CA1037636A - Polymers and processes therefor - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

The present invention relates to thermoplastic graft copolymers comprised of copolymeric backbones containing a plurality of uninterrupted repeating units of the backbone polymer and at least one integrally copolymerized moiety per backbone polymer chain having chemically bonded thereto a substantially linear polymer which forms a copolymerized side-chain to the backbone, wherein each of the polymeric sidechains has substantially the same molecular weight and each polymeric sidechain is chemically bonded to only one backbone polymer. The polymers of the present invention are formed from comonomers which were not possible to polymerize in the prior art. The polymers of the present invention are formed by a novel process which permits the formation of "tailor made"
polymers having the most desirable physical characteristics for their end use.

Description

~3~7~3~
The present invention xelates to chemically joined, phase separated thermoplastic graft copolymers.
More particularly this invention relates to a novel composition of matter comprising: high molecular weight poly-merizable monomers, each of said polymerizable monomers com-prising at least one polymeric segment having at least about 20-30 uninterrupted recurring monomeric units of an anionical-ly polymerized vinyl-containing compound, each of said poly-merizable monomers terminating with no more than one polymer-izable end group containing a moiety selected from olefinic,epoxy or thioepoxy groups per mole of said polymerizable mono-mers, said polymerizable monomers denoted as having a substan-tially uniform molecular weight distribution such that their ratio of Mw/~n is less khan about 1.1, wherein ~w is the weight -average molecular weight of the high molecular weight polymer--izable monomers and Mn is the number average molecular weight of the high molecular weight polymerizable monomers, said poly-merizable monomers being further denoted as capable of copoly-merizing with a second polymerizable compound having a rela-tively low molecular weight to yield a chemically joined,phase separated thermoplastic graft copolymer, said copolymer-ization occurring through said polymerizable end group, said polymerizable end group thereby occurring as an integral part of the backbone of said chemically joined, phase separated thermoplastic graft copolymer.
This invention also discloses a monofunctional polymerizable macromolecular monomer composition represented by the formula:

R - - Z ~ X
_ _~
wherein R is lower alkyl, Z is a repeating monomeric unit of a ~Q37~3!~i vlnyl-containing compound, n is a positive integer having a value of at least about 209 and X is a polymerizable end group containing a moiety selected from olefinic~ epozy or thioepoxy groups~ said polymerizable macromolecular monomer being denoted as having a substantially uniform molecular weight distribution such that its ratio of Mw/Mn is less than about lo 13 wherein MW is the weight average molecular weight of the macromolecu-lar monomer and Mn is the number average molecular weight of the macromolecular monomer.
Further there is disclosed herein a process for pro-ducing high molecular weight polymerizable monomers~ said pro-cess comprising the st~ps ofO (a) polymerizing an anionically - polymerizable vinyl~containing monomer in the presence of an anionic .I.nitiator to produce a monofunctional living polymer denoted as having a substantially uniform molecular weight distribution such that its ratio of Mw/Mn is less than about lol~ wherein Mw is the weight average molecular weight of the monofunctional living polymer and Mn is the number average molecular weight of the monofunctional living polymer~ (b) re-acting said monofunctional living polymer with either a halo-gen-containing compound which also contains either a polymer-izable olefinic group or an epoxy or thioepoxy group or a com-pound whlch contains a reactive ~ite to the anion of the liv-ing polymer whlch also conta.ins a polymerizable moiety which does not preferentially react with said anion3 said polymer-izable moiety being comprised of an olefinic group9 said re-action with said monofunctional living polymer being conducted at substanti.ally the same temperature at which the living polymer was prepared~ said compound being reacted with sa~d monofunctional living polymer on a mole-for mole basis with respect to the amount of anionic initiator used to prepared --2~

~7~3$
said monofunctional living polymer, and ~c) recovering said high molecular weight polymerizable monomers, each of said polymerizable monomers comprising at least one polymeric segment having at least about 20 uninterrupted recurring monomeric units of an anionically polymerized monomer, each of said polymerizable monomers terminating with no more than one polymerizable end group per mole of said polymerizable monomers, said polymerizable monomers denoted as having a substantially uniform molecular weigh~ distri- ;
bution, such that their ratio of Mw/Mn is less than about l.l, said poly-merizable monomers being further denoted as capable of copolymerizing with a second polymerizable compound having a relatively low molecular weight to produce a chemically joined, phase separated thermoplastic graft copolymer, said copolymerization occurring through said polymerizable end group, said polymerizable end group thereby occurring as an integral part of the back-bone of said chemically joined, phase separated thermoplastic graft co-polymer, The present inv.ontion provides a chemically joined, phase separated thermoplastic graft copolymer of a copolymerizable macromolecular monomer represented by the formula I - ~Pl)n (X) - (Y) and at least one copolymerizable backbone-forming comonomer; wherein I is the residue of a monofunctional anionic initiator, Pl is at least one anionically polymerized monomer, X is a capping agent, Y is a terminating agent having a copolymerizable end group, n is at least about 20, w is zero or l, and wherein said copolymerizable end group and said backbone-forming comonomer form the backbone of the graft copolymer and the macromolecular monomers form the sidechains of the graft copolymer, characterized in that a. said copolymerizable macromolecular monomers comprise from about 1%
to about 95% by weight of the graft copolymer and said backbone-forming comonomers comprise from about 99% to about 5% by weight of the graft co-polymer, said copolymerizable macromolecular monomers having a substantially ~s ~, , ~ - 3 -~L~37!~3!~

uniform molecular weight distribution such that the ratio of Mw/Mn is less than about 1 1, wherein Mw is the weight average molecular weight of the macromolecular monomers and Mn is the number average molecular weight of the macromolecular monomers, and b. the polymeric sidechains of the graft copolymer which are copolymerized into the backbone are separated by at least about 20 uninterrupted recurring polymerized units of the backbone-forming comonomer, the copolymerizable end group o:E the macromolecular monomers and the backbone-forming comonomer having been chosen with regard to their reactivity ratios so as to control the distribution and copoly-merization of the macromolecular monomers along the backbone, and c. said graft copolymer contains a member selected from the group consisting of:
~i) at least one backbone-forming comonomer selected from the group con-sisting of acrylic acid, methacrylic acid, acrylamide, N-alkylacrylamide, N,N-dialkylacrylamide, methacrylamide, N-alkylmethacrylamide, N,N-dialkyl-methacrylamide, acrylonitrile, methacrylonitrile, vinyl chloride, vinyl-idene cyanide, vinyl acetate, vinyl propionate, vinyl chloroacetate, fumaric acid and its esters, and maleic anhydridesJ acids and esters; and at least one graft monomer containing members selected from the following groups (ii) a residue of an alkali metal salt of a tertiary alcohol as the anionic polymerization initiator, I; ~iii) a capping agent, X, selected from 2-butenylene or 2-methyl-2-butenylene radicals; (iv) a terminating`agent, Y, selected from fH2 CH2 = C - CH = CH2, ~0 - R C - C
Il \
Il /
HC C
~0 ~37~ii36 ~0 OR
OR, - C
~0 R3 ~ _ CH = C~l2, R3- O-CH2 ~ CH = CH2, o HO C - CH
O
; OH O

- R CH - CH2 - O - Ci - CR =`CH2, and OH O

-R3- CH - CH2 - O C - CH ; and HO - C - CH
o wherein R3 is an alkylene radical, and R is a hydrogen or an alkyl group;
(v) a macromolecular monomer polymeric portion ~Pl)n, comprising a polymeric segment of a vinyl aromatic hydrocarbon having a molecular weight in the range of from about 5,000 to 50,000 and a polymeric segment of a conjugated diene containing 4 to 12 carbon atoms per molecule.
The present invention also provides a process for preparing a graft copolymer comprising polymerizing at least one anionically poly-merizable monomer in the presence of an anionic polymerization initiator to thereby form a monofunctional living polymer; and where required reacting the monofunctional living polymer with a capping agent; reacting the .

~ _ 5 _ 7~3~

monofunctional living polymer with a terminating agent to thereby form copolymerizable macromolecular monomers with a copolymerizable end group, and thereafter, copolymerizing by free radical, cationic, anionic, con-densation, Ziegler or Natta processes from about 1 to 95% by weight based on the weight of the resulting graft copolym~r oflsaid copolymerizable end group with from about 99 to 5% by weight of the resulting graft copolymer of a backbone-forming comonomer; wherein said copolymerizable end group and said backbone-forming comonomer form the backbone of the graft co-polymer and the macromolecular monomers form the side-chains of the graft copolymer, characterized in that ~a) said copolymerizable macromolecular monomers comprise from about 1% to about 95% by weight of the graft co-polymer and said backbone-forming comonomers comprise from about 99% to about 5% by weight of the graft copolymer said copolymerizable macromole-cular monomers having a substantially uniorm molecular weight distribution such that the ratio of ~w/~n is less than about 1.1, wherein ~w is the weight average molecular weight of the macromolecular monomers and Mn is the number average molecular weigh~ of the macromolecular monomers, and (b) the polymeric sidechains of the graft copolymer which are copolymerized into the backbone are separated by at least about 20 uninterrupted recurring polymerized units of the backbone-forming comonomer, the copolymerizable end group of the macromolecular monomers and the backbone-forming monomer having been chosen with regard to their reactivity ratios so as to control the distribution and copolymerization of the macromolecular monomers along the backbone, and ~c) said graft copolymer contains a member selected from the group consisting of: (i) at least one backbone-forming comonomer selected from the group consisting of acrylic acid, methacrylic acid;
acrylamide; N-alkylacrylamide; N,N-dialkylacrylamide; methacrylamide;
N-alkylmethacrylamide; N,N-dialkylmethacrylamide; acrylonitrile; meth-acrylonitrile, vinyl chloride; vinylidene cyanide; vinyl acetate; vinyl propionate; vinyl chloroacetate; fumaric acid and its esters;and maleic anhydrides, acids and esters; and at least one graft monomer containing a ~ r~
~ - 5a -76i3~

member selected from the following groups (ii) a residue of an alkali metal salt of a tertiary alcohol anionic polymerization initiator; (iii) a capping agent selected from butadiene or isoprene; (iv) a copolymerizable end group derived from a terminating agent selected from 2-halome~hyl-1,3-butadiene, haloalkylmaleic anhydride, haloalkylmaleate esters, vinyl haloaryls, vinyl haloalkaryls, maleic anhydride, acrylic anhydride, methacrylic anhydride, and a epihalohydrin, the epoxy group of which is hydrolyzed and then reacted with acrylyl halide, methacrylyl halide or maleic acid halide; ~v) a macro-molecular monomer having a polymeric segment of a vinyl aromatic hydrocarbon with a molecular weight in the range of from about 5,000 to 50,000 and a polymeric segment of a conjugated diene containing 4 to 12 atoms per molecule;
and combinations thereof.
In accordance with the present invention there is also provided a polyblend comprising: (1) from about 1 to about 50 parts by weight of the chemically joined, phase separated thermoplastic graft copolymer from 99 to about 50 parts by weight of a polymer selected from polyethylene, poly-propylene, polybutadiene, polyisoprene, polystyrene, poly~vinyl chloride), polyacrylonitrile, polyacrylamides and mixtures thereof.
Polymer technology has developed to a high degree of sophisti-cation and extensive research efforts in this direction are being undertaken to obtain improvements in polymer properties. Some of these efforts lead to polymer materials capable of competing with metals and ceramics in engineering applications. Generally, it is a requirement that these polymers be crystalline, since crystalline polymers are strong, tough, stiff and generally more resistant to solvents and chemicals than their non-crystalline counterparts.
Many poly alpha-olefins are crystalline and have excellent structural integrity; and, accordingly, have acquired increasing commercial acceptance as materials for competing with metals and ceramics. As one example, polyethylene has been regarded as one of the most important ~ / ~ - 5b -~37~i3~ :
polymers among the major plastics, with its production reaching about 6 billion pounds in 1970 (1.7 billion pounds of high density linear poly-ethylene and 4.3 billion pounds of low density polyethylene).
Despite the widespread use of this important plastic, its use has been limited to flexible, translucent, molded articles or flexible, clear films, due to its softness. The uses of polyethylene have also been limited due to its poor adhesion of many substrates and its low heat distor-tion, rendering it unsuitable for many high temperature applications.

- 5c -~3t7~,3~, Attempts by prior art workers to co~bine the proper_ ties of polyole~ins and other polymers by either chemical or mechanical means generally has resulted in a sacrifice o~ many of the beneficial proper~ies of both the polyolefin and the additional polymerO ~or example, graft copolymers of poly-ethylene and polypropylene have been prepared only with di~
culty du~ to the inertness these polymers have with many other polymerizable monomers and polymers. The resultant graft ¢o-polymer generally has been a mixture which also contains free homopolymers Polyblends o~ a polyalefin with another polymer pre-pared by blending quantities of the two polymers together bY
mechanical means have been generally unsuitable for many ap-plications due to their adverse solubility or extractability properties when used with various solvent systems, particular-ly when containing a rubbery, amorphous component.
The above consideratio~s recognized by those skilled in the art with respect to the incompatibility of polyolefins with other polymers ~ind almost equal applicabili~y ln the case of other plastics such as the polyacrylates, polymeth-acrylates, polyvinylchlorides, etc. Thus, the incompatability o~ both natural and syn~hetic polymers becomes increasingly apparent as more and more polymers having particularly good properties for special uses have become available, and as efT
forts have been made to combine pairs of these polymers ~or the purpose of incorporating the di~erent~ good properties o~
each polymer into one product, More often than not, these e~-forts have been unsuccessful because the resulting blends have exhibited an instability, and in many cases the desirable properties o~ the new polymers were completely lost, As a specific example, polyethylene is incompatible with poly-~3763~
styrene and a blend of the t~o has poorer physical propert~es than either o~ the ~omopolymers. These failures were at first attributed to inadequate mixing proceduresg but aventually ~t was concluded that the ~ailures were due simply to the inher-ent incompatibilitiesO Although it i8 now believed that this is a correct explanation, the general nature o~ such incompat-~bility has remained somewhat unclear, even to the presentO
Polarity seems to be a factor, i.e., two polar polymers are apt to be more compatible than a polar polymer and a non-polar polymer. Also9 the two polymers must be structurally and com-positionally somewhat similar if they are to be compatible.
Still ~urther, a particular pair of polymers may be compatible only within a certain range o~ relat:Lve proportions of the two polymers; outside that range they are incompatible.
Despite the general acceptance of the fact of incom-patibility of polymer pairs, there is much interest in devis-ing means whereby the advantageous properties of combinations of polymers may be combined into one product.
One way in which this ob~ective has been sought in-volves the preparation of block or gra~t copolymers. In thisway, two different polymeric segments, normally incompa~ible with one another, are ~oined together chemically to give a sort of forced compatibility. In such a copolymer, each poly-mer se~ment continues to manifest its independent polymer propertiesO Thusg the block or graph copolymer in many in-stances possesses a combination o~ properties not normally found in a homopolymer or a random copolymer.
Recently9 there has been described a method Por pre-paring gra~t copolymers of controlled branch configuration~
It is described that the gra~t copolymers are prepared by first preparing a prepolymer by reacting a vinyl metal com--7~

`:`' ~Q37~:i3~
pound with an ole~inic monomer to obtain a vinyl terminated prepolymer. A~ter protonation and catalyst removalg the pre-pol~mer is dissolved in an inert solvent with a polymerization catalyst and is thereafter reacted with ei:ther a di~erent polymer having a reactive vinyl group or ~ different vi~yl monomer under free-radical conditions.
The current limitations on the preparation of these copolymers are mechanisticO Thus, there is no means ~or con-trolling the spacing of the sidechains along the backbone chain and the possibility of the sidechains having irregular sizes. Due to the mechanistic li~itations of the prior art methods, i.e.g the use of an alPha-olefin terminated prepoly-mer with acrylonitrile or an acrylate monomer, complicated mixtures o~ free homopolymers result.
In ~iew of the above considerations, it would be highly desirable to devise a means for preparing graft copoly-mers wherein the production of complicated mixtures of free homopolymers is minimized and the beneficial properties of the sidechain and backbone polymer are combined in one product.
Moreoverg it is recognized and documented in the literature that vinyl lithium is one of the slowest anionic polymerization initlators. The slow initiator characteristic of vinyl lithium when used to polymerize styrene pr~duces a polymer having a broad molecular weight distribution due to the ratio of the overall rate of propagation of the styryl anion to that of the vinyl lithium initiation. In other wordsJ
the molecular weight distribution of the polymer produced will be determined by the effective reactivity of the initiator compared with that of the propagating anionic polymer species3 i.e., vinyl lithium initiator reactivity compared to the styryl anion. Accordingly~ following the practice of UOSo Patent No.

~ ~ ~ -7~3~
3,235,626, a gra~t copolymer having sidechains of uniform mo-lecular weight cannot be preparedO
The prior art also describes processes for term.in-ating free-radical and ionic polymerized polymers with func-tional groups which are described as capable of copolymerizing with polymerizable monomersO The ~unctionally terminated pre-polymers descri.bed by these patentees also would be expected to have a broad molecular weight distribution and, therefore, would not be capable of producing a chem~cally ~oined, phase separated thermoplastic gra~t copolymer The present invention relates to thermoplastic graft copolymers comprised o~ copolymeric backbones containing a plurality of uninterrupted repeating units of the backbone polymer and at least one integrally copolymerized moiety pçr backbone polymer chain having chemica~ly bonded thereto a sub-stantially linear polymer which forms a copolymerized side-chain to the backbone, wherein each of the polymeric side-chains has substantially the same molecular weight and each polymeric sidechain is chemically bonded to only one backbone polymer.
The gra~t copolymers o~ the present invention assume a "T~ type structure when only one sidechain is copoly~erized into the copolymeric backbone, However, when more than one sidechain is copolymerized into the backbone polymer, the graft copolymer may be characterized as having a comb-type structure illustrated in the following manner:
c-c-c-b.-c-c-c-b-c-c-c b-c-c-c a a a .
a a a .
a a a wherein "a" represents a substantially linear, uniform molecu-_g _ .
7~3~
lar weight polymer or copolymer having a suf~icient molecular weight such that the physical prqperties of at least one o~
the substantially linear polymers are manifest; "b" repre~ents a reacted and polymerized end group chemically bonded to the sidechain, t'a", which is integrally polyme-rized into the back-bone polymer3 and "c" is the backbone polymer having uninter-rupted segments of sufficient molecular weight such that the physical properties o~ the polymer are manifest The backbone of the graft copolymers o~ the present invention pre~erably contains at least about 20 unlnterrupted recurring monomeric units in each segment. It has been found that this conditlon provides the graft copolymer the properties of the polymer. In other words, thq presence o~ segments con-talning at least about 20 unlnterrupted recurring monomeric units provides the graft copolymers with the physical proper-ties attributed to this polymer, such as crystalline melting point (Tm) and structural integrit~.
The backbone polymeric segments of the chemically joined, phase separated thermoplastic gra~t copolymers o~ the present invention are derived from copolymerizable monomers, preferably the low molecular weight monomersO These copol~-merizable monomers include polycarboxylic acids, their anhy-drides and amides, polyisocyanates, organic epoxides, includ-ing the thioepoxides, urea-formaldehydes, siloxanes, and ethylenically unsaturated monomers. A particularly preferred group of copo ymerizable monomers includes the ethylenically-unsaturated monomers, especially the monomeric vinylidene type compounds, i.e,, monomers containing at least one v~nylidene t CH2 = C- group. The vinyl type co~pounds represented by the ~3~36 H
formula CH2 = C - wherein a hydrogen is attached to one of the ~ree valences o~ the vinylidene group are cont~mplated as falling within the generic scope of the vinylidene compounds re~erred to hereinabove.
The backbone polymers o~ the pre~sent invention are also comprised oP polyolefins which includes polymers of alpha-ole~ins of the formula-C~2 = CHR
wherein R is either hydrogen, or an alkyl or aryl radical con-taining 1 to about 16 carbon atoms, and include ethyl~ne., pro-pylene, butene-l, pentene~l, hexene-lg styrene, etcO, copoly-mers o~ alpha-ole~ins including the ethylene-propylene copoly-mers; and polymers o~ poly~erizable dienes including butadiene, isoprene, etcO
The copolymerizable monomers useful in the practice o~ the present invention are not limited by the exemplary classes o~ compounds,mentioned above. The only limitation on the particular monomers to be employed is their capability to copolymerize with the polymerizable end groups of the sidechain prepolymer under free-radical, ionic, condensation, or coordin~
ation ~Ziegler or Ziegler-Natta catalysis) ~o~ymerization re-actions. AB it will be seen ~rom the description o~ macromo-lecular monomers, described hereinbelow, the choice of poly-merizable end groups includes any polymerizable compound com-mercially avail~ble. Accordingly, the choice o~ respective polymerizable end group and copolymerizable monomer can be chosen, based upon relative reactivity ratios under the respec-tive copolymerization reaction conditionR suitable ~or copoly-merization reaction, For example, alPha-olefins copolymerize with one another using Ziegler catalysts, and acrylates co-:
~3'~i3i polymerize with vinyl chloride, acrylonitrile and other alkyl acrylates. Accordingly, an ~ olefin terminated macromolec-ular monomer copolymerizes with ethylene and ~ olefins us-ing a Ziegler catalyst and an acrylate or methacrylate termin-ated macromolecular monomer copolymerizes with vinyl chlorideg acrylonitrile, acrylates and methacrylates under ~ree radical conditions in a manner governed ~y the r~spective reactivity ratios for the comonomersO
As will be explained hereinafterg the excellent com-bination o~ beneficial properties possessed by the gra~t co~polymers o~ the present invention are attributed to the large segments of uninterrupted copolymeric backbones and the in-tegrally copolymerized llnear sidechains o~ controlled molecu-lar weight and narrow molecular weight distribution.
The term "linear", referred to hereinaboveJ is being used in its conventional sense, to pertain to a polymeric back-bone that is ~ree ~rom cross-linking.
The sidechain polymers having substantially uni~orm molecular weight are comprised o~ substantiallg linear poly-mers and copolymers produced by anionic polymerization o~ anyanionically polymerizable monomer~ as will be described herein-after. Preferably, the sidechain polymer wlll be di~ferent than the backbone polymerO
It is pre~erred that at least one segment of the sidechain polymer of the graft copolymers of the present in-vention have a molecular weight su~icient to manifest the bene~icial propertles of the respective polymerO In other words, physical properties o~ the sidechain polymer such as the glass transition temperature (Tg) will be mani~estO Gen-3Q erally, as known in the art, the average molecular weight o~the segment of the polymeric sidechains necessary to estab-~37~3 Ei lish the physical properties of the polymer will be ~rom about5,000 to about 50,0000 In light of the unusual and improved physical proper-ties possessed by the thermoplastic graft copolym~rs of the present inventiong it is believed that the mono~unctionally bonded polymeric sidechains having substantially uniform mo-lecular weight form what is known as "glassy domains" repre-senting areas of mutual solubilit~ of the respect~ve sidechain polymers from separate backbone copolymersO
Figure I illustrates the normalized stress~strain properties versus percent polystyrene macromolecular monomer incorporation in polyethyleneO
Figure II illustrates the normalized ~lexural modu-lus and heat deflection versus percent polystyrene macromolec-ular monomer incorporation in polyethylene.
Briefly, the chemi~ally joined, phase se~arated thermoplastic gra~t copolymers of the present invention are prepared by first preparing the sidechains in the ~orm of mono~unctional living polymers o~ substantially uniform molecu-lar weight. The living polymers are therea~ter terminated, asby reaction with a halogen-containing compound that also con-tains a reactive polymerizable group, such as, for example, a polymerizable olefinic or epoxy group, or a compound which contains a reactive site to a carbanion of the llving polymer and a polymerizable moiety which does not pre~erentially react - with the carba~ion~ e.gO, maleic anhydrideO The monofunction-al terminated living polymer chains are then polymerized, together with the backbone monomer9 to form a chemically joined, phase separated thermoplastic gra*t copolymer wherein the polymeric sidechains are integrally polymerized into the backbone polymer~

~3'7~3~
The chemically joinedg phase separated thermoplastic graft copolymers derived ~rom ethylenlc~lly unsaturated mono-mers as the backbone comonomer generally correspond to the ~ollowing structural ~ormulau H~---- C ~ H2- C ~ C~z X' X X' y wherein R' and R" are each selected from the group consisting o~ hydrogçn, lower alkylJ cycloalkyl, and aryl ~adicals; X and X' are each selected ~rom the group consisting~of hydrogen, _ _ , alkylene radicals (i.e., - CH2 _ - , x is a positive integer whereln the terminal methylene group in X' i~ either hydrogen, lower alkyl, e.g., methyl, halogen, etct, and in the case o~
X, joins the backbone polymer with the sidechain polymer) a O O
" ..
saturated ester (i.e., - C--OR or -O- C -Rj wherein R is alkyl or aryl), nitrile (i.e., C-N), amide (i.eO, 0 / Rl - C--N wherein R~ and R" are either hydrogen, alkyl or \ R"
~ R' aryl radicals)J amine (i.e.3 - N wherein R' and R'9 are R"
either hydrogen, ~lkyl or aryl radicals), isocyanate, halogen ti,e., F, Cl, Br or I) and ether (i.e.j O---R, wherein R is either alkyl or aryl radicals)~ X and X' may be the same~or di~erent, However, in the case where X9 iS, an ester, X should be a functional group such as ester9 halogen, nitrile, etc., as explained hereinabove with respect to the respective re-wl4 ~ ~

~7~i3$

activity ratios o~ the comonomers used to prepare the gra~tcopolymers; Y is a substantially linear polymer or copolymer wherein at least one segment of the polymer has a suf~icient molecular weight to mani~est the properties of the respective polymer, iOe., a molecular weight of ~rom about 5,000 to about 150,000, very suitable polymers having a molecular weight in the range of from about 5,000 tq about 50,000, pre~erably a molecular weight o~ from about 10,000 to about 35,000~ more preferably 12JOOO to about 25,000; the symbols ~, b and c are positive integersj wi~h the proviso that a and b are each a value such that the physical properties o~ the uninterrupted segments in the backbone, e.gO, Tm, are mani~st, preferably at least about 20; and the symbol c is at least one, but pre~-erably greater than one, eOg., a value such that the molecular weight of the graft copolymer will be up to about 2,000,0~0.
The formation of the graft copoly~ers o~ the present invention may be better understood by reference to the ~ollow-lng reactions illustrated by the equations set ~orth below wherein the invention is illustrated in terms of polystyrene sldechains and polyethylene backbones. It can be seen ~rom these equations that the first reactions involve the prepara-tion of living polymers of polystyrene. The living polymers are thereafter reacted with a molar equivalent o~ allyl chlo-ride, wherein the reaction takes place at the carbon-chloride bond) rather than at the carbon-carbon double bond~ The vinyl terminated polystyrene, referred to herrein as the alPha-ole~in terminated macromolecular monomer, is then copolymerized with ethylene to produce a graft copolymer of polyethylene, whereby the vinyl moiety o~ the polystyrene is integrally polymerized into the linear polyethylene backbone.
Alternatively, the living polymer can be reacted ~7~3~
with an epoxide such asJ for example) ethylene oxide, to pro-duce an alkoxide ion which can then ~e reacted wi~h the halo~
gen-containing olefin~ i.eO, allyl chloride, to produce an alpha-ole~in termlnated m~cromolecular monomerO This, in es-sence) places the terminal alpha-ole~in ~arther away from the aromatic ring of the ~olystyrene and there~ore reduces any steric hindering influence that migh~ be exerted by the aro-matic ring.

