and other polymer chemicals. TMA,
    BTDA, PMDA, etc. are petroleum-based compounds and are manufactured by
    only a few companies in the world. Since these are strategic materials, their
    availability is uncertain particularly in times of emergency. It is, therefore,
    highly desirable to develop a suitable substitute material for TMA and allied
    petroleum-based products.
    In an attempt to find a suitable alternative and renewable substitute
    for petroleum-based TMA and allied chemicals we have recently developed
    Rosin-Maleic Anhydride Diels-Alder Adduct (RMA) from gum rosin, a
    pine wood exudate, and maleic anhydride. 2-6 Large amounts of gum rosin
    are available in India, particularly in the lower foothills of the Himalayas.
    Gum rosin is made to react with maleic anhydride to form the Diels-Alder
    Adduct. The Diels-Alder Adduct, RMA, is also known as maleopimaric
    acid. The molecule of RMA, like TMA, contains one carboxyl group and
    one anhydride group - the two reactive functionalities capable of undergoing
    various chemical reactions with appropriate reagents. The hydrophenanthrene
    ring system present in the rosin moiety of RMA offers thermal and oxidative
    stability to the RMA molecule just as the benzene ring does to the TMA
    molecule. It is expected from the above structural similarities that RMA may be
    a suitable substitute for TMA in most, if not all, of its applications. Since rosin
    is a cheap and renewable material, the price of RMA and its derivatives is
    expected to be lower than that of TMA and TMA derivatives. The most
    important point to be noted here is that the supply of rosin will be unhindered
    as this is derived from a forest product abundantly available in India and many
    other countries.
    ROSIN 299

    ,CH[CH3)t

    0 CH~ ~0

    NOOC C HO0
    TMA RMA

    I. !. Source of rosin
    Rosin is a thermoplastic acidic product isolated by widely different
    procedures from exudates of pine trees and freshly cut and/or aged bole and
    stump wood of various species of pine.
    Rosin is classified, according to its source, into three main types viz. (a) gum
    rosin (b) wood rosin and (c) tall rosin. 7-9 The specifications of three types-of
    rosin are given in Table 1. Gum rosin is obtained as the residue from the
    distillation of turpentine from crude turpentine pitch. Wood rosin is produced
    by naptha extraction of waste pine wood after recovery of pine oil and turpen-
    tine. Tall rosin is obtained from the distillation of tall oil. ~°Among the various
    rosins the most important is common rosin or colophony obtained from various
    species of pine trees.

    i.2. Chemistry of rosin


    Rosin is a complex mixture of naturally occurring high molecular weight
    organic acids and related neutral materials. ~ The acidic constituents that make
    up the major portion of rosin are known as rosin acids. They are monocarboxylic
    acids of alkylated hydrophenanthrene nuclei. The non-acidic or neutral minor
    constituents of rosin are a mixture of high molecular weight esters, alcohols,
    aldehydes and hydrocarbons which vary in nature but their structures are
    related to those of the rosin acids. They may vary in relative amounts according
    to the source of the rosin and the extent to which it is refined.
    Generally rosin contains 90% acidic and 10% neutral materials. ~j The overall
    chemical reactivity of rosin is that of a monocarboxylic acid. The predominant
    rosin acid in pale refined unmodified rosin is abietic acid, which has the empiri-
    cal formula C20H3002. Other resin constituents of rosin differ mainly from
    abietic acid in that they are isomers of abietic acid having double bonds at

    TABLE 1. Physical properties of various rosins n

    Rosin Specific Saponification Acid Melting


    gravity value number point (°C)

    Gum rosin 1.070 172 164 76


    Wood rosin 1.067 167 163 73
    Tall rosin 1.070 174 165 77
    300 S. MALT1 et aL

    /c.3 CH

    CH3 CH C C~ ICH~cH3
    CHz

    H3C COOH H3C COOH


    Abietic acid Levopimaric acid

    C ~ cH3 CH

    CH3 "CH

    ~CH 3

    H3 C COOH H3C COOH

    Neoabietic acid Palustric acid


    CH
    CHmCH2

    ~
    CH3

    H3C COOH H3C COOH

    Dehydroabietic acid Pimaric acid

    CH3
    CH "'" CH=CH2

    H3C COOH
    Isopimaric acid

    FIG. 1. Structure of rosin acids.

    different positions in the hydrophenanthrene ring or having a methyl and vinyl


    group instead of the isopropyl substituent. The structures of the rosin acids are
    shown in Fig. 1.
    Among all the isomeric rosin acids only levopimaric acid possesses the
    optimum cyclic diene structure for Diels-Alder addition. It, alone, readily forms
    a crystalline white Diels-Alder adduct with maleic anhydride. Although the
    other isomeric rosin acids cannot form p e r se Diels-Alder adducts, they can,
    ROSIN 301

    Rosin J)
    Abiotio
    acid
    Heat
    Acid I=
    HOOC
    ~ CH3
    CH (CH3)t
    Maloi¢-anhy drido
    Oiels-Alder reaction •

    Levopimaric acid
    CHCO\
    CHtCH3)= I o
    CHCO/
    HOOC CH3
    rosin-moleic anhydride odduct (RHA)

    FIG. 2. Synthesis o f rosin-maleic anhydride adduct ( R M A ) .

    however, isomerize to levopimaric acid on heating, preferably in the presence of


    a strong acid, and can subsequently react with maleic anhydride (Fig. 2).

    2. R O S I N S AS P O L Y M E R CHEMICALS

    Rosin and its derivatives have been extensively used in various applications
    within the chemical industry. In almost all of these applications, rosin and its
    derivatives are used as industrial chemicals to modify the properties of existing
    formulations or to bring forth altogether new performance characteristics of the
    products. Rosin and rosin derivatives are widely used in paints, varnish and
    coatings, ink formulations, adhesives, etc.

    2. !. Rosin in paint, varnish and coatings


    The application of rosin derivatives in paint, varnish and coatings had begun
    before 1960 in an effort to improve the properties and performance of these
    materials. ~2-t6 Research has been carried out on rosin as a potentially cheap
    source of ingredients for paints, varnishes, etc. during the last twenty-five years.
    In rosin-modified alkyd resins, generally rosin is used as a part of the mono-
    basic acid ingredient. The presence of rosin or rosin derivatives in the polymer
    imparts better brushing, faster drying, better gloss and gloss retention, greater
    hardness, and better adhesion. It is also used as a substitute for phthalic
    anhydride to reduce cost. Uses of rosin derivatives in surface coatings have been
    reviewed earlier, t7'~8
    The adhesive strength of a sound-deadening paint containing polyisobutyl-
    ene, polyethylene, polyvinyl acetate, natural rubber, etc. was found to increase
    ten times when rosin along with starch was added to it. t9 The water resistance
    and drying time of enamels prepared from water soluble alkyd resin, linoleic acid
    and TMA, etc. were improved by the addition of Pentalyn 255 (a rosin-maleic
    acid-pentaerythritol resinS°). The drying time of a paint for printed circuit
    boards was decreased, and the solublity of the film in alkali was increased, by
    the addition of an alkyd resin modified with linseed oil, rosin and maleic
    302 S. MAITi et al.

    anhydride.2! Formaldehyde-modified rosin and hydroxymethylated rosin were


    heated at 270 ° C with zinc oxide to obtain a Zn-salt which was used to prepare
    an anticorrosive paint with good resistance to H2SO4 and H:S gas, for fertilizer
    plants. 22 Rosin or rosin esters have been used in the manufacture of conductive
    paints. 23A paint having hardness and gloss values similar to those of alkyd resin
    was reported to contain a rosin derivative which was prepared by heating
    rapeseed oil, rosin and maleic anhydride at 200°C, then treating the product
    with polyester fiber at 260°C and finally esterifying with pentaerythritol.24

    2.1.1. Antifouling paint formulations - Rosin and rosin derivatives are import-
    ant chemicals in antifouling paint formulations. They may be used either as the
    vehicle or as the antifouling agent. Maleated rosin bis(tributyltin) oxide was
    reported to be used in antifouling paint formulations used for fishing nets. ~5A
    marine antifouling paint for ship bottoms contains a reaction product of rosin
    and hydrazine as the toxicant.26 Triphenyltin rosinate, obtained by reacting
    triphenyltin hydroxide and rosin, was also used as an antifouling agent. 27 An
    antifouling paint with good resistance to the erosive effects of water motion was
    reported to contain a chlorinated rubber-rosin matrix, Cu20 and ZnO toxicant
    mixtures, CaCO3 extenders, etc. 28 Acoustically transparent, camouflage anti-
    fouling paints for coating rubber substrates without adversely affecting their
    chemical stability or sound absorbing characteristics, have been prepared from
    polyisobutylene rubber, rosin, Bu3SnF and pigment. 29A paint with a completely
    seawater soluble film forming base and a long service life has been reported to
    contain a resin ester prepared from rosin and a hydroxy acid such as salicylic
    acid as the binder. 3° Good performance was observed for antifouling paints
    based on rosin-chlorinated rubber mixtures plasticized with tricresyl phosphate
    containing Cu20 and a small amount of ZnO as toxicants.3~ Cu20, ZnO,
    CaCO3, chlorinated rubber, rosin, chlorinated paraffin etc. were mixed to
    formulate an antifouling paint with good performance. 32

