FI57267B - YMPPOLYMER ANVAENDBAR VID FRAMSTAELLNING AV FILMER OCH MED EN STOMDEL OCH DAERTILL FAESTA SIDOKEDJOR SAMT FOERFARANDE FOER DESS FRAMSTAELLNING - Google Patents

Description

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Patent cedJelat ^ ^ (51) Ky.ik? /Int.a.3 C 08 P 257/02, 212/12 ENGLISH —Fl N LAN D (21) P «» nttlh »k * mu · - Ptt * nttn »6knlnf 1 + U8 / T2 l8 · 02 · 72 * * (23) Alkupltvl — GittlihMad ·! 18.02.72 (41) Tullut lulklMktl - Bllvlt offantllf 2 3.08.72

National Board of Patents and Registration (44) Date of publication and date of publication. - _ Qrt

Patents and Regulations "AmbIcm uthfd och uti ^ krifun puMfcmd 31.03.o0 (32) (33) (31) Requested" toikms — B «glr4 priorltat 22.02.71 USA (US) 117733 (71) CPC International Inc., International Plaza, Englewood Cliffs,

New Jersey, USA (72) Ralph Milkovich, Naperville, Illinois, Mutong Thomas Chiang,

Palos Heights, Illinois, USA (US ·) (7 * 0 Oy Kolster Ab (5 * 0 Qxaspolymer, which can be used in the manufacture of films and has a body part and associated side chains, and a method of making the same - Envelope polymer for framing and filming) The present invention relates to a graft polymer which can be used in the manufacture of films and which has a body part and associated side chains.

The graft polymer of the invention is characterized in that a) the side chains have a rather narrow molecular weight distribution between 5,000 and 50,000 and consist of a residue of an anionic polymerization initiator having an alkali metal alkyl, at least 20 polymerized monomer units, anomerically polymerized monomer units wherein the monomer is styrene or Q (-methylstyrene or a mixture thereof), and a terminating group whose copolymerizable vinyl end group is derived from a vinyl haloalkyl ether having an alkyl group containing up to 6 carbon atoms or a halide of a halide of a halide of up to 6 carbon atoms; and optionally further comprising a protective agent comprising lower alkylene oxide or 1,1-diphenylethylene, and b) the backbone consists of polymerized units of a polymerizable vinyl end group of the side chains and at least one e of a ethylenically unsaturated backbone monomer comprising ethyl acrylate, butyl acrylate or isobutylene, said side chains being located at regular intervals in the backbone and having at least 20 repeating backbone monomer units therebetween.

The invention further relates to a process for the preparation of said graft polymer, which process is characterized in that a living polymer is prepared by polymerizing in an inert solvent an anionically polymerizable, ethylenically unsaturated monomer having styrene or Of-methylstyrene as an alkylating agent in the presence of monofunctional living polymers with a molecular weight of of 5,000 to 50,000 and having a narrow molecular weight distribution, the resulting monofunctional living polymer, which may be protected with a lower alkylene oxide or 1,1-diphenylethylene, is reacted with a vinyl haloalkyl ether having an alkyl group containing up to 6 carbon atoms or up to 6 carbon atoms. with a vinyl ester of a haloalkanoic acid containing an atom, or with an allyl halide, a methallyl halide, an acrylic halide or a methacrylyl halide to form a macromolecular monomer with a or ethylene, or a mixture of two or more of said backbone monomers to form a graft polymer, wherein each side chain contains at least 20 units of anionically polymerizable monomer and wherein the side tjut are located substantially evenly spaced in the backbone with at least about 20 backbone monomer units therebetween.

Most polymers, both natural polymers and synthetic polymers, are unmixed with each other a. This has become increasingly apparent with the emergence of more and more specialty polymers with special properties, and in an effort to combine these polymers in pairs to give each polymer different properties. In most cases, these attempts have not been successful because the resulting blends have proved to be unstable, and in several cases the desired properties of both polymers were completely lost. For example, polyethylene is immiscible with polyisobutylene and the physical properties of the two blends are 3,5267 inferior to those of either homopolymer. These failures were first considered to be due to inappropriate mixing methods, but finally it was concluded that the failures were simply due to the fact that the substances were not inherently miscible with each other. Although it is now believed that this is the correct explanation, the general nature of such immiscibility has remained somewhat unclear, even to this day. One factor seems to be polarity, i.e. the two polar polymers have a greater tendency to mix with each other than the polar and polarized polymer. The two polymers must also be somewhat similar in structure and composition if they are to be miscible with each other. Furthermore, a particular pair of polymers can be miscible with each other only when the ratio of the amounts of polymers is within certain limits; outside this range they do not mix with each other. However, despite the fact that the miscibility of polymer pairs is generally accepted, there is a great deal of interest in finding ways in which the advantageous properties of polymer combinations could be imparted to a single product.