~3763~
with an epoxide such as, for example, ethylene oxide, to pro-duce an alkoxide ion which can then be react~d wi~h the halo gen-containing ole~in, io e., allyl chloride, to produce an alpha-olefin term~nated macromolecula~ monomer. This, in es-sence, places the terminal alpha-ole~in ~arther away ~rom the aromatic ring o~ the polyst~rene and there~ore reduces any steric hindering in~luence that migh~ be exerted by the aro-matic ring.

.

~037636 FORMATION OF THE GRAFT COPO~YMER 0~ ALPHA-OLEFIN
.. ., . . . . . . , , . . .. . " ., ~ TERMINATED POLYSTYRENE SIDECHAIN AND POLYETHYLENE BACKBVNE
, -- , .. . . . . .
: CH3C~I2(CH3)CHLi + CH2 = CH

CH CH (CH )C~ ~3 6?
',, 0 Propagation: (n-l)CH2 = CH
¢~

3 2(C 3)CH l GH ~ ~ CH ~ + Li~9 ~0 Termdnation ~ith Active End Group. CH2 ~ CHCH Cl ~ 2 CH3CH2(CH3)CH ~ CH ~ ~ CH2CH ~ CH2 + LiCl Gra,~t Co~o,l.vmeriz,ation: xCH2 = CH2 ~ Polymerization Catalyst

2- ~ ( 2 CH ~ H2 CH ~ ,~

] ~ I

~0 In the equations above, the symbols a, b, ç, n.and X
are positive inte~ers wherein a and b are at least abo~t 20~ n has a value of from about 50 to about 500, and x has a ~lue -- \
`` ` ~037636 FORMATION OF THE GRAFT COPOLYMER OF ALPHA~OIEFIN
TERMI~ATED POIi~STYRENE SIDECHAIN AND POLYl~T~IYLENE BACKBON:E
.... .....
Initlatlon: CH3CN2(CH3)CHLl + CH2 = CE

CH~CH2 ( CH3 ) CHCH2~H -~ Li~) ~, ~
Pro~a~atlon: ¦ (n-l)CH2 = C

3 2( 3) H--CH2CH--- CH ~)H

L ~ ~n~
10 Termina~lon ~i~h Active End Group:CH2 =~ CHCH2Cl CH3CH2(CH3)CH~CH[~ CH2CH - CH2 + LiCl Gra~t coDol.~merization: XCH2 - CH2 ~ polyrnerizatiQn`~ca~alyst r ~CH2--CH2 ~ ( 'H- , . -CH ~ EH2 C

~13CH2(CH3)C ~ CH2- CH ~ ¦ ~

~Q In the equatlons ab~ve, the symbols a, b, c, n.and X
are positive integers wherein a and b are a~ least about 20~ n has a value of ~rom about 50 to about ~00, and x has a v~lue ~03763~;
correspondi.ng approximately to the sum o~ a and b.

The sidechains o~ the chemically joinedg phase sepa-rated graft copolymers, above, are preferably prepared by the anionic polymerization of a polymerizable monomer or combina-tion of monomersO In most instancesg such monomers are those having an ole~inic group, such as the vinyl containing com-pOU~9 although the olefinic containing monomers may be used 1. in combination with epoxy or thioepoxy containing compounds.
The living polymers are conveniently prepared by contacting the monomer with an alkali metal hydrocarbon or alkoxide salts in the presence o~ an inert organic diluent which does not participate in or inter~ere with the polymeriæation reactlonJ
Those monom~rs susceptible to anionic polYmerlzation are well-known and the present invention contemplat.cs the use of all anionically pqlymerizable monomersO Non-limiting il-lustrative spécies include vlnyl aromatic compounds, such as styrene, alpha-methylstyrene, vinyl toluene and its isomer$, vlnyl unsaturated amides such as acrylamide, methacrylamide, N,N-dilower alkyl acrylamidesJ e.gO, N,N-dimethylacrylamlde;
acenaphthalene; 9-acrylcarbazole~ acrylonitrile and methacrylo-nitrile; organic isocyanates including lower alkyl, phenyl, lower alkyl phenyl and halophenyl lsocyanates, organic dilso-cyanates including lower alkylene, phenylene and tolylene di-isocyanates, lower alkyl and allyl acrylates and methacrylates, including methyl, t-butyl acrylates and methacrylates; lower olefinsg such as ethylene, propylene, butylene, isobutylene, pentene, hexene, etcO; vlnyl esters o~ aliphatic carboxylic acids such as vinyl acetate~ vinyl propionate, vinyl octoate, vinyl oleate, vinyl stearate, vinyl ~enzoate; vinyl lower alkyl ethers, vinyl pyrldinesg vinyl pyrrolidones; dienes ~n-~376;~i cluding isoprene and butadiene. The ter~ "lower" is used aboveto denote organic groups containing eight or ~ewer carbon atomsO The pre~erred ole~inic containing monomers are con~u.
gated dienes containing 4 to 12 carbon atoms per molecule and the v~nyl-substituted aromatic hydrocarbo.ns containing up to about 12 carbon atomsO
Many other monomers suitable for the preparation of the sidechains by anionic polymeri~atlon are known in the prior art~
The initiators ~or these anionic polymerizations are any alkali metal hydrocarbons and alkoxide salts which produce a mono~unctional living polymer, iOe., only one end of the polymer contains a reactive anion, Those catalysts ~ound suitable include the h.ydrocarbons o~ lithium, sodium, or po-tassium as representea by the formula RMe wherein Me is an al-kali metal such as sodium, lithium or potassium and R repre-sents a hydrocarbon radical, ~or example, an alkyl radi¢al containing up to about 20 carbon atoms or more, and pre~erably up to àbout eight carbon atoms, an aryl radical, an alkaryl radical or an aralkyl radical, Illustrative alkali metal hy-drocarbons include ethyl sodium, n-propyl sodium, n-butyl po-tassium9 n-octyl potassium, phenyl sodium~ ethyl lithium, sec-butyl lithium, t butyl lithium and ~ethylhexyl lithium. Sec-butyl lithium is the preferred initiator because it has a fast initiation which is important in preparing palymers of narrow molecular weight distribution. It is preferred to employ the alkali metal salts o~ tertiary alcohols, such as potassium, t-butyl alkoxylateg when polymerizing monomers having a nitrile or carbonyl ~unctional group.
The alkali metal hydrocarbons and alkoxylates are either available commercially or may be prepared by known `~ ~

)37636 methods, such as by the reaction of a halohydrocarbon, halo benzene or alcohol and the appropriate alkali metal.
An inert solvent generally is used to ~acilitate heat trans~er and adequate mix~ng o~ initiator and monomer.
Hydrocarbons and ethers are the preferred solvents. Solvents use~ul in the anionic polymerization process include the aro-matic hydrocarbons such as benzene, toluene, xylene, ethyl-benzene, t-butylbenzene, etc. Also suitable are the saturated aliphatic and cycloaliphatic hydrocarbons such as n-hexane, n-1~ heptane, n-octane, cyclohexane and the like. In addition, aliphatic and cyclic ether solvents can be used, for example, dimethyl ether, diethyl ether, dibutyl ether, tetrahydro~uran, dioxane~ anisole, tetrahydropyran, diglyme) glyme, etc. The rates o~ polymerization are ~aster ln the ether solvents than in the hydrocarbon solvents, and small amounts o~ ether in the hydrocarbon solvent increase the rates of polymerization.
The amount of initiator is an important ~actor in anionic polymerization because it determlnes the molecular weight of the living polymerO If a small proportion of initi-ator is used, with respect to the amount o~ monomer~ the molec-ular weight of the living polymer will be larger than i~ a large proportion of initiator is used. Generally, it is ad-visable to add initiator dropwise to the monomer (when that is the selected order o~ addition) until the persistence of the characteristic color of the org~nic anion, then add the cal-culated amoun~ o~ initiator for the molecular weight desired.
The preliminary dropwise addition serves to destroy contamin-ants and thus permits better control o~ the polymerization.
To prepare a polymer of narrow molecular weight dis~
tribution, it is generally preferred to introduce all o~ the reactive species into the system at the same time. By this .

techniqueJ polymer growth by consecutive addition of monomertakes place at the same rate to an active terminal ~roup, without chain trans~er or termination reaction. When this i~
accomplishedJ the molecular weight of the polymer is control-led by the ratio Q~ monomer to initiatorJ as seen from the following representationO
Molecular Weight Moles of Monomer Molecular Weight Of = ~ - -~ Of Living Polymer Moles of Initiator Monomer As it can be seen from the above formula, high con-centrations of initiator leads to the ~ormation o~ low molecu-lar weight polymersJ whereas, low concentrations of initiator leads to the production of high molecular weight polymers.
The concentration of the monomer charged to the re-action vessel can vary widely, and is limited by the ability o~ the reaction equipment to dissipate the heat o~ polymeriza-tion and to properly mix the resulting vlscous solutions of the living polymer. Concentrations of monomer as high as 50%
by weight or higher based on the weight of the reaction mix-ture can be used. However, the preferred ~onomer concentra-tion is from about 5~ to about 25% in order to achieve ade-quate mixing.
As can be seen from the formula above and the ~ore-going limitations on the concentration of the monomer, the in-itiator concentration is critical, but may be varled according to the desired molecular welght of the living polymer and the relative concentration of the monomer~ Generally, the initi-ator concentration can range from about OoO01 to about 0~1 mole of active alkali metal per mole of monomer, or higher.
Preferably~ the concentration of the initiator wili be from about 0.01 to about 0.004 mole of active alkali metal per mole of monomer~

10~7636 The temperature of the polymerization will depend on the monomer. Generallyg the reaction can be carried out at temperatures ranging ~rom about -100C. up to about 100Co When using aliphatic and hydrocarbon diluents, the preferred tempera~ure range is from about -10C. to ~bout 100Co With ethers as the solvent, the preferred ~emperature range ~5 ~rom about -100C. to about 100C. The polym~rization of the sty-rene is generally carried out at slightly above room te~pera-ture; the polymerization of al~ha-methylstyrenç prefera~ly is carried ou~t at lower temperatures, eOg., -80C.
The preparation of the living polymer can be carried out by adding a solution of the alk~li metal hydrocarbon ini-tiator in an inert-organic so~ven~ to a mixture of monomer and diluent at the desired polymer~ation temperature and allowing the mixture to stand with or without agitation until the poly-merization is completedO An alternative procedure is to add monomçr to a solution of the catalyst in the diluent at the desired polymerization temperature at the same rate that it is being polymerized. By either method the monomer is converted ao quantitatively to a living polymer as long as the system re-mains free of impurities which inactivate the anionic species.
As poin~ed out above, however, it is important to add all of the reactive ingredients together rapidly to insure the forma-tion of a uniform molecular weight distribution to the poly~
merO
The anionic polymerization must be carried out under carefully controlled conditions, so as to exclude substances which destroy the catalytic effect of the catalyst or initi-ator. For example, such impurities as water, oxygen, carbon monoxide, carbon dioxide, and the likeO Thus, the polymeriza~
tions are generally carried out in dry equipment, using anhy-~037636 drous reactants, and under an inert gas atmosphere3 such asnitrogen, helium~ argon~ methanç, and the like~
The above-described living polymers are susceptible to ~urther reactions including further polymerizationO Thus, if additionàl monomer, such as styrene, is added to the living polymer, the polymerization is renewed and the chain grows un~
til no more monomeric styrene remainso Alternatively, if an-other different a~ionically polymerizable monomer is added, such as butadiene or ethylene oxide, the above-described liv-ing polymer initiates the polymerization of the butadiene orethylene oxide and the ultimate living polymer whlch resu}ts consists o~ a polystyrene segment and a polybutadiene or poly-oxyethylene segmentO
A poly(styrene-ethylene) block copolymer can be pre-pared by contacting living polystyrene with ethylene in the presence of a compound of a transition metal of Group V-VIII
in the periodic table, e.g.~ ~itanium tetrachloride. This technique is also applicable to the alpha-ole~ins, such as propylene. The resulting copolymer is still a living polymer 2Q and can be terminated by the methods in accordance to the prac-tice of the present inventionO
As noted above~ the living polymers employed in the present invention are characterlzed by relatively uniform molecular weight, iOe., the distribution of molecular weights of the mixture o~ living polymers prQduced is quite narrowO
This is in marked contrast to the typical polymer, where the molecular weight distribution is quite broad, The difference in molecular weight distribution is particularly evident from an analysis of the gel permeation chromatogram of commerical O polystyrene (Dow 666u ~prepared by free-radical polymerization and pol~styrene produced by the anionic polymerization process ~r~ Q ~

~ (~3763q~utilized in accordance with the practice o~ the present inven-tion.

By Termination Of The Llv~ Po ymers The living polymers herein are terminated by reaction with a halogen-containing compound which also contains a poly-merizable moiety, such as an ole~inic group or an epoxy or thio-epoxy group. Suita~le halogen-containing terminating agents in-clude: the vinyl haloalkyl ethers wherein the alkyl groups contain six or fewer carbon atoms such as methyl, çthyl, pro-pyl, butyl, isobutyl, sec-butyl,~-amyl or hexyl; vinyl esters or haloalkanoic acids wherein the alkanoic acid contains six or ~ewer carbo~ atoms, such as acetic/ propanoic, butyric, penta-noic, or hexanoic acid; alefinlc halides haring six or fewer carbon atoms such as vinyl halide, allyl halide, methallyl halide, 6-halo-1-hexene, etc.; halides of dienes such as 2~
halomethyl-1~3-butadiene, epihalohydrins, acrylyl and metha-crylyl halides, haloalkylmaleic anhydrides; haloalkylmaleate esters; vinyl haloalkylsilanes; vinyl haloaryls; and vinyl haloalkarylsJ such as vinylbenzyl chloride (VBC); haloalkyl norbornenes, such as bromomethyl norbornene, bromonorbornane, and epoxy compounds such as ethylene or propylene oxide. The halo group may be chloro, fluoro, bromo, or iodo; pre~erably, it is chloro. Anhydrides of compounds having an olefinic group or an epoxy or thioepoxy group may also be employed, such as maleic anhydride, acrylic or methacrylic anhydride.
The ~ollowing equations illustrate the typical termination re-actions in accordance with the practice o~ the present inven-tion:

~03763~

Livin~; Polymer:
Rl R
R--CH2~ ~ C----C~2 - C(3 + L~
R2 n R2 Te rminat ing A~;ent s;
( a ) X_ R3 _O--p = CH2 (b) X~ R3--C--O--C 5 CX2 ( c ) X_R3_C = CH2 /\
( d ) X--R3-- CH CH2 ,0, ( e ) X~ C ,C = CH2 ( f ) X__ R C C~

2û (g) X--R3--Cj--CoOR3 R4~ C- CooR3 (h) ~R-- SiRR,C CH?

3~ = CH2 1~376:~

PH2 = C - C _, CH2 R ;F,l (a) R~ - CH2 - C ~ ~ C--R3 OC = CH
R2 Irl R2 r t 2 , ~ C~C--R--C~OC = CH

~ Rl_ 1~ ~ c ) R ~ - CH2 C,----C~2 - C . R3--C = CH2 _ R2 r~ ~2 R4 (d~ R~GH2 C~CH~ ,C R C ~2 R2 n ~2 R4 ,1 o ~e) R--CH2 C ~CH2_ C ~ . C--C = CH2 _ R2 , n R2 R4 r Rll Rl (f) R--~H2 C -- CH2~ C R3C ~ CO
2û _ R2 ,n R2 R4C~C~

_ 1- ¦ R
g ) R--CH~ C I CH2. C--R3 Cj ~COOR2 _ R2 n 3R2 ~4--C--COO R2 -26, ~37~3$

Rl I
(h) R - -CH2 - C - r CH~ C R3 - SiRRC = CH2 R2 n R2 R4 Rl- ~,1 (i) R~H2--C~CH2~ ' CH2 R Rl CH
(j) R - -CH C - CH2- C - CH2 - ,C, _ R2_ n ~2 CH2 In the above equations, R) R1, R2J R3 and R 4 are each selected from the group consisting o~ hydrogen and lower alkyl, and aryl radicals, Preferab~y, R will be lower alkyl, such as sec-butyl; Rl will be either hydrogen or methyl; R2 will be phenyli R3 will be hydrogen or lower alkylene radi.cal;
and R4 will be either hydrogen or lower alkyl radical, The symbol n i8 a positive integer such that the properties of the polymer are manifestJ i,e., a value such that the polymer wlll have a molecular weight in the range of ~rom about 5,000 to about 50~000, preferably a molecular welght in the range of from about 10,000 to about 35jO00~ more preferably a molecular weight in the range o~.from about 12J 000 to about 25,000.
Termination o~ the living polymer by any o~ the above types o~ terminating agent~ is accom~lished simply by adding the terminating agent to the solution of living polymer at the temperature at which the living polymer is prepared. Reaçtion is immediate and the yield is theoretical. A slight molar ex-cess o~ the terminating agent~ with respect to the amount of r~
~03~;~i36 catalystg m~y be used although the reaction proceeds on a mole-~or-mole basisO
The te~mination may be conducted in any suitable in-ert solvent. Generally, it is advisable to utilize -the same solvent system employed in the preparation of the ll~lng poly-mer. A preferred embodiment of thç inventlon comprises con-ducting the termination reaction in a hydrocarbon solvent rather than the polar ether type solvents such as tetrahydro-furanO It has been found that the hydrocarbop solvents such as the aromatic hydrocarbons, saturated aliphatic and cyclo-aliphatic hydrocarbons cause several differences in the reac-tion conditions and the resulting product. For example, the termination reaction can be conducted at higher temperatures with hydrocarbon solvents as opposed to the ether solvents.
In some instances, because of the nature of the liv-ing polymer and the monomer from which it is pr,epared, or be-cause of the nature of the terminating agent, certa~;-deleter ious side reactions occur which result in an impure product.
For example, the carbanion of some living polymers have a ten-dency to react with functional groups or any active hydrogensof the terminating agent. Thus, for example, acrylyl or meth-acrylyl chloride while they act as terminating age~ts because o~ the presence of the chlorine atom in their structure, they also provide a carbonyl group in the terminated polymer chain, and this carbonyl group may provide a center for attack by a second highly reactive living polymer, The resulting polymer either has"twice the expected'molecular weight or contains some chlorine, indicating that some of the living polymer has been terminated by reaction with a second living polymer or with one of the active hydrocarbons of the acrylyl or metha-cryly] chloride, ~03763~

It has been discovered that one means for overcoming the foregoing problem is to render the reacti~e carbanion less susceptible to reaction with the functlonal groups or any ac~
tive hydrogens of a terminating agentO A preferred method to render the living polymer less susceptible to the adverse reac-tion is to "capt' the highly reactive living polymer with a lesser reactive reactantO Examples of some ~referred "capping agents" include the lower alkylene oxides, io eO ~ one having eight or fewer cairbon atoms such as ethylene and propylene oxide; diphenyl ethylene, etc. The "capping" reaction yields a product which still is a living polymerg but yields a purer product when subsequently reacted with a termlnat~ng agent contalning a ~unctional group or active hydrogenO
It ha~ been ~ound that diphenyl ethylene is an ex-cellent "capping agent" when terminating agents such as, for example9 vinyl chloroalkanoates are employedO
A particularly preferred "capping agent" is an alkylene oxide, such as ethylene oxideO It ~eac~s with the living polymer, with the destruction of its oxirane ringO The following is a typical illustration of the "capping reactionN
whlch shows the reaction of ethylene oxide as a capping agent with a living polymer prepared by the polymerization of sty rene with sec-butyl lithium as theiinitiatoro sec-~u~ E2C ~ CH ~ Li + CH2/GH2~sec-~u ~ ~ ~ CH ~ -CH2CH2~ ~i The capping reaction is carried out quite simiply, as in the case o~ the terminating reaction, by adding the capping reactant to the living polymer at polymerization temperatures.
The reaction occurs immediately. As in the case of the termin--29~

~L03~;3E;

ation reaction, a slight molar excess of the capping reactant with respect to the amount of initiator may be used. The re-action occurs on ~ mole-for~mole basis.
It will be understood that when a large molar excess o~ alkylene oxide is reacted with the living polymer, a living polymer having two polymeric blocks is producedO A typical example with polystyrene segments and polyoxyalkylene segments is illustrated as ~ollowsO
sec-Bu ~ H ~ ~ CH ~ CH2CH20)x _ CH2CH20 + Li wherein x is a positive integer.
Either of the above-described ethylene oxide t'capped"
polymers can be conveniently terminated with a compound con-taining a moiety reactive with the anion o~ the c~pped polymer and a polymerizable end group9 including the following typical compounds. acrylyl chloride, methacrylyl chloride~ vinyl-2-chloroethyl ether, vinyl chloroacetate, chloromethylmaleic an-hydride and its esters, maleic anhydride (yields-half ester of maleic acid following protonation with water), allyl and meth-allyl chloride and vinylbenzyl chloride.
The reaction of the above-described "capped living polymers with either acrylyl or methacrylyl chloride can be represented by the following reaction~