    2.1.2. Traffic paint - A hot-melt traffic paint giving films resistant to abrasion,
    impact and weather, was prepared from maleic acid modified rosin ester resin,
    sunflower oil modified alkyd resin, talc, TiO2, glass fiber, etc. 33 Rosin or modi-
    fied rosin was blended with the reaction product of an ethylenically unsaturated
    carboxylic acid or derivative with a resin made by copolymerizing a linear
    conjugated diene with styrene, to obtain a pavement marking composition with
    improved compressive strength at low temperature, a4 Maleated rosin, alkyd
    plasticizer, MgO, TiO2, and glass beads were mixed to prepare a road marking
    composition with good compressive strength, abrasion, weather and chemical
    resistance. 35Water thinnable traffic marking paints were prepared from maleated
    rosin, drying oil, NH3, shellac, etc. and were reported to have better performance
    than commercial brands. 36A reaction product of a cyciopentadiene derivative,
    rosin and a fatty acid was esterified with an alcohol. This ester was used as the
    ROSIN 303

    main ingredient in a hot-melt traffic marking composition forming a pinhole


    free coating with excellent crack resistance. 37
    A varnish containing rosin, cyclohexanone-formaldehyde resin, polyvinyl
    butyral, polyethylsiloxane, etc. was reportedfl In a thermoplastic varnish compo-
    sition, modified rosin was used. 39 Electrically insulating varnishes4° containing
    rosin modified phenolic resins, and an electrically conductive varnish4t contain-
    ing rosin were reported. An air drying varnish suitable as an anticorrosive
    primer for construction and metallic equipment was formulated from rosin,
    phenol-formaldehyde resin and esters. 42 A modified alkyd resin prepared by
    reacting rosin, phthalic anhydride, a phenolic resole and partial esters of linseed
    oil fatty acids with glycerol and pentaerythritol was used to manufacture drying
    varnishes resistant to water and alkali solutions.43
    The properties ofoil based paints were improved by using wood rosin modified
    with maleic anhydride and formaldehyde, and rosin polymers (a by-product from
    the distillation of flotation oils in the manufacture of wood rosin). 44Coating com-
    positions containing castor oil and rosin were reported to have good adhesion,
    gloss and scratch resistance. 45Scale formation during the polymerization of vinyl
    chloride was prevented by coating the reactor with modified rosin.~'47 The shock
    resistance of a coating has been increased by adding industrial oil, rosin and
    fatty acid to a coating composition containing rubber latex, vulcanizing agent,
    etc. 48 Reaction products of rosin with ethylene terephthalate oligomers or fatty
    acids were used as components of a protective and decorative coating with high
    hardness and strength?9 A polymeric product is expected to be formed after
    curing. Rubber, phenol-formaldehyde oligomers, dimerized rosin, etc. were
    mixed to prepare a sprayable undercoating composition for automobiles?° Uses
    of rosin modified phenolic resins in oil based coatings were recently discussed? I .
    Radiation curable colored coating compositions for metals contained Hari-
    mac 135 G (a rosin-modified maleic acid resin). 52 Reaction products of rosin
    with ~t,fl-unsaturated dicarboxylic acids or anhydrides were esterified with a
    compound having hydroxyl groups and radically polymerizable unsaturated
    groups to prepare a component for photocurable coatings.53
    Polyfunctional compounds synthesized by the reaction of maleic anhydride
    with renewable raw materials like cashew nut shell liquid, rosin, sunflower oil, etc.
    can be used in water-borne coatings, s4 Polyurethanes have been combined with
    polyol esters of rosin acids to prepare water thinned coating compositions,s5
    Another water thinned composition forming a coating with excellent water and
    blister resistance was found to contain an epoxy resin and a rosin-modified
    maleated linseed oil varnish, s6 Blends of chlorinated polypropylene and the
    glycerol ester of rosin acids were mixed with water to form storage stable
    dispersions useful as coatings and adhesives. 57A reaction product of castor oil,
    rosin, glycerol, maleic anhydride, phthalic anhydride and propylene glycol,
    along with triethanolamine and water, was used to manufacture an electro-
    phoretic coating for metalsfl
    304 S. MAITI et al.

    2.2. Rosin in printing ink formulations


    Applications of rosin and rosin derivatives in printing inks were previously
    reviewed in 198017 and 1983J s Some recent information is now given here. An
    electron beam curable offset printing ink containing rosin esters and acrylic
    monomers has been reported. 59 It was claimed that resistance of the print to
    water and acid has been increased by using a pentaerythritol ester of fumarated
    rosin with a molecular weight of 1100-1400 along with an organic amine. 6° A
    reaction product of rosin with 2-alkenoic acid derivatives was treated with
    calcium-compounds and then used as binder in inks useful in intaglio printing. 61
    Carbon black, aromatic oil, phenol-formaldehyde resin, modified rosin, etc.
    were used in a printing ink formulation for rotary presses. 62Vehicles for printing
    inks for plastics have been prepared from polyamide-rosin esters and nitro-
    cotton. 63 Rosin and an acrylic isocyanate were used to prepare a photocuring
    resin for printing inks. u A dispersant prepared by condensing polyethylenimine
    with esters of hydroxystearic acid and rosin was used in oil-based printing inks. 65
    Phenolic resins modified by rosin and esterified with pentaerythritol, and penta-
    erythritol esters of maleated rosin, were used as components for inks with
    increased smearing resistance, abrasion resistance, gloss and sharpness. 66 A
    lithographic ink with excellent physical properties contained a phenolic resin
    modified by rosin and polyhydroxy compounds. 67

    2.3. Rosin in adhesive formulations


    Rosin has been widely used in various adhesive formulations. In a recent
    review such applications of rosin in adhesive formulations have been discussed. 6s
    Some current information is reported here.
    Electroconductive hot-melt adhesives were reported to contain thermoplastic
    resin and/or wax, silver, nickel and rosin. 69 Glycerol esters of hydrogenated
    rosin acids, ethylene vinyl acetate copolymer and fluorinated surfactants were
    used as components of a foamed hot-melt adhesive useful for rough substrates. 7°
    A transparent hot-melt adhesive was reported to contain ethylene-vinyl acetate
    copolymer, a rosin ester and wax. 7~
    An adhesive for bonding foamed polystyrene or poly(vinyl chloride) to
    various substrates contained styrene-butadiene rubber, rosin, etc. 72An adhesive
    for an exfoliatable film for protecting metal surfaces was prepared from ethylene-
    vinyl acetate copolymer, ester gum H (glycerol ester of hydrogenated rosin
    acids) and modifed polypropylene.73 Reaction products of rosin and phenol,
    neoprene, ammonia etc. were used to prepare an adhesive with excellent bond-
    ing strength for metal to cotton cloth. 74A vulcanizable composition with good
    adhesion to brass contained natural rubber, a nickel salt and Vinsol (Na
    rosinate). 75
    A heat sensitive adhesive polymer dispersion - which becomes a good
    pressure sensitive adhesive upon heating briefly above its minimum film forming
    ROSIN 305

    temperature - has been manufactured from butyl methacrylate-N,N-dimethyl-


    aminoethyl methacrylate-lauryl methacrylate copolymer, a glycerol ester of
    rosin acids, ethylene-vinyl acetate copolymer, etc. 76A blend of an alkyl acrylate-
    acrylic acid copolymer with rosin or rosin derivatives was used in the prepar-
    ation of a water dispersible pressure sensitive adhesive. This adhesive was useful
    for repulpable splicing tapes which are used to splice carbonless paper without
    deactivating its color generating system. 77Polypale (a rosin-type resin) was used
    as a radiation curable tackifier in a radiation curable pressure sensitive
    adhesive. 78
    Certain adhesives used in making adhesive paper contained a rosin ester 79 or
    a natural rubber-rosin ester mixture, s° Pentaerythritol esters of rosin and par-
    tially polymerized rosin were used to formulate tackifiers for adhesivesfl
    Properties and uses of rosin acid derivatives as tackifying resins have been
    discussed earlier. 82

    2.4. Miscellaneous uses of rosin and rosin derivatives


    It has been reported that the addition of polyol esters of rosin acids to an
    ethylene-alkyl acrylate copolymer gave films having a lower heat sealing tem-
    perature, s3 A mixture of Penseru A (pentaerythritol ester of rosin acids) and CI
    Pigment Violet 19 was coated on an aluminium-laminated film support to
    obtain an electrophotographic film.u Pressure sensitive copying desensitizer
    compositions were reported to contain the reaction product of rosin with an
    alkylene oxides5 or a polyaikylene glycol86 as one of the components. Synthetic
    amber was prepared by curing a mixture of rosin, an unsaturated polyester
    containing a curing agent, and the reaction product of succinic acid and nitric
    acid) 7 An electrophotographic photoreceptor with high sensitivity to white light
    was prepared by treating the surface of the selenium-containing photosensitive
    layer with an isoparaffinic solution containing a rosin-modified maleic acid
    polymer, a rosin-modified polyester and an acrylic polymer, a8
    Rosin amides were reported to behave as multifunctional ingredients in
    rubber compounds. 89Incorporation of these amides facilitated the dispersion of
    filler, minimized mill sticking and improved the plasticization, flow properties
    and moldability of the compounds. Dewaxed and hydrorefined petroleum
    distillation residues were mixed with rosin and/or polyolefins to give an impreg-
    nating composition for the paper insulation of electric cables. 9°

    3. R O S I N S AS P O L Y M E R FEEDSTOCKS

    Rosin acids are monocarboxylic acids based on alkylated hydrophenanthrene


    nuclei. They have two reactive sites - one being the carboxylic acid group and
    the other being the latent conjugated unsaturation centre. These reactive sites
    can be used for further modification of the rosin molecule to convert it to a
    306 S. MALT! et aL

    monomer or various suitable intermediates to be used for the synthesis of


    polymers.
    Various types of polymers from rosin have been reported in the literature.
    Most of the information regarding rosin polymers is found in the patent
    literature. Copolymers have been prepared from rosin or rosin derivatives with
    vinyl monomers. Copolyimides, polyurethanes, and epoxy resins from rosin
    have also been reported. Rosin has also been polymerized or dimerized using its
    reactive sites. The reports available in literature on these different types of rosin
    based polymers are discussed below.