One way in which this goal has been pursued is the preparation of block or graft polymers. Using this route, two different polymer segments that are not normally miscible with each other are chemically bonded together to provide a kind of mandatory miscibility. Thus, in many cases, the block or graft polymer has combinations of properties that are not normally present with a homopolymer or a randomly assembled copolymer.

However, recourse to block copolymers or graft polymers has its limitations in the case of block copolymers, since only monomers suitable for anionic polymerization are useful and this eliminates some of the possible polymer segments. In the case of graft polymers which have been available in the past, they have regularly been characterized by their high content of homopolymer, either the original 'backbone homopolymer' or the graftable monomer. If such a homopolymer is present, it not only acts as a diluent but also substantially impairs the effectiveness of the desired properties that graft polymers have been sought to impart.

U.S. Patent 3,029,221 discloses the anionic polymerization of? Examples of reactive groups include ester, amido, cyano, keto, sulfonyl, epoxy, aldehyde and pyridyl groups. There is no mention in the patent of the termination of union polymers with a vinyl group or other copolymerizable group. Nor does it show a copolymerization reaction for the formation of graft polymers, but the anionic polymers are incorporated into a preformed backbone. Furthermore, it does not mention the protection of the anionic polymer with alkene oxide or 1,1-diphenylethylene, nor how important it is for the 20 backbone groups to separate the side chains in order to preserve the physical properties of the backbone polymer.

U.S. Pat. No. 3,135,716 relates to the preparation of "terminally reactive polymers", defined as polymers containing a reactive group at each end of the polymer chain, which polymers are formed by reacting monomers such as dienes, e.g., butadiene or styrene, with anionic initiators. These polymers are, of course, not suitable for the purpose of the present invention because they require macromolecular monomers with only one reactive end group, and the prepolymer is reacted according to another U.S. patent. with a reactive group other than that proposed in the present invention, for example -OH-, CN, -CO-R, -CO-Cl or -CO-CR, where R is hydrogen or an aliphatic, cycloaliphatic or aromatic group. in accordance with the patent ta with heat-activated crosslinking agents. All of these factors distinguish the subject of U.S. Patent 3,135,716 from the graft polymers of the present invention.

U.S. Patent 3,627,837 relates to a process for preparing graft polymers by grafting a preformed polymer side chain onto a metallized backbone polymer. Preformed polymer side chains are prepared by polymerizing a monomer, such as styrene, with alkyllithium to give a reactive polymer with an active metal at one end of the polymer chain. The reactive polymer is reacted with a bifunctional compound. The other end of the bifunctional compound reacts with the reactive polymer to replace lithium. The second functional group of the bifunctional compound remains at the end of the reactive polymer chain and must be able to react with the preformed lithium backbone polymer to form side chains. The patent does not disclose a copolymerization reaction for the formation of graft polymers. Instead, the side chains are attached to a preformed frame. The patent also does not mention the protection of the anionic polymer with alkali oxide or 1,1-diphenylethylene or the importance of the 20 backbone groups separating the side chains in order to preserve the physical properties of the backbone polymer.

U.S. Patent 3,135,717 relates to a process very similar to U.S. Patent 3,029,221. In the process of this patent, styrene or butadiene is anionically polymerized using, for example, phenyllithium or hutyllithium as an initiator. The graft polymer is then formed by grafting the reactive polymer into a preformed polyvinyl chloride backbone polymer. Grafting occurs by reacting the lithium of the reactive polymer with the chlorine of the preformed polyvinyl chloride backbone. Again, this patent does not disclose the copolymerization reaction, the termination of the reactive polymer in a copolymerizable end group, the protection of the reactive polymer, or the importance of the distribution of side chains along the backbone.