~l~)3763~

CH =`C-C-Cl sec~R~ ~ 2 ~ ~ (CH2CH20)x~~~2C~20 + Li R4 ' i ., F ~2 ~ ~ (cx2cH2o)x--cN2cH2occ = CH2 ~ L1Cl wherein n is a positive integer of about at least 509 x is either 0 or a positive integer and R is either hydrogen or methyl~
When an epihalohydrin is used as the terminating reagent, the resulting polymer contains a terminal epoxy group.
This terminal epoxy may be used as the polymerizable group it-self, such as in the preparation of a polyisobutylene or a polypropylene oxide backbone graft copolymer or may be con-verted to various other use~ul polymerizable e~d groups by any one of several known reactions.
As one embodiment of the invention9 the terminated polymer containing an epoxy or thioepoxy end group may be re-acted with a polymerizable carboxylic acid halide, such as acrylic, methacrylic, or maleic acid halide, to produce a beta-hydroxyalkyl acrylate, methacrylate or maleate ester as the polymerizable terminal moiety of the substantially uniform molecular weight polymer. These same polymer~xa~le esters ~ay be prepared from the terminal epoxy p~lymer by first convert-ing the epoxy group to the corresponding glycol by warming the polymer with aqueous sodium hydroxide, followed by convention-al esterification of the glyco~ end group with the appropriate ~37~i36 polymerizable carboxylic acid, or ~cid halideO
The resulting glycol obta~ned by the aqeuous hydrol-ysis o~ the epoxy group in the pr~sence o~ a baæe may be con-verted to a c~po4ymer by reaction with,a high molecular weight dicarboxylic acid which may be prepared, e.g., by the polymer-ization of a glycol or diamine with a mol&r excess of phthalic anhydrideJ maleic anhydrideJ succ~nic anhydride, or the like.
These reactions can be modified to obtain a polystyrene block and a polyamide block (Nylon), The glycol terminated polymer may also be reacted with a diisocyanate to form a polyurethane The diisocyanate may be e.g., the reaction product of a poly-ethylene glycol having an average molecular weight of 400 wlth a molar excess of phenylene dilsocyanateO
In another embodiment of the invention, an organic epoxide is copolymerized with a terminated polymer containing an epoxy or thioepoxy end group, The graft copolymer which results is characterized by a backbone having uninterrupted segments of at least about 20, and preferably at least about 30, recurring units of the organic epoxide. Preferred organic epoxides include ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, cyclohexene epoxide and styrene oxide, i.e., those having 8 or ~ewer carbon atoms.
When a haloalkylmaleic anhydride or haloalkylmaleate ester is used as the terminating age~t, the resulting terminal groups can be converted by hydrolysis to carb~xyl gro~psO The resulting dicarboxylic polymer may be copolymerized with glycols or diamines to form polyesters and polyamides having a graft copolymer structureO
If it is desired to isolate and further puri~y the macromolecular monomer from the solvent from which it was pre-pared, and of the known techniques used by those skillecl in the art in recovering polymeric materials may be u~ed. These techniques includeO (1) solvent-non-solvent precipltation;
(2) evaporation of solvent in an aqueous media, ~nd (3) evapo-ration of solventJ such as by vacuum roll drying, spray dr~y-ing~ freeze drying, and (4) steam jet coagulation~
The isolation and recovery of the macromolecular monomer is not a critical feature of the invention In ~act, the macromolecula~ monomer need not be recovered at all~
Stated otherwise, the macromolecular monomer, once ~ormed, can be charged with the suitahle monomer and polymeriza~ion cata-lyst to conduct the graft copolymerization in the same system as the macromolecular monomer was prepared, providing the sol-ve~t and materials ln the macromolecular monomer preparation reactor do not poison the catalyst or act in a dele~erious man-ner to the graft copolymerieation process. Thus~ a ~udicious selection of the solvent and purification of the reactor system in the preparation of the macromolecular monomer ca:n ultimate-ly result in a large savings in the production of the graft copolymers of the present invention.
As pointed out above, the maçromolecular monomers~
which ultimately become the sidechains of the gra~t copolymers by being integrally polymerized into the backbone polymer, must have a narrow molecular weight distribution. Methods ~or de-termining the molecular weight distribution o~ polymers such as the macromolecular monomers are known in the art. Using these known methods, the weight average molecular weight (Mw) and the number average molecular weight (~n) can be ascertain-ed~ and the molecular weight distribution (Mw/~n) for the macromolecular monomer can be determinedO The macromolecular monomers must have nearly a Poisson molecular weight distribu-tion or be virtually monodisperse in order to have the highest ~3763~
degree of ~uncti~nality~ Preferably, the ratio of ~w ~ o~the novel macromolecular monomers will be less than about 1. lo The macromolecular monomers of the prçsent invention possess the aforementioned narrow molecular weight distribution and purity due to the method of their preparat;ion~ described here-inabove. Thusg it is important that the sequence o~ step~ ln preparing the macromolecular monomers be adhered to in order to produce the optimum results in beneficial properties in the graft copolymers.
Prior to the invention herein, gra~t copol~mers were prepared by synthesizing a linear ~backbone") then grafting onto this backbone, growing polymeric or preformed polymeric chains. These methods generally re~uire elaborate equipment and produce a mixture of products having inferior properties unless further puri~i.ed~ Because o~ the additional processing conditions and the use of special equipment, these proce~ses are not economically feasible.
Although some of the prior art graft copolymers re-semble the gra~t copolymers of the present invention, neuer-theless generally, the present graft copolymers are differentcompositions, not only because they are prepared by signifi~ ;
cantly di~ferent processes, but because the pendant polymeric chains of the graft copolymers of this invention are of rela-tively uniform, minimum length, and are each an lntegral part o~ the backbone, Furthermore~ the backbone o~ the graft co-polymers o~ the present invention contain polymeric segments of certain minimum length. Thus~ the present graft copolymers differ structurally because the macromolec~lar monomer is interposed between polymeric segments of the backbone polymer, rather than being merely attached to the backbone polymer in a random manner. These characteristics contribute materially ~ 37636 to the advantageous propertles which inhere in these novel graft copolymers.
The graft copolymers of the present invention are prepared by first synthesizing the pendant polymeric chains ~the polymerizable terminated living polymers) then copolymer-izing the terminal portions of the polymeric chains with the second monomer during the formation of the backbone polymer.
In accordance with the practice of the present in-vention, the substantially pure macromolecular monomers of high controlled molecular weight and mol~Gular weight distribu-tion have an appropriate reactive end group suitable for any mechanism of copolymerization, e.g,, ~ree-radical, cationic, anionic, Ziegler catalysisJ and condensa~ion. Thus, the re-actlve end group is selected ~or easy copolymerizatlon with low cost monomers by conventional means and within existing polymerization equipment.
The copolymerization with the macromolecular mono-mers and the secand reactive monomer is a gra~t-like structure where the pendant chain is a polymer whose molecular weight and distribution are predetermined by independent synthesis.
The distribution of the sidechain polymer along the backbone is controlled by the reactivity ratios of the comonomers.
Since the reactive end group of the macromolecular monomer is copolymerized with the second monomer, it is an in-tegral part of the backbone polymer. Thus, the polymerizable end group o~ the macromolecular monomer is interposed between large segments of the backbone polymer.
The present invention provides a means ~or control-ling the structure of the graft copolymer. More specifically, the control of the structure o~ the gra~t copolymer can be ac-complished by any one or all of the following means: (1) by ~376;~
determining the reactivity ratio of the macromolecular monomerand a second monomer during the copolymerization reaction, a pure graft polymer free from contamination by homopolymers can be prepared~ (2) by controlling the monomer addition rates dur-ing the copolymerization o~ a macromolecular monomer and a sec-ond monomer, the distance between the sidechains in the poly-mer structure can be controlled; and (3) the size of the graft chain can be predetermined and controlled in the anionic poly-merization step o~ the preparation of the macromolecular mono-mer.
It will be apparent to those skilled in the art that by the proper selection o~ terminating agents, all mechanisms o~ copolymerization may be employed in preparing the controlled phase separated gra~t copolymers.
As alluded to hereinabove, the chemically joined, phase separated graft copolymers o~ the present invention are pre~erably copolymerized with any ethylenically-unsaturated monomer including the vinylidene type compounds containing at .1 least one vinylidene CH2 = C - group and preferably the vinyl-type compounds containine the characteristic CH2 = CE- group wherein hydrogen is attached ~o one o~ the free valences of the vinylidene group. The copolymerization, as pointed out above, is only dependent upon the relative reactivity ratios of the terminal group and the comonomerO
Examples of some of the preferred ethylenically-un-saturated compounds used as the comonomers include the a~rylic acids, their esters, amides and nitriles including acrylic acid, methacrylic acid, the alkyl esters ~f acrylic and meth-acrylic acid, acrylonitrile, methacrylonitrile9 acrylamide,methacrylamide, N,N-dimethacrylamide (NNDMA); the ~inyl ~037~3~i halides such as vinyl chloride, and vinylidene chloride; the vinyl cyanides such as vinylidene cyanide (l,l-dicyanoethyl-ene); the vinyl esters of the fatty acids such as vinyl ace-tate, vinyl propionate and vinyl chloroacetate, etcO; and the vinylidene containing dicarboxylic anhydrides, acids and esters, such as maleic and ~umaric anhydride, acids or esters thereofO
A particularly important class of vinylidene type compounds useful as comonomers with the alpha-olefin and sty-rene terminated macromolecular monomers include the vinyl ole-finic hydrocarbons, such as ethylene, propylene, l-butene~ iso-butylene~ l-pen~ene, l-hexene, styrene, 3-methyl-1-butene, 4-methyl-l-hexene and cyclohexene~ Also, there may be used as the comonomers the polyolefinic materials containing at lea~t one vinylidene group such a~ the butad~ene-1,3 hydrocarbons including butadiene, isoprene, piperylene and other conjugated dienes, as well as other conjugated and non-conjugated poly-ole~inic monomers including divinyl benzene, the diacrylate type esters of methylene, ethylene, polyethylene glycols, and polyallyl sucroseO
The most preferred ethylenically unsaturated comono-mers are the commercially available and widely used monomers such as methyl acrylate, butyl acrylate, 2-ethyl hexyl acry-late, methyl methacrylateJ vinyl chloride, vinylidene chlo-ride, vinylidene cyanide, acrylonitrile, and the hydrocarbon -monomers such as ethylene, propylene, styrene, and the con~û-g~ted dienes such as butadiene and isopreneO
In addition to the hereinabove described ethylenic-ally-unsaturated comonomers use~ul in the practice of the in-vention, there are included the comonomers capable of copoly-merizing by condensation or step reaction polymerization con-~037636 ditions with the polymerizable macromolecular monomer~ o~-the invention~ In this connection, the polymerizable macromolecu-lar monomers w~11 contain the appropriate terminal groups ne-cessary to ~acilitate the condensation reactionO For example, living ~olymers terminated with eplchlorohydrin will contain OH OH
an epo~y tenminal group w~ich co~verts to a CH- CH2 group upon saponification. This vicinal hydroxy group is capable of copolymerizing with polybasic acids and anhydrides to ~orm polyesters, such as adiplc acid, phthalic anhydride, maleic anhydride, succinic anhydride, trimellitic anhydride, etc.;
aldehydes to form polyacetals, such as polg~ormaldehyde, u~ea-formaldehydesg acetaldehydes, etc.; polyisocyanates and poly-lsocyanate prepolymers to ~orm polyurethanes3 and siloxanes to ~orm polysiloxanesO The living polymers terminated with halomaleic anhydride or halomaleate ester may be converted to terminal carboxyl groups by conventional hydrolysisO The re-sulting dicarboxylic terminated po}ymer can be copolymerized with glycols to form polyesters or with diamines to form poly-amides having a graft copolymer structure. Alternatively, themaleic anhydrlde or ester terminal group or the polymer can be used ln the candensation polymerization with the glycols or diamines. ~he vicinal hydroxy or carboxyl terminated pol~mers of the invention can also be copo1ymerized with epoxy c~m-pounds, and the imine compounds, such as ethylene~mineO
The placement of the sidechain in the polymer back-bone is dependent on the terminal group o~ the macromolecular monomer and the reactivity of the comonomer~
The macromolecular monomers of the invention are stable in storage and do not significantly homopolymerize, Furthermore, the macromolecular monomer copolymerizes through ~)3763~
the terminal double bond or reactive end group and is not in-corporated into the polymeric back~one by grafting reactions to the polymer o~ the macromolecular monomer segment.
As indicate4 hereinabove, the macromolecular mono-mers of the invention copolymerize with commercial vinyl mono-mers in a predictable manner as determined by relative reac-tivity ratios. It can be shown that the instantaneous copoly-mer equation:

lQ (1~ dM1 ~ Mll rrlMl ~ 2 L ~ L 1 + r2 simply ~educes to ~he approximation:
(2) d 1 ~ M1 when ~ is in very low molar concentra~ion~.
Thus~ the macromolecular monomer (Ml) copolymerizations with other monomers (M2) are described only by r2 values and mono-mer feed compositions. Rearra~gement of equatio~ (2) gives:
~3) dM2/M? % Conversion M2 2 dMl/Ml ~ ~Convërsion Ml The reactivity ratio~ r2~ can be estimated ~rom a relatively low conversion sample o~ a single copolymerization experiment. The validity of this con~ept of a predictable and controllable reactivity o~ the macromolecular monomer can thereby be established. It has been shown that the re~ctivity of ¢ommerçial monomers with the macromolecular monomers of the present invention with vàrious end groups correlate with avail-able literature values for reactivity ratios of r2, The method of the present invention permits the ~)37636 utilization o~ all types o~ polymerizable monomers ~or incor-poration into backbone polymers, and makes it poss~ble ~or the ~irst time to design and build gra~t copolymers of controlled molecular structure, and of backbone and gra~t segments with di~erent properties, such as hydrophobic and hydrophilic seg-ments, crystalline and amorphous segments~ polar and non-polar segments, segments with widely di~ferent glass transition tem-peratures, whereas prior work on SDA terblock copolymers had been limited to the incompatibility of glassy polystyrene blocks with rubbery polydiene blocks.
The cDpolymerization o~ the polymerizable macro-molecular monomers with the comonomers may be conducted in a wide range o~ proportions. Generally spea~ing~ a suf~icient amount o~ the macromolecular monomer should be present to pro-vide the chemically ~oining of at least one of the uniform molecular weight sidechain polymers to each backbone polymer, so that a noticeable ef~ect on the properties o~ the graft copolymeric properties can be obtained. Since the molecular weight of the polymerizable macromolecular monomer generally exceeds that of the polymerizable comonomers, a r~latively small amount o~ the polymerizable macromolecular monomer can be employed, However, the chemically ~oined, phase separated thermoplastic graft copolymers may be prepared by copolymer-izing a mixture containing up to about 95% by weight, or more, of the polymerizable macromolecular monomers of this inven-tion, although mixtures containing up to about 60% by weight of the polymerizable macromolecular monomer are preferred.
Stated otherwise, the resinous thermoplastic chemically joined, phase separated graft copolymer of the invention is comprised o~ (1) from 1% to about 95~ by weight of the polymerizable macromolecular monomer having a narrow molecular weight clis--40~-1~37636 utilization of all types of polymerizable monomers for incor-poration into backbone polymers, and makes it possible for the first time to design and build graft copolymers of controlled molecular structure, and of backbone and gra~t segments with different properties, such as hydrophobic and hydrophilic seg-ments, crystalline and amorphous segmentsg polar and non-polar segments, segments with widely different glass transition tem-per~tures, whereas prior work on SDA terblock copolymers had been limited to the incompatibility of glassy polystyrene blocks with rubbery polydiene blocks.
The copolymerization of the polymerizable macro-molecular monomers with the comonomers may be conducted in a wide range of proportions. Generally speakingg a sufficient amount of the macromolecular monomer should be present to pro-vide the chemically joining of at least one of the uniform molecular weight sidechain polymers to each backbone polymer, so that a noticeable effect on the propertles of the graft copolymeric properties can be obtained. Since the molecular weight of the polymerizable macromolecular monomer generally exceeds that of the polymerizable comonomers, a r~latively small amount of the polymerizable macromolecular monomer can be employedO ~owever, the chemically joined, phase separated thermoplastic graft copolymers may bè prepared by copolymer-izing a mixture containing up to about 95~ by weight, or more, of the polymerizable macromolecular monomers of this inven-tion, although mixtures containing up to about 60~ by weight of the polymerizable macromolecular monomer are pre~erred.
Stated otherwise, the resinous thermoplastic chemically joined, phase sqparated graft copolymer of the invention is comprised of (1) from 1~ to about 95% by weight of the polymerizable macromolecular monomer having a narrow molecular weight clis--40~--~,o3763~ , .
tribution (iOeO~ a Mw/~n o~ less than about lol)g and ~2) from 99% to about 5~ by weight o~ a copolymerizable comonomér de-~ined her~inabove.
The polymerizable macromolecular monomers copoly-merize with the hereinabove re~erred to comonomers in bulk, in solution, in aqueous suspension and in aqueou~ emulsion systems suitable for the particular pol~merizable macromolecular mono-mer, its end group and the copolymer employedO I~ a catalyst is employed, the polymerization environment suitable ~or the catalyst should be employed. For example~ oil- or solvent-soluble peroxides such as benzoyl peroxldes, are generally ef-fective when the polymerizable macromolecular monomer is co-polymerized with an ethylenically unsaturated comonomer in bulk~ in solution in an organic solvent such as benzene, cyclo-hexane, hexane, toluene, xylene, etc. 9 or in aqueous suspen-sion, Water~soluble peroxides such as s~dium9 pqtassium9 lithium and ammonium persul~ates) etc. are use~ul ln aqueous suspension and emulsion systemsO In the copolymerization o~
many o~ the polymerizable macromolecular monomers, such as those with an ethylenically-unsaturated end group and a poly-st~rene, polyisoprene or polybutadiene repe~ting unit, an emulsi~ier or dispersing agent may be employed in aqueous sus-pension systems~ In these systems, particular advantage can be achieved by dissolving the water-insoluble polymerizable macromolecular monomer in a small amount of a suitable sol-vent, such as a hydrocarbon. By this novel technique, the co-monomer copolymerizes with the polymerizable macromolecular monomer in the solvent, in an aqueous system surrounding the solvent-polymer system. 0~ course, the polymerization cata-lyst is chosen such that it will be soluble in the organicphase of the polymerization systemO
~41-~03763$

As previously stated, various di~ferent catalyst systems can be employed in the present invention ~or the co-polymerization processO It will be apparent to those skilled in the art that the particular catalyst sy~tem used in the co-polymerization will vary, depending on the monomer feed and the particular end group on the macromolecular monomerO For example, when using a macromolecular monomer having a vinyl acetate end group, best results are generally obtained by em ploying free-radical catalyst systemsO On the other hand, co-polymerization u~ilizing isobutylene monomer feed with eitheran allyl, methallyl or epoxy terminated macromolecular mono-mer, best results are accomplished by utilizing the cationic polymeri,zation techniques, Since the particular polymerizable end group on the macromolecular monomer will depend on the co-monomer feed employed because of the relative reactivity ra-tio:sJ the polymerization mechanism commonly employed for the particular comonomer will be used. For example, ethylene poly-merizes under free-radical, cationic and coordination polymer-ization conditions; propylene and higher alpha-olefins only polymerize under coordination polymerization conditions; iso-butylene only polymerizes under cationic polymer~z~tion condl-tions; the dienes polymerize by free-radical anionic and co-ordination polymerizatian conditions; styrene polymerizes under free-radical, cationic, anionic and coordination condi-tions; vinyl chloride polymerizes under free-radical and co--ordination polymerization conditions, vinylidene chloride polymerizes under free-radical polymerization conditlons;
vinyl fluoride polymerizes under free-radical conditions;
tetra~luoroethylene polymeri~es under ~ree-radical and co-ordination polymerization conditions; vinyl ethers polymerizeunder cationic and coordination polymerization conditions;

-4?--~376;~6 vinyl esters polymerize under free-radical polymerization con-ditions, acrylic and methacrylic esters polymerize under free-radical, anionic and coordination polymerization condi~ions, and acrylonitrile polymerizes under free-radical3 anionic and coordination polymerization conditionsO
It will be understood by those skilled in the art that the solvent9 reaction conditions and feed rate will be partially dependent upon the type of catalyst system utilized in the copolymerization process, One of the considerations, - 10 of course, will be that the macromolecular monomer be dis-solved in the solvent system utilized. It is not necessary, however, ~or the monomer feed to be soluble in the solvent system, Generally, under these conditions during the forma-tion o~ the copolymer, the graft copolymer will precipitate out of the solvent wherein it can be recovered by techniques known in the polymer artO
The temperature and pressure conditions during the copolymerization process will vary according to the type of catalyst system utilized. ThusJ in the production of low den-sity polyolefin backbones under free-radical conditions, ex-tremely high pressures will be employed. On the other hand, the high density substantially linear polyolefin backbone polymers produced by the coordination type catalyst generally will be prepared under moderately low pressures.
When preparing graft copolymers having a poly41efin backbone of ethylene or propylene or copolymers of ethylene and propylene together with a macromolecular monomer, it is preferred to employ a coordination catalyst known in the art as the Ziegler catalyst and Natta catalysts (the latter being commonly used for polypropylene). That is, materials ad~
vanced by Professor DrO ~arl Ziegler of the Max Planck 10376,~6 Institute of Mulheim, Ruhr, Germany, and Dr. Giulio Natta o~
Milan, Italy~ These catalysts are prepared by the interaction of a compound of transition metals of group IV-VIII in the periodic table, the catalyst, and an organometallic compound derived from group I-III metals~ as co-catl~lyst. The latter are compounds such as metal hydrides and alkyls capable o~
giving rise to hydride ions or carbanionsJ such as trialkyl aluminum. Compounds of the transition elements have a struc-ture with incomplete d-shells and in the lower valence states, can associate with the metal alkyls to ~orm complexes with highly polarlzed bonds. Those elements hereinabove re~erred to as the catalysts are pre~erably titanium, chromium, vana-dium, and zirconlum. They yield the best Ziegler catalysts by reaction of their compounds with metal alkyls.
Compounds Or these transition metals in the higher valence stage, e.g., titanium tetrachloride, are reduced by the metal alkyls to a lower valence state. The reswltant prod-ucts containing the transition metal in the lower valence ~t~te, e.g., titanium dichloride, react directly with the metal alkyl to yield active catalysts possessing hydride ions or car~anions. If the reduction of the transition metal com-pound proceeds to the ~ree metal, the resultant products are either suitable for catalysis of the displacement reaction, e.g~, nickel, cobalt, platinum, or an active polymerization catalyst.
Also included among the coo~dination catalysts con-templated for the copolymerization process of the present in-vention are those catalyst systems comprising a compound of one or more of the elements o~ titaniuml zirconium, cerium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, wherein at least a part o~ the metal is present in a valence ~ i3~;state of three or below and preferably two3 or is associatéd with a su~ficient quantity of a reduci~g agent capable of re-ducing the valence state o~ the polyvalent metal to such a lower state, Suitable reducing agents include Grignard re~ -agents, metal alkyls or aryls, zinc metal and metals above zinc in the electromotive series, and the metal hydrides.
As is well-kn~wn, the Ziegler catalysts which are e~fective for the polymerization of ethylene to linear, high density, high molecular we~ght polyethylene, and the stereo-specific polymerization of other al~ha-olefins to crystalline, stereoisomeric polymers are g~nerally heterogeneousO
The various Ziegler catalysts referred to above are approximately equally capable of polymeriæing either ethylene, higher ~le~-olefins, such as p~opylene, 1-butene, isobutylene, l-pentene, l-hexene, styrene, 3-methyl-1-butene and 4-methyl-l-hexene and conjugated diolefins such as butadiene and iso-prene. They can also be used in the copolymerization o~ any of these monomers with ethylene and other al~ olefins in con-junction with the macromolecular monomers of the present in-vention. The difference between the polymerization of ethyl-ene and that o~ alpha-olefins lies in the possibility of at-taining structural regularity in higher polyolefins.
Genera~ly speaking, the production of the high den-sity graft copolymers having olefin backbones will be conduct-ed at pressures of ~rom about 1 to about 1,000 pSiJ preferably from about 1 to 200 psi~ The pressure may be increased by the use of nitrogen gas, i~ desired.
As previously stated, the solvent system utilized will most conveniently be the solvent employed ln the prepara-tio~ of the macromolecular monomer. Solvents useful for thepolystyrene macromolecular monomers are those which dissolve 103763~
' polystyreneO Typical solvents for polystyrene include cyclo-hexane, benzeneg toluene, xylene, decalin, tetraling etcO
The copolymerization reaction may be conducted at any suitable temperature9 depending on the particular cata-lyst, macromolecular monomer, monomer feed~ resulting graft copolymer and solvent usedO Generally, the graft copolymeriza-tion will be conducted at a temperature of from about 10Co to about 500C., preferably from about 20C. to about 100C.
The gra~t copolymeri~ation rqaction is pre~erably conducted by placing a predetermined amount of the macromo lecular monomer dissolved in the appropriate solvent in the reactorO The polymerization catalyst and monomer are there-after fed into the solvent system to produce the gra~t co-polymer.
It is generally desirable to provide a graft co-.polyme~ having at least about 2~ macromolecular monomer incor-porated in the backbone polymeric material, however, satis-factory results can be obtained wlth up to about 40% by weight macromolecular monomer lncorporationO Preferablyg the gra~t copolymers of the present invention will have about 5% to about 20% by weight incorporation of the macromolecular mono-mer into the backbone polymeric material to obtain the opti-mum physical properties of both the sidechain polymer and the backbone polymerO However, graft copolymers having up to about 95% by weight of the macromol~cularri~onomers incorporat-ed therein may be prepared and are contemplated within the scope of the inventionO
~ he means for providing the proper amount of incor-poration of the macromolecular monomer can be determined simply 3Q by adding the appropriate weighed macromolecular monomer used in the copolymerization processO For example, i~ a graft ~L~3763i~
copolymer having 10~ by weight incorpo~ation of the macro~molecular monomer into the backbone polymer is desired, one simply employs 10 parts by welght of the macromolecular mono-mer for each 90 partæ by weight of the monomer feedO
Following the procedures ~ d above, graft co-polymers having unique combinations o~ properties are ~roducedO
These unique combinations of properties are made possible by the novel process herein which forces the compatibility of ~otherwise incompatible polymeric segmentsO These in~mpatible segments segregate into phases of their own kind.
The chemieally joined, phase separated gr~t copoly-mers of the invention microscopically possess a controlled dispersion of the macromolecular sidechain in one phase (domain) within the backbone polymer phase (matrix). Because all of the macromolecular monomer sidechaln domains are an in-tegral part or interposed between large segments of the back-bone polymer, the resulting graft copolymer will have the properties of a cross-linked polymer, if there is a large dif-ference in the Tg or Tm of the backbone and sidechain segmentsO
~his is true only up to the temperature required t~ break the thermodynamic cross-link of the dispersed phase, I~ ~ssense, a physically cross-linked (as opposed to chemical cross-linked) type polymer can be made that is reprocessable and whose prop-erti~3. are established by simple cooling~ rather than vulcan-ization or chemical cross-linkingO
The graft copolymers of the present invention are ' differentiated from the macroscopic opaque and weak blends of incompatible polymers of the prior art. The graft copolymers of this invention contain separate phases which are chemically joined and the dispersion of one segment into the ma-trix poly~
mer is on a microscopic l~yel and below the wavelength of ~ - .

~ 0~7636 copolymer having 10% by weight incorporation of the macro-molecular monomer into the back~one polymer is desired, one simply employs 10 parts by weight of the macromolecular mono-mer for each 90 parts by weight o~ the monomer ~eedO
Following the procedures ~tlin~d above, gra~t co-polymers having unique comblnations o~ properties are ~roducedO
These unique combinations o~ properties are made poss~ble by the novel process herein which forces the compatibility of otherwise incompatible polymeric segments. These ~n~Pmpatible segments segregate into phases of their own kind.
The chem~cally joined, phase separated graft copol~-mers of the invention microscopically possess a controlled dispersion o~ the macromolecular sidechain in one phase (domain) within the backbone polymer phase (matrix)~ Because all of the macromolecular monomer sidechain domains are an in-tegral part or interposed between large segments of the back-bone polymer, the resulting graft copolymer will have the properties of a cross-linked polymer, if there i9 a large di~-~erence in the Tg or Tm of the backbone and sidechain segments.
This is true only up to the temperature required to break the thermodynamic cross-link of the dispersed phaseO I~ ~ssense, a physically cross-linked (as opposed to chemical cross-lin}ced) type polymer can be made that is reprocessable and whose prop-~erties are established by simple cooling~ rather than vulcan-ization or chemical cross-linkingO
The graft copolymers of the present invention are ' -differentiated from the macroscopic opaque and weak blends of incompatible polymers of the prior artO The graft copolymers of this invention contain separate phases which are chemically ~oined and the dispersion of one segment into the matrix poly-mer is on a microscopic leyel and bel~w the wavelength of ~03763~:i light of the matrix polymer. The gra~t copol~mers herein are, thereforeg transparent9 tough, and truly thermoplasticO
An illustrative exa~ple of the present invention in-cludes combining the advantageous properties of polystyrene with the advantageous properties of polyethylene, although these two polymers normally are incompatible with one another and a mere physical mixture of these polymers has very little strength and is not usefulO To combine these advantageous properties in one product, it is necessary that the different polymeric segments be present as relatively large segmentsO
The properties of polystyrene do not become apparent until the polymer cQnsists essentially of at least about 20 r~ul~
ring monomeric units. This same relationshlp applies to the polymeric segments present in the gra~t copolymers herein, i.e.J i~ a graft copolymer comprising polystyrene se~ments is to be characterized by the advantageous properties of poly-styrene, then those polystyrene segments must9 individually9 consist essentially of at least about 20 recurring monomeric units. This relationship between the physical properties of a polymeric segment in its minimum sige is applicable to the polymeric segment of all graf~ copolymers herein. In general, the mlnlmum size of a polymeric segment which is associated with the appearance of the physical properties of that polymer in the graft copolymers herein is that which consists of about 20 recurring monomeric units. Preferably, as noted earlier herein, the polymeric segments both of the copolymeric back-bone and the sidechainsg will consist essentially of more than about 30 recurring monomeric unitsO However, as it is well-known, the highly beneficial properties of polymers such as polystyrene are generally apparent when the polymer has a m~-lecular weight of from about 5,000 to about 50JOOO9 preferably -~8-~D3763~6 from about 10,000 to about 35gO00, more preferably 12gO00 toabout 25~000O
The polymeric segments of the graft copolymers of the invention may themselves be homopolymeric or they may be copolymericO Thusg a graft copolymer of this invention may be prepared by the copolymerization o~ ethylene, propylene, and a terminated polystyrene containing a polymerizable alPha-ole~in end groupO The uninterrupted polymeric segments of the back~
bone of such a graft copolymer will be copolymeric segments of ethylene and propylene.
The graft copolymers comprising polymeric segments having ~ewer than about 20 recurring monomeric units areg nevertheless, useful for many applications, but the preferred gra~t copolymers are those in which the various polymeric seg-ments have at least about 20 recurring monomerlc unitsO
Although, as indicated, the gra~t copolymers herein are charactbrized by a wide variety o~ physical properties, depending on the particular monomers used in their preparation, and also on the molecular weights of the various polymer seg-ments within a par~ular graft copolymer, all o~ these gra~tcopolymers are useful, as tough, flexible, self-supporting films, The~e ~ilms may be used as ~ood-wrapping m~terial~
painters' dropcloths, protective wrapping for merchandise dis-played for sale9 and the likeO
Gra~t copolymers of the macromolecular monomer9 polystyrene, wlth ethylen~-propylene, isobutylene9 or propyl-ene oxide monomers have been found to be stable materials that behave like vulcanized rubbers, but are thermoplastic and re-processable~ Thus9 an extremely toughg rubbery plastic is ob-tained without the inherent disadv~ntages of a vul~anizedrubber. These copolymerized rubber-~orming monomers with the ~037S3~ci macromolecular monomers of the present invention have the ad-ditional use as an alloying agent for dispersing additional rubber for impact plasticsO
Just as metal properties are improved by alloyingy so are polymer propertiesO By adding the appropriate amount of an incompatible material to a plastic in a microdispersed phase~ over-all polymer properties are improvedO A s~all amount of incompatible polybutadiene rubber correctly dispersed in polystyrene gives high impact polystyrene. The ke~ to this microdispersion is a small amount of chemical graft copolymer that acts as a flux for incorporating the incompatible rubb~r.
In a similar mannerJ a copolymer o~ the macromolecu~
lar monomer of the present lnvent~on can be the ~lux for in-corporating or dispersing incompatible polymers into new matrices making possible a whole new line of alloys, impact plastics, malleable plastics, easy-to-process plasticsq The use of the graft copolymers as alloying agents is particularly e~emplified in the case of polyethylene-poly-styrene blendsO As it is well-knQ,wnJ polyethylene and po~y-styrene are incompatible when blended together. However~ whenusing the graft copolymers of the present invention as an alloying agent, the polyethylene and polystyrene phases can be conveniently ~oined.
For example, a blend prepared by mixing 90 to 51 parts by weight o~ commercial polyethylene ~either low or high density), 10 to 49 parts by weight of com~ercial poly-styrene and 5 to 30 parts by weight of a graft copolymer of the present invention comprising polystyrene sidechains and a polyethylene backbone are useful in making automobile parts, such as inner door panels~ kick panelsg and bucket seat backs~
or appliance parts such as television components. Such blends -5o ~3763!6 are also useful as structural foams, sheets and films, con-tainers and lids in packaging9 beverage cases9 pails, in the manufacture of toys~ molded sheets ~n furniture9 hot mold ad-hesives and computer and magnetic tapes.
The use of the graft copolymers of the present in-vention as an alloying agent offers a distinct advantage over the prior art blends9 ~asmuch as the plastic blend can be processed with minimized phase separation of the polyst~rene and polyethylene polymers in the blendO The strength of the novel blends of the present invention is also ~mproved over the blends of the prior art~
If polystyrene in the macromolecular mono~er is re-placed by a poly(alpha-methylstyrene) and is copolymerized with ethylene9 a similar polyblend can be prepared as describ-ed above, However, these blends will have heat stability which will allow the resulting plastics to be use~ul in making hot water pipes, sheets in warm areas, and automobile parts, having oxidative stability over rubber-containing materials.
These plastics also have utility in preparing reinforced fiberglass and fillers due to their good adhesion to fiber-glass. Polyblends of poly(alpha-methylstyrene) graft copoly-mer with large amounts, i.e.~ 51-90~ by weight of poly(alpha-methylstyrene) and 10-49% polyethylene, exhibit a higher heat distortion9 together wlth high impact strength and high modu-luso These plastics are useful in various engineering applica-tions and in the manufacture of parts for aircraft, auto bodies9 recreational vehlclesg appliancesg gearsg bearings, etcO
Another useful blend utilizing the graft copolymers of the present invention comprises mixing 10 to 49 parts of low density polyethylene9 51 to 91 parts by weight of poly--51~