    3.1. Polymerization of rosin


    Rosin has been polymerized most commonly by the use of acidic catalysts.
    In most cases the available information regarding the polymerization process
    and particularly the structure and characteristics of the polymers is incomplete
    or sketchy. Only some information on the properties of the final product is
    available.
    Sulfuric acid was used to catalyze the polymerization of rosin dissolved in an
    organic solvent.9j This process was claimed to produce a product with kinematic
    viscosity 35-40 mm2/s in 92% yield (the kinematic viscosity of the rosin solution
    was 17-18mm-'/sec initially). 9-" A continuous method of polymerization was
    reported which used sulfuric acid as catalyst and acetic acid as solvent at 70°C.93
    Polymerization in the same solvent and by the same catalyst at room tem-
    perature produced a high yield of dimer.94 Dimerization of rosin in high yield
    in the presence of concentrated sulfuric acid, and conditions affecting dimeriz-
    ation, were also reported. 95
    Rosin was polymerized at 35°C in the presence of 85% sulfuric acid as
    catalyst in benzene or gasoline to give a polymer having a softening point of
    85°C. Besides sulfuric acid, zinc chloride, boron trifluoride and boric acid have
    also been reported as polymerization catalysts. They require higher tem-
    peratures for polymerization, but are easier to dispose of after use than sulfuric
    acid.96The origin, chemical characteristics and polymerization of rosin and its
    derivatives were reviewed in 1964 by Morillon.97 Morillon also reported the
    polymerization of methyl abietate in the presence of boron trifluoride as cata-
    lyst. One of the isolated products was identified as a dimer by its IR spectrum. 97
    Metal halides were also used as catalysts in the polymerization of rosin. Rosin
    was polymerized in the presence of stannic chloride or titanium tetrachloride.98
    Hydrofluoric acid could also be used. The softening point, melting point and
    molecular weight of the final product were 92°C, 127°C and 400 while those of
    the initial rosin were 54°C, 105°C and 300 respectively. The molecular weight of
    the final product indicated that it was not even a dimer. 98 Rosin, on polymeriz-
    ation in the presence of halides of aluminium, titanium, iron, cobalt, zinc, tin,
    antimony and mercury along with mineral acids or strong organic acids, gave a
    ROSIN 307

    polymer with 35% dimer content and a softening point of 124°C, useful for
    paints, inks, construction materials, adhesives, paper additives, etc. 99
    Titanium tetrachloride ~°°and aluminium chloride '°~ were used to polymerize
    rosin in organic solvents. In the case of the former catalyst, '°° the molecular
    weight of the product was found to be only 364. Rosin having a molecular
    weight of 317 and a softening point of 71 °C was polymerized in the presence of
    40% stannic chloride ~°2 at 59°C in ligroin to yield a product with a molecular
    weight of 1319. When the reaction was carried out in benzene at 80°C, the
    molecular weight of the product was found to be 1346, indicating that the
    product was a tetramer or pentamer) °2
    Rosin polymerization in an organic solvent in the presence of a catalyst at
    20-100°C was reported. '°3 Melt polymerization of rosin at 220°C in the presence
    of an aluminosilicate catalyst was also reported.~°4 Rosin, on heating in an inert
    atmosphere in the presence of methanesulfonic acid or a trihalomethanesulfonic
    acid as the catalyst at 60-180°C, polymedzed to a product having a softening
    point of 85°C and a viscosity of 285 MPas) °5 It was reported that rosin, on
    heating at 60-180°C for 4-6 hr in an inert solvent in the presence of an insoluble
    polymer having pendant sulfonic acid groups, gave 31.9% dimer with a soften-
    ing point of 91°C. t°6
    The double bond of the rosin molecule is sterically hindered. Since it
    is difficult to use this unsaturation for polymerization, the molecular weight of
    the product formed is generally very low. This fact is reflected in the literature
    reports on rosin 'polymers'; in most of the cases the products are less than a
    dimer except in one case in which the product was reported to be a tetramer or
    pentamer.~°2

    3.2. Copolymerization of rosin and rosin derivatives


    Copolymers have been synthesized using rosin or rosin derivatives as
    comonomers. Though the structure of the polymers was not reported, it is
    expected that the double bond of rosin or its derivatives took part in the
    copolymerization with vinyl monomers. Copolymerization of ethylene with
    esters of unsaturated fatty acids such as abietic acid to form materials useful in
    agricultural products was claimed.~°7 This copolymerization reaction, although
    reported, is somewhat doubtful because rosin is a solid containing a sterically
    hindered double bond which would be expected to have low tendency to
    copolymerize with ethylene. Rosin acids were copolymerized with terpenes from
    turpentine oil with hydrofluoric acid as catalyst. The softening point and
    melting point of the polymer were found to be higher than those of unmodified
    rosin.~°7
    The use of glycerol, acrylic acid-colophony condensate and bis(3-amino-
    propyl)amine-acrylic acid-colophony condensate in synthetic resins was
    reported. ~°8 Two different routes could be suggested for the above polymer
    308 S. MAITI et aL

    synthesis as shown in Fig. 3. It is difficult to determine which of the two routes


    shown was actually followed, although routes 2 and 2' (Fig. 3) are more
    favorable.
    Marvel and coworkers reported the polymerization and copolymerization of
    a vinyl ester of perhydrogenated rosin. Since the polymerization involved the
    vinyl group a somewhat higher molecular weight polymer having an inherent
    viscosity of 0.16 dl/g was obtained. Copolymerization with vinyl chloride, vinyl
    acetate or butadiene resulted in a copolymer having 90% vinyl chloride and
    10% rosin ester, 80% vinyl acetate and 20% rosin ester or 39% butadiene and
    61% rosin ester units in the copolymer chain. Inherent viscosity values for the
    above copolymers were 0.68, 2.23 and 0.52dl/g, respectively. However, the
    inherent viscosity of the copolymer decreased with an increase in the ratio of rosin
    ester to vinyl monomer in the feed. The authors also terpolymerized rosin ester
    with styrene and acrylonitrile. The tercopolymer contained 10.8% rosin ester,
    61.2% styrene and 28% acrylonitrile. It had an inherent viscosity of 5.44dl/g.
    With increase in the concentration of rosin ester in the monomer feed, the
    inherent viscosity of the tercopolymer decreased. This indicates that the polymer-
    ization of rosin ester is hindered by the bulky rosin moiety. Such polymers could
    be crosslinked with peroxides. The proposed reaction scheme is shown in Fig. 4.
    A rosin copolymer was prepared by reacting rosin with a polyol and then with
    an g,fl-unsaturated dicarboxylic acid or anhydride to form a half acid ester
    mixture. The mixture was treated with a vinyl monomer to form the product.
    A probable reaction scheme is shown in Fig. 5. Here, also, the polymerization
    proceeds through the vinyl double bond rather than through the unsaturation
    of the diene group present in the rosin molecule.
    Diels-Alder adducts of rosin with maleic anhydride or fumaric acid were
    copolymerized with styrene in the presence of peroxide initiators using hydro-
    carbons, esters or ketones as solvents at 150-300°C and 0-50 atm. n~00ligomers
    obtained by reacting maleated rosins with vinyl monomers containing hydroxyl
    groups were mixed with vinyl monomers containing acryloyl or methacryloyl
    groups to give crosslinkable coating compositions which could be hardened. I"
    The problem of steric hindrance was also observed here. When the concen-
    tration of rosin derivative was increased, the molecular weight of the product
    was found to decrease. Most of the rosin residues were found as pendent groups
    attached to the polymer chain.

    3.3. Alkyd resins


    The carboxyl group of rosin may react with alcohols to form alkyd resins.
    Since rosin has only one carboxyl group, it must either be modified to form a
    difunctional molecule or else mixed with a diacid in the reaction medium with
    a polyol in order to undergo this type of polymerization. In the second case the
    I CH2=CH CH2 = CH! CH2=CH
    C + c + C o,H 7
    0 0 0
    ~-c.2- cp-c.2-c~ -- c.2-c~ 0 0 0 HOO"CH2-CH-CHz'O~N
    -
    ~"2- cl" c~2 c"2-c.-c'.2
    OOCR O0cROOCR
    I oc
    ~ ~ ~.(c.~21
    CH2-CH-CH
    ?2' CH~-CH-|
    ~ I ?
    CH~ n l
    OOCR OOCROOCR

    c.2.c._c..~I I z[ H,.2- c,. - :,.2


    OH OH OH i OH OH OH

    [~c.(c.~2 c,"2 --'~ CH( CH3)21 COOH


    2
    CH~CH O
    CH - COOH
    ~ HOOC HH3 HOOC CH3 Z
    .~'-(c.2)~-."
    (C H2)3- NH-OCR
    CH2= HH 1 NH [(CHz)5 NHz] z 2"1 NH [(CHz)3 NHz]z
    I
    H
    0
    PIN - (CH2)~N

    I IocC~H~ " HC
    ( CH3 ) 2[CONH(CHz)3 NH(CH2)3NH
    (CH2)3-NH -OCR

    R = Rosin Moiety

    FIG. 3. Reaction scheme for synthesis of copolymers from rosin.


    310 S. MAITI et al.

    CH2-- CH c.2-
    ( ~ - OC-- R OOCRJF1
    Vinyl ester of perhydrogenoted Homopolymer
    Rosin
    R = Rosin moiety

    CH2= CH 4" CH 2 = CH
    I
    O-OC-R I~ I
    oocR .In
    RI
    RI---A¢ / C L
    Copolymer

    CH2"CH *'t" CH2--- CH .~ CH 2 -_ CH

    O-OC-R CN

    -- C H 2 - - C H - - CH 2 -- CH - - CH2 ~ CH Cat
    Crosslinked polymer
    O-OC-R CN

    Terpolymer

    Fit;. 4. Copolymersfrom rosin esters.

    rosin molecule will be present either as an endgroup or as a pendent group on


    the main chain.
    Alkyd resins useful for coating compositions were prepared by esterifying the
    adduct of a rosin acid and an ~,fl-unsaturated polycarboxylic acid with a poly-
    hydric alcohol) '2'1'3 Another alkyd resin was prepared by reacting a plant oil
    with an acrylic acid or maleic anhydride adduct of rosin followed by esterifi-
    cation with an alcoholJ ~4 An oil-free alkyd resin was prepared ~'5 by adding
    acrylopimaric acid and a rosin acid to a reaction product of a polyol, maleic
    anhydride and aliphatic acids (Fig. 6).