U.S. Patent 3,235,626 relates to the preparation of a prepolymer by anionic polymerization using a vinyl alkali metal compound as an initiator, for example, vinyl lithium, allyl lithium, etc. Anionic polymerization occurs with a variety of vinyl compounds, such as styrene. For example, the prepolymer consists of 100 or more monomer units joined together and having an initiating terminal vinyl group. According to this patent, this terminal vinyl group may participate in other reactions, e.g., a graft polymerization reaction similar to the graft polymerization reaction of the present application. Examples U and 5 of the patent state that graft polymers are prepared by first preparing a polystyrene prepolymer by anionic polymerization with vinyl lithium, followed by copolymerizing the prepolymer with either acrolonitrile or methyl methacrylate. However, this is not true, and in fact this method cannot form a graft polymer. Attempts have been made to use free radical conditions for copolymerization, but the proposed backbone comonomers do not polymerize under free radical conditions.

An important difference between the process of U.S. Patent 3,235,626 and the present invention is that in the process of the invention the side chains have a substantially uniform molecular weight due to the very rapid anionic polymerization with the alkyllithium compounds. In contrast, the lithium compounds used in U.S. Patent 3,235,626 result in a much slower polymerization reaction rate, resulting in a much more uniform and uncontrolled molecular weight of macromolecular side chain monomers. Even when, for example, the polystyrene prepolymers of the U.S. patent are allowed to react in a manner in which graft polymers can be formed, the graft polymers of the present invention have superior properties due to uniform molecular weight of side chains and uniform distribution of side chains along the body, e.g.

U.S. Pat. Nos. 5,726,7,370,20β and 3,511,050.0 describe an addition polymer containing an unsaturated end group. The patents state that the graft polymer can be formed by copolymerizing this substance with an ethylenically unsaturated monomer. It should be noted that said addition polymer is prepared by a free-radical reaction. Such a reaction yields a polymer with a very wide molecular weight distribution compared to the narrow molecular weight distribution of the anionically polymerized intermediates of the present invention. Thus, the graft polymers of these patents would not have side chains with a narrow molecular weight distribution. They would thus be completely different from the graft polymers of the present invention. The macromolecular monomers used in the present invention are prepared with an anionic polymer surface that produces monomers with a narrow molecular weight. from the division. In contrast, the process used to prepare macromolecular monomers used in the aforementioned patents involves free radical polymerizations that produce macromolecular monomers with a very wide molecular weight distribution.

The graft polymers of the invention differ from those previously available in that the polymer side chains are first prepared using anion polymerization. Such a method makes reactive. a polymer that can be terminated by reacting it with a halogen-containing compound, and by selecting a suitable terminating agent for T 57267, a polymer having a polymerizable group at the end can be formed. This polymer itself can be further polymerized to form graft polymers of the type described above. Alternatively, copolymerization of this high molecular weight polymerizable compound with another compound, usually a relatively low molecular weight compound, also results in this type of graft polymer.

Particularly useful graft polymers of this type are those in which the copolymer backbone and the polymer side chains are thermodynamically immiscible with each other. Such graft polymers are obtained when the unitary polymer segments and polymer side chains of the copolymer backbone are large enough to impart to the graft polymer the physical properties characteristic of the polymers corresponding to these polymer segments. Therefore, the polymer segment, whether as part of a backbone or side chain, should have substantially at least 20 interconnected repeating monomer units, and most preferably at least about 30 repeating monomer units.

The graft polymer of the present invention has a T-type structure when only one side chain copolymerizes with the copolymer backbone. However, if one or more side chains have been copolymerized in the backbone polymer, the graft polymer can be characterized as having a comb-type structure, which can be described as follows: c-c-c-b-c-c-c-b-c-c-c-b-c-c-c I 1 »a a a

I t I

a a a

t I I

aaa "wherein" a "corresponds to a substantially linear, uniform molecular weight polymer or copolymer having a molecular weight so high that the physical properties of at least one of the substantially linear polymers are obvious;" b "corresponds to a reacted and polymerized end group chemically bonded to the side chain. a ”which is fully polymerized to the polymer backbone, and“ c ”is a backbone polymer having homogeneous segments having a molecular weight so high that the physical properties of the polymer are obviously obvious.

The preparation of these graft polymers begins, as noted above, by polymerizing the anionically polymerizable monomer. In most cases, this is a monomer having an olefinic group, although it may be an epoxy or thioepoxy group.