.
~)37~i3~
(alpha~methylstyrene) and zero to 30 parts by weight o~ poly-styrene and 5 to 30 parts by weight of the gra~t cop.olymer of the present invention comprising polyethy:lene backbone with poly(alpha-methylstyrene) or styrene sidechains. The blend is extruded in a Imill and the resultant plastic is found use-ful in making appliances such as co~fee makers, humidifiers, high intensity lamps, color television setsJ kitchen-range hardware, blenders, mixers, and electric toothbrushes. These plastics are also useful in preparing recreational ~ehicles such as snowmobile parts and helmets, machine parts such as gears, bearings; plumbing pàrts such as shower heads, ~alves~
fittings and ballcocks; and motor housing, stamping, lawn sprinklersg stereo tape or cartridges, etc.
The rein~orcement o~ plastics by adding glass fibers or other materials is difficult to achieve because of poor wetting character of many basic polymersO The macromolecular monomers of the present invention, particularly those contain-ing reactive polystyrene, have a tendency to wet and bond to glass with facility, By proper dispersion o~ glass in a macromolecular copolymer, it is possible to upgrade the bond between the dispersed phase and glass. Thus, the macromoleçu-lar graft copolymers o~ the present invention can also be used as reinforcing adhesion aids to glass fibers~
The invention is illustrated further by the ~ollow-ing examples which, however, are not to be taken as limiting in any respectO In each case, all materials should be pure and care should be taken to keep the reacted mixtures dry and free of contaminantsO All parts and percentages~ unless ex-pressly stated to be otherwise, are by wei~t.

~037636 Preparation 0~ Macromolecular Monomer ular Weight . ~ , ~
(a) PreParation ~ Pol~st_r~ n~ With All,yl Chloride:
A sta~nle~s steel reactor is charged with 76~56 parts of A~Co5~ grade benzene (thiophene-free), which had been pre-dried by Linde molecular sieves and calcium hydrideO The re-actor is heated to 40Co and 00015 parts of diphenylethylene is added to the reactor by means of a hypodermic s~ringeO A
0 1201% ~olution o~ sec-butyl lithium in hexane iB added to the reactor portionwise until the retention of a permanent orange-yellow color9 at which point an additional o.885 parts (1.67 moles) of sec-butyl lithium solution is addedJ followed by the addition of 22,7 parts (218 moles) of styrene over a period of 44 minutesO The reactor temperature i8 maintained at 36-42Co The living polystyrene is terminated by the addition of Oo 127 parts of allyl chloride to'`the reaction mixture. 'The result-ing polymer is precipitated by the addition of the alpha-olefin terminated polystyrene-benzene solution into methanol, whereupon the polymer precipitates out of solution, The alpha-olefin terminated polystyrene is dried in an air circu-lating atmosphere drier at 40-45~C~ and then in a ~luidized bed to remove the trace amounts of methanol. The methanol con-tent after purification is 10 parts per millionO The molecular weight of the polymer, as determined by membrane phase osmo-metry~ is 15,400 (theory: 13,400) and the molecular weight distribution is very narrow, iOeO~ the Mw/Mn ls less than 1~05.
The macromolecular monomer has the following structural .
formulaO

,~

~037~3~i CH3CH2(C~3)CH CH2~CH - _ CH2 -CH = C~2 _ ~ In wherein n has a value such that the molecular weight of the polymer is 15,4000 (b) The procedure of Example l(a) is repeated using~
in place o~ allyl chloride, an equivalent amount of methallyl chloride to produce a metha~lyl terminated polystyreneO
(c) The procedure of paragraph (a) is repeated using, in place o~ styrene, an equivalent amount of ethylene oxide to produce a crystalline polyoxyethylene living polymerO The living polymer is terminated by the addition o~ a molar equiva-lent amount o~ vinylbenzyl chloride to produce a pol~mer hav-ing the following structural formula:

CH3CH2(C~3)C~ ~ CH2CH2 ~ CH2 ~ CH - CH2 n (a) Prepara~tion 0~ Pol,Y-(-alpha-met-hry-l-s~t-~yrene) Terminated With All~L ChlorideO
A solution o~ 472 grams (4.0 moles) of ~le~_-methyl-styrene in 2500 ml. of tetrahydrofuran is treated dropwise with a 12% solution o~ n-butyl lithium in hexane until the persistence of a light red color. An addltional 30 mlO
(oOo383 mole) of this n~butyl lithium solution is added, re-sulting in the development o~ a bright red color. The tempera-ture o~ the mixture is then lowered to -80C., and a~ter 30 minutes at this temperature3 4.5 grams (o.o6 mole) of allyl chloride is added. The red color disappears almost immedi-ately9 indicating termination o~ the living polymerO The re-sulting colorless solution is poured into methanol to precipi-~03763i tate the alpha-ole~in terminated poly(alPha-methylstyrene) which is shown by vapor phase osmometry to have a number average molecular weight of 11~000 (theoryo 12,300) and the molecular weight distribution is very nar:row9 iOeO~ the ~w/Mn is less than 1.05O The macromolecular monQmer produced has the following structural formula:

CH3CH2C~2C~12 tCH2_C~ C~2CH = CH2 wherein n has a value such that the molecular weight o~ the polymer is 11,000.
The procedure of paragraph (a) is repeated using~ in place o~ n-butyl lithium, a solution of an equivalent amount of potassium t-butyl alkoxylate and in place of ~ -methyl-styrene9 an equivalent amount respectively of:
(b) 4-vinyl pyridine, terminatihg with a molar equiv-alént of allyl chloride to produce a polymer having the follow-ing structural ~ormula:

(CH3)3 C--0 _CH2--CH _ CH2CH = CH2;

_ ~ _ n (c) methacrylonitrile, terminating with a molar equiv-alent of vinylbenzyl chl~ride to produce a polymer having the following structural formula-r CH3 (CH3)3 C - O - -CE~ C - CH2 ~ CH = CH2 ;
. CN .
n ~()376;~
(d) methyl methacrylat~9 terminating with vinylbenzyl chloride to produce a polymer having the ~ollowing structural ~o~mulaO

(CH3)3 C - O - -CH2 C - CH~ ~ C~ = CH2 C=O
_ OCH3 n (e) N,N-dimeth~lacrylamide~ terminating with p-vinylbenzyl chloride ~o produce a pol~mer having the following structural formulaO

(CH3)3 - C ~ 2 , ~ CH ~ CH = CH2 C = O
_ N(CH3)2, Ln Preparation 0~ Polystyrene Terminated With Vinvl Chloroacetate A solution of one drop o~ diphenyl ethylene in 250Q
ml. o~ cyclohexane at 40C. is treated portionwise wlth a 12%
solution of sec-butyl lithium in cyclohexane until the per-sistence o~ a light red color~ at which point an additional 18ml. (0.024 mole) o~ the sec-butyl lithium is addedg followed by 312 grams (3.0 moles) of styrene. The temperature of the polymerization mixture is maintained at 40C. for 30 minutes, whereupon the living polystyrene is capped by treatment with 8 ml. (00040 mole) of diphenyl ethylene, then terminated by treatment with 6 ml. (0.05 mole) o~ vinyl chloroacetate~ The resulting polymer is precipitated by addition of the cyclo-hexane solution to methanol and the po~ymer is separated by ~iltration. Its number average molecular weight9 a~ deter--56~

~ ~3763$
mined by vapor phase osmometry9 is 129000 ~theory~ 13,265)3 and the molecular weight distribution is very narrow9 ~eO~
the ~w/Un is ~ess than lu060 The macromo:Lecular monomer pro-duced has the following structural formula:
~ ..
CE3C~2(C~3)c~c~2--~j CH ~--C~2COCH = CH2 wherein n has a value such that the molecular weight of the polymer is 12,000.
EX~MPLE 4 Preparatio~ ~f Pol,y~alpha-met~lst~ e) Terminated With Vinyl Chloroacetate A solution of 357 grams (300 moles) of al~_-methyl-styrene in 2500 ml. o~ tetrahydrofuran is treated dropwise with a 12% solution of t-butyl lithium in pentane until the persistence of a light red color. Thereupon, an additional 15.0 mlO (0-.03 mole) of the t~butyl solution is added, result-ing in the development of a bright red color. The temperature of the mixture i5 then lowered to -80Co and after 30 minutes at that temperature, 5.6 ml. of diphenyl ethylene is added~
The resulting mixture is poured into 5~0 ml. (0.04 mole) of vinyl chloroacetate and the thus-terminated poly(alpha-methyl~
styrene) is precipitated with methanol and separated by filtra-tionO Its number average molecular weight, as determined by vapor phase osmometry9 is 14,280 (theory: 12,065) and the molecular weight distribution is ~ery narrowO The macromolecu-; lar monomer produced has the following structural formulaO

, ~03763~i r CH31 ~o CH3C~2(C~3)CH ~ L2--~ ~ N ~--CE2CCOCH = Cl2 wherein n has a value such that the molecular weight of the polymer is 14,280~

Pre~aration Of Polystyrene Terminated With Vinyl-2-Chloroeth21_~ther A solution o~ one drop o~ diphenyl ethyle~e at 40C.
is treated portionwise with a 12% solution of t-butyl lithium in pentane until the persistence of a light red color, at which point an additional 30 ml, (0,04 mole) of the _-butyl lithium solution is added, followed by 312 grams (3~0 moles) of styrene. The temperature of the ~olymerization mixture is maintained at 40Co ~or 30 minutes, whereupon the living poly-styrene is terminated by treatment with 8 ml. (o.o8 mole) of vinyl-2-chloroethyl ether. The r~sulting polymer is precipi-tated by addition of the benzene solution to methanol and the polymer is separated by filtration. Its number average molecu-lar weight, as determined by vapor phase osmometry, is 7,200(theory: 7,870) and the molecular weight distribution is very narrow, i.e., the Mw/Mn is less than 1. o6. The macromolecular monomer produced has the following structural formula:

)3c - - CH CH- ~ ~2C~20CH = CH2 - ~- in wherein n has a value such that the molecular weight of the polymer is 7,200.

.. ... . . .
Preparation Of Polystyrene Termi ated With E~ichlor ~ in A benzene solution of living polystyrene is prepared in Example 5 and terminated by treatment with 10 grams (OolO
mole) of epichlorohydrinO The resulting term~nated polysty-rene is precipitated with methanol and separated by filtra-tion. Its molecular weight, as s~own by vapor phase osmometry, is 8, 660 (theory~ 7,757) and its nu~er average molecular weight distribut~on is very narrow. The macromolecular mono-mer produced has the ~ollowing structural formu~a:

~CH3)3 C ~ CH~---CH ~ / \
L ~ J n wherein n has a value such that the molecular weight of the polymer is 8,660.

(a) Preparation Of Polystyene Terminated With Methacrvl.
Chloride:
To a solution of 0. 2 ml. o~ diphenyl ethylene in 2500 mlO of benzene there is added dropwise a 12~ solution of n-butyl lithium in hexane until the persistence of a light reddish-brown color. An additional 24 mlO (0~031 mole) of this n-butyl lithium solution is added, and then, 416 grams (4.0 moles) of styrene, resulting in the development of an orange color. A temperature of 40C. is maintained throughout by external cooling and by controlling the rate at which the styrene is added. Th~s ~emperature is maintained for an addi-tional 30 minutes after all of the styrene has been added, and then is lowered to 20Co~ whereupon 4O4 grams (Ool mole) of ethylene oxide is addedJ causing the solution to hecome color-~37~3~i lessO The living polymer is terminated by reaction with 10 ml. (Ool mole) o~ methacrylyl chloride. The resulting poly-mer has a number average molecular weight as shown by vapor p~ase osmometry o~ 10,00~. The macromolecular monomer has the ; following structural ~ormula- -_ _ CH3CH2CH2CH2 - 2 1 CH2C~2CC = CH2 _ ~ CH3 wherein n has a value such that the molecular weigh~ of the polymer is 10,000.
(b) Acrylyl chloride is substituted ~or methacrylyl ch}oride in the above procedure to give an acrylic acid ester end group on the polystyrene chain.
(c) Allyl chloride is substituted ~or meth~crylyl chloride in procedure (a) to produce an allyl ether terminated polystyrene.
(d) Methallyl chloride is substituted for methacrylyl chloride in procedure (a) to produce methallyl ether terminated polyætyreneO
(e) Maleic anhydride is substituted ~or methacrylyl chloride in procedure (a), ~ollowed by protonation with water to produce polystyrene terminated with the hal~ este~ o~
maleic acid.
(~) Epichlorohydrin is substituted ~or methacrylyl chloride to produce an epoxy ether terminated polystyreneO
(g) The procedure of (a) is repeated uslng in place o~ styrene, an equivalent amount of isoprene and in place of n-butyl lithium an equivalent amount of sec~butyl lithium to produce primarily a rubbery cis-1,4 polyisoprene~ The low Tg living polymer is terminated by the additi~n o~ a molar equiva-103763~
lent9 based on sec-butyl lithium, ethylene oxide as a capping agent, followed by a molar equivalent amount of allyl chloride to produce a polymer predominantly having the ~ollowing struc-tural formulao ~ ~ C C / ~ 2 .
Pre~aration Of Pol~Yst~y~r-ene Terminated With Methacrylyl Chloride A stainless s~eel reactor is charged with 32 gallons o~ A,C.S. grade benzene (thiophene-free), which had been pre-dried by Linde molecular sieves and calcium hydrideO The reac-tor is heated to a temperature o~ between 38-40C. and 10 ml.
of diphenyl ethylene is added to the reactor by means of a hypodermic syringe. An 11.4~ solution o~ secondary butyl lith-ium in hexane is added to the reactor portionwise until the retention of a permanent orange-yellow color is obtained (60 ml.), at which point an additional 3.44 pounds of the secondary butyl lithium in hexane is added to the reactor, followed by the addition of 8205 pounds of purified styrene over a period of 1 hour and 40 minutes. The reactor temperature is main-tained at 38-~0C The living polystyrene is capped by the ad-dition of 0.28 pounds of ethylene oxide and the reaction solu-tion changes from a red-orange çolor to yellowO The resulting capped living polystyrene is thereafter reacted with 260 mlO
of methacrylyl chloride and the solution changes to a very pale yellow colorO The methacrylate terminated polystyrene is pre-3Q cipitated by the addition of the polymer benzene solution intomethanol, whereupon the polymer precipitates out o~ solution.

~13763~;
The polymer i9 dried in an air circulating atmosphere drier at40-45C. and then in a fluidized bed to remove the trace ~
amounts of methanol, The molecular weight of the polymer as determined by membrane phase osmometry, is 13,400 and the molecular weight distribution is very narrow, i.eO, the Mw/Mn is less than~l.O5.

Preparation Of Polys~yrene Te ~
A stainless steel reactor is charged with 2.5 liters of A.C,S. grade benzene (thiophene-~ree), which had been pre-dried by Linde molecular sieves and calcium hydride. The re-actor is heated to 40C. and 0.2 ml. of diphenyl eth~lene is added to the reactor by means of a hypodermic syringe. A 12.1%
solution of sec-butyl lithium in hexane is added to the reactor portionwise until the retention of a permanent orange-yellow color is obtained (0.7 ml.), at which point an addi~ional 22.3 ml. of sec-butyl lithium solution is added, followed by the ad-dition of 421.7 grams of styrene over a period of 16 minutes.
The reactor temperature is maintained at 40-45C. Five minutes after styrene addition is completed, ethylene oxide is added from a lecture bottle subsurface intermittently until the solu-tion is water white. One hour after ethylene oxide addition is complete, 20055 ml. of maleic anhydride-benzene solution (the maleic anhydride solution was prepared by dissolving 84 grams of maleic anhydride in 550 grams of purified benzene) is added to the capped living polymer. One hour after the addition of the maleic anhydride solution, the contents of the reactor are discharged and precipitated in methanolO The maleic half ester terminated polystyrene had a molecular weight of about 149000, a~ determined by Gel Permeation Chromatography. The polymer-~376~
izable macromolecular mono~er has a structural ~ormula repre-sen~ed as follows:
Sec-Butyl ¦CH2 ~H2~H20 HOC
o Preparation Cf Polvbutadiene Te~minated With Allyl Chloride C.P, grade 1,3-butadiene (99.0% purity) is condensed and collec ed in l-pint soda bottles. These bottles had been oven baked ~or 4 hours at 150C., nitrogen purged duri~g cool-ing, and capped with a perforated metal crown çap using butyl rubber and polyethylene ~ilm liners. These bottles containing the butadiene are stored at -10C. with a nitr~gen pressure head (10 psi) in a laboratory ~reezer before use. Hexane sol-vent is charged to the reactors and hçated to 50C., followed by the addition of 0.2 ml. of diphenyl ethylene by way of a syringe. Secondary butyl lithium is added dropwise via syringe to the reactor ~ntil the red diphenyl ethylene anion color persists for at least about 10-15 minutes. The reactor temper-ature is lowered to 0C., and 328.0 grams of butadiene is charged into the polymerization reactor, followed by the addi-tion of 17.4 ml. (0.02187 mole) of a 12~ secondary butyl lith-ium solution in hexane, when hal~ of the butadiene charge has been added to the reactor. The butadiene is polymerized for 18 hours in hexane at 50Co Following the polymerization, 400 ml. portions of the anionic polybutadiene solution in the reactor is trans~erred under nitrogen pressure into capped 3763~i bottlesO Allyl chloride (oO48 mlO~ o-oos88 mole) is injected into each of the bottles, The bottles are clamped i~ water baths at temperatures of 50C. and 70Co for pçriods o~ time ranging up to 24 hours. The s~mples in each o~ the bottles are short stopped with methanol and Ionol solution and anal-yzed by Gel Permeation ChromatographyO Each of the samples is water white and the analysis of the Gel pe~meation Chromato-g~aphy scans reveals that each of the samples had a narrow molecular weight distribution.
Several comparison samples were conducted in bottles coming from the same lot of living polybutadiene) which were capped with 2-chlorobutane (0.4 ml., o.oo376 mole) as the ter-minating agent. The resulting polymers terminated with 2-chlorobutane were yellow in color and ~ter standing ~or a period of 24 hours at 70C., appeared to have a broad molecu-lar weight distribution as revealed by the Gel Permeation Chromatography scan. It is clear that the reaction and reac-tion product of 2-chlorobutane with anionic polybutadiene are different than the reaction and reaction product of allyl chlo-20 ride and anionic polybutadiene.

C Preparation ~ Methacr,~late Terminated Pol,yisoprene A one-gallon Chemco glass-bowl reactor is charged with 2.5 liters of purified heptane which had been preq~ied by a Linde molecular sieve and calcium hydride, followed by the addition of 002 ~1~ of diphenyl ethylene as an indicator and the reactor is sterilized with the dropwise addition of tertiary butyl lithium solution (12~ in hexane) untll the re-tention of the characteristic light yellow color is obtained.
The reactor is heated to 40C. and 19.9 ml. (00025 mole) of a 12% solution of tertiary butyl lithium in hexane is in~ected ~rQd~m~fk -64_ ~ 3~63~
into the reactor via hypodermic syringe, followed by the addi-tion of 33104 grams (4.86 moles) of isopreneO The mixture is allowed to stand ~or one hour at 40Co ancl 0013 mole of ethyl-ene oxide is charged into the reactor to cap the living poly-isopreneO The capped living polyisoprene is held at 40CO for 40 minutesJ whereupDn 0.041 mole of methacrylyl chlorlde is charged into the reactor to terminate the capped living poly-mer~ The mixture is held for 13 minutes at 40C~ ~ followed by removal of the heptane solvent by vacuum strippin~. Based upon the Gel Permeation Chromatography scans for polystyrene, the molecular weight of the methacrylate terminated polyiso-prene by Gel Permeation Chromatography was about 10,000 (theory: 13,000). The methacrylate terminated polyisoprene macromolecular monomer has a structural formula repre~ented as followsO
o ~C~3 Préparation Of Alpha-Olefin Terminated Polyisoprene _, .
~J ~ A one-gallon Chem~o glass-bowl reactor is charged with 2,5 liters of purified heptane which had been predried by a Linde molecular sieve and calcium hydride, followed by the addition of 002 mlO of diphenyl ethylene as an indicator. The reactor~and solvent are sterilized by the dropwise addition of tertiary butyl lithium solution (12% in hexane~ until the re-tention of the characteristic light yellow color is obtained.
The reactor is heated to 40Co and l9o 03 mlO (Oo 02426 mole) of 30 tertiary butyl lithium solution is in~ected into the reactor ~ dQ~r k -65-~ 11~763~i via hypodermic syringe3 followed by the addltion of 31505 grams (4~63 moles) of isopreneO The polymerizatio~ is per~
mitted to proceed at 50Co for 66 minutes and at th~s time 20 0 ml. (0002451 mole) o~ allyl chloride is added to the living polyisoprene. The terminated polyisoprene is held at 50Co for 38 minutes, whereupon the polymer is removed from the reactor to be used in copolymerization reactionsO The polymer was analyzed by Gel Permeation Chromatography and had a very narrow molecular weight distribution, iOeO> an MwjMn of less ~han about 'lo o60 The theoretical molecular weight of the polymer is 1390000 The polymerizable macromolecular monomer has a structural formula represented as ~ollows:

~H3CH2~CH3)CH ~ C ~ ~ CH2 ~ H2 CH = CH2 /C = C\
_CH3 H

C ~ Polymerization Of Styrene With Vinyl Lithium To a one gallon Chemco~reactor, there is added 2500 ml. of tetrahydro~uran and cooled to 15~C., at which time 6.5 mlO of a 11.2~ solution of vinyl lithium in tetrahydrof~lran (0.2 mole lithium) is added to the reactor, imparting a light tan color to the solution. The vinyl lithium was purchased from Alpha Inorganics Ventron of Beverly, Massachusetts, as a two molar solution in tetrahydrofuranO Analysis of the solu-tion by several methods showed that the solu-tion contained llo 2~ active lithiumO After the vinyl lithium solution is added, a 0025 mole styrene charge is added to the reactor via syringe with the observation of a small exotherm q~ about 1Co (the reactor temperature is controlled by liquid nitrogen cooling coils inslde the reactQr at a temperature o~ 15C.).
~ 66-l~rc~d~ k ~03763~
Ten minutes afrer the styrene is addedg 306 ml. of water is added to the reactor, resulting in an almost immediate change in color from deep orange brown to water white and a consider-able gas evolution is observed ~the internal pressure in the reactor increased from 8 psig to 12 psig)" A sample is taken from the head space (about 20 5 liters ln volume) and from the liquid phase at the same time (the two samples are analyzed and identified as containing largè amounts of ethylene). The styrene polymer is withdrawn from the reactor and analyzed.
The GPC molecular weight o~ the polystyrene is 108gOOO~ as measured against the Pressure Chemical Company sample 2tb) standard certi~ied as Mw/Mn = 1~06g Mw = 20,800 ~ 800 and Mn =
20,200 ~ 600. Measured against the same standard, the weight average molecular weight of the po~ymer is 99gOOO and the number average molecular weight is 66,oooO The polydisper-sity of the polymer i8 1.49~ Based upo~ the limiting poly-dispersity of about 1.33 for living p~lymers, several side reactions obviously occur when using vinyl lithium as a poly-merization inltiatorO In addition, the broad molecular weight distribution and the inability to control the molecular weight of the polymer is indicative that the initiation rate of vinyl lithium is e.xtremely slowO Accordingly, the vinyl lithium initiated polystyrene is not suitable in the preparation of the graft copolymers of the present invention in preparing chemically ~oinedg phase separated graft copolymersg which have sidechains of controlled and uniform molecular we~gh~sO
Attempted copolymerization of the vinyl lithium in-itiated polystyrene with methyl methacrylate and acrylonitrile under free-radical conditions only results in a mixture of polystyrene and the respective poly(methyl methacrylate) or polyacrylonitrile~ AlSOg attempted copolymerization of the -~7-1~3763~
alpha-olefin terminated polystyrene of Example l(a) with methyl methacrylate and acrylonitr'~le under free-radical conditions only resulted in a mixture of homopolymers as de termined by IR analysis of the benzene and cyclohexane ex-tractsO This result is expected due to the inability of alPha-olefins to polymerize under free-radical conditionsO
Preparation 0~ Graft Co,pol~ers ~ving Macromolecular Prepàration Of Graft Copol,ymer From Pol,v(al~h~,-methylstyrene) Macromolecular ~onomer Terminated With Allyl Chloride And ., .
h.Ylene A solutlon of 20 grams of poly(alpha-methylstyrene) macromolecular monomer terminated with allyl chloride and hav-ing an average molecular weight of 10,000 prepared as in Ex-ample 2(a) in 100 ml. of cyclohexane is prepared and treated with 5.5 ml. of oO645 M (901% solution) dlethyl aluminum chlo-ride in hexane and 2 ml. of vana~ium oxytrichloride, then pressured with ethylene to 3,0 psig. This system is agitated gently ~or about one hour at 30C.~ whereupon a polymeric material precipitates from the solutionO It i.s recovered by filtratiQn and pressed into a thin transparent film which is tough and flexibleO
EXAMPLE 1~
(a) Preparation Of Graft Copol,ymer Havin A :Pol,yeth,ylene Back-~