    3.4. Polyurethanes
    Rosin can be converted to hydroxy terminated compounds which can then be
    reacted with diisocyanates to obtain polyurethanes. A polyurethane was
    prepared by reacting a polyisocyanate with a polyester having a viscosity of
    5,000-10,000 M Pa at 25°C in the presence of a blowing agent. The polyester was
    obtained by the reaction of tall oil containing 15-35% (by weight) rosin acids
    with a polyhydric alcohol. '~6 The reaction product of rosin with ethylene or
    propylene oxide was used tIT in the manufacture of polyurethane foam.
    Hydroxymethylated derivatives of rosin acids, tolylene diisocyanate and a
    polyol were reacted to obtain a polyurethane elastomer)~8 Polyols obtained by
    reacting rosin acids with formaldehyde and alkoxylating the hydroxymethylated
    ROSIN 311

    R-COOH + R'-{OH) n R- COOR-IOH )n_~

    R-COOH -I- RL (OH)n = R- COOR"- (OH) n-i


    Rosin Po[yol or
    (R - CO0 )2 - R'-- (OH) n -2
    etc.
    (CH3)t
    ~H~ cH
    R=

    n>l
    OOC-CH
    R-COOR'-(OHIn_4 -I- CH- COOH . R- COOR'< ~HCOOH
    CH- COOH (OHln_ 2
    or
    .(OOC CH= CH COOH)2
    R-COOR~(OHln_ 3
    etc.
    R-COOR%00C CH =CH COOH + CH2=CH
    I I
    (OH)n-2 X
    Vinyl monomer

    c°t" 1
    -•CH 2 -CH - ~
    X
    CH - CH - } ~ - - - i -
    I
    CO0- R- O'OCR Jn
    I
    (OH)n_ 2
    Copotymer

    FIG. 5. Synthesis of rosin copolymers.

    product with an alkene oxide were mixed with conventional polyols and poly-
    isocyanates to give rigid polyurethane foams with reduced flammability.I]9 Poly-
    urethane fibres were prepared using N-(2-hydroxyethyl) maleimidopimaric acid
    salts. Then, the effects of incorporation of these compounds on mechanical
    properties and oxidative thermal aging properties of polyurethanes were
    studied, t2°

    3.5. Epoxy resins


    Epoxy resins were prepared by reacting the carboxyl groups of rosin or rosin
    derivatives with epichlorohydrin. Penczek reviewed the synthesis of epoxy resins
    312 S. MAITI el al.

    HOOC
    ~ CH 3
    '-CHlCI'~)2 ] COOH

    COOH
    CH=--CH--CHt
    I
    OH
    I
    OH OH
    I

    O,v~. 0,.~,
    I I
    CO-O-CHt--CH- CH =
    , i ~ "CH [CH3)t ]
    CO-O- CHt--CH -- CHz--O
    0,,,~
    ,vv,v, O-OC CH=

    FIG. 6. Alkyd resin from rosin.

    from rosin derivatives/2'


    /o\ / O\
    R-COOH + CICH2. CH. CH 2 -o R-COO-CH2CH. CH2
    Epichlorohydrin and the glycidyl ester of rosin were polymerized in the
    presence of a catalyst. ~22''23Rosin maleic anhydride adduct was reported to be
    used as a curing agent for epoxy resin. '24 Poly(propylene glycol) or polyoxy-
    propylene diamine was heated with rosin and maleic anhydride at 300°C to
    obtain an abietic acid-levopimaric acid-maleic anhydride-polypropylene glycol/
    polyoxypropylenediamine copolymer containing terminal anhydride groups for
    use as a plasticizer and crosslinking agent for epoxy resin. Mixtures of the epoxy
    resin and this curing agent were cured at 100-200°C to a solid material. '25 Rosin
    was refluxed with acetic anhydride to give an anhydride of rosin acids. This
    anhydride in turn was reacted with maleic anhydride to form an acid anhydride
    (softening point 102°C) that yielded a thermosetting composition when mixed
    with a low molecular weight bisphenol A type epoxy resin and N,N-dimethyl-
    benzylamine.~26 The same acid anhydride, when treated with an additional
    amount of maleic anhydride, produced a more reactive hardener for epoxy
    resin. 127
    Polymers with good heat and chemical resistance were prepared by first
    esterifying epoxy resins prepared from maleopimaric acid and epichlorohydrin
    with acrylic or methacrylic acid and then crosslinking with styrene. ~2s Maleic
    anhydride modified rosin has been treated with potassium hydroxide and epi-
    chlorohydrin to give an epoxy resin which could be hardened with acid anhy-
    drides. 129 Rosin was reacted with the reaction product of bisphenol A and
    epichlorohydrin at 200-300°C for 5 hr to obtain a modified epoxy resin (soften-
    ing point 114°C).m3°
    ROSIN 313

    Epoxy resins were also prepared from epichlorohydrin and a reaction product
    of rosin with maleic anhydride, 13~'~32acrylic acid) 33'~34or methacrylic acid. 134
    Methyl epichlorohydrin has also been used in place of epichlorohydrin) 34 Some
    of these resins were cured by anhydrides to yield products having good process-
    ability at 80-90°C and physical-mechanical properties similar to those of com-
    mercial epoxy resins. 13~'t33 Epichlorohydrin-maleopimaric acid copolymers of
    molecular weight 675 + 20 and 1080 + 80 respectively were synthesized and cross-
    linked, and their dielectric and physical-mechanical properties were reported.~35
    Unsaturated polyesters with increased heat and chemical resistance were
    prepared by polymerizing maleic anhydride with propylene glycol in the
    presence of the reaction product of diglycidyl acrylopimarate with methacrylic
    acid.t36 Glycidyl esters of saturated, branched chain C9_. acids were reacted with
    an adduct of pine rosin and maleic anhydride at 200°C to give polyester resins.137
    Glycidyl esters of rosin acids were polymerized in the presence of cationic
    catalysts to give film forming polyesters with increased elasticityJ 3s A nonflam-
    mable polyester resin capable of being crosslinked and having a high molecular
    weight was prepared by reacting epoxy resin with chlorinated rosin in the
    presence of carbon dioxide. The final product (melting point 85-120°C) was
    reported to be useful in coating formulations) 39 Novel rosin polyesters have
    been prepared by treating a dicarboxylic acid or its anhydride with rosin glycidyl
    esters. The product has a M. 4266, .~,/.~r,, 1.63, and glass transition tem-
    perature 82°C. This patent also reported that glycidyl esters of gum rosin and
    hydrogenated rosin had been polymerized) 4° A reaction scheme for the syn-
    thesis of epoxy resins from rosin is shown in Fig. 7.

    3.6. Polyesters
    For one to prepare polyesters from rosin, the rosin needs to be converted to
    a dicarboxylic acid by reaction with suitable reactants before polyesterification.
    A method of converting rosin to a dicarboxylic acid is to react it with/~-propiol-
    actone. The dicarboxylic acid thus obtained was reacted with diethylene glycol
    to form a polyester) 4t (Fig. 8). In a subsequent patent, these authors have used
    the rosin polyester resin thus prepared in hot-melt adhesive compositions) 42 It
    was further reported that gum rosin could also be modified with acrylic acid
    instead of the carcinogenic /~-propiolactone) 42 The polyester resin prepared
    from rosin, /~-propiolactone and diethylene glycol was further modified with
    fumaric acid or maleic anhydride and mixed with styrene. The mixture was

    CHtGH.~I= CH~GH (CH3}z

    COOHI~ I ~ COOH
    HOOC CH3 HOOC CH3
    314 S.MAITIet al.
    R

    H3C CO-O-OC
    HOOC CH3
    Rosin I c.-co, II o
    c H- COs
    o

    "o
    HOOC CH 3 H3C CO-O-OC " "CH 3

    RMA

    LPOXYRESIN I I EPOXYRESll
    = Polymer

    CL-CH2-CH-CH 2 CL-CH2-CH- C H 2
    \/ \ /
    0 o
    + +
    .,-co-o- c.2-c.-c.2 RMA
    o
    glycidyl e s t e r of rosin R=-CH (CH3) 2
    R i = Rosin moiety

    FIG.7. Synthesis of epoxy resin from rosin.


    polymerized with or without glass fibre webbing to form laminated products. 143
    The preparation of propiolactone-modified rosin-based polyesters was also
    reported.l"
    It has been reported that a Diels-Alder reaction was carried out between an
    unsaturated polyester and a glycerol ester of rosin acids to obtain a new
    polyester with good chemical resistance.145"J~ However, the Diels-Alder reaction
    between the double bonds of the bulky rosin molecule and the maleic- or
    fumaric-type unsaturation of a polyester is difficult and, therefore, most of the
    ROSIN 315

    m~

    HOOC CH
    "-cH|CH3)tCHt-CHt - c
    I o J
    HOOC CH
    ~ CH lC~) t
    ~ COOH

    HO(CHzCHt)zOH
    ..}-coo-,c,, ot
    tOG CH~3 CH(CH3It ..mR

    FIG. 8. Synthesisof polyestersfrom propiolactoneand rosin.