Monomers suitable for anionic polymerization are well known and the use of all anionically polymerizable monomers is contemplated to be included in this invention. Exemplary compounds include styrene, alpha-methylstyrene, acrylamide, Ν, Ν-lower alkyl acrylamides, N, N-di-minialkyl acrylamides, acenaphthalene, 9-acryliccarbazole, acrylonitrile, methacrylonitrile, methacrylonitrile, organic isocytes alkyl phenyl and halophenyl isocyanates, organic diisocyanates including lower alkylene, phenylene and tolylene diisocyanates, lower alkyl and allyl acrylates and methacrylates, such as carboxylates of carboxylates, low molecular weight olefins, aliphatics vinyl propionate, vinyl octoate, vinyl oleate and vinyl stearate, vinyl benzoate, vinyl lower alkyl ethers, vinyl pyridines, isoprene, butadiene and lower alkylene oxides.

The catalyst used in these anionic polymerizations is alkali metal alkyl, the alkyl being lower alkyl, i. it has up to eight carbon atoms. Preference is given to butyllithium, especially sec-butyllithium. Particularly useful are lower alkyl lithium and lower alkyl sodium. Other suitable catalysts include isopropyllithium, ethyl sodium, n-propyl sodium, n-butyl potassium, n-octyl potassium, n-butyllithium, ethyl lithium, t-butyllithium and 2-ethylhexyllithium. Alkali metal alkyls are either commercially available or can be prepared by known methods. Phenyl lithium or phenyl sodium can also be used as a catalyst, and they can likewise be conveniently prepared by reacting bromobenzene with a suitable elemental metal.

The amount of catalyst is an important factor in anionic polymerization because it determines the molecular weight of the reactive polymer. If a small amount of catalyst is used relative to the amount of monomer, the molecular weight of the reactive polymer becomes higher than when a larger amount of catalyst is used. It is usually recommended that the catalyst be added to the monomer by dropwise addition (this method being chosen as the order of addition) until the typical color of the organic anion remains constant, after which the calculated amount of catalyst is added. The purpose of the initial dropwise addition is to destroy the impurities, and thus allows better control of the polymerization.

The anionic polymerization must be carried out under carefully controlled conditions with protection against moisture and other contaminants. The monomer and catalyst should be freshly purified and the apparatus in which the polymerization is to be carried out should be thoroughly cleaned. Methods for purifying reactants and reaction equipment are well known and need not be presented herein. The alkali metal catalyst may be added to the monomer, or the monomer may be added to the catalyst.

.s λ · '57267 9 A solvent is usually used to facilitate heat transfer and sufficiently efficient mixing of the catalyst and monomer. The solvent must be neutral. Preferred are hydrocarbons and ethers including benzene, toluene, dimethyl ether, bis- (2-methoxyethyl) ether (formula (CH 2 OCH 9 CH 2) g O), ethylene glycol dimethyl ether (formula CH 2 OCH 8 CH 2 OCH 4), diethyl ether, N-hydropurane, tetrahydrofuran, tetrahydrofuran and N-heptane. The polymerization temperature depends on the monomer. The polymerization of styrene is usually carried out at a temperature slightly above room temperature, the polymerization of alpha-methylstyrene is carried out mainly at -80 ° C. The anion polymerization temperature is not critical to this invention.

The polymer product is so-called "living" or reactive and is not terminated in the true sense of the word, which is used in polymer chemistry, but is able to react further, also to further polymerize. Anionic polymerization is described by the following equation, which corresponds to the polymerization of styrene. using sec-butyllithium:

Sec-BuLi + n CH CH—> sec-Bu-CH? CH CH CH ία ό 6 ό _ A n “1

If styrene is added to the above-mentioned reactive polymer, the polymerization begins again and the chain grows until no more styrene monomer remains. Alternatively, if another different anionically polymerizable monomer such as butadiene is added, the aforementioned reactive polymer will begin to polymerize butadiene, and the resulting final reactive polymer will have a polystyrene portion and a polybutadiene portion. The reactive polymer can be terminated by reacting it with a halogen-containing compound. The termination of the above reactive polystyrene with methyl iodide is described by the following equation: «· Mi _ _

Sec-Bu-CHgCH-CH2CH__ £ i + CH3J_ ^ eek-Bu_CHgCH_SHgCHC ^ + Lii όό Ί6 6 _ Jn-1 _ _n-1 10 57267

Living polymers are characterized by their molecular weights being fairly equal, i. the molecular weight distribution of the average reactive polymer is very narrow. This is significantly different in a conventional polymer where the molecular weight distribution is very broad.

A significant feature of this invention is that the molecular weights of the graft polymer side chains are uniform and this molecular weight uniformity is an essential feature of living polymers prepared as the first step in the overall synthesis of these graft polymers.