One gram of the alpha-olefin terminated polystyrene of uniform molecular weight prepared in Example lta) is dis-solved in 1500 mlO of cyclohexane and charged into a 2-liter "Chemco" reactor. The reactor is purged with prepuri~ied ni-trogen for 30 minutes9 and 22 mlO of 25% ethylaluminum sesqui-~0376~6 chloride solution (in heptane) is added. The reaction i9 pressured to 40 psi with 20 grams of ethylene into the solu-tion. Thereafter~ Ool mlO of vanadium oxytrichloride is added and the ethylene pressure drops from 40 psi to 1 psi in about 1 minuteO The reaction is terminated in 3 minutes by the ad-dition of isopropanolO The polymer is recovered by flltration and slurried with cyclohexane and then with isopropanolO The yield is 18.0 grams of a ~luffy, white copolymer having a macromolecular monomer sidechain content ~ 508%, as deter-mined by I~Ro Extraction and analysis of the extracts ~ndi-cate all of the macromolecular monomer and 17~0 grams of the ethylene copolymerized.
(b) The procedure in Exa~ple 8(a) is repeated, ex-cept that 200 grams of the macromolecular monomer is used in-stead of 1.0 gramO The yield of the copol~mer is 2005 grams and the macromolecular monomer sidechain content, as deter-mined by IoRo~ is 10%.
EX~MPLE 16 (a) Preparation Of Gra~t Copoly~er Having A Pb~_thylene Backbone And Polvstyrene Sidechains:
A 2-liter "Chemco" reactor is charged with 1500 ml.
of purified cyclohexaneO 20 Grams of alpha-ole~in terminated polystyrene prepared in Example l(a) is added and dissolved in the puri~ied cyclohexaneO The reactor is thereafter purged with prepurified nitrogen for one hour with concurrent slow agitation. Ethylene is added to the reactor at the rate of 5 liters per minute to a pressure of 5 psio The contents of the reactor is heated and controlled at 25Co,and high speed stir-ring is started, ethylaluminum sesquichloride ~22.8 mlO~ 25%
in heptane) catalyst is injected into the reactor by a hypo-dermic syringe, followed by the addition of 0.1 ml. of vanadium ~3763~i oxytrichloride. Polymerization begins immediately a~d theethylene pressure in the reactor drops to nearl~ zero in about a minute. At this point, the ethylene rate is reduced to 0 liter per minute, and cooling is used to maintain a ~empera-ture of 25Co At the-end of one hour~ a total of 43 grams of ethylene has been charged into the reactor, and the reactor is full of a fluffy polymer slurryO The reaction i5 stopped by the addition of 50 mlO of isopropanol to inactivate the cata-lyst, The polymer is recovered by filtration, slurried and boiled in 1. 5 liters of benzene for one h~ur, then re-filtered to remove all the unreacted alpha-olefin terminated polysty-- ~ J' rene from the copolymer. The polymer is then slurried in lo 5 liters of isopropanol and 0.03 gram of Irganox~1010 antl-oxidant is added and then filtered and dried in a vacuum oven at 50CC. The yield is 49 grams of a M~ffy, white copolymer having an alpha-olefin terminated polystyrene content o~ 16%, as determined by I.R. of a pressed film.
(b) Preparation Of Graft Copolymer Having A Pol~eth~lene Back-bone An~ Pol~(alpha-meth~lst~rene) Sidechains.
The macromolecular monomer used to produce the side-chains is first prepared by repeating ~he procedure described in Exanple 2(a), except that in place of the n-butyl lithium, 14 ml. (0,0178 mole) of sec-butyl lithium (12% solution in heptane) is used as the initiatorO The number average molecu-lar weight, as determined by gel permeation chromatography, is 26,000 (theory: 26,500) and the molecular weight distribution is very narrow, iOeO~ the Rw/Mn is less than 1.05.
Four liters of cyclohexane ~Phillips polymerization grade) and 200 grams of the alpha olefin terminated poly(alPha methylstyrene) macromolecular monomer produced as described rr~dt ~a rk ~7~

~3763~i above are charged into a "ahemco" reactorO The mixture is heated to 70Co with concurrent Stirring~ to dissolve the macromolecular monomer, The reactor is purged with high pur-ity nitrogen ~or one hour with stirr~ngO Ethylene gas is in-troduced into the reactor to a pressure o~ 5 psi, followed by 228 mlO o~ ethylaluminum sesquichloride ~25~ in heptane) and lo O mlO vanadium Qxytrichloride. Agitat~on is increased and polymerization begins immedi~tely, as noted by the pressure in the reactor dropping to nearly ~ero. The ethylene ~low rate 10 is ad~usted to 5 liters per minute, and the internal tempera- ;
ture is controlled at 70Co At the end o~ one hour, the re-action i8 terminated by the addition o~ 500 mlO o~ isopropanol to inactivate the catalystO
The polymer is isolated by centrifugation, slurried with benzene for one hour, and recentrifugedO The copolymer is then slurried in 5 liters o~ methanol and 0.3 gram o~
Irganox 1010 for one hour, centrifuged and dried in an oven at 50C. The yield is 260 grams having an alpha-ole~in terminat-ed poly(alpha-methylstyrene) content of 22~, as determined by I,R. analysis o~ a pressed film.

Preparation 0~ Graft Copol~ avin~ An Ethylene-Prop!ylene Copolymeric Backbone And Polystyrene Sidechains A 2-liter "Chemco" reactor is charged with lz liters o~ dry benzene and 50 grams of poly(alpha-methylstyrene) ter-minated with allyl chloride (as prepared in Example 2). The macromolecular monomer i$ dissolved by stirring and thereafter purged with nitrogen. The reactor is then charged with ethyl-ene and propylene gases at the rate o~ 200 ml./minute and 800 ml./minute~ respectively, to build-up lO psi pressure in the reactorO While maintaining a reaction temperature of 25-30C,~

~3763~
2 mlO of vanadium oxytrichloride and 4 mlO of ethylaluminum sesquichloride solution (25% in heptane) are added to the re-action mixture by means o~ syringe to initiate polymerizationv As the polymerization is started, additional macromolecular monomer (335 mlO of 10% macromolecular solution) is added in solution formJ iOeO~ 70 grams of the macromolecular monomer is dissolved in 630 mlO of dry benzene, and pumped in by Micro-Bellow-pump. During the reaction9 the flow rate o~ the gases are checked constantly to insure that the ethylene and propyl-1~ ene ~eed rate are at the same initial levelO Additional cat-alyst, Et3 A12 C13 (27 mlO in 25% heptane) and VOC13 (108 mlO) is added by syringe during the reaction, as the rate of poly-merization slowed down, which is observed by a build-up of the internal pressure in the reactor. A~ter one hour, the poly-merization is terminated by the additlon o~ 20 mlO o~ opro-pyl alcoholO The product is precipitated in methanol and 51 grams of a white9 rubbery polymer is obtainedO

Preparation Of Gra~t CopolYm~r Having Ethylene-Propylene Copolvmeric Backbone And Polyst~rene Sidechains A l-gallon "Chemco" reactor is charged with 3 liters of dried cyclohexane and 10 grams o~ polystyrene terminated with allyl chloride (as prepared in Example l)o The solution is pur~ed with nitrogen for 30 minutesO 20 Ml. o~ tri-n-hexylaluminum (25%)solution is added, followed by the addition of 139~5 grams of propylene to obtain a pressure of 26 psi and 2004 grams of ethylene to obtain a pressure of 48 psio Finally there is added 0.2 ml. of vanadium oxytrichloride and a drop in pressure i~ observedO The polymerization is terminated after 10 minutes by the addition of 10 mlO of isopropanolO
The terpolymer solution is added slowly, wi-th stir~

` ~3763Çi ring, to a 4-liter beaker containi~g methanol to coagulate the polymer. The polymer which separated is air dried overnightO
To remove the trace of catalyst residue, the gray colored polymer is dissolved in 500 mlO of cyclohexane and placed in a 2-liter resin flaskg together with 1 liter of distilled water containing Ool gram of NaOH9 and refluxed at 80Co for 2 hoursO The contents are transferred into a 2-llter separatory funnel, and the bottom water layer is drainedO The upper cyclohexane layer is added to methanol slowly, with stirring, to coagulate the polymer. The recovered polymer ls dried in a vacuum ovenO The unreacted macromolecular monomer is removed from the dried polymer by first dlssolving in cyclohexane and adding dropwise to methyl ethyl ketone, with stirringO The terpolymer which is insoluble in methyl ethyl ketone is fil-tered and dried in a vacuum ovenJ and a yield of 52 grams is obtained. The terpolymer has improved tensile strength com-pared to ethylene-propylene copolymers prepared in the same manner without the macromolecular monomer.

PreParation Of Graft Co~olymer Havin~
PolYlsoprene Backbone And Pol~Ystyrene Sidechains 500 Ml. of dried cyclohexane is charged into a re-actor, followed by the addition o~ 100 mlO (68 grams) of freshly distilled isoprene (Phillips polymerization grade), together with 17 grams of polystyrene terminated with allyl chloride (as prepared in Example l)o The reactor is sealed, followed by the additiQn of 2.5 mlO of tri-n-hexylaluminum solution (25% in heptane) and 0016 mlO of titanium tetra-chloride with hypodermic syringesO The reactor is agitated at 55Co for 16 hours, whereupon the contents of the reactor are slowly poured, with stirring, into a 4-liter beaker con-76;~i taining 2 liters of a 1% solution of Ionol antioxidant in iso-pr~panol. A tough, ru~bery, copolymer is obtained.

Preparation 0~ Gra~t Copol~mer Havin~ A Polvstyrene Backbone And Polyoxyethylene Sidechains Equal parts o~ the polyoxyethylene terminated with vinylbenæyl chloride prepared in Example l(b) and styrene mon-omer are placed in a reactor containing 1,000 mlO o~ benzene.
The reactor is heated to 60C. and one part by weight of azo-bisisobutyronitrile ~ree-radical polymerization catalyst is added. The polymerization is complete in three hours, ob-taining a graft copolymer having hydrophilic-hydrophobic properties. The gra~t copolymer also reduces hydrostatic charges ~nd is an allo~Ying agent for polystyrene and pol~oxy-ethylene.

Prepara~ion Of Graft Copolymer Havin A
PolyPropylene Backbone And Cis-1,4-Pol~yiso~rene Sidechains A l-gallon "Chemco" reactor is charged with 3 liters of heptane and 10 grams o~ allyl ether terminated cis-1,4-pol~isoprene (as prepared in Example 7(g)). The macromolecu-lar monomer is dissolved 4y stirring and therea~ter the solu-tion is purged with n~t~ogen for 30 minutes. 10 M1. o~ di--ethylaluminum chloride (25% solution in heptane) is added, followed by the addition of 0.3 gram of TiC13. 139.5 Grams of propylene is added to obtain a pressure o~ 26 psi. The reac-tor is heated to 60C., and polymerization is terminated ~ter 18 hours, whereupon the contents o~ the reactor are slowly poured, with stirring, into a 4-liter beaker containing C 30 2 lite~s of 1% solution of Ionol antioxidant in isopropanol.
The graft copolymer has higher impact properties than poly-~r~ ~ nnark -T4-3763~;
propylene homopolymer~
EXAMPLE ?2 Preparation Of Graft Copolymer Havin~ Pol~yisobut~ene Bac~bone And Polyst~rene Sidechains To a solution o~ 20 grams o~ ~o:Lystyrene maçromer terminated with epichlQrohydrin and having an ave~age molecu-lar weight of 10,000 ln 1,000 ml. o~ toluene at -70C., there is added 80 grams o~ isobutylene. 45 Ml~ of boron trichloride ethyl ether complex is added slowly, the temperature being maintained at -70C. throughout. Polymerization occurs as the catalyst is added and is complete almost immediately a~ter all o~ the catalyst has been added. The resulting graft co-polymer is obtalned by evaporating away the toluene and wash-ing the residual solid with methanol.

PreParation Of Graft Copol~mer Having PolYisobutylene Backbone And Pol~stYrene Sidechains To l~000 ml. of methyl chloride at -70C~ there is added 10 grams of polystyrene macromer terminated with epi-chlorohydrin, having an average molecular weight of 10~000.To this resulting solution maintained at -70C~, there is added concurrently and dropwise, a solu~ion o~ 2 grams of aluminum chloride in 400 ml. o~ methyl chloride and 90 grams of isobutylene. The time required ~or these additions is one hour and at the end of this time polymerization is subst~nti-ally comple~e. The resulting insoluble graft copolymer is isola~d b~-~Q~r~i~n-o~ t-h~7m~b~1~ne chloride. Similar results are obtainable by employing either a methallyl or methacrylyl end group on the polystyrene such as the product prepared in Examples l(b)9 7(a) and 7(d)~

~,037~3~;
EXAMPLE, ?4 ~a) Preparation Of Pol~styrene Macromolecular Monomer~Capped With Butadiene And Terminated With Al~yl ChlorideO
2.5 Liters of benzene ~thiophene-free) are charged into the reactor and heated to 40C. 0. 2 Mlo of diphenyl ethylene is added as an indicator and the reactor is steril-ized with dropwise addition of a 12~ solution of sec-butyl lithium until the persistence of an orange-red color. At this point, an additional 18 mlO (0.024 mole) o~ sec-butyl lithium solution (12% in hexane) is added, foll!owed by 416 grams (4.0 moles) of styrene. The temperature of the polymerization mix-ture is maintained at 40C. for 5 m~n~tes. Then ~he living polystyrene is capped with butadiene by bubbling butadiene gas into the reactor until the color o~ the ~olution ch~nges ~rom dark red to orange. The living polymqr is terminated by treat-ment with 4.1 ml. ~0.05 mole) of allyl chloride. The macro-molecular monomer thus prepared is precipitated with meth,anol and separated by ~iltration. Its number average molecular weight estimated from gel permeation chromatography is 25,000 ~theory: 18JOOO) and molecular weight distributlon i5 very narrow. The macromolecular monomer produced has the ~ollow-ing ~tructural formula:

CH3 ~ ~ CH2 -CH = CH--CH2 ~ CH2- CH - CH2 where m equals l or 2.
~b) Prep_ration 0~ Graft CoE~lymer Having A Polvethylene Back-bone And Polyst~Yrene Sidechains~
2 Grams of butadiene capped, alpha-olefin terminated polystyrene macromolecular monomer as prepared in Example 18(a) above, is dissolved in 1500 ml. of cyclohexane and charged ~37636 .
into a 2-liter ~'Chemco" reactorO T~e reactor is purged with prepurified nitrogen for 30 minutes, and 22 mlO o~ 25% ethyl-aluminum sesquichloride solution (in heptane) is addedO The reactor is pressurized with 21 grams of ethylene to 40 psio Therea~ter, 0.1 ml. of vanadium oxytrichloride is added and ethylene pressure is dropped ~rom 40 psi to 1 psi in about 1 minute. The reactor is terminated in 3 minutes by the addi-tion o~ isopropanolO The polymer is recovered by ~iltrationO
It is known that the physical properties of l:Lnear high density pol~ethylene are dependent on its extent o~
crystallinity, molecular weight and molecular weight distribu-tion. It is a balance o~ these characteristicæ that generally governs the end use properties of ~abricated items. The gra~t copolymers o~ the present invention, part~çularly those having a polyethylene backbone and polystyrene sidechains, modifies the physical properties of polyethylene without a~-fecting the bene~icial crystalline properties o~ polyethylene.
In order to demonstrate these beneficial properties of the graft copolymers, as well as the crystalline nature of the copolymers, several tests were conducted. The ~ollowing data illustrates the properties of gra~t copolymers having a polyethylene backbone and polystyrene sidechains prepared by the procedure described in Examples 9 and 10.
Determination 0~ Macromolecular Monomer ~; .
Content By ID RD SPeCtrOSCOP!Y
Calibration curve of ethylene/polystyrene macro-molecular monomer copolymerD
C ; Commercial high density polyethylene9 U~SoI~ Micro-,~ ~ ~
thene ML 708 and Dow polystyrene, Styron~666u are blended in the ratiosD 80/209 70/30g 60/40, and 5a/50, and extruded ~P `
twice through a Killion extruderD The extruded blends are 1md~ rk 1~37~3~
pressed into thin films (about one mill) and the infrared spectrum run on a Beckm~n IoR~ 12 infrared spectrophotometerO
The benzene ring absorbance at 710 cm~l, and the methylene absorbance at 1480 cm~l are measured and the ratios calculat-edO The calibration curve is drawn by plotting ab~orbance ratio vs. % styrene.

Monomer Content Of Copolymers Ethylene-macromolecular monomer copolymers are pressed into ~hin films and their IoR~ spectrum obtained on the Beckman I.R. 12 spectrophotometerO The absorbance at 710 cm 1 for polystyrene-macromolecular monomer is compared to ab-sorbance at 1480 cm~l, and the macromolecular monomer is de-termined from the calibration curveO The I.R. spectra is evidence that a graft copolymer having a polyethylene backbone and polystyrene sidechains (M~Wo 27,000) having 20~ by weight incorporation.
Samp~e PreParation And Testing The copolymers are compression molded into sheets of about 20 mil thickness for stress-strain testing. The mold is two 7 inch x 7 inch x 0.040 inch steel plates separated by a 7 inch x 7 inch x 0.020 inch steel shim cut out to make a 5 inch x 5 inch x 0.020 inch center ca~ity. Surfaces are coated with Dow Corning R-671 Resin as a mold releaseO
Approximately eight grams of polymer are placed in the mold, and molded at 400F. for 10 minutes at 30 tons pressure, and cooled down by circulating water~
Three test specimens are cut out of the sheet with a dumbbell "C" die (ASTM D412-67T) and dimensions are measured by a micrometer.
Tensile properties are obtained on an Instron Tester de~ rk - -78-~3763$

according to ASTM D638 at a cross head speed of 2 inches/min-uteO
Flexual modulus of the copolymers is obtained on bars with Instron Tester according to ASTM D790.
Heat de~lection is obtained on bars according to ASTM D640.
Crystalline Structure 0~ Graft Copolymer Of Polyeth~lene Backbone And Macromolecular Monomer Sidechains . _ . ... . .. .
The crystalline nature of copolymers having poly-ethylene backbones is studied from:
Crystallinity - - X-ray di~fraction3 Melting behavior - - Diffç~ntial Scanning Calorime~ry;
Crystallite orientatlon - - X-ray dif~ractlon; and Spherulite ~ormation - - Light mlcroscopy.
Crystallinit~
The measurement of crystallinity by x-ray diffrac-tion takes many forms but an effective simple method ls to calculate a crystallinity index (CrI) as follows:
IllO - Iam CrI a ------ - X 100 IllO
where l11o is the intensity, above background scrattering, of the llO diffraction peak taken at 21.6 20. Iam is the amor-phous scattering at 19.8 2~.
For polyethylene, the separation of the x-ray scat-tering ascribed to the crystalline and amorphous fractLons is simplified, since the amorphous peak is clearly distinguished from the crystalline peaks on diffraction patterns. A diffrac-tometer tracing has been illustrated of a polyethylene with 12% integrally copolymerized alpha-olefin terminated poly-1~3~7636 styrene showing the separation of the two ~ractions and the measurement of peak heights, When .used on published di~rac-tion patterns of polyethylene, the me~hod gives crystallinity values in accord with those in which the authors used lnte-grated intensity measurements ~or the respective crystalline and amorphous-material.
CrI values o~ several polyethylenes range~ from 72-77. The CrI of polyethylene decreases for copolymers in proportion to macromolecular monomer content (6-30~o It is significant, that within experimental error, CrI values are not lower than those expected by a simple dilution of the polyethylene crystallinity with an amorphous macromQlecular monomer.
The diffractometer tracings used for the CrI mea-surements are also inspected ~or crystal lattice changes and for di~fractlon line-broadening with macromolecular monomer addition. Changes in the crystal lattice are not observed, which means that the macromolecular monomer is not incorpor-ated into the polyethylene crystal lattice, but rather in the amorphous regions of the sample... Measured half-widths o~
the 200 diffraction peak shows no decrease in.crystalline size with macromolecular monomer additionO Thus, di~fractometer tracings, such as the one wi~h 12% macromolecular copolymer, and the graph o~ CrI versus macromer content demonstrate a significant feature of the invention; namely, that the crys-tallinity o~ the polyethylene fraction is maintained in the presence of the macromolecular monomerO
Melting Behavior 0~ Macromolecular Monomer-Polyethylene Copolvmers A di~erential scanning çalorimeter (DSC) ~s used to determine the melting behavior of the copolymers and to seek ~ 03763~
confirmation of the lack o~ ~nterference by macromolecl~lar monomers with polyethylene crystallitesO A typical endother-mic DSC trace of a copolymer melting under a programmed ~em~
perature rise has been illustrated. The macromolecular mono-mer is an alpha-olefin terminated polystyrene having a molecu-lar weight of 279000. The copolymer has 20% o~ the macromo-lecular monomer lntegrally copolymerized into the polyethylene backbon0 polymerO The melting behavi.or of the copolymer closely matches literature data for unmodified hlgh~density polyethyleneg even though the sample contains 20~ of the macromolecular monomer. Undue premelting9 for exampleg does not occur ln copolymers and the melting point (Tm) is the same for both 100% polyethylene and copolymer samp~0 Al~o9 on the basis o~ comparable polyethylene~ made without macromolec-ular monomers using the same polymerizationg the initlA1 lift-o~f temperature (89Co )averaged 7C. higher for macromolecular monomer procedures containing samplesO In one sampleg the temperature increase is 19 co over the base polyethyleneO
Crystallinity measurements are calculated from heat of fusion (~H) data obtained from the area under the DSC
traceO The calculations are based on an ~H of 680 4 cal/gO for 100~ crystalline polyethyleneO Al~hough at a differe.nt level9 the crystallinlty values by thls method generally paralleled those obtained by x rayO
The thermal data on melting and crystallinity thus confirms the x-ray data that the integrity of the polyethylene crystallites is maintained ln the copolymer of the present in-vention. The reverse effect is generally observed, howeverg in polyethylene copolymers of the prlor art or ln polyethylene w~th sidechains simply attached to the polyethyleneO Often in these instances~ crystallinlty not only decreases by more than ~81~

~1~3763~
a simple dilution factorg but also the pol~eth~lene crystal~
lites may show low values for Tm and ~0 '9_ ~ ray di~raction patterns were taken o~ s~retched Instron test samples to determine crystallite orientation and the ef~ect of macromolecular monomer addition on the ability of the crystallltes to orien-t,0 The degree of orientation is determined from the size of the angle sub~kended by the arcs of the 110 and 200 di~fraction peaks that are shown by ori-ented ~amplesO Commercial high density polyethylene9 un stretched and stretched (500%) are shown in Fi'gures VIII~a) and (b) for comparison with a gra~t copolymer of a pol~e-thyl-ene backbone having 20~ by we~gh.t incorporation o~ polystyrene ' sidech~in~9 stret.ched, 800~o A stretched homopol~ner ~hG~S a small 110 arc that subtends an angle o~ 179 whereas the angle for the copolymer is 48~ even though it is stretched more than the homopolymerO Henceg the macromolecular monomer phase acts within the amorphous regions to tie and hold the crystallite together at high elongations, In molded ~ilmsg on the other hand9 a somewhat op posite ef~ect is noted,since copolymers show higher degrees o~ crystal plane orientation than homopolymersO The ratio o~
the 110 peak over the 200 peak height i.s used in these in~
stancesO When the ratio of peak intensities i3 . in the order of 30 3g the polyethylene s~mple is consi'dered to have random orientation. For ~omopolymer polyethylenes9 we prepared and tested the 110/200 peak ratio varied -from 300 to 4~6. The orientation ratio ~or copolymers varied ~rom about 3 to as high as 703 ~or samples mounted .in the dif~ractormeter with their film surface parallel to the sample holder. Molded specimens responded in an opposite sense9 howeverg upon subse-~82 ~3763~
quent heatin~ and cooling but without the p~essure used during molding. Under these circumstances, a copolymer decreased from 7.3 to 4.8 ~hile the base polyethylene increased from 4.6 to 5.0 in orientation. Similar changes are shbwn in other samples. These observations on changes in orientation further illustrate differences in polyethylene properties due to the presence of macromolecular monomers integrally copolymerized into the polyethylene backbone.
Spherulite For~ation .
Spherulitic structures are noted by microscopic exam-ination in several of the polyethylene or ethylene~macromolec-ular monomer copolymers prepared. In molded samples, large (10-30 ~m) spherulites in some of the 100~ polyethylene speci-mens are observed to decrease in size and in optical perfec-tion with macromolecular monomer addition. This behavior is confirmed by crystallization from solvent (Tetrahydronaphthal-ene) where large and individually separated spherulitic units can be observed. Polarized light is used and pictures are taken of spherulites from a homopolymer and copolymers wikh 6, 8 and 20% macromolecular styrene contents. The majority of the spherulites obtained from the copolymers are smaller and show more imperfections in structure than those obtained from the homopolymer. Similar effects are assumed to take place in samples where spherulitic structures are on the order of 1.0 to 3.0 ~m in diameter but where it is difficult to clearly distinguish changes in structure.
To demonstrate that the observed effects are a func-tion of copolymerization, pictures were taken of crystals from THN that were obtained from physical blends with 5, 10 and 20%
levels of macromolecular monomer. The spherulitic structures of the blends were unchanged from the homopolymer.