    rosin molecules will be present as pendent groups on the main chain. Polyester-
    based water-resistant coating compositions which hardened at room tempera-
    ture were prepared by dissolving a maleopimaric acid-monoallyl glycerol
    ether-allyl glycidyl ether-diethylene glycol-sebacic acid copolymer in an
    isopropanol-isobutanol mixture. The copolymer was prepared by refluxing
    maleopimaric acid with the other constituents at 230°C with continuous removal
    of reaction water, t47 Colored polyesters were recently prepared by reacting
    RTS-12 (pentaerythritol-esterified maleated rosin) with azo or anthraquinone
    disperse dyes. t4s Copolyesters useful for coatings resistant to abrasion, water,
    alkali, acid and solvents were prepared by esterifying glycerol simultaneously
    with rosin and poly(bisphenol A maleate) or poly(bisphenol A phthalate). 149
    Dimethyl terephthalate, glycerol and zinc acetate were heated for 3 hr at 210°C,
    and then rosin was added and the mixture was again heated at 275°C for 3 hr
    to obtain a modified polyester resin having a softening point of 113°C. ~5°In the
    last two cases, rosin, being a monocarboxylic acid, will act as a chain terminat-
    ing agent.
    One well-known method of polyester synthesis from rosin is to react rosin
    with unsaturated acids like acrylic acid or fumaric acid (Diels-Alder reaction)
    followed by polyesterification with a diol. This type of polymer has a softening
    point in the range of 60-100°C and is used as a hot-melt coating material for
    road marking, t53 A polyester prepared by reacting fumaric acid-modified rosin
    with a polyol at 220°C (softening point = 147.5°C, .O', = 1,200) was further
    modified by dehydration followed by reaction with tolylene diisocyanate and
    neutralization with aminoethanol to give a copolymer which was used in print-
    ing ink. t54 A polyester resin was also prepared by reacting a rosin-polyhydric
    alcohol melt with dicarboxylic acids or their anhydrides. '55
    A new polyester was prepared from a rosin-acrylic acid adduct and hexa-
    nediol, t56'~57Rosin was first reacted with acrylic acid in the presence of hydro-
    quinone at or above 150°C for 5 hr. The finely powdered white product (yield
    68%, m.p. 220°C) was refluxed with thionyl chloride for 10 hr to yield a diacid
    316 S. MAITI et al.

    CC C ~ H 3 cH(CH3]2Grit =ell

    HO0
    I
    COOH ~ CHICH3}= ] COOH

    HOOC CH3 I SOCtt

    1 HO(CH=)6
    OH C tH3/~CH {CH312[

    foe COG[

    FIG. 9. Synthesis of a polyester from rosin-acrylic acid adduct.

    chloride (yield 90%, m.p. 150°C). The diacid chloride was reacted with hexa-
    nediol in D M F : N M P (3:1) solution containing 4% LiC1, first at ambient
    temperature and then at higher temperature (100°C), to obtain the polyester;
    yield 71%, inherent viscosity 0.28dl/g (Fig. 9).

    3.7. Polyamides
    Polymers for printing ink were prepared by reacting fumaric acid-modified
    rosin with urea or with a diamine) 5~ Rosin-maleic anhydride adduct was also
    reacted with urea to obtain a polymeric product) 58 Polyamides were probably
    obtained in those cases. A polyamide was also prepared by reacting a diamine
    or amine alcohol with dimerized or more highly polymerized natural rosin) 59
    An amber colored polyamide was prepared by heating at 140-225°C a mix-
    ture of rosin-maleic anhydride adduct, polymeric fatty acid, tall oil fatty acid,
    adipic acid and bis(hexamethylene) triamine. This polyamide was used as a
    binder for quick drying water resistant printing inks. 16° A water soluble poly-
    amide was prepared by reacting polymerized fatty acids, maleated rosin, and
    aromatic or aliphatic diamines for 2 hr at 200°C/50 mm. The softening point of
    the polyamide was about 129°C) 6~
    Maiti and coworkers have investigated the synthesis of various polymers
    using maleopimaric acid (RMA) or similar Diels-Alder adducts as the starting
    material. One of the polymers, a polyamide, was synthesized from the acid
    chloride of rosin-acrylic acid adduct and hexamethylene diamine in 76% yield.
    It had an inherent viscosity of 0.30dl/g '56''57 (Fig. 10).

    3.8. Polyesterimides
    Polyesterimides are an important class of engineering plastics due to factors
    such as good processability, generally high glass transition temperature, solubility
    in common solvents, relatively low cost, and good thermal and outdoor stability.
    ROSIN 317

    1 COOH SOCtz ,~
    I
    cocl
    _

    HOOC CI.I~ CtOC CH3


    HtN-(CH~-NI"~

    tOC
    ~ CH~
    "CH {CH3)z ] CONH--{CHt),--NH~

    -an
    -HCI

    Polyomide

    FIG. 10. Synthesis of a polyamide from rosin-acrylic acid adduct.

    Polyesterimides from rosin have been studied by Penczek and c o w o r k e r s 162 a s


    well as by Maiti et al. 2.4,5a63.~64
    Penczek and coworkers reported the preparation of polyesterimides from
    maleopimaric acid. Maleopimaric acid was reacted with an aminoalcohol
    to form maleimidopimaric acid. Polyesterimides were synthesized by poly-
    condensation of maleimidopimaric acid with glycols, glycerol, dimethyl
    terephthalate, polyethylene terephthalate, trimethylolethane or trimethylol-
    propane. A polymer (mol. wt. 2,000) was thus prepared using zinc acetate as
    catalyst. ~62
    Maiti et al. prepared polyesterimides by different routes. In the one-step
    method2'5'~64rosin-maleic anhydride adduct (RMA) was reacted with a diamine
    in 2 : 1 mole ratio in the presence of excess diol, with an antimony trioxide-
    cadmium acetate mixture used as the catalyst. The mixture was first heated
    gently at 120°C for 30 min and then refluxed at 200°C for 3 hr. The excess
    diol was distilled off under reduced pressure to obtain the polyesterimide
    (Fig. 11).
    In the two-step process4'5''~ RMA was first converted into rosin maleimidodi-
    carboxylic acid (RIDA) by reacting RMA with para-aminobenzoic acid (1 : 1
    mole ratio) in dimethylformamide solution for 3 hr at 150°C. RIDA was
    isolated, purified and reacted with excess diethylene glycol in the presence of a
    mixed catalyst of antimony trioxide and zinc acetate under a nitrogen atmos-
    phere. The reaction mixture was heated at 260°C for 3 hr, at 280°C for 2 hr and
    finally at 300°C for 1 hr. The final 15 min of the reaction was carried out under
    slightly reduced pressure ( ~ 93 kPa) (Fig. 12).
    In both the one-step and the two-step methods the yields and the inherent
    viscosities of the polymers are almost the same. If RIDA prepared in the
    two-step method is converted to the diacid chloride, the polymerization with the
    diol can be carried out at lower temperatures ( ~ 100°C).
    318 S. MAIT1et aL

    ~ _ CHlCH3h CHCO\
    I /0
    CHCO

    HOOC CH3 I 4" I"l,zN- R" NHt

    CHCO. _OCHC
    ~ - C H (CH~)= \
    I /N-R-N
    , ~
    I (c~)=Hc
    CHCO ~OCHC

    HOOC CH3 [ H3C COOH

    -t" HOROH

    ~_~ oc c~
    CHCO
    [
    c.co /
    N-R-N
    .OCHC

    %c.c
    (CHair HC

    CH~ CO.O.
    RPEI Jn

    POLYMER R R"
    RPEI I -CH.z--CH z - -- (CHt) s -
    RPEI 2 - CHt-CH,z-
    RPE= 3 - CHz-CI'.It- -.~)-- CHz-.,~)-
    RPEI 4 -- (Cl'lt)~,-0 - (CI"lt}z- -'~'-C H=e--~-"

    FIG. I 1. One step synthesisof polyesterimidesfrom RMA.

    3.9. Polyamideimides
    Schuller and Lawrence reported the preparation of polyamideimides from
    maleopimaric acid (RMA) derivatives. ~65-~67Maleopimaric acid, on treatment
    with thionyl chloride, was converted into maleopimaric acid chloride which was
    reacted with diamines to form bisamides. The bisamides were fused with dia-
    mines to give head-to-head and tail-to-tail linked polyamideimides.165-~67
    Treatment of one mole of monoacid chloride with excess diamine in a modi-
    fied Schotten-Baumann procedure followed by acidification with hydrochloric
    acid gave an amide amine hydrochloride salt of maleopimaric acid. This salt was
    then fused with a diamine to give a head-to-tail linked polyamideimide resin.
    Fusion of maleopimaric acid chloride with one mole of diamine gave randomly
    linked polyamideimides.~65-~67Treatment of maleopimaric acid chloride with
    methyl alcohol gave trimethylmaleopimarate, which, when fused with various
    diamines, gave polyamideimide resins t66 (Fig. 13).
    Molecular weights of the polyamideimides were reported to be in the range
    of 6,000 (inherent viscosity 0.10 dl/g for a 1% solution in dimethylformamide at
    30°C). Films and fibres have been prepared from these polymers.
    ROSIN 319

    CH.,, CH(CH.,,)'z CHCO~,


    CHCO

    + HIN-~ COOH

    CH(CH~ I _ N".~"~F COON " & CH~, CH (CH=). ~ H C O N H . . ~ COON


    CC H ~ H3 CHCO
    ~ ~
    CHCO\ HOOC
    CH~Hs CHCOOH
    HOO
    Rosin-moleimido
    dicor box ylic ocid CHCOx I
    (RIOA) [ ~ c"tc"=)' CHCO-
    I /N "~/~)-COO
    -~ ¢C')' O(C'1=O
    J,o(c,.~o tC,.~OH J
    OC' CH3
    T Polyesterimide
    (RPEI-5}

    FIG, 12. Two-stepsynthesisof polyesterimides.