The reactive polymers mentioned herein are terminated by reacting them with a halogen-containing compound which also has either a polymerizable olefinic group or an epoxy or thioepoxy group. Suitable terminating agents are vinyl haloalkyl ethers having up to 6 alkyl atoms, vinyl esters of halogen fatty acids having six or less carbon atoms in the fatty acid, allyl halides, halide halides, epihalohydrides, acrylyl halides, methacrylic halides, methacrylic halides, methacrylic halides. Halogen may be chlorine, fluorine, bromine or iodine, mainly chlorine.

Termination of a reactive polymer with any of the above types of terminating agents is accomplished simply by adding the terminating agent to a solution of the reactive polymer at the temperature at which the reactive polymer is prepared. The reaction takes place immediately and the yield is 100%. The terminating agent is used in an amount slightly above the equivalent amount relative to the amount of catalyst.

$ Βΐ5 ··: 'a. 57267

The following equations illustrate typical reactions according to the practice of this invention:

Reactive polymer: r R1-! R1 I ta. © R-CH 2 - C - CH 2 - (P + Li U 4 I ·

Terminating agents: (a) X-R3-O-C-CH_10 (b) X-R3-C-O-C = CH2 (c) X-R3-C CH2 3 / ° (a) X-RJ-CH -CHg o (e) X1-C-CH2 p (f) X-C-CO * CH2

iU

ΰδϋ.ΑΛί, 1¾ 57267 Γ κ1Ί κ1 J I 3 (a) R - CH0 — C —- CH - C - R ° -OC = CH_] 2 -U i2 Rk Γ R1 “T R1 0 ,, I I 3 J!

2 l2 n la U

L R R R

Γ R1 ~ | R1 I 5 3 (c) R - CH2 -C - CH2 - (3R - C = CH2 _ i2 J- E2 ik Γ R1 -1 E1 II 3 (d) R— CH6-c-- CH - C R - C-CH0 iTy I2 i * · r r1 ~ j R1

i I

(e) R - CH, r - C - CH - C-C-C = CHO! 1i2 lk - R1 - | R 1 (f) R - CH - C - CH - C-C-CO 2.

2 l2 n 2 l2 U i / ° LRJRR —- C-CO ^ Γ R1 “I R1 I 1 2 (g) R-CH2 -C - CH2-CC-COOR ^ R2 _n R2 R — C-COOR2 r1 —I r1

I I

(h) C - ςϋ ^ -C SiRRC = CH2 i2 Jn l2 every 57267 i3

1 2 3. U

In the above equations, R, R, R, R and R are hydrogen, lower alkyl or aryl. R is mainly lower alkyl, such as sec-butyl, R1 is either hydrogen. . U.

or methyl, R is phenyl, R is hydrogen or a lower alkylene group, and R is either hydrogen or a lower alkyl group.

In some cases, due to the nature of the reactive polymer and the monomer from which it is made or the nature of the terminating agent, it is advisable to "protect" the reactive polymer with a reactive agent such as lower alkylene oxide or diphenylethylene. This "protection" reaction results in a product which is still a reactive polymer but has a "lower tendency to react with the reactive groups of the terminator or any active hydrogen. Thus, for example, acrylic chloride acts as a terminator and also causes the formation of a carboxyl group in the terminated polymer chain. The use of acrylic chloride as a terminating agent is greatly facilitated if the reactive polymer is first protected and then allowed to react with the acrylic chloride. acrylyl chloride molecule.

If the preservative is not used in this intermediate step, the resulting polymer either has twice the molecular weight than expected or contains some chlorine, indicating that part of the reactive polymer is terminated upon reaction with another reactive polymer or acrylic chloride with some active hydrogen.

A particularly preferred terminating agent is ethylene oxide. It reacts with the reactive polymer when its oxirane ring breaks as follows:

Sec-Bu - CH "CH - CHNCH

06 n-1

Li + CHgCHg—> sec-Bu — CHgCH-CHgCH-CHgCHgÖ ti Y ..... 6 6

; ϊ λ Λ I

· .. · - -N'1

The above equation shows the reaction of ethylene oxide used as a preservative with a reactive polymer prepared by polymerizing styrene with a sec-butyl lithium compound. The protection reaction is carried out in a very simple manner, for example in the case of a termination reaction, by adding a protecting reagent to the reactive polymer at the polymerization temperature. The reaction takes place immediately. As with the terminating agent, the reagent is used in a mild excess relative to the amount of catalyst.