~3763~
Thus3 a second feature of graft copol~mers of the ln~ention is evident in that while the polyethylene crystal-lites themselves are not lmpaired9 the macromolecular monomer molecules lnterfere with the aggregation o~ crystallites into larger morphological units such as spheru:LltesO Their action fits the pattern of being in the amorphouæ region of the sample and interferrlng with cr~stallite aggregation but con-tributing as tie molecu~es to fllm strength and elongationO
The interference wi~h spherulite ~ormation is also , 10 postulated as contributing towards materia~s with improved I stress-cracki~g and low temperature flexibility properties.
¦ A number of gra~t co~olymers having polyethylene backbones and polystyre~a ~idechains are prepared using the procedure set ~orth in Examples 9 and 10. Also, a number o~
polyeth~lene homopol~mers are prepared in the same manner as described for the copolymersg except for the omission of the macromolecular monomer. Chain transfer agents are not used ' to control molecular weight. Products obtained with cont~n-uous ethylene addition have broad molecular weight distribu-tions, whereas those obtained by batch polymerizations havenarrow molecular weight distributions.
The graft copolymers and the homopolymers of poly-ethylene are pressed into filmsg whereby they are each sub-~ected to tests to determine yield strength~ elongation, ten-sile ~trength, flex modulus~ and other properties hereinafter set forth (us ng methods outl~ned aboYe) to demonstrate the I improved properf.~es of the graft copolymers over the homo-! polymer of polyethylene. The results of these tests are I summarized in Tables I III below~
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~03763~:i The data presented are on unannealed compression molded samples and therefore illustrate trends o~ physical propertiesO Optimization o~ physical properties desired re-quires the synthesis o~ a copolymer with a balance o~ molecu-lar weightg MWD9 macromolecular monomer content and macro-molecular monomer molecular weightO
It can be seen ~rom Table I tha-k the physical prop-erties of polyethylene homopolymers as a ~unction o~ molecular weight and molecular we~ght distrlbution (MWD) follow the ex-pected trends~ AlSOg the yield strength does not vary signi-ficantly wlth either molecular weight or MWDo The elongation and tensile strength increase with increasing molecular weight, whereas the modulus9 heat de~lection and melt index decrease with lncreasing molecular weight, Examples 25 and 26 have a narrower MWD and show significant increases in elongation and tensile strength over equival.ent weight average molecular weight polyethylenes of a broader MWD.
The summation of data for the graft copolymers are divided into two groups, those having a polydispersity (P.D.) less than 10 given in Table II and a PoD~ greater than 10 given in Table III in order to establish a logical comparison o~ the properties as can be seen ~rom the corresponding di~-ference in properties with polyethylene homopolymers.
By comparing the various properties of the graft copolymers with the homopolymers of the same average molecular weight, it is clear that the incorporation of the macromolecu-lar monomer in the backbone o~ hydrocarbon polymers, such as polyethylene~ improves many of the properties of polymer sig-nificantly withQut a sa~rifice o~ beneficial properties pos-sessed by the homopolymerO Such an improvement in propertiesis not expected in view o~ the ~act that the macromol.ecular ~03763~

monomer is actually copolymerized into the backbone o~ poly-ethylene and interrupts the polyethylene segmentsO GenerallyJ
such copolymerization with polyethylene results in a loss of beneficial properties~
It ls also evident ~rom the data shown that the use of very low molar percent concentrations of the macromolecular monomer does not alter the crystalline content of polyethylene.
Thus, the spherulitic structure is greatly reduced in the graft copol.ymers but not affected by simple blends of poly-1~ ethylene homopolymer with the macromolecular monomer. The evidence, therefore, indicates that the macromolecular monomer sidechain seg~ents are in the rubbery amorphous regions o~
polyethylene. In other words, the crystalline portion of poly-ethylene is the matrix having a rubbery dispersed phase which, in turn, has a gl.assy dispe.rsed phaseO The high T~ amorphous polystyrene macromolecular monomer apparently reinforces the low Tg rubbery phase at low macromolecular monomer contents in a similar way that the polystyrene domains behave in block C polymers such as Krato ~
As the content of the macromolecular monomer is in-creased, the nature of the matrix and dispersed phase of the amorphous areas of the polyethylene will change until an inver-sion o~ phases takes place. Now the crystal matrix o~ poly-ethylene will have a plastic amorphous dispersed phase which, in turn, will have a rubbery dispersed phase to the extent that the chain configurations of the amorphous and crystalline portions of polyethylene will permitO
The ratios of the property value~ set forth in Tables I - III for polyethylene homopolymers and graft co~
polymers (polyethylene backbone and polystyrene sidechains having a uniform molecular weight of 15,400) are shown in ~89 ~r~ ~ nn~

" ~03763~;

Figures I and II as normalized values vsO the macromolecular monomer content. These graphs show a definite e~ect of the macromolecular monomer in increasing all o~ the phys~cal prop-erties studied over those of polyethylene homopolymers of the same molecular weight and molecular weight distributionO As it can be seen in the graph (Figure I) the yield strength shows a sharp increase in the range o~ 4-12% by weight macro-molecular monomer content, then a gradual increase with higher macromolecular content. The elongation and tensile strengths lQ go through a maximum at about 12% macromolecular monomerO The ~lexural modulus has a sharp increase up to 4% incorporation of sidechain polymer then plateaus to about 14~-16~ macro-molecular monomer and again rises but less sharply at higher concentrations o~ the macromolecular monomer. The heat de-~lection shows a steady gain with increasing macromolecular content from 5~ incorporation.
The above data and illustrations demonstrate some of the advantageous results obtained from gra~t copolymers having polyethylene backbones and polystyrene sidechains integrally copolymerized into the polyethylene backbone. Si~ilar bene-~icial results are obtained using polymerizable hydrocarbon monomers o~her than ethylene which produce polymers having a high Tm and a low Tg, e.g., lower alpha-ole~ins such as propyl-ene, butene-lgpentene-l, etc.
As it is illustrated in Example 24, sidechain poly-mers having a high Tg, such as polystyrene can be replaced with low Tg polymers such as polybutadiene and predomi~an~ly cis-polyisoprene~ For exampleg isoprene can be anionically polymerized with secondary butyl lithiumg preferably to a molecular weight of about 15,000 and terminated with allyl chloride. Alternatively, the rubbery living polymer can be ~3*~3~
"capped" with an alkylene ox~de such as ethylene oxide follow-ed by termination with allyl chlorideg methallyl chloride9 or methacrylyl chloride to obtain low Tg macromolecular monomers~
The alpha-olefin terminated (allyl chl~ride and anionically polymerized isoprene) can be used to prep~re super impact poly-ethylene or polypropylene copolymers util:Lzing known polymer-ization techniques. For example~ the alpha-olefin terminated polyisoprene referred to above can be copolymerized with ethylene using a Ziegler type catalyst system or with propyl ene using a Natta type catalyst system~
Still another alternative illustrated in the ex-amples includes the use of hydrocarbon monomers which produce rubbery polymers in the backbone o~ the copolymer~ Included among these monomers are isobutylene, butadiene, isoprene9 ethylene-propylene comonomers3 etc~ The physical properties of the rubbery backbone polymers are enhanced by copolymeriza-tion or incorporation into the backbone polymer a wide variety of macromolecular monomers, such as linear polymers anionical-ly polymerized from s~yrene~ alpha-methylstyrene, ethylene 2Q oxide, ~-vinyl pyridine, methacrylonitrileg NgN-dimethylacryl-amide, methyl methacrylate, etc. A preferred example being the macromolecular mono~er of Example 24(a) wherein the poly-styrene capped with butadiene or ~soprene is terminated with either allyl chloride or 2-bromomethyl-5-norbornene. The lat-ter end group is particularly useful in preparing an ethylene-propylene backbone graft copoly~er ~ollowing the procedure o~
Exam~les 17 and 18.
As it can be seen from the abo~eg the present inven-tion provides a convenient and economical means for preparing copolymers utilizing a large variety of hydrocarbon monomers in forming the backbone polymeric blocks and a wide variety of ~al376al$
anionically polymerizable monomers in forming the sidechain polymersO The copolymerization is facilltated by a ~udicious selection of the terminal end group on the anionically poly merized polyrnerO Thus, the problem of copolymerizing ~ncom-patible polymers is solved providing an economical means for preparing copolymers having a backbone and sidechain polymer designed to fit one's needs and the particular end product desired.
EXAMPIE~51 ~10 Preparation Of PolystYrene~pol~iso~e-~ene MacP;omolecular Monomer Terminated With _ lyl Chloride To a l~gallon Chemco reactorg 2.5 liters of pur~fied benzene was added, and heated to 40 Co After sterilization with sec-butyl lithium using diphenyl ethylene as an indica-; tor, 15.3 ml. (0.019~ mole) of sec-butyl lithium (12~ in hex-ane) was added via hypodermic syringeO 193 G~ of styrene mon-omer was added in 5 minutes while maintaining the reactor tem-perature at 40C~ .6 Minutes after styrene monomer was added, 193 g. of isoprene monomer was added in 405 mi~utes. The re-actor was held at 40Co for 60 minutes, then 204 ml. of allyl chloride was added to terminate the reactionO The alPha--olefin terminated polystyrene-polyisoprene macromolecular mon-omer has a structural formula represented as follows:

wherein n is a value such that the molecular weight of the polystyrene is about 109000 and m is a value such that the molecular weight of the polyisoprene segment of the diblock macromolecular mono~er;is about 10,000.
-92 ~
k ~3763~i ,; ~
To a one~half-gallon Chemco~reactorg 60 gO of the alPha-ole~in terminated diblock macromolecular monomer (poly~
styrene-polyisoprene te~minated with allyl chl~ride) prepared in the previous example l~as charged together with lo 5 liters of dry N-heptaneO The reactor was purged with nitrogen-~or 40 minutes. 30 Mlo of diethyl alumlnum chloride (25~ in N-heptane) was addedg ~ollowed by 2005 gO o~ titanium trichlo-ride. The reactor was heated to 75Co, and propylene gas was introduced to the reactor at the rate o~ 1 liter/minuteO
Polymerization was carried out at 75C,, at 20-25 psi pressure while ~eeding prupylene at the average rate o~ 005 liter/min-ute. A~ter 2 hoursg the reaction was terminated by the addi-tion of ethanolO The resulting copolymer was washed with di-lute sodium hydroxide solution and dried in a vacuum oven. IR
analysis showed that the diblook macromolecular monomer was incorporated into the polypropylene backbone. The physical properties of the copolymer were tested and the results o~ the te~ts were as follows:
Tensile Strength4970 psi Yield Strength4720 psi ~ elongation 810%
Flexual Modulus2~05 x 105 psi Heat Distortion Temperature144Fo Izod Impact 1.0 ~to - pound/inch 3o T~ mQr 1 3~63$

Macromolecular Monomer Term~nated With All,vl Chloride ~ ..
To a l~gallon Chemco~rçactorg 205 liters of dry ben-zene was added and heated to 40Co After sterilization with sec-butyl lithium using diphenyl ethylene as a~ indicator, 15.8 ml. ~0.0199 mole) o~ sec~butyl lithium (~2~ in hexane) was added via hypodermic syringe. 80 Go of styrene monomer was added while maintaining the reaction temperature at 40C.
1~ Thereafterg 319 g. o~ lsoprene monomer was added and polymer-ization was carried out at 40Co for 1 hour9 and the living diblock polymer was terminat2d with 3.0 mlO of allyl chlorideO
The diblock macromolecular monomer had a formula represented as f~llows-CH3CH2 - CH ; CH2~ C ~ / H2 ~ CH2 CX ~ CH2 wherein n is a value such that the molecular weight of poly-styrene is about 49000 and m ls a value such that the molecu-lar weight of polyisoprene is about 16,000. Analysis o~ the diblock macromolecular monomer by gel permeati.on chromatography reveals that the molecular weight distribution of the polymer is extremely narrow9 i~e.9 the ratio of Mw/Mn is less than about 1.1.

Preparation ~f~G_aft C~pol~ er Fr m Polystyrene-Pol ~ opre~_DiO]o~ M~OrO~IG - la~ Mo omer To a one-half-gallon Chemco~reactor, 300 ml. of the diblock macromolecular monomer as prepared in Example 52 (40 ~r~ r~

\ ~ ~

g. on dry basis) was charged together with 102 liters of dry cyclohexane. The reactor was purged with high purity nitrogen for 50 minutes. 22 Ml. of ethylaluminum sesquichloride solu-tion (25~ in heptane) was added via hypodermic syringeO
~t~ylene was introduced to the reactor until the pressure reaohed 44 psi, and the mixture was stirred as rapidly as pos-sible. 0.2 Ml. o~ vanadium oxytrichloride was injected and polymerization started imme~lately. During the addition of the vanadium oxytrichloride, the temperature rose ~rom 25C.
1~ to 60C. As the pressure droppedg ethylene was fed at the rate o~ 2 liters/minuteO Polymerization was carried out ~or 12 minutes, and terminated by the addition o~ 10 ml. of ethanol. The polymer was purified by washing wlth cyclohex-ane, dilute sodium hydroxide solution, and dried in a vacuum oven, U.V. analysis of the copolymer showed that the copoly-mer contained 24% of the diblock macromolecular monomer. The physical properties of the copolymer were tested and the re-sults of these tests are as follows:
Yield Strength 2500 psi Tensile Strength 2160 psi ~ Elongation 490~
Flexual Modulus o.6 x 105 psi Heat Distortion Temperature 98F.
Iz~d Impact 12.8 ft. - pound/inch (specimen did not break) Preparation Of Polyst~rene-Polyiso~rene Diblock Macromolecular Monomer Terminated With Allyl Ch oride 3 ~ To a l~gallon Chemco~reactor~ 3.0 liters of purified benzene was added and heated to 40C, After sterilization with sec-butyl lithium using diphenyl ethylene as an indicator, T~Qn1~ ~C

- ~a3763~
4605 mlO ~000585 mole) of sec-butyl lithium (12~ in hexane) was added via hypodermic syringeO 761 Go of styrene monomer was added in 15 mlnutes while maintaining the reàction tem-perature at 40~Co 5 Minutes after completlon of styrene mono-mer addition9 410 gO of isoprene monomer was added in 4 min-utesO The reaction was held at 40Co for one hour, then the reaction was terminated by the addition of 15 mlO of allyl chloride0 The diblock macromolecular monomer had a structural formula as described in Examples 50 and 52 hereinabove, where-in the value of n was such that the molecular weight of poly-styrene w~s about 13~000 and the value o~ m was such that the molecular wèight of polyisoprene was 79000O The diblock macro-molecular monomer was analyzed by gel permeation chroma-tography and this analysis revealed that the molecular weight distribu-tion oP the polymer was extremely narrow, iOe.9 the Mw/Mn ratio was less than about lo 1 EXAM
PreParation Of Graft Copo~mer ~rom PolYs-~rene Polyisoprene Diblock Macromolecular Monomer Terminated With A11V1 Chloride a~d Eth~ene J To a one-half-gallon Chemco~reactor, 200 mlO of the diblock macromolecular monomer prepared in Example 54 (40 g.
on dry basis) was charged together with 103 liters of cyclo-hexane. The reactor was purged with high purity nitrogen for 1 hour. 22 Mlo of ethylaluminum sesquichloride solution (25%
ln heptane) was addedO Ethylene was introduced to the reactor until the pressure reached 44 psio Thereafter9 0~2 mlO of vanadium oxytrichloride was added and polymerization started immediately, and the temperature rose from 27Co to 55C. As the pressure dropped, ethylene was ~ed at the rate of 2 liters/minuteO Polymerization wa$ carried out for 8 minutes, 'rrû dQfn C~ r 1~

~3763~

and terminated by the addition of lO ml. of ethanolO The polymer was puri~ied by wash~ng with dllu~e sodium hydroxide solution~ cyclohexane, and dried in a vacuum ovenO UOVo anal~
~sis showed that the copol~mer contained 3815~ of the diblock macromolecular monomerO The physical prope:rties of the copoly-mer were tested and the results are as follow~o Yield Strength 5790 psi Tensile Strength 5920 psi ~ Elongation 77~
Flexual Modulus lo 6 x 105 psi Heat D~stortion Temperature 120Fo Izod Impact lo 0 ft. - pound/inch EXAMPLE ~1 Pre~arati.on ~ Diblock CMacrom~le~u~r Vonome~ "erminated With Allyl Chloride To a l-gallon Chemco reactor, 2~ 5 liters of purified benzene was chargedg and heated to 40C~ After sterilization with sec-butyl lithium using diphenyl ethylene as an indica-20 tor, 35~1 mlO ~0~044 mole) of sec-butyl lithium (12% in hex-ane) was added hypodermic syringeO 442 G. of styrene was added in 13 minutes while maintaining the reactor temperature at 40C. Ten minutes a~ter styrene monomer was added, 8804 gO
of isoprene monomer was added in 4 minutes. The reactor was held at 40Co for 30 minutes, then 3O6 mlO of allyl chloride was added to term~nate the reactionO The recovered diblock macromolecular monomer had the same structural formula as rep-resented in Examples 50 and 52 hereinabove9 with the exception that the value of n was such that polystyrene had a molecular 30 weight of about lO~000 and the value o~ m was such that the molecular weight of polyisoprene was about 2,0000 The polymer ~c,do. ~ k 97 1l~37/~3~
was analyzed by gel permeation chromatography and the anal~sis revealed that the molecular weight distribution o~ the polymer was very narrow~ iOe~9 the Mw/Mn ratio was less than about 1.1, PreParation Of Gra~t Copol~mer Pol~isoPrene Diblock Macromolecular Monomer Terminated ~ L~LI_ __ ___nd A

To a onerhal~-gallon Chemco~reactor, 155 g. o~ 19~3%
lQ by weight of the diblock macromolecular monomer prepared in Ex-ample 56 solution (30 gO on dry basis) was charged together with 106 liters o~ puri~ied cyclohexaneD 22 Ml. of ethylalu minum sesquichloride solut,ion ~25~ in heptane) was added via hypodermic syringe. Then 19 liters (35 g.) o~ prop~lene gas was introduced into the reactor. As soon as 0.2 ml. o~ vana-dium oxytrichloride was in~ected, polymerization was started by continuous ~eed of ethyleneO Ethylene was addéd to the re-actor at the rate o~ 2 liters/minute for 14 minutes (35 g.).
Polymerization was carried out for 24 minutes, and terminated by the addition of isopropyl alcohol.
The copolymer solution was placed in a stainless steel beaker and 1 liter of dilute sodium hydroxlde solution C ~ and 1 g. of Irganox 1010 antioxidant was added. The mixture was stirred by Arde-Barinco Mixer to remove catalyst residue from the polymer The copolymer was coagulated and dried9 and evaluated as (1) thermoplastic elastomer, ~2) alloying agent ~or blending commercial EPDM and polyisoprene ~or developing high impact plastics, (3) EP rubber which can be cured with conventional diene-based rubber to improve compatibility and 3Q ozone resistance, T~ad~rn Q ~ ~ -98-376;~

Ox~de ~nd ~ lb~ sY~ _Chloride A sta*nless steel reactor was charged with 1950 22 kgo o~ puri~ied benzeneO The reactor was hea-ted to 40Cg and the solvent and reactor were sterilized with sec-butyl lithium us-ing diphenyl ethylene as an indicator. Following steriliza-tion~ 126058 g, (lo 9764 moles) of sec-butyl lithium ~12% in hexane) w~s added to the sterilized solventg ~ollowed by the addition o~ 19.47 kg~ of styrene over a period of 30;45 min~
utesJ while maintaining the reactor temperature at 36-42C.
Following the additlon of the styrene, 48~62 kgo o~ isoprene wa~ ~dded to the reactor ~ollowed by the addition o~ o.38 kg.
of ethylene oxide to "cap" the diblock living polymerO The "capped" diblock polymer was terminated by the addition o~
0.22 kg. of methacrylyl chloride to obtain the methacrylic aci~ ester,represented by the formula~
Q

CH3CH2--CH_ ~CH2 ~ H~ CH ~ CH2 -~H2cH2-o-c~c = CH2 CH3 ~ ~ ~ ,n / C ~ C CH3 wherein n is a value such that the molecular weight o~ poly-styrene is about 10~000 and m is a value such that the molecu-lar weight o~ polyisoprene is about 25gO00~ Analysis o~ the diblock macromolecular monomer by gel permeation chromatography reveals that the molecular weight distribution of the polymer is extremely narrow9 i.e,g the ratio o~ Mw/Mn is less than about 1.1. Following recovery o~ the macromolecular monomer9 68 g. of Agerlite Superlite (~nti-oxidant) wa~ added to the polymer to stabilize it against premature oxidationO
_99_ ~r~de~rk 103763~
The procedure o~ Example 59 w~ repeated using in pl~ce of methacrylyl chlorlde, an equivalent amount o~ maleic anh,ydrlde to produce the maleic half ester o~ the polystyrene~
polyisoprene diblock macromolecu~ar monomer having the ~ormula:

CH3CH2--CH ~ CH2 CH ~ ~C ~ ~CH2- , 2 ~ \
3 L ~ / C = C jCH
n ICH3 H m CH

~IOC
o wherein n and m are positive inte~ers as hereinabove de~ined.
The hereinabove maleic hal~ ester terminated macromolecular monomer was copolymerized with vinyl chloride (10 parts by weight o~ the macromolecular monomer with 90 parts by weight o~ vinyl chloride and a chain trans~er agent) to produce a chemically ~oined, phase separated gra~t copolymer possessing superior properties with respect to processability and strength. The gra~t copolymer was blended with polystyrene (DOW 666) to impart excellent properties.
20 ` EXAMPLE 60 Preparation Of Gra~t Copol~mer From Methacr,ylate Ester Poly-st~rene-Poly1,saprene Diblock Macromolecular Mono~r~i~Lo_lL~lL~
A suspension copolymerization using the methacrylate ester terminated polystyrene-polyisoprene diblock macromolecu-lar monomer prepared in Example 59 was conducted by the pro-cedure described below. An aqueous solution and a monomer solution were both ~reshly prepared b~ore use~ The ingredi-ents of the aqueous stabillzer solution and monomer solution were as ~ollows:

~103763~i `
Aqueous ; Distilled Water 375 g~
Polyvinyl~pyrrolidone 0.625 g.
(Luviskol K-90) . ..~, Monomer Solution Methacrylate terminated macr~molecular monQmer (Example 59) 291 g. (2509% solids solution in benzene, 7504 g.) S-tyrene 177 g-Benzene (solvent) 52 g~
AIB~ ~ lo 33 g.
(poiymerization initia~or) The aqueous stabillzer solution was charged to a rinsed quart bottle, and the bo~tlç was capped with a butyl rubber gasketed cap having a Mylar~ ilm lining. ~he bottle was purged with nltrogen via syrlnge need~e be~ore in$~oducing the monomer solution. The mo~o~er solution was then ~hargçd to the bottle with a hypodermic syringe, and the bQtt1e was placed in a bott~e polymerizat~on ~th and rotated at 30 rpm at 65C~ ~or 20 hours. The ~uspensio~ was then cooled, fil-tered, washed with water, air dried, and screened at ambient temperature, 117 G. of the copolymer was recovered, repre-sentin~ a 95~ conversion o~ styr~ne.
The chemically ~o~ned, phase separated gra~t copoly-mer was compressio~ molded tq a clear plastic and ~ad the fol-lowing physical properties:
Flexual Modulus 190,000 psi (13,360 kg./cm3) Heat ~istortion Temperature 170QF~ (77C.) Izod Impact Strength 1.1 fto/ ound inch - 9.5 ft. ~pound inch As it can ~e seen ~rom the above data, the copolymer r~a~m~r k -lo~

had remarkable physical properties and had the added advantage of being a çlear plastic.

PreParation Of Graft Copol,ymer ~rom Pol.Yst~rene Terminated With Vin,yl-2-Chloroeth!yl Ether ~nd Eth.~l Acr,vlate To a solution of 18 grams of octylphenoxy polyethoxy ethanol (emulsifier) in 300 grams of deionized water there is added, with vigorous agitation in a Waring Blender, a solution of 30 grams of the polystyrene product of Example 1 and 70 grams o~ ethyl acrylate~ The resulting dispersion is purged with nitrogen, then heated with stirring at 65C.~ whereupon 0.1 gram of ammonium persulfate is added to initiate polymer-ization. Thereupon, 200 grams of ethyl acrylate and 0.5 gram o~ 2~ aqueous ammonium persul~ate solution ar.e.added p~rtion-wise over a period o~ three hours, the temperature being main-tained through~ut at 6~C. The resulting graft copolymer emulsion is cast on a glass plate and allowed to dry in air at room temperature to a ~lexible self-supporting filmO The film is shown to contain polystyrene segments by extraction with cyclohexane which dissolves polystyrene; the cyclohexane ex-tract on evaporation yields no residue.

Preparation~;Of...~ t CoPo-l.ymer Of Poly~alpha-methvlstYrene?
Terminated ~ith VinYl Chloroacetate And Butyl Acrvlate A solution o~ 50 grams of poly(alpha-methylstyrene) macromer terminated with vinyl chloroacetate and having an average molecular weight of 12,600 and 450 grams of butyl acrylate in 1,000 grams of toluene is purged with nitrogen at 70C., then treated with 1 gr~m of azobisisobutyronitrileD
The temperature is maintained at 70q CD for 24 hours to yield a solution of graft copolymer which is cast as a film on a ~qdQ ~r~

1~3763 .~;.?
glass plateO The dri.ed film is sli.ghtly tacky and is shown to contain polystyrene ~egments by extraction with cyclohexane and evaporation of the cyclohexane extract, as aboveO
EXAMPLE 6~
Preparation 0~ Graft Copol~mer Of P~lystyrene Macromer Terminated With Methacr~LYl Chloride And Eth~l Acr~ _ e A mixture o~ 21 grams of polystyrene macromer termin~
ated with methacrylyl chloride and having an average molecular weight of 10,000 prepared as in Example 6, 28 grams of ethyl acrylate and 0 035 gram o~ azobisisobutyronitrile is prepared at room temperature and kept ~or 18 hoursl under nitrogen, at 67C. The resulting product is a tough, opalescent material whlch can be molded at 160C. to g~ve a clear, tough, trans-parent sheetO

HomopQlymerization Of Met acr~late Terminated Polystyrene The methacrylate terminated polystyrene bf Example 8 is sub~ected to homopolymerization conditions by suspension polymerization as followsO
Aqueous Solutiono 5% Lemol~42-8~8 (Polyvinyl alcohol) 3.0 g.
Distilled water 300.Q g.
Monomer Solution-Methacrylate terminated polystyrene 20.0 g.
Lauroyl peroxide 0.16 g.
Benzene (thiophene-free) 30.0 g.
The aqueous polyvinyl alcohol solution is charged into a clean quart bottle and sparged with nitrogen for 15 minutes. The methacrylate terminated polystyrene macromolecu-lar monomer solution is added to the bottle, and the bottle iscapped after flushing with nitrogen for 2 mi~utesO The bottle is placed in a 70Co bottle pol~merization bath for 17 hours.

~de~ k -103~

~037636 The product is filtered, dried, and dissolved in tetrahydrofuran (THF) for Gel Permeation Chrom~tograph (GPC) analysis. No gel is found in the THF solution~ In the GPC
chromatogram, the ratio of the area of the unreacted macro-molecular monomer peak at 32 counts to the total peak area showed that 75.9% of the macromolecular monomer remained un-reac~ed. The analysis of the GPC, theref3re9 reveals that only 24% of the macromolecular monomer reacted, and this con-version resulted only in a low molecular weight polymer.