    Schullcr and Lawrence also reported a synthesis of dihydromaleopimaric acid


    from dihydrofumaropimaric acid by heating under pressure at 250-325°C in the
    presence of hydrochloric acidJ 68'~69 The dihydromaleopimaric acid was con-
    verted to the acid chloride by treatment with thionyl chloride. The acid chloride
    derivative was then reacted with 4,4"-mcthylenedianiline to obtain a polyamide-
    imideJ 6s'169 Aldrich reported synthesis of a polyamideimide useful for ink
    formulations from maleopimaric acid and hexamcthylenediamineJ 7° Maleopi-
    marie acid was mixed with hexamethylcnediamine to get a salt which was heated
    to obtain the polymer.
    Maiti et al. prepared a polyamideimid¢ from the imidodicarboxylic acid
    obtained by reacting RMA with p-aminobenzoic acid. The imidodicarboxylic
    acid was converted to the diacid chloride derivative by refluxing with excess
    thionyl chloride for 15 hr. The final product was obtained by removing excess
    thionyl chloride under vacuum and recrystallizing the product from chloroform
    (yield 65-70%, m.p. 186-187°C). 3'5'6'~64The diacid was then reacted with suitable

    ¢~-------~--CHCO\ .,,,~--;-r- co0 Ck~


    CHCO CH3
    CIO 0
    I Diamine
    fusion

    Polyomideimide
    FIG. 13. Synthesis of polyamideimides.
    320 S. MAlTi et al.

    R ::
    ;“G
    +
    CHdO
    HOOC CH, II
    R = CH ICH,),

    :
    CHC,
    I COOH
    CHC’
    x
    HOOC CH,
    RMID

    I
    P

    COC’

    8
    CIOC CHS
    RMIDC

    POLYMER R’
    HN
    RPAI I H:N&
    NH2
    RPAI 2 H24

    RPAI 3 H2N-@-NH2

    RPAl 4 HzN-(CHzh-NH2

    RPAI 5 &No-CHeoNH,

    FIG. 14. Synthesis of polyamideimides via RMID.


    ROSIN 321

    14~C~CMI~ I X~O HzNI~NH'

    RMA HMDA
    O
    O II
    ~.~N-RI CH~,~/~------..-~[~ C-OH

    RIAA
    CH~ Amic acid
    R : -CH~
    CH3

    RIAA RI RIAA R~
    RIAA ! --(CHt)t-- RIAA 4 -~)--CHt-~'-
    RIAA 2 -(CHt) . - RIAA 5 "~'-50"~-'~'-
    RIAA 3, ~ RIAA 6 -Cb-cH,-C)
    -

    FIG. 15. Reaction scheme for synthesis of RIAA.

    diamines in equimolar proportion in dimethylformamide solution in the


    presence of pyridine as an acid acceptor. The reaction was carried out at room
    temperature for 3 hr and finally at 60-70°C for 5 hr. The polymer was isolated
    by precipitating in ice/water and was then purified by repeated precipitation
    from dimethylformamide solution by methanol3'5'6J64 (Fig. 14).
    In another method RMA was converted to the monoacid chloride by reflux-
    ing with thionyl chloride for 6 hr in the presence of a catalytic amount of
    dimethylformamide. The product was isolated by azeotropic distillation with
    benzene and purified by crystallization from chloroform (yield: 92%, m.p.
    170°C). '~''7'- ~73This acid chloride derivative was reacted with different diamines
    in equimolar proportion in the presence of an acid acceptor such as triethyl-
    amine, m56''TH73The reaction was carried out at 30°C for 2hr, 60°C for 2hr and
    i 35°C for 4 hr. Different solvents, mixed solvents and salt solutions were tried
    as the reaction medium. It was found that a mixed solvent of dimethyl form-
    amide and N-methyl 2-pyrrolidone ( D M F : N M P = 3 : 1) containing 4% lithium
    chloride was the best reaction m e d i u m ) 56J73
    In another method the selfopolycondensation of rosin-imidoamino acid
    (RIAA) was carried out in the presence of thionyl chloride. 'ssJTH73 RIAA was
    prepared by reacting RMA with a diamine in DMF in equimolar proportion
    (Fig. 15) at 135°C for 2.5-3.5 hr depending on the reactivity of the diamine. The
    final product was isolated by precipitating in water; yield = 86-96%.
    322 S. MAITI et al.

    0 0
    CH:~ ~0
    ~o~,N-RI-NHt

    HOOC CH~ CIOC CH'q


    -HCI l SOCIt
    1"
    ° •1
    f
    jo
    CtOC CH=

    R= --CH[CH3)=

    POLYMER RI
    pat 6 - (CHub-

    PAX 7 --(CHt)s -
    PAI 8 ,-,@-
    PAl ~ -@-c H,-@-
    PAZ to -@-so,-@-
    PAI It -O'c.='O-

    FIG. 16. Polyamideimides from RIAA.

    The polymerization of RIAA was carried out in NMP in the presence of


    thionyl chloride (with trimethylamine as the acid acceptor) at 0°C for 1 hr, 30°C
    for 2 hr, 60°C for 3 hr and finally at 100°C for 2 hr. The same polymer may be
    obtained by heating a mixture of RMA-C1 with a diamine (Fig. 16). It was
    noticed that the addition of LiCI to the reaction medium decreases the molecular
    weight of the polymers, t~J73
    In order to produce high molecular weight polyamideimides from rosin
    derivatives, RIAA was polymerized in the presence of a triphenylphosphine-
    polyhalocompound mixture as the activating agent and triethylamine or
    pyridine as the acid acceptor. ]74J75The improvement in the inherent viscosity of
    the polymer was only marginal over the thionyl chloride method; of all the
    polyhalocompounds tested, carbon tetrabromide appeared to be the best. ~75
    It appears, however, that the reactivity of the diamine used influences the
    molecular weight of the polyamideimides. Aliphatic diamines, being more
    basic than aromatic diamines, produces polymers with higher molecular
    weights.
    ROSIN 323

    3.10. Miscellaneous rosin polymers


    Intermediates for fire resistant plastics were obtained by chlorinating rosin-
    maleic anhydride adduct with sulphuryl chloride in the presence of azobisiso-
    butyronitrile, m
    Polymers have been prepared by condensing phenol-formaldehyde or xylene-
    formaldehyde resin oligomers with rosin or rosin derivatives. The methylol
    groups of the formaldehyde-based resins react with the carboxyl groups of the
    rosin to form such polymers. A heat resistant resin was prepared by heating a
    mixture of rosin and maleic anhydride with formaldehyde-xylene resin at
    2 6 0 ° C / 2 0 m m . 177 A foundry binder resin was produced by combining a phenol
    formaldehyde oligomer with an unsaturated rosin ester of glycerol or a glycol
    at 95-230°C for 0.5-5 hr.~78A transparent thermoplastic resin (molecular weight
    570-730) was manufactured by the condensation of rosin or disproportionated
    rosin with phenol and formaldehyde at 130-155°C in the presence of a mag-
    nesium oxide catalyst. '79 However, these are oligomers only.

    4. PROPERTIES OF POLYMERS
    Due to the steric effect of the bulky rosin moiety, it is difficult to prepare very
    high molecular weight polymers from rosin, and the polymers are usually
    amorphous or poorly crystalline.4'172Rosin-based polymers are generally soluble
    in aprotic polar solvents like dimethylformamide, dimethylacetamide, dimethyl
    sulfoxide, N-methyl 2-pyrrolidone, hexamethylphosphoric triamide, etc. They
    tend to be partially soluble in tetrahydrofuran, cyclohexanone and 1,4-dioxane.
    Maiti and coworkers determined the solubility parameters of rosin-based
    polyesterimides and polyamideimides from the relationship

    where ~ refers to the solubility parameter, 0 to density, G to Small's group


    contribution and M to the molecular weight of the repeat unit of the polymer.
    These solubility parameter values were compared with those experimentally
    obtained from the solubility map. 4''56''s4''72 Table 2 shows solubility parameter
    values for some polymers from rosin.
    Tables 3 and 4 show some characteristic properties of polyesterimides and
    polyamideimides from rosin, respectively.
    Attempts were made to prepare high molecular weight polyamideimides from
    rosin by optimization studies. The highest molecular weight polymers were
    obtained by reacting the acid chloride of maleopimaric acid (RMA) with a
    diamine in exact stoichiometry in a mixed solvent (DMF : NMP = 3 : 1 vol/vol)
    containing 4% anhydrous lithium chloride. It has been argued that lithium
    chloride enhances the basicity of the solvent which in turn solubilizes the
    polymer to a large extent so that the polymer chains can grow. ~
    324 S. MAITI et al.