The reaction takes place in a molar ratio.

When epihalohydride is used as the terminating agent, the resulting polymer contains a terminal epoxy group. This terminal epoxy group can be converted to the corresponding glycol by heating with aqueous sodium hydroxide. The resulting glycol can be - converted to a copolymer by reacting it with a high molecular weight dicarboxylic acid which can be prepared, e.g., by polymerizing glycol or diamine using moles of excess phthalic anhydride, maleic anhydride, succinic anhydride or other anhydride. It can also be reacted with a diisocyanate to form polyurethane. The diisocyanate may be, for example, the reaction product of polyethylene glycol having an average molecular weight of i + 00 and, in moles, an excess of the phenylenediisocyanate used.

In another aspect of the invention, the organic epoxide is copolymerized with a terminated reactive polymer having an epoxy or thioepoxy end group. The copolymer formed is characterized by a backbone having continuous segments of at least about 20 and most preferably at least about 30 repeating organic epoxide units. Preferred organic epoxides are ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, cyclohexene epoxide and styrene oxide, i. epoxides having 8 or less carbon atoms. When halomaleic anhydride or halo maleate ester is used as the terminating agent, the polymer formed has ester groups that can be converted by hydrolysis to carboxyl groups. The resulting dicarboxylic polymer can be copolymerized with glycols or diamines to form graft-polymeric polyesters and polyamides.

It should be noted that the reaction of the reactive polymers mentioned herein with the above-mentioned termination reagents yields products which, although not reactive polymers, are themselves still polymerizable. Such further polymerization can take place either by the double bond of the terminating reagent or by the glycol moiety or the epoxy moiety, so that the terminating reagent in this case acts like the Y graft polymer: ·· £ 5 .S-U. ..

m 57267 formation. It should be further noted that these graft polymers, although generally similar in structure to prior graft polymers, are prepared in a manner that differs significantly from prior art graft polymers. In addition, they are structurally significantly different. Prior to the present invention, graft polymers were prepared by synthesizing a linear "backbone", then grafting growing polymer chains into that backbone, and the end result was a backbone with multiple polymer side chains dependent thereon.

On the other hand, the graft polymers of the present invention are prepared by first synthesizing these dependent polymer chains (reactive polymers) and then polymerizing - the end portions of these polymer chains to the backbone. That is, dependent chains, i.e. side chains, are synthesized first, followed by the backbone. The side chains are thus essential parts of the body. Apparently, although the two types of graft polymers generally resemble each other, their structures are different, not only because they are made by significantly different methods but because the graft polymer dependent chains of this invention are relatively uniform in minimum size and are an integral part of the backbone, and because the body has polymer segments of a certain minimum length. These properties contribute substantially to the advantageous properties that are essential for these new graft polymers. As previously mentioned, the graft polymers of this invention have unique properties and unique combinations of properties. The creation of these unique properties and combinations of properties has been made possible by the novel method of this invention, which forcibly causes miscibility of otherwise immiscible polymer segments. Thus, the advantageous properties of polystyrene can be combined with the advantageous properties of polymethyl acrylate, although the two polymers are normally immiscible with each other and their physical mixtures alone are very weak and not useful. In order to combine these advantageous properties into the same product, it is necessary that the graft polymer contains different polymer segments in relatively large proportions. The properties of polystyrene do not appear until the polymer has predominantly at least 20 repeating monomer units. The same applies to the polymer segments present in the graft polymers of the present invention, i.e., if the graft copolymer containing the polystyrene segments must have the preferred properties of polystyrene, these polystyrene segments must each contain substantially at least 20 repeating monomer units. This relationship between the physical properties of the polymer segment and the minimum size applies to all polymer segments of the graft polymers of this invention. In general, the minimum size of a polymer segment that results in the appearance of the physical properties t 57267 1Θ of that polymer in the graft polymers of this invention is about 20 repeating monomer units. Primarily, as noted above in this context, the polymer segments, both in the copolymer backbone and in the side chains, have substantially more than about 30 repeating monomer units. These polymer segments themselves may be homopolymers or copolymers. Thus, the graft polymer of this invention can be prepared by copolymerizing methyl methacrylate, lauryl methacrylate and terminated polystyrene having a polymerizable olefinic group. The unitary polymer segments of such a graft polymer backbone are copolymer segments formed by