Polymerization Of Acr,ylates In The Presence Of Po}Yst~rene This example illustrates that a polystyrene does not graft to an acrylate backbone at the polystyrene segment, es-tablishing that the macromolecular monomers of the invention copolymerize with acrylates and other polymerizable monomers through the terminal dDuble bond.
The attempted polymerization was conducted in a stirred 3-neck flask fitted with a condenser by the following recipe and procedure:
Po~ymerization Recipe~
Polystyrenel 18.0 g.
r' ~ Ethyl acrylate (R & H No. 3871) 42.0 g.
~o AIBN (VAZ0)~ 0.158 g.
Benzene (thiophene-free) 120.0 g.
DMS0 (reagent grade) 12000 g.
lLiving polystyrene having a molecular weight of - about 10,000 terminated with methanol.
The materials are charged into the flask and the clear solution is heated under a slow flow of nitrogen ~or 13 hours at room temperature of 61Co to 80C. After completion~
the polymer solution has a total solids content of 190 6 (theoreticalO 20.0%).
The product mixture is precipitated and dissolved in Trqde~n~ r k ~3763!~i THF for GPC analysis. The unreacted polystyrene i8 determined ~rom the area of the polystyrene peak in the GPC chromatogram of a known sample weight in~ected, and using the polystyrene peak area/gram calibration from polystyrene standards shown in the ~ollowing Table.
CPC Determin_tion Of Unreacted P~ st,Yrene , Unreacted Polystyrene Unreacted ~t. Product Polystyrene In In~ected Polystyrene 10 In~ected Peak In (Grams) Area(Grams) ~ Product o.oo8039 0.1778 0.00268 33.3 (a)Calculated ~rom standard 66.5 g. area/l.000 g.
macromolecular monomer.
The above determinat~on shows that the polymer prod-uct cont&ined 33.3~ unreacted polystyrene. There~ore9 little or no grafting of ethyl acrylate to polystyrene macromolecular monomer occurred during the polymerization.

Pre~aration Of Graft Co~gl,rmer Havi~ng'Pol,Yst,rrene Sidechains And Poly(butrl acrrlate) Backbone The following ingredients are charged into a quart bottle which had been washed, dried, capped and flushed with nitro,gen.
Methacrylate terminated polystyrene ~prepared by procedure of Example 8, except that ~n = 11,000) 15.0 g.
Ut~l acr,rlate (Rohm & Haas 3480) 45.0 g.
AIBN~(VAZ0) ~ Oo09 g.
DMS0 (reagent grade) 195.0 gO
Benzene (thiophene free) 19500 gO
The methacrylate terminated polystyrene ls first dissolved in the benzene/DMSO solution9 followed by dissolving ' the butyl acrylate and V~Z0 in the solutionO The homogeneous ~r~dQr~a, k ~03763~
solution is introduced i~to the nitrogen filled bottle via syringe. The bottle ls placed in a 67Co bot~le polymeriza-tion bath and rotated at 30 rpm. Samples are removed by syringe and sh~rb stopped wi~h 10~ ME~Q at 75 minutes, 120 minutes and 210 minutes. At 300 minutes polymerization time, the remainder o~ the bottle is short stopped with 4 drops 10 MEHQ in ethanol.
The butyl acrylate conversions are obtained by total solids determination on portions o~ the samplesO The remain-der of the samples are precipitated in methanol, dried, anddissolved in T~ifor GPC analy$is. The methacrylate termin-ated polystyrene has a peak at 31 counts on the GPC chromato-gram. The GPC chromatograms of products of 75, 1209 210 and 300 minutes Rhows the disappearance of the peak at 31 counts.
Analys's o~ the GPC çhromatogram revealed that 25~6~ of the graft copolymer is polystyrene and 74.4% is poly(butyl acry-late)0 The above procedure is repeated several times using the same methacryla~e tçrminated polystYrene having a malecu-lar weight of 11,000 and a Mw/Mn of less than about 1.1, bycopolymerizing increased amounts of butyl acrylate~ replacin~
butyl acrylate wlth ebhyl acrylate andlmebhyl methacrylate.
Table 4 below summarizes the res~lts of these copolymeriza-tions.

-106_ ~AB~E 4 C_mpositions 0~ Methacrylate Terminated Pol~styrene-Acr,ylic Copolymers Prepared i~ DM;S ~ e~nzene Solution % Macro-(a) Copolymer molecular Macro Com-Monomer Polyme~- molecular position in ization Comonomer Manomer (~ Macro-Monomer Time, Conver- Conver- molecular ComonomerFeed Hours si~n % _sion ~ Monomer~
BA 25 2, 36.2 37^3 2506 3.5 62.3 65.7 26.0 ' 5 75.6 85.5 2704 BA 50 2 13.5 18.4 57.7 4.75 ~7.0 7700 53.5 EA 25 2 23.2 30~1 30.2 3.5 58.3 67.2 2708 77.6 90.4 28.0 EA 50 4.75 69.o 80.7 53-9 MMA 25 2 15.5 10.~ 18J2 ~8.3 530~ 26~9 MMA 50 2 12.0 22.9 6506 4.75 35.7 32.0 47.3 (~)SllMA = Methacrylate termin~ted polystyrene~ 11,000 ~n - ~ethacrglate terminal group EA = Ethyl Acrylate BA = Butyl Acrylatq MMA ~ Methyl Methacrylate XAMPIE~r 6,7 Prepartion 0~ Gra~t Co~olym~er,Havln~ Pol,vstyrene Sidechains And PolY(meth,Yl methacr,ylate) Backbone The ~ollowing ingredients are charged into a clear quart bottle, capped, purged with nitrogen, and polymerized for 17~ hours in a 7~$~ bottle polymerization bathO

~37~3~i Methacrylate termin~ted polystyrene ~product o~ Example ~) 2705 gO
Methyl methacrylate llOo O go Benzene (thiophene-~ree) 41300 g~
; C AIBN~(VAZ0 64) lolO g~
t-Dodecyl mercapt~n 0070 mlO
The resulting graf~ copolymer is recovered by pre~
cipitation of part of the copolymer in methanol and the other part in cyclohexane to give a combined yield of 87~9 Glear, brittle films are obtained from the cyclohexane - or methanol -precipitated products, The methaGrylate terminated polysty rene alone has a peak at 32 counts on the chromatogram of the GPC. Howeverg a GPC chromatogram on the unworked-up product o~ the gra~t copolymer illustrates that no unreacted methacry-late macromolecular monomer is detectable at 32 countsO There-~ore, it m~st be assumed that all of the methacrylate termin-ated polystyrene copolymerized with the methyl methacrylateO
EXAMP~E 68 .
Preparation Of Graft Copolymer Havi ~Pol~styrene Sidechains And PolY(butyl acrylate) Backbone BIY Suspension Copolymeriza-tion By emplaying the same methacrylate terminated poly-styrene used ~n Example 66 ~i.e., M.W. = 11~00 and Mw~Mn less than about lo 1~ prepared by the procedure of Example 8), the following ingredients are charged into a clean~ capped3 ~nitrogen purged quart bottle:
Distilled water 150~0 gO
Lemol~42-88 (5% solution of polyvinyl alcohol) 3~0 gO
Disodium phasphate o.80 g.
Monosodium phosphate OOQ5 g~
Therea~ter, the following solution is introduced into the bottle via syringe-~r~d~rn~ ~ k -108-~l)3763$
Methacrylate terminated polystyrene 2000 gO
But~l acrylate 30~0 gO
Lauroyl peroxide 0uI gO
The bottle is rotated for 16 hours, at 65Co 9 ~ol-lowed bv heating ~or 2-3 hours at 86Co I'he product beads are washed with water, filtered and driedO The molded film i~
clearg rubberyg and strong. The transparency of the film ~n-dicates that little unreacted methacrylate terminated poly-styrene is presentO
Unlike copolymerization in DMS0/benzene solution, the reactivity of methacrylate terminated polystyrene ~ith acrylic monomers in suspension polymeri.zation is that predlct-ed ~rom llterature reacti~ity ratios. It is seen l~ Table 3 below that the polymerizable macromolecular monomer has a greater relative reactivity than the butyl acrylate monomerO
The relative reactivity ratio~ r2, o~ the methacrylate ter-minated polystyrene (Ml) with butyl acrylate (M2) is about 004 (Ta~le 5). This corresponds with the literature value o~ 00 37 ~or methyl methacrylate/butyl acrylate.
TABLE~
Composition Of Methacr~late Terminated Polyst!yrene-But~
Acr,vlate Copolymers Prepared By Suspension Polvmerization -r2-Copolymer version % Macro- Macro- Com- % Macro-molecular Pol~ymeri- ~utyl molecular position molecular Monomer zation Acrylate Monomer (% ~acro- Monomer In Monomer Time, Conver- Conver- molecular Con-30 Feed Minutes sion ~ sion~ Monomer) versflon . . _ _ . .. . _ 2902 4700 4105 o.6 135 6004 7906 35~6 180 6809 8109 33~1 700 15~ 5 68~ 9 0.1~5 lOo 1 26~ 3 710 g 0~ 38 135 67~ 4 8100 5406 180 7900 85~ 6 5200 ~109 -~L~3763$

.V Suspension Co-polymerization A suspension copolymerizatio~ using a methacrylate terminated polystyrene prepared by the procedure of Example 8 having a molecular weight of about 16,000 and a Mw/Mn of less than about 1.1 is Gonducted by the procedure described below.
An aqueous ~olution and a monomer solution were both freshly prepared before useO The ingredients of the aqueous stabil-izer solution and monomer solution are as followsO
Aqueous_St bilizer_Solution:
Distilled water 30000 gO

5~ Lemo ~2-88 poly~lnyl alcohol solution ~Borde~)3.0 gO
Disodium phosphate 106 gO

Methacrylate terminated poly-styrene 3. g-Ethyl acrylate (Rohm ~ H~as)35.0 g, Butyl acrylate (Rohm & Haas)35.0 g.
Benzene (thiophene-free)14.0 g~
Lauroyl peroxide oOo84 gO
The 5% polyvinyl alcohol solution is prepared by dissolving Lemol~42~88 in distilled water. The aqueous sta-bilizer solution is charged to a rinsed quart bottle, and the bottle is capped with a butyl rubber gasketed cap having a Mylar film liningO The bottle is purged with nitrogen via syringe needle before introducing the monomer solutionO
The monomer solution is then charged to the bottle with a hypodermic syringeg and the bottle is placed in a bottle polymerization bath and rotated at 30 rpm at 55Co for 16 ~tr~dem~rk ~(~3763i hours. The polymerization reaction is completed using the follow~ng temperature cycle. The bath temperature is raised to 65C. for 3 hoursg 80C~ for one hour and 4 hours at 92-95C. The suspension is then cooled9 ~ilteredy washed with water and dried at ambient temperatureO
The beads are milled for 2 minutes at 145Co roll temperature for analysis and physical testing, The yield is ~1~6~ of theoretical ~there is some loss of material during milling). The amount o~ unreacted methacrylate terminated polystyrene in the product is 303~.
The samples are prepared for physical testing by briefly milling the dried polymer beads prior to molding spec-imens in order to eliminate insoluble gelO The milled prod-ucts are dissolved in THF for GPC determination ~or unreacted methacrylate terminated polystyrene. The molded specimens which had not undergone shearing by milling did not generally develop optimum physical properties. All products for analy-sis are milled 2 minutes on a lab mill with a tight nip and 145C. roll temperature. Specimens ~or tensile ~esting are compression molded for 10 minutes at 170Co and 1100 psio Only contact pressure is applied until the platens reach the required temperature, then full pressure is applied to the mold. Pressure is maintained while cooling the mold to pre-vent the formation of bubbles.
The molded sheets (19 mils) of the 30~ incorporated methacrylate terminated polystyrene copolymer of this example are tough and transparent and the properties are described in Table 6 below.

711~3~

~perties 0~_~0~ Methacrylate Termi Unreacted macromolecular monomer (~) 3.3 THF-insoluble.gel content of milled and molded .
sample, % o~4 Tg of acrylic elastomer component by DSC9 C. : -37 Water absorptiong 24 hours9 % approximately 0.3 Yleld strength3 psi (a) 360 lO Tensile $trength, psi (a) 1630 Ultimate elongationg % ~a) 1~75 Tensile set (% increase of original length) ~a) 35 (a)Tensile testing was conducted on Instron at lO inches/min-ute crosshead rateO

Pre~aration O~ Gra~t Copol2~e Havin~_Polyst~rene Sidechains And Poly(!but~l acr~late)_Backbone B~Suspension Copol~meriza-tion A 2-liter glass resin kettle (5 inch diameter) emersed in a temperature controlled water bath is charged with 600 grams o~ an aqueous stabilizer solution containing 600 grams of distilled water, 300 grams of 5% Lemol 42-88 poly-vinyl alcohol solution (Borden), and 3020 grams o~ disodium phosphate. The reactor is equipped with a condenser, thermom-eterg nitrogen inlet, and a stirrer with a 4-3/8 lnch crescent shaped l-piece Teflon paddleO While heating up the aqueous solution, the reactor is purged with nitrogen at 100-200 mlO/min. ~or 50 minutes, The nitrogen flow.is-reduced~ and 225.2 grams of a monomer solution is charged to the reactorO
The monomer solution consists o~ 6000 gram~ o~ a methacrylate terminated polystyrene prepared by the procedure o~ Example 8 and having a molecular weight of about ll,000 and 140.0 grams of butyl acrylate, 2800 grams of benzene (thiophene~free)g and 0.280 gram of lauroyl peroxi.de (Alperox, Lucido)~ The stirrer is adjusted so the blade is lo 5 inches below the surface, and rk -112-~37~3~i stirring i6 started at 300 rpm, then reduced to 230 rpm.
(Monomer pooling is observed at slower stirrlng speedsO) The bath temperature is maintained at 62Co with an internal tem-perature of 60-61C, After 12 hours, monomer droplets are ob-served as bein~ converted into be~ds. The internal tempera-ture is raised t~ 90C. after 5~ hours, and the polymerization is finished in another 1~ hours, The produc~ is filtered through ~ 6a-mesh screen, washed with distilled water and al-lowed to dry at room temperatureO The ~eight o~ the dried polymer beads (5-12 mm. lengthJ 3-4 mm. diameter) is 19007 grams. After milling (2 minutes at 145Co ) then molding of the product ~or 10 minutes at 170C.~ a transparent ela~tomer is obtained~
Table 7 below illustrates the physical propqrtles obtained by çopolymerizing the macromolecular mono~ers of the present invention prepared by suspension polym~rization by the procedure in the examples above.

103763~
TA~LE 7 Physical Properties Of Macromolecular .~
Monomer/~crylic Co~olYmers(a) Macro-( ) (b) molecular Elon_ Pçrma- ~mmedl-Monomer Yield Tensile ga- nent ate Type 5trength Strength tion Set Recovexy Wt. % Comonomer (PSi~ ~Si~_ (%) ~.
SllMA 20 1 ol EA oBA ~ 820800 0-2 9805 10SllMA 25 1 1 ~AoBA 130 1420 790 5 95 SllMA 30 1 ol EA oBA 380 1500810 4 87 SllMA 35 1 1 EA:BA 560 1930 56050 77 S16MA 25 lal EAaBA - 1310 73010 96.8 S16MA 25 2:1 EABA ~ 1800 70023 91 S16MA 30 1:1 EA:BA 270 1660 55022 91 S16MA 40 1:1 EAaBA1220 2170 l~oo108 S16MA 45 1~1 EA:BA1760 2490 350128 SllMA 45 EA 2090 2400 290140 20S16MA 50 1:1 EA:BA2680 2950 240125 (a) Specimens 18-19 mills thickne~$ pulled on Instron at 10 inches/minute.
(b) % Recovery = ~ Elongation - % Set/~ Elongatio ~ x 100 (c) SllMA - Polystyrene, 11~000 molecular weight, metha-cr,~late terminal group.
S16MA = Polystyrene, 16,000 molecular weight metha-crylate terminal ~,roup.
The examples (Examples 66 ~ 67) above illustrate thab the polymerizable macromolecular monomer of the present invention copolymerizes and is incorporated into the backbone polymer at a uniform rate that does not change with conver-sion (Table 4). This data (Table 4) illustrate that the ini-tial composition of the copolymer is the same as the initial charge ratio (r2 = 1). The rea$ons for this behavior of the methacrylate terminated macromolecular monomer is not under-stood3 but the effect is reproducable~ The results of these -114~

~Qa7~i3~i experiments indicate that with very large monomers9 eOgOg the macromolecular monomers in very low molar concentra~ ons9 a Po~sson distributl~n of segments can be achievedO This dls~
tribution permits the synthesis o~ predictable9 uniform graft polymer structure~O It is shown in Table 3 that the r values correspond to the literature r values in this type of copoly-merizatlonO
It can be seen from the table that at low macromo~
lecular monomer levels (20~30%) the products are thermoplastic elastomers with good recovery. At 30-45% macromolecular mono mer contents9 the products are ~lexible thermoplastics with increasing tensile strength and yield strength, and decreasing elong~tion and recovery, as the macromolecular monomer Content increasesO
As it would be expected, the macromolecular monomer/
~crylate copolymers have many potential uses as thermoplastic elastomers~ For example, emersion of a macromolecular mono mer/EA/BA terpolymer in machine oil ~or 5 days at room temper-ature produces a weight increase o~ only 0.9~. The s~rength and recovery of the specimen appears to be une~fected by the emersion in oilO The estimated use temperature range of this thermoplastic elastomer is about -30C. to +50Co Oil resist-ance and brittle temperatures can be modified by comonomer composition used in the macromolecular monomer copolymeriza tionsO The use of macromolecular monomers with higher glass transi.tion temperatures than polystyrene will produce a signi-ficant increase in the upper temperature limits o~ these prod-uct~.
These products have been found to be useful in nu-merous applications such as gaskets, O-rings, sealants9 adhe-sives9 etc.g in contact with hydrocarbon solvents and oils, ~376~`6~
water9 glycolsg etc. The capabi.lity of being injection molded,and the lack of e~tractable curing ingredients are among the advantages offered by the novel macromolecular monomer gra:ft copolymers of: the inventionO

And Poly~but~l a_r~l.ate) Backbone Prepared By Latex Copolymer~
izatiorl Stabl.e ~atexes are prepared by copolymerization of a 10 methacrylate terminated polystyrene macromolecular monomer prepared by the procedure of Example 8 and having a molecular welght of about; 139000 with acrylic monomers is accomplished by the :~ollow.~ng recipe and procedureO
Solution A~
Distilled water (boiledJ nitrag~n purged) 4760 0 gO
Sodium bicarbonate solution (570~ 160 0 gO
rD Igepa~Co-880 solution (10% aqueous ~d solution, GAF) 80Jo gO
SolutiorI B.
Butyl acrylate 28000 gO
Methacrylate te~ninated pol:Ystyrene (M~Wo = 139 000,~ ~w/~n 1.1)120.0 g.
- Toluene ~ 40 g.
Ninate~01 (60~ active, Stepan, calcium dodecylbenzene sulfonate) 130 6 g.
t-Dodecyl mercaptan 0.20 mlO
Solution C~
~ ~ .
Lauroyl peroxide solution ( 1. 6 go in 2000 g., toluene)2106 g.
The molecular weights of the copolymer products can be increased by elimination of mercaptan in the recipe.
The emulsion is prepared in a 105 liter S~ beaker., cooled in an ice bath and made with a Ty~e CS 4AMP 8,ooo rpm Black and Decker homogenizerO Solution A is placed in the beaker and a nitrogen purge ls startedO The homogenizer is started and Solution B is introduced in one minute and stirred ~116 ' \ r~nQr ~

- ~37~ii3~i;
~or an additional lO minu~esO Solution C is therea~ter added and the entire contents stirred for an additional 2 minutesO
The above emul.sion is charged ~nto a 2-liter glass resin kettle fitted with ~our baffles slx inches by ~ inch and stirred with a 3 inch diameter six blade turbine agitatorO
~itrogen purge and stirring (500 rpm) are started while the temperature is raised to and held at 67Co After 5 minutes at 500 rpm~ the speed o~ the agitator is reduced and held at 175 rpmO After l9 hours at this temperature, the reactor con-tents are cooled to room temperatureO The latex is ~iltered through clothO The resulting polymer has a total solids con-tent of 3902% and a Brook~ield viscosity at 25 (LVI 60 rpm) 0~ llo9 CPSJ a parti.cle s:Lze o~ 2 microns, a pH o~ 7.6 and a ~reeze-thaw stability o~ 2 cyclesO Analysis reveals that only lo 5% 0~ the methacrylate terminated polystyrene remained un reactedO
ExAMpLE, 7?
Preparation Of Graft Copol~mer Havin~Polystyrene Sidechains And Pol!Y(but~l acr,vlate)/Pol,y(eth.vl acr.~late) Co~ol2~eric Backbone B~ Latex CoPol~m-erization A l.atex copolymerization employing the same procedure as described in Example 71 above is employed with re~pect to the following recipeO
Solution A:
Distilled'water (boiled~ nitrogen purged) 401050go .
Sodium bicarbonate (5% solution) 17.6 g.
Igepal'~C0-880 solution (10% aqueous solutiong GAF) 7700 g.

-rr~ ~It n~ r )C

~117 Solution B: ~7636 Ethyl acrylate 15400 gO
N-butyl acrylate 15400 gO
Methacrylate terminated polystyrene ~MoWo = 13,000) 132-o gO
~r~ Xylene 4400 gO
~inat ~ 01 (60~ active, ste~
calcium dodecylbenzene sulfonate) 120 9 go t-Dodecyl mercaptan 0007 mlO
Solutio, ~ ,:
Lauroyl peroxide solution (009 grams ln 2200 grams xylene) 2209 g~
As pointed above, the emulsion is prepared in the same manner as described in Example 71, however, the polymer-ization is run at 55aC. for ~ hours and ~inished at 95Co ~or 2 hours. The solids content o~ the butyl acrylate/ethyl acrylate/macromolecular monomer polymer latex is 43.6% and has a part~cle size of` 3-4 microns and a pH of 7.5. There is ho coagulum in the latex polymer~ ~ust as there was none in the polymer prepared in Example 710 The gra~t copolymers prepared in the manner describ-ed in Example 71 and Example 72 had physical properties s~mi-lar to those prepared by suspension polymerization described above.

Preparatl~on 0~ Gra~t Copolymer Havin~ Polystyrene Sidechains ~nd Polyacrylonitrile Backbone A solution consisting of 3000 grams of a methacry-late terminated polystyrene prepared by the procedure o~ Ex_ ample 8 and having a molecular weight of 11,000 dissolved in 12000 grams of dimethyl formamide containing 0.10 gram o~ AIBN
(VAZo~34) are charged into a quart bottleO The bottle is capped, and purged with nitrogen for 15 minutes. 3105 Grams o~ acrylonitrile is syringed into the bo~tle, and the clear solution is rotated for 18 hours at 67Co in a bottle poly-~rrQ~ ~ f 1<

~ 3763~merization bath. The bottle is then post-heated for 5 hours at 90-95C. The viscous solutlon is then diluted with dimethyl formamide and the product recovered as a powder by precipita-tion into methanol~ A film molded ~or 5 minutes at 150Co had good ~low properties and was yellow, but clearO The absence of opacity in the molded film clearly demonstrates that little or no unreacted polystyrene macromolecular monomer was present, sin^e polyacrylonitrile products containing unreacted poly-s~yrene are cloudy or opaqueO

Preparation 0~ Graft Copolymer Havin~ Pol~st~rene Sidechains And Polyvinyl Chloride Backbone A methacrylate terminated polystyrene prepared by the procedure of Example 8 and having a molecular weight o~
about 16,000 and an ~w/Mn o~ less than about lol~ is copoly~
merized essentially to completion with vinyl chloride by charging the following ingredients in order into a quart bottle.
Disti~led water 300.0 g.
Lemo~2-88, 5~ solution (PVAL) 300 g, C i Disodium phosphate 0.40 g.
Lauroyl p~eroxide 0.34 g.
Methacrylate terminated pol~styrene 14.56 g.
Vinyl chloride 85.4 g.
The methacrylate terminated polystyrene and lauroyl peroxide are added to the aqueous solution of distilled water, Lemol and disodium phosphate and the quart bottle is chilled in ice water. Vinyl chloride is condensed in the bottle, and allowed to evaporate to the correct weight to drlve out airO
Then, the bottle is immediately capped with a butyl rubber gasketed, Mylar-lined cap. The bottle is rotated in a 55C.
bottle polymerization bath and after l9 hours in the polymer-ization bath, the excess vinyl chloride is bled of~ and the '~r~ m~ f k -119o ~3763~
solids content in the bottle is filtered in a Buchner funnel and rinsed with distilled waterO A yieId v~ 9205 grams of graft copolymer is obtained, whlch corresp~nds to a 91o 2~
~inyl chloride conversionO A GPC chromatogram of the product reveals that no detectable unreacted methacrylate terminated polystyrene occurs at 30.5 counts. (The peak on the GPC
chromatogram for the methacrylate terminated polystyrene having a molecular weight of 16,000 is 3005 counts~ Accord-ingly, it is shown that copolymerization of the methacrylate terminated polystyre~e with vinyl chloride is essentially complete.