    TABLE 2. Solubility parameters of some polymers from rosin

    Polymer code Solubility parameter (6)

    from SmaU's group from solubility map


    contribution (plot of 6 , ~ . , vs ~ , . ~ )

    Polyesterimides (Figs 11, 12)


    RPEI-2 10.10 10.30
    RPEI-3 10.10 10.30
    RPEI-4 10.23 10.30
    RPEI-5 10.34 10.30
    Polyamideimides (Figs 14, 16)
    RPAI-1 9.70 10.50
    RPAI-2 9.40 11.00
    RPAI-3 10.20 10.50
    RPAI-4 10.90 10.50
    PAI-6 10.63 10.80
    PAI-7 11.96 10.80
    PAI-8 10.96 11.40
    PAI-9 11.25 11.40
    PAI-10 10.19 10.80
    PAI-I 1 10.67 11.50
    Polyester
    PE-I 10.62 10.80
    Polyamide
    PA-1 11.45 10.80

    5. T H E R M A L BEHAVIOR

    The thermal behavior of rosin polymers, particularly polyesterimides and


    polyamideimides, was studied by Maiti and coworkers. Because of the bulky and
    highly substituted hydrophenanthrene ring structure of levopimaric acid, the
    rosin polymers are in general amorphous and not very high molecular weight
    materials. These two factors tend to lower the thermo-oxidative stability of

    TABLE 3. Polyesterimides from rosin

    Polymer Inherent Density Ts


    code viscosity (g/cm 3) (°C)
    (Figs 11, 12) (dl/g)

    RPEI-I 0.21 1.16 180


    RPEI-2 0.17 1.20 225
    0.19 1.29 -
    RPEI-3 0.20 1.29 180
    RPEI-4 0.20 1.33 210
    RPEI-5 0.21 1.16 180
    ROSIN 325

    TABLE4. Polyamideimides from rosin

    Polymer code Inherent Density ,Q, Ts


    (Figs 14, 16) viscosity (g/cm3) (°C)
    (dl/g)

    RPAI-I 0.07 1.06 - 75


    RPAI-2 0.06 1.12 - 120
    RPAI-3 0.14 1.20 - 220
    RPAI-4 0.12 ! .27 - 235
    RPAI-5 0. ! 3 ! .06 - 125
    PAI-6 0.33 1.32 13,500 265
    PAI-7 0.35 1.34 14,000 260
    PAI-8 0.31 1.35 - 285
    PAI-9 0.31 1.36 13,000 280
    PAI-10 0.28 1.32 - 275
    PAI-I 1 0.37 1.30 16,500 280

    r o s i n - b a s e d p o l y m e r s . A l t h o u g h the i s o p r o p y i g r o u p a t t a c h e d to the h y d r o -
    p h e n a n t h r e n e ring system o f l e v o p i m a r i c acid is sterically shielded in the m a l e o -
    p i m a r i c acid ( R M A ) molecule, it c a n u n d e r g o o x i d a t i o n at higher t e m p e r a t u r e s .
    Nevertheless, rosin p o l y m e r s have shown satisfactory high t e m p e r a t u r e stability.
    Results o f t h e r m o g r a v i m e t r i c analysis ( T G A ) o f r o s i n - b a s e d p o l y e s t e r i m i d e s
    a r e s h o w n in Fig. 17. R P E I - 1 was f o u n d to be the m o s t stable o f the p o l y m e r s
    tested. 4 Results o f i s o t h e r m a l a g i n g in air are s h o w n in T a b l e 5.
    T h e t h e r m a l stability o f the p o l y a m i d e i m i d e s f r o m rosin a p p e a r s to be b e t t e r
    t h a n t h a t o f the polyesterimides. This is expected f r o m the fact t h a t

    RPEI-I A
    I00
    " ~ t RPEI-2
    RPEX-3 •
    RPEI-4 o

    .~ 60

    ~ 4o

    20

    Ol
    I00 200 300 400 SO0 6 0 0
    Temperature, °C
    FIo. 17. Thermogravimetric analysis of polyesterimides.
    326 S. MAITI et al.

    TABLE 5. Isothermal aging of the polyesterimides from rosin in Air*

    Polymer Ts Weight loss for 12hr at, %


    (°C)
    200°C 300°C

    RPEI- 1 180 -
    RPEI-2 225 12.0 10.3
    RPEI-3 180 9.0 35.7
    RPEI-4 210 5.2 19.7
    RPEI-5 245 3.2 28.0

    *From Refs 4, 163, 164.

    0 0
    II II
    the thermal stability of the - C - N H - linkage is higher than that of the - C - O -
    linkage and the degree of intermolecular association is also higher in the former
    than in the latter. TGA curves of a few polyamideimides are shown in Fig. 18.
    The effect of isomerism on the thermal stability of polyamideimides synthesized
    from three isomeric diamines is shown in this figure. The order of thermal
    stability is para-isomer > meta-isomer > ortho-isomer. This is consistent with
    the higher degree of crystallinity of the para-isomer due to chain symmetry.

    I00

    80
    AI-2
    60

    .~ 40 ~ P~I~'~ PAt-5
    e 20
    I I I~ % '~ | I I I~ I

    IO0

    PA•I-11
    7:
    ~ 80

    60-- AI-8
    pAI-9
    40-- PAI'IO
    20-
    0 I I I l ~,\
    tO0 300 500 700 IOO 300 500 700
    Temperoture p "C
    FIG. 18. Thermal stability of polyamideimides by TGA.
    ROSIN 327

    TABLE6. Isothermal aging of the polyamideimidesfrom rosin in air*

    Polymer Cumulative weight loss (%)

    at 275°C after at 300°C after

    2 hr 12hr 36 hr 2 hr 12 hr 36 hr

    PAI-6 2.55 3.90 6:25 5.15 7.56 11.20


    PAI-7 2.80 4.75 7.45 5.70 8.96 13.25
    PAI-8 0 0 0 2.70 3.70 5.05
    PAI-9 0 0 0 3.15 4.12 6.06
    PAI- l0 0 0 0 3.50 4.80 7.05
    PAl- 1i 0 0 0 3.08 4.15 6.05

    *From Refs 156 and 173.

    Isothermal thermogravimetry of the polyamideimides (Table 6) indicates that


    some of the polymers in this series, viz. PAI-8 to 11, possess satisfactory thermal
    stability to be used at temperatures higher than 200°C, possibly at 250°C. The
    nature of the diamine used for the synthesis and the molecular weight of the
    polymer are the major factors in the thermal stability of the polymers. RPAI-1
    to 5 are low molecular weight polymers and hence their thermal stability is also
    very low.

    6. POLYMER MODIFICATION
    It has been reported earlier that the rosin moiety offers interesting possibilities
    for modification of p o l y m e r s : There are at least two sites which are amenable
    for polymer modification. First, the residual unsaturation in the hydrophen-
    anthrene ring of the rosin molecule can be utilized for crosslinking reactions.
    Second, the isopropyl group may be oxidized under suitable reaction conditions
    to yield materials which may be further exploited for graft copolymerization
    and/or crosslinking. The possibilities are schematically shown in Fig. 19. 5

    6.1. Crosslinking
    Rosin polymers, on heating to 150°C or above for about 10hr, do not
    crosslink, presumably due to the shielding o f the residual double bond. Even
    heating at 100°C for 10hr with free radical initiators like A I B N or benzoyl
    peroxide failed to initiate the crosslinking reaction. However, at higher tempera-
    tures crosslinking occurs with or without free radical initiators. For example,
    the polymers could be fully cured by heating at 250°C for 2 hr in the presence
    of dicumyl peroxide) s°'lBI
    Evidence for crosslinking included the observed insolubility of the cured
    material in polar solvents and 10% sodium hydroxide solution, as well as the
    absence o f the olefinic double bond in the IR spectra o f the polymers after
    328 S. MAIT! et aL

    °OH -t" 4- CH~,CO CHz

    CROSSLINKEO f"~ qO ~ I N }n + H0 "~' (N)~" v


    PRooucr ~"~'J
    ,I \ c.~

    Graft Homopoiymer
    Copolymer
    M =Vinyl monomer

    FIG. 19. Schematics of modification of rosin polymers.

    heating. Crosslink density and Mc values were determined by an equilibrium


    swelling method using the Flory-Rehner equation:
    [ln (1 - ~) + z, + xV,2]
    vlV = v0(K ' / 3 - K/2)
    Table 7 lists the various crosslinking parameters of the polyamideimides from
    rosin. On the average one crosslink is formed per five repeat units of the
    polymers. A polymer sample crosslinked by heat alone showed a weight loss of
    6.5% on heating at 180°C for 350hr while the same polymer crosslinked by
    peroxide initiator lost only 4.5% of its weight under the same condition. This
    is due to the higher crosslink density, i.e. lower Jl4c value, of the latter.
    Since crosslinking reduces the segmental mobility of polymer chains, both the
    Tg of the polymer and its thermal stability increase on crosslinking. These facts
    are supported by the data presented in Table 8. It appears that crosslinking, to
    the degree used, increases the Tg by about 20°C. Relative weight loss on
    isothermal aging in air at 275°C and 300°C was reduced to about 40% or less
    of the weight loss of the original uncured polymers.

    7. P O L Y M E R B L E N D S

    New and unusual properties of polymers can be achieved by developing


    multicomponent polymer systems in the form of polyblends of two or more
    homopolymers. Often the polyblends exhibit superior properties to those of the
    component polymers.
    TABLE7. Crosslinking parameters* of rosin-based polyamideimides

    Polymer Reactants X** ~'c x 10-3 (g/mol)


    ~x I(P
    v
    at 30°C Swelling Thermal
    (mol/cm3) method analysis
    method

    PAI-I RMA-CI Ethylencdiamine 0.28 4.5 2.933 3.900


    PAI-I RMA-CI Hexamethylencdiamine 0.298 5.2 2.576 2.600
    PAI-I RMA-CI p-Phenylemxtiamine 0.305 5.4 2.500
    (6.4)t (1.870)
    PAI-I RMA-C1 Diaminodiphcnyi-methane 0.33 5.2 2.615 2.600
    PAI-I RMA-Ci Diaminodiphcnyl-sulfone 0.335 5.0 2.640 2.600
    PAI-I RMA-CI p,p'- Bis(aminocyclohexyl) methane 0.365 4.8 2.708 2.600
    PA-I RMA-CI Hexamethylencdiamine 0.29 6.1 2.229 1.950
    PE-I RMA-CI Hexanedioi 0.325 5.9 2.228 1.950

    *From Ref. 181.