Preparation Of Graft Co~ol~mer Having Pol~tyrene Sidechains And P~l~vinyl Chloride Backbone A graft copolymer of the methacrylate terminated polystyrene having a molecular weight of about 11,000 and pre-pared by the procedure in Example 8 with vinyl chloride is prepared by suspension copolymerization using the ~ollowing recipe and procedure.
Solution A:
Distille~ water 15000 g, ~q 5% Lemol 42-88 polyvinyl alcohol 105 go Disodium phosphate 002 g.
Solution B:
Methacrylate terminated polystyrene 5000 gO
Lauroyl peroxide 00125 gO
Vinyl chloride 50O0 g.
Into each of three quart bottles there is charged 150 grams o~ stock solution A above, and the solution is sparged with nitrogen ~or 30 minutesO The methacrylate ter~
minated polystyrene and lauroyl peroxide are added, and the bottle is chilled in ice waterO A slight excess of vinyl chloride is con~nsed in the bottle, and allowed to evaporate ~d~fl~ -120_ ~3'~36 to the correct weight to drive out a~O Then the bcttle is C immediately capped with butyl rubber gasketedg M~lar-lined capO The bottlefi are rotated in a 50Co bottle polymerization bath at 30 rpmO Bottles are removed from the bath at 20 5 hours~ 5 hours, and 15.5 hours9 and vinyl chloride is bled im-mediately upon removal of each bottleO The solids content of each bottle is filtered in a Buchner funnel and rinsed with distilled water. The producb is first dried in air9 then dried in vacuum oven at 50C.
Each of the total product mixtures is dissolved in THF. One portion of the THF solution is used for GPC analysis, and the other portion of the solution is added to excess 302 cyclohexane:hexane to precipitate the copolymerO The precip-itate i8 ~iltered and washed with 3:2 cyclohexane:hexane sol-vent to remove unreacted macromolecular monomer. The purified copolymer is dried, and submitted for chlorine analysisO The copolymer compositions calcula~ed from the chlorine contents of the ~ractionated products are presented in Table 8 below.
T~BLE 8 Copolymer Compositions ~f 5 ~50 Methacrylate Terminated Pol~-styrene ~ in,vl Chloride Monomer Charge At Various Con~ersions VCl C~pol~mer Com~osition Polymerization Con~ ~ Macromer ~ ~acromer Time, Hours ~ (From Cl Analvsis) (by GPC) 2.5 4.6 94 87 5~0 9.8 88 89 (a) Calculated from product yield.
The unfractionated portions o~ the THF solutions are filtered and me~sured. Volumes o~ the solutions o~ known I ~
solids are injected into the GPC. The unreacted methacrylate terminated polys~yrene peaks at 31.4 counts o~ the chromato--~2~_ Tr~lema~)c ~1037~36 grams are cut out, weighed, and unreacted macromolecular mono~
mer in the samples is determinedO The copolymer compositions calculated from the GPC data compare ~ell with those calcul~t-ed fram chlorine analysis and these calculations are also pre-sented in Table 80 As lt can be seen from the above examplesg the poly-meri.zable macromolecular monomers of the present invention offer a convenient route to the preparation of polystyrene graft copolymers with vinyl chlorideO These graft copolymers with vinyl chloride do not require processing aidsg since the melt flow of the graft product is improved over the PVC homo-po}ymer. Even with low le~els of macromolecular monomer co-polymerized with vinyl chloride~ milled sheets and molded specimens have greater clar~ty than .PVC homopolymer controlsO
Macromolecular monomers of the present invention can be copolymerized with vinyl chloride in solution, bul.k9 or in conventional suspension polymerization systems with free-radical initiators, The methacrylate terminated polystyrene macromolecular monomers have been copolymerized with vinyl chloride by suspension polymerization at macromolecular mono-mer levels of 10~ to 50~. The copolymer composition~ of the low and intermediate conversion samples have been determined by GPC analysis of the polymer mixture, and by chlorine anal-ysis of the fractionated samples. A series of GPC chromato-grams of the product mixtures of polymerizations of a 5~/50 macromolecular monomer~VCL monomer charge at varlous vinyl chloride conversions have been madeO Analysis of these chro-m~tograms reveals that the macromolecular monomer peak at 310 4 counts disappears rapidly early in the polymeriz.ationO In all these copolymerizations, it has been found that most of the methacrylate termina~ed polystyrene copolymerizes at 10~20%
~122--' !

1~137~;3$vinyl chloride con~er~i~n. Some low conversion copolymer com-positlon3 of severai monomer feed composition~, calculated from GPC and product yield data are presented in Table 90 The last column in this Table gives the theoretical instant~neous copolymer composition calculated from the Al~rey-Goldfinger copolymerization equation (2)9 assuming literature r values o~
methyl methacrylate (Ml), ana vinyl chloride ~M2) for metha-crylate terminated polystyrene and vi.~yl c~lorideg respective-ly (rl = lOg r2 = 0.1). It c~n be seen from this data that the copolymer compositions correspond reasonably well to the theoretical values, within the limits of experimental accuracy set by the very low molar concentrations of the macromolecular monomer double bond.
The relative reactivities o~ ~inyl chlorlde with vin~l ether-terminated macromolecular monomers and with maleic half ester-terminated macromolecular monomers prepared by the procedure described in Examples 5 and 9, respectively9 have also been determined. The vinyl chloride conversion and re-activity ratio data with the various macromolecular monomers are summarized in Table lO. The vinyl ether terminated macro-molecular monomer appears to copolymerize uni~ormly with vinyl chlorlde (r2 = 1). The methacrylate terminated macromolecular monomer and maleic half ester-terminated macromolecular mono-er copolymerize with vinyl chloride, as predicted from litera-ture reactivity ratios of methyl methacrylate or maleic esters with vinyl chloride. Although the macromolecular monomers are incorporated at much faster rates than vinyl chloride and give compositionally heterogeneous ccpolymers without resorting to special polymerization techniques such as gradual addition the copolymerization studies of the methacrylate or maleic half ester terminated macromolecular monomers and vinyl -123~

1~3763~i chloride sqrve~ to~ s~w that,~ in th,~s~ systems~ ~e ~ ,nal groups o~ t~e ~4~r~e~u~ar ma3~onl~qrs are gove~ed ~ ç same copoly~eri~atiqn kln~ti~s ~s th~ ~rr~ond~,ng low m~le~ular weight mo~Qmer8~

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3~71~36, EXA,MPLE 76 A 370 gram cha~ge o~ the 701~ m~thacrylate terminated polyisoprene macromolecular monomer prepared in Example 11 is vacuum stripped 1~ hours at 50Co on a rot;ary evaporator (601 grams of heptane ~s not removed by stripping)0 The round bot-tomed flask containing the concentrated macromolecular monomer is ~ealed with a septum and purged with n~troge~. A solution eonsisting of 61.2 grams of styrene, 6.1 grams benzene (thio-s' C phene-free) and 0.31 gram o~ AIBN ~ 0.5~ by weight styrene) is ~ntroduced by syr~nge and the macromolecu~ar monomer is allow-ed to dissolve, The clear monomer solutio~ is tran~ferred by syringe into a well-purged 12 ounce bottle containing an aque-ous polyvinyl pyrrolidone solution (300 grams of water, 0.24 gram Luviskol~ -90 (PVP, 0.3~ by w~lght)). The bottle is cap-ped, briefly purged with nitrogen) and rotated in ~ 65C.
bottle polymerization bathO A~ter 17.5 hours at 65C., the bottle is finished at 95C. for-3 hours.
The product beads are filterad on a screen~ washed with distilled water, and dried at 40C. under vacuum. The product is milled for 2 minutes at 150Co and 0.40 gram Ionol CP antioxidant is added on the mill. A yield of 75.8 grams of transparent milled product is obtained. The styrene ~~onver-sion is 98~

Preparation Of Graft Copolymer Of Polytetramethylene Ether Di-isoc,yanate And Pol,vst,vrene Macrometer Terminated With E~
chlorohydrin Polytetramethylene ether diisocyanate is prepared by dissolving 290 grams of polytetramethylene ether glycol having ~nC~

~.~3t~36 an average molecular weight of 29 900 in 600 ml. of tetrahydro-furan purging this solution with nitrogen and then adding 1~.4 grams (0.05 mole) of a liquid dlisocyanate similar in struc-f~
~J ture to diphenylmethane diisocyanate and available as Isonate 143L from the Up~ohn CompanyO The bottle containing the$e re-actantæ is capped and placed in a water bath at 50Co in which it i8 tumbled at about 30 rpmO After 8 hours, an additional 7.2 grams (00025 mole) of the above liquid d~isocyanate is added and the reaction is continued for another 8 hours~ At 10 this point, 4035 grams (0.05 mole) of 2,4-tolylene diisocyan-ate is added and the polymerization is continued under the same conditions for another 8 hours.
To a solution of 200 grams of polystyrene macromer terminated with epichlorohydrin and having an average molecu-lar weight of 12,000 in 100 mlO of tetrahydro~uran and 100 ml.
of water there is added dropwise a sufficient quantity of di-lute sulfuric acid to ad~ust the pH to 2Ø The resulting solution is stlrred at 65Co for 8 hours resulting in complete hydrolysis of the epoxide groups to glycol groups.
A mixture o~ a solution of 60 grams of the above polytetramethylene ether diisocyanate in 60 ml. of tetrahy-drofuran, 60 grams of the above polystyrene glycol and 100 ml.
of tetrahydrofuran is placed in a polymerization bottle to-gether with o.6 gram of stannous octoate. The bottle is cap-ped, purged with nitrogen and placed in a water bath at 65C~
for 8 hours to produce a graft copolymer. A portion is cast on a glass plate and allowed to air dry to a flexible, elastic film. It is cut into small pieces and molded at 150Co and 20-30 psig to a film the tensile strength of which is found to 30 be 1500 psig.
~r~de~ k ~o37636 Preparation O~ Gra~t Copol,ym Diisocyanate And Polyst,Yrene G~
A react~r bottle containing a mixture o~ 87 grams of polytetramethylene ether glycol having an average molecular weight of 2,900 and 4.3 grams (0~015 mole) of the liquid di-isocyanate re~erred to in Example 77 is cappedg purged with nitrogeny and placed in a water bath at 65co for 8 hours, The resulting high molecular weight polyurethane glycol is cooled to room temperature and 43 grams of polystyrene glycol (prepared as i,n Example 11) having an average molecular weight of 8,600 and 350 ml. o~ tetrahydro~uran are added and the bottle capped~ A~ter purging with nltrogen, 5~9 grams (0.023 mole) o~ the above liquid diisocyanate is added and the bottle is rot~ted at 65C. ~or 8 hours. The resulting graf't copoly~
mer is isolated as a ~lexible, elastic film by depositing it on a glass plate and air drying. Its tensile strength i5 19 000 psig.
Pol,yblends Emplo,ying Macromolecular Monomers AB Allo~ing Agents Polyvlnyl chloride blends with low levels of the macromolecular monomer/polyacrylate graft copolymers o~ the invention provide products that are clear~ have improved pro-cessing and high impact propertiesO Notched Izod impact strengths o~ 22 ft. pounds/inch are obtained with little loss in flexural modulus in rigid polyvinyl chloride blends con-taining as little as 3~ of the macromolecular monomer/poly-(butyl acrylate) gra~t copolymerO The graft copolymers of the invention also function as processing aids by improving polyvinyl chlor~de fusion in milling and compression molding, The graft copolymers also impart high strength to higher ~lo376~
molecular weight polyvi~yl chloride polymers, such as Vygen 110 and 120, when low levels o~ the graft copolymer macro-molecular monomer-poly(butyl acrylate) is blended after the polyvinyl chloride is banded on the millO

Prepara n O~_P lyvinyl Chloride/Macromolecular Monomer Gra~t Copolymer Polyblend The ~ollowing ingredients are mixed, and banded on a 150C, lab mill:
Initial ~lend Vygen*120 (Lot 71-20 polyvinyl chloride) 9600 g.
Stearic Acid 1 0 g Cadmium Stearate 1 5 g Barium Stearate lo 5 g~
During the entire milling operatingJ the roll gap i8 ad~usted to maintain a rolling bank, and the stock is cut and turned every one-half minute, After the initial blend has been banded on the mill 3 minutes, 4.0 grams of the gra~t copoly~er having polystyrene sidechains and poly~butyl acrylate) backbone (30/70) prepared by the procedure o~ Example 70 is added to the rolling bank and milling is continued an additional 3 min-utes.
The compression-molded specimens (5 minutes at 170C.) are transparent, and had an average notched Izod im-pact strength of 22 fto pounds/inch notchJ whereas the control without the graft copolymer has an Izod impact stre~gth of Q~4-oo8 ~t. pounds/inchO
In addition to using the rubbery polystyrene/butyl acrylate graft copolymer as an alloying agent to polymers o~
vinyl chloride, the addition o~ this rubbery component can also be added to polymers of styrene or styrene-acrylonitrile copolymers for impact engineering plastics. The polyvinyl ~k -130-TrQGk~r k ~(~3763~
chloride polyblends with the graft copolymers have exceptional-ly high impact strength and are useful in pipe, siding~ down-SpoutsJ cases, etc. This is unexpected because polyvinyl chloride is known ~or its low impact strength~ Pol~(methyl methacrylate) also has low impact strength, however* when methyl methacrylate is either blended or copolymerized with the lower Tg or rubber macromolecular monomers o~ the inven-tion, the impact strength is enhanced.
The gra~t copolymers of the invention which ~ave polystyrene sidechains, particularly those having polyvinyl chloride backbones~ improve the melt rheology of those poly-mers having a poor melt rheology and are difficult to process when small amounts o~ the gra~t copolymer is blended with the polymer. Examples o~ polymers which can be blended with the gra~t copolymers o~ the invention to improve the melt rheology include polymers o~ vinyl chloride, methyl methacrylate, acrylonitrile, and others.

Claims (52)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for preparing a graft copolymer comprising polymerizing at least one anionically polymerizable monomer in the presence of an anionic polymerization initiator to thereby form a monofunctional living polymer;
and where required reacting the monofunctional living polymer with a capping agent; reacting the monofunctional living polymer with a terminating agent to thereby form copolymerizable macromolecular monomers with a copolymer-izable end group, and thereafter, copolymerizing by free radical cationic, anionic, condensation, Ziegler or Natta processes from about 1 to 95% by weight based on the weight of the resulting graft copolymers of said copoly-merizable end group, with from about 99 to 5% by weight of the resulting graft copolymer of a backbone-forming comonomer; wherein said copolymerizable end group and said backbone-forming comonomer form the backbone of the graft copolymer and the macromolecular monomers form the side-chains of the graft copolymer, characterized in that (a) said copolymerizable macromolecular monomers comprise from about 1% to about 95% by weight of the graft copolymer and said backbone-forming comonomers comprise from about 99% to about 5% by weight of the graft co-polymer said copolymerizable macromolecular monomers having a substantially uniform molecular weight distribution such that the ratio of ?w/?n is less than about 1,1, wherein ?w is the weight average molecular weight of the macromolecular monomers and ?n is the number average molecular weight of the macromolecular monomers, and (b) the polymeric sidechains of the graft copolymer which are co-polymerized into the backbone are separated by at least about 20 uninterr-upted recurring polymerized units of the backbone-forming comonomer, the copolymerizable end group of the macromolecular monomers and the backbone-forming monomer having been chosen with regard to their reactivity ratios so as to control the distribution and copolymerization of the macromole-cular monomers along the backbone, and (c) said graft copolymer contains a member selected from the group consisting of:
(i) at least one backbone-forming comonomer selected from the group consisting of acrylic acid, methacrylic acid; acrylamides; N-alkyl-acrylamide; N,N-dialkylacrylamide; methacrylamide; N-alkylmethacrylamide;
N,N-dialkylmethacrylamide; acrylonitrile; methacrylonitrile, vinyl chloride;
vinylidene cyanide; vinyl acetate; vinyl propionate; vinyl chloroacetate;
fumaric acid and its esters; and maleic anhydrides, acids and esters;
and at least one graft monomer containing a member selected from the following groups (ii) a residue of an alkali metal salt of a tertiary alcohol anionic polymerization initiator;
(iii) a capping agent selected from butadiene or isoprene;
(iv) a copolymerizable end group derived from a terminating agent selected from 2-halomethyl-1,3-butadiene, haloalkylmaleic anhydride, haloalkylmaleate esters, vinyl haloaryls, vinyl haloalkaryls, maleic anhydride, acrylic anhydride, methacrylic anhydride, and a epihalohydrin, the epoxy group of which is hydrolyzed and then reacted with acrylyl halide, methacrylyl halide or maleic acid halide;
(v) a macromolecular monomer having a polymeric segment of a vinyl aromatic hydrocarbon with a molecular weight in the range of from about 5,000 to 50,000 and a polymeric segment of a conjugated diene con-taining 4 to 12 atoms per molecule; and combinations thereof.

2. The process of claim 1, characterized in that the backbone-forming comonomer is selected from the group consisting of alpha-olefins or a mixture thereof.

3. The process of claim 1 characterized in that the backbone-forming comonomer is a vinyl monomer or mixtures thereof selected from conjugated dienes, or alpha-olefins of the formula:
CH2 = CHR
wherein R is either hydrogen or an alkyl or aryl radical containing one to 16 carbon atoms.

4. The process of claim 1 or 2, characterized in that the backbone-forming comonomer is a vinyl-containing compound selected from acrylic acid, methacrylic acid and their alkyl esters.

5. The process of claim 2, characterized in that the backbone-forming comonomer is hydrophilic and is selected from acrylamide, N-alkyl acrylamide, N,N-dialkylacrylamide, methacrylamide, N-alkylmethacrylamide and N,N-dialkylmethacrylamide.

6. The process of claim 1, 2 or 5, characterized in that the back-bone-forming comonomer is N,N-dimethylacrylamide.

7. The process of claim 1 or 2, characterized in that the backbone-forming comonomer is a vinyl chloride.

8. The process of claim 1 or 2, characterized in that the backbone-forming comonomer is acrylonitrile.

9. The process of claim, 1 or 2, characterized in that the backbone-forming comonomer is vinyl acetate.

10. The process of claim 1, 2 or 3, characterized in that the backbone-forming comonomer is ethylene.

11. The process of claim 1, 2 or 3, characterized in that the backbone-forming comonomer is propylene.

12. The process of claim 1, 2 or 3, characterized in that the backbone-forming comonomer is a mixture from about 1 to 99% of ethylene and from about 99 to 1% of propylene.

13. The process of claim. 1, 2 or 3, characterized in that the backbone-forming comonomer is styrene or alpha-methylstyrene.

14. The process of claim 1 characterized in that the macromolecular monomer which is copolymerized with said copolymerizable comonomer is derived from a monofunctional polymerizable macromolecular monomer repre-sented by the formula:

wherein R is lower alkyl, Z represents repeating polymerized units of at least one monomer selected from the group of styrene, alpha-methylstyrene, isoprene or butadiene, n is a positive integer of at least about 20, X is a polymerizable end group containing an olefinic, epoxy or thioepoxy group, said macromolecular monomer denoted as having a substantially uniform molecular weight disbribution such that its ratio of ?w/?n is about 1.1 or less.

15. The process of claim 14, characterized in that X is a polymer-izable end group selected from:

(a) , (b) , (c) , (d) , (e) , wherein R is either hydrogen or methyl.

16. The process of claim 1 or 14, characterized in that the macro-molecular monomer is represented by the structural formula:

wherein n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000.

17. The process of claim 1, 2 or 14, characterized in that the macro-molecular monomer is represented by the structural formula:

wherein n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000.

18. The process of claim 1, 2 or 14, characterized in that the macromolecular monomer is represented by the structural formula wherein n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000.

19. The process of claim 1, 2 or 14, characterized in that the macromolecular monomer is represented by the structural formula wherein n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000.

20. The process of claim. 1, 2 or 14, characterized in that a macromolecular monomer of the structural formula wherein R is an alkyl group and n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000 is reacted with styrene as the backbone-forming comonomer.

21. The process of claim 1, characterized in that the macromolecular monomer is represented by the structural formula wherein n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000; m is a positive integer of 20 or greater; R1 is an alkyl group, R2 represents a hydrogen atom or a methyl group and X is a copolymerizable end group selected from wherein R3 represents an alkylene radical and R4 represents a hydrogen atom or an alkyl group.

22. The process of claim 1, 2 or 21, characterized in that the macromolecular monomer is represented by the structural formula:

wherein n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000 and m is a positive integer of 20 or greater.

23. The process of claim 1, 2 or 21, characterized in that the macromolecular monomer is represented by the structural formula:

wherein n is a positive integer such that the molecular weight of the polymer is in the range of from 5,000 to about 50,000 and m is a positive integer of 20 or greater.

24. The process of claim 1, 2 or 21, characterized in that the macromolecular monomer is represented by the structural formula:

wherein n is a positive integer such that the molecular weight of the polymer is in the range of from 5,000 to about 50,000 and m is a positive integer of 20 or greater.

25. The process of claim 1, 2 or 21, characterized in that the macro-molecular monomer is represented by the structural formula wherein n is a positive integer such that the molecular weight of the polymer is in the range of from 5,000 to about 50,000 and m is a positive integer of 20 or greater. 140

26. The process of claim, 1J 2 or 3, characterized in that the graft copolymerization reaction is conducted either in a solution, suspension or latex polymerization system in the presence of a polymerization catalyst selected from the group of free-radical, cationic, anionic, Ziegler, Natta and condensation catalysts.

27. A chemically joined, phase separated thermoplastic graft copolymer of a copolymerizable macromolecular monomer represented by the formula I - (P1)n - (X)w - (Y) and at least one copolymerizable backbone-forming comonomer; wherein I is the residue of a monofunctional anionic initiator, P1 is at least one anionically polymerized monomer, X is a capping agent, Y is a terminating agent having a copolymerizable end group, n is at least about 20, w is zero or 1, and wherein said copolymerizable end group and said backbone-forming comonomer form the backbone of the graft copolymer and the macromolecular monomers form the sidechains of the graft copolymer, characterized in that a. said copolymerizable macromolecular monomers comprise from about 1% to about 95% by weight of the graft copolymer and said backbone-forming comonomers comprise from about 99% to about 5% by weight of the graft co-polymer, said copolymerizable macromolecular monomers having a substantially uniform molecular weight distribution such that the ratio of ?w/?n is less than about 1.1, wherein ?w is the weight average molecular weight of the macromolecular monomers and ?n is the number average molecular weight of the macromolecular monomers, and b. the polymeric sidechains of the graft copolymer which are copoly-merized into the backbone are separated by at least about 20 uninterrupted recurring polymerized units of the backbone-forming comonomer, the copoly-merizable end group of the macromolecular monomcrs and the backbone-forming comonomer having been chosen with regard to their reactivity ratios so as to control the distribution and copolymerization of the macromolecular monomers along the backbone, and c. said graft copolymer contains a member selected from the group consisting of:
(i) at least one backbone-forming comonomer selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, N-alkylacryl-amide, N,N-dialkylacrylamide, methacrylamide, N-alkylmethacrylamide, N,N-dialkylmethacrylamide, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene cyanide, vinyl acetate, vinyl propionate, vinyl chloroacetate, fumaric acid and its esters, and maleic anhydrides, acids and esters;
and at least one graft monomer containing members selected from the following groups (ii) a residue of an alkali metal salt of a tertiary alcohol as the anionic polymerization initiator, I;
(iii) a capping agent, X, selected from 2-butenylene or 2-methyl-2-butenylene radicals;
(iv) a terminating agent, Y, selected from , , , and ; and wherein R3 is an alkylene radical, and R is a hydrogen or an alkyl group;
(v) a macromolecular monomer polymeric portion (P1)n, comprising a polymeric segment of a vinyl aromatic hydrocarbon having a molecular weight in the range of from about 5,000 to 50,000 and a polymeric segment of a conjugated diene containing 4 to 12 carbon atoms per molecule.

28. The graft copolymer of claim 27, characterized in that the back-bone-forming comonomer is selected from the group consisting of alpha-olefins or a mixture thereof.

29. A graft copolymer of claim 27, characterized in that the backbone-forming comonomer is a vinyl monomer or mixtures thereof selected from conjugated dienes, or alpha-olefins of the formula:
CH2 = CHR

wherein R is either hydrogen or an alkyl or aryl radical containing one to 16 carbon atoms,

30. The graft copolymer of claim 27 or 28, characterized in that the backbone-forming comonomer is a vinyl-containing compound selected from acrylic acid, methacrylic acid and their alkyl esters.

31. The graft copolymer of claim 27 or 28, characterized in that the backbone-forming comonomer is hydrophilic and is selected from acrylamide, N-alkyl acrylamide, N,N-dialkylacrylamide, methacrylamide, N-alkylmethacryl-amide, and N,N-dialkylmethacrylamide.

32. The graft copolymer of claim 27 or 28, characterized in that the backbone-forming comonomer is N,N-dimethylacrylamide.

33. The graft copolymer of claim 27 or 28, characterized in that the backbone-forming comonomer is a vinyl chloride.

34. The graft copolymer of claim 27 or 28 characterized in that the backbone-forming comonomer is acrylonitrile.

35. The graft copolymer of claim 27 or 28, characterized in that the backbone-forming comonomer is vinyl acetate.

36. The graft copolymer of claim 27, 28 or 29, characterized in that the backbone-forming comonomer is ethylene.

37. The graft copolymer of claim 27, 28 or 29, characterized in that the backbone-forming comonomer is propylene.

38. The graft copolymer of claim 27, 28 or 29, characterized in that the backbone-forming comonomer is a mixture from about 1 to 99% of ethylene and from about 99 to 1% of propylene.

39. The graft copolymer of claim 27, 28 or 29, characterized in that the backbone-forming comonomer is styrene or alpha-methylstyrene.

40. The graft copolymer of claim 27 characterized in that the macro-molecular monomer which is copolymerized with said copolymerizable comonomer is derived from a monofunctional polymerizable macromolecular monomer represented by the formula:

wherein R is lower alkyl, Z represents repeating polymerized units of at least one monomer selected from the group consisting of styrene, alpha-methylstyrene,isoprene or butadiene, n is a positive integer of at least about 20, X is a polymerizable end group containing an olefinic, epoxy or thioepoxy group, said macromolecular monomer denoted as having a sub-stantially uniform molecular weight distribution such that its ratio of ?w/?n is about 1.1 or less.

41. The graft copolymer of claim 40, characterized in that X is a polymerizable end group selected from:

(a) , (b) (c) , (d) , (e) wherein R is either hydrogen or methyl.

42. The graft copolymer of claim 27 or 40 characterized in that the macromolecular monomer is represented by the structural formula wherein n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000.

43. The graft copolymer of claim 27, 28 or 40, characterized in that the macromolecular monomer is represented by the structural formula:

wherein n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000.

44. The graft copolymer of claim 27, 28 or 40, characterized in that the macromolecular monomer is represented by the structural formula:

wherein n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000.

45. The graft copolymer of claim. 27, 28 or 40, characterized in that the macromolecular monomer is represented by the structural formula:

wherein n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000.

46. The graft copolymer of claim. 27, 28 or 40, characterized in that a macromolecular monomer of the structural formula:

wherein R is an alkyl group and n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000 is reacted with styrene as the backbone-forming comonomer.

47. The graft copolymer of claim. 27, 28 or 40, characterized in that the macromolecular monomer is represented by the structural formula wherein n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000; m is a positive integer of 20 or greater; R1 is an alkyl group; R2 represents a hydrogen atom or a methyl group and X is a copolymerizable end group selected from wherein R3 represents an alkylene radical and R4 represents a hydrogen atom or an alkyl group.

48. The graft copolymer of claim 27 or 40, characterized in that the macromolecular monomer is represented by the structural formula:

wherein n is a positive integer such that the molecular weight of the polymer is in the range of from about 5,000 to about 50,000 and m is a positive integer of 20 or greater.

49. The graft copolymer of claim 27 or 40, characterized in that the macromolecular monomer is represented by the structural formula:

wherein n is a positive integer such that the molecular weight of the polymer is in the range of from 5,000 to about 50,000 and m is a positive integer of 20 or greater.

50. The graft copolymer of claim 27, 28 or 40, characterized in that the macromolecular monomer is represented by the structural formula:

wherein n is a positive integer such that the molecular weight of the polymer is in the range of from 5,000 to about 50,000 and m is a positive integer of 20 or greater.

51. The graft copolymer of claim 27, 28 or 40, characterized in that the macromolecular monomer is represented by the structural formula:

wherein n is a positive integer such that the molecular weight of the polymer is in the range of from 5,000 to about 50,000 and m is a positive integer of 20 or greater.

52. A polyblend comprising:
(1) from about 1 to about 50 parts by weight of the chemically joined, phase separated thermoplastic graft copolymer of claim 27, 28 or 40, and (2) from 99 to about 50 parts by weight of a polymer selected from polyethylene, polypropylene, polybutadiene, polyisoprene, polystyrene, poly (vinyl chloride), polyacrylonitrile, polyacrylamides and mixtures thereof.