    **For NMP solvent at 30°C.
    tData in parenthesis indicate the result obtained with a polymer sample having an inherent viscosity value of 0.14dl/g.
    TABLE 8. Effect o f crosslinking on the thermal behavior of rosin polymers

    Polymer Ts Weight loss (%) during isothermal heating in air


    (*C)
    at 2750C alter at 3000C after at 3500C after

    2hr 12hr 36hr 2hr 12hr 36hr 2hr 12hr 36hr

    RPAI-6 265 2.55 3.90 6.25 5. i 5 7.56 1 ! .24


    Crosslinked 275 1.03 1.56 2.34 2.25 3.26 4.60 4.50 6.75 I i. 10
    RPAI-6
    RPAI-7 260 2.80 4.75 7.45 5.70 8.96 13.25
    Crosslinked 275 1.08 1.65 2.40 2.42 3.54 4.95 4.97 6.95 13.90
    RPAI-7
    RPAI-8 285
    Crosslinked 305 . . . . . . ! .75 2.85 4.95
    RPAI-8
    RPAI-9 280
    Crosslinked 295 . . . . . . 2.05 3.05 5.35
    RPAI-9
    RPAI-10 275
    Crosslinked 290 . . . . . . 1.95 2.90 5.05
    RPAI-10
    RPAI- l 1 280
    Crosslinked 295 . . . . . . 2.55 4.90 7.25
    RPAI- I l
    PA-I 225 3.80 6.25 9.80 6.95 I 1.95 19.40
    Crosslinked 245 1.34 1.79 2.84 3.05 4.65 6.05 6.55 10. i 0 18.55
    PA-I
    PE-I 200 4.85 7.50 12.40 8.10 15.20 27.10
    Crosslinked 220 1.76 2.02 3.34 4.02 5.65 7. ! 5 7.50 13.70 25.05
    PE-I
    ROSIN 331

    TABLE9. Activation energies of polyblends involving rosin-based


    polymers and of the component polymers

    Polymer systems Activation energy E


    (kJ mole-i ) 10

    PAl* 2.66
    80% PAl, 20% novolac* 2.62
    60% PAl, 40% novolac* 4.82
    40% PAI, 60% novolac* 4.22
    Pure novolac*: 1st decomposition 0.50
    : 2nd decomposition 4.15
    80% PAl, 20% resole** 3.32
    60% PAI, 40% resole** 5.50
    40% PAl, 60% resole** 4.63
    Pure resole**: 1st decomposition 0.19
    : 2nd decomposition 8.06
    80% PAl, 20% shellact 2.90
    60% PAl, 40% shellact 2.95
    20% PAl, 80% shellact 0.72
    Pure shellact: 1st decomposition 0.68

    *From Ref. 182.


    **From Ref. 183.
    tFrom Ref. 184.

    A polyamideimide from rosin was blended with phenolic resins, both


    novolac ~s2 and resole, ~83 and also with shellac, 184 a resinous material of animal
    origin. Blends were prepared by solution blending techniques. Appropriate
    quantities of component polymers were dissolved separately in dimethyl-
    formamide or a mixture of dimethylformamide and tetrahydrofuran and mixed
    carefully with stirring so that no precipitation or turbidity occurred. The mixed
    solution was kept at room temperature for 2 hr to attain equilibrium, followed
    by removal of the solvent.
    The miscibility of the component polymers has been evaluated by various
    techniques, such as absence of turbidity on mixing the polymer solutions,
    similarity of the solubility parameter values of the polymers, single T~ values,
    heat of mixing data and viscometry. Determination of the activation energy
    for thermal degradation showed that in most blend compositions the acti-
    vation energy is increased in the polyblend as compared with the components
    (Table 9). This accounts for the observed marginal increase of thermal
    stability of the blends (Table 10). This enhancement of activation energy and
    thermal stability of the blends has been explained on the basis of the onset of
    crosslinking in the blend. Some tentative mechanisms for cross-linking were
    suggested, presumably through the involvement of formaldehyde liberated
    during the heating of blends containing phenol formaldehyde resins, or
    through the double bond of rosin polymers and/or the unsaturation of shellac
    material.
    332 S. MAITI et al.

    TAel~ 10. Thermal behavior of polyblends from rosin polymers

    Polymer systems % of weight loss after heating at 300°C in air for

    4 hr 8 hr 12hr 24 hr

    PAl* 16.20 21.50 25.70 32.90


    Novolac 18.89 21. I0 26.20 36.52
    Resole 3.01 4.85 16.58 27.20
    Shellac 29.70 34.25 45.20 5I. l0
    PN** 60:40 14.41 19.41 22.10 26.40
    PN 40:60 14.82 19.89 22.80 27.90
    PRt 60:40 11.86 17.16 20.89 24.50
    PS~ 60 : 40 18.20 21.90 26.20 31.20

    *Polyamideimide.
    **Polyamideimideblended with novolac (Ref. 182).
    tPolyamideimideblended with resole (Ref. 183).
    :~Polyamideimideblended with shellac (Ref. 184).

    8. ROSIN-MALEIC ANHYDRIDE ADDUCT


    VS TRIMELLITIC ANHYDRIDE
    It has been mentioned earlier that an attempt was made to develop rosin-
    maleic anhydride adduct (RMA) as a suitable substitute for trimellitic anhydride
    (TMA) as the key chemical for synthesis of polyesterimides, polyamideimides
    and other copolyimides. In this section an attempt has been made to qualitatively
    compare the polymers synthesized from both o f these chemicals.
    The solubility behavior of polymers synthesized from T M A and RMA
    is almost identical. Both types of polymers are soluble in highly polar sol-
    vents. Both types of polymers also are almost equal in solubility parameter
    (~ = 10-11.5).
    The density of the RMA-based polymers ranges from 1.30-1.36 g/cm 3. This
    density range is higher than that of the TMA-derived polymers (density
    ,-, 1.20 g/cm3). One would expect that the former should be lower in density than
    the latter in view of the bulky nature o f the rosin moiety. However, other
    workers have reported higher density values (l.4g/cm 3) for TMA-based poly-
    mers (Table 11).
    The thermal stability of both types of polymers, having otherwise similar
    structures, is compared in Table I I. Both types of polymers possess similar
    thermal stability, although TMA-based polymers having higher inherent vis-
    cosities are more thermostable. Although the inherent viscosities, as listed in
    Table 11, for both types of polymers are almost identical, this should not be
    considered as meaning that both types of polymers have similar molecular
    weights. And since molecular weight influences the thermal properties of poly-
    mers, our comparison between these two types of polymers may not reflect the
    actual state of affairs. At best, only a qualitative picture about the comparative
    TABLE i 1. Comparative studies of the physical properties of TMA- and RMA-based polymers

    Polymer Inherent Density Tg Weight loss at Weight loss on heating


    viscosity (g/cc) (°C) 350°C in air, % isothermally in air, %
    (dl/g) (from T G A curve)
    at 200°C for at 300°C for
    12hr 36 hr

    TP-P 0.32 i.20 235 5 5.3 11.20


    PAl- 1 0.33 1.32 265 6 0 11.20
    TP-2" 0.33 1.17 225 6 6.5 13.25
    PAI-2 0.35 1.34 260 7 0 13.25
    TP b 0.32 1.27 275 3 5.05
    PAI-3 0.31 1.35 285 1 0 5.05
    TP-4c 0.35 1.26 226 4 6.06 ~o
    PAI-4 0.31 1.36 280 2 0
    ;Z
    TP d 0.19 i.20 220 4 5.9
    PAI-5 0.28 1.32 275 3 0 7.05
    TP-6c 0.23 1.23 280 5 3.3
    PAI-6 0.37 1.30 280 2 0 6.05
    TP-7 f - 1.40 - - 6.17 g
    TP-8 h 0.70 - - 0 9.8 i
    TP-9 h 1.60 275 0 7.4 j
    TP-11Y' 3.64 - 330 -
    TP-II ~ 3.53 - 330 -
    TP- 12k 2. I 1 - 285-295 -

    aRef. 185, bRef. 186, CRef. 187, dRef. 188, CRef. 189, fRef. 190, gat 260°C, hRef. 191, iin vacuo, Jat 3250C for 120hr, kRef. 192.
    334 S. MA1TI et aL

    thermal stability of these two types of polymers may emerge. It appears that the
    aromatic ring of TMA possesses similar thermal stability to the hydrophenan-
    threne ring of RMA.
    Substitution of TMA by RMA in the synthesis of polyamideimides from
    TMA and diphenylmethane diisocyanate reduces the thermal stability. The
    standard sample prepared from 100% TMA and diphenylmethane diisocyanate
    shows no weight loss up to 400°C (thermogravimetric analysis) in a helium
    atmosphere, but those containing 10, 50 and 100% RMA in place of TMA show
    5, 9 and 13% weight loss, respectivelyJ93 However, molecular weights of the
    polymer samples were not reported. It may, therefore, be argued that the
    replacement of TMA by RMA, which is less reactive due to steric factors, might
    cause a reduction in the average molecular weight, thereby reducing the thermal
    stability of the polymers.

    9. C O N C L U S I O N

    Gum rosin, a plant exudate, is a renewable feedstock for the synthesis of


    various types of polymers. Although rosin is a mixture of a number of isomeric
    monocarboxylic acids having a substituted hydrophenanthrene ring system,
    crystalline maleopimaric acid (RMA) can be easily prepared in a pure form.
    RMA may be regarded as a substitute for trimellitic anhydride for the synthesis
    of copolyimides such as polyesterimides, polyamideimides and other polymers.
    The bulky nature of the rosin moiety offers some steric hindrance to the
    reactivity of its two functional groups, viz. carboxyl and cyclic anhydride groups,
    compared with the TMA molecule. However, the residual unsaturation in RMA
    opens up the possibility of curing the polymers, which is absent in the TMA-
    based polymers. The prospect of crosslinking makes RMA-based polymers
    attractive for enhanced thermal stability in the cured state and for better
    blending with other polymers like phenolics or shellac.

    ACKNOWLEDGEMENTS

    The authors wish to thank the Council of Scientific and Industrial Research
    (CSIR), New Delhi, for partial financial assistance.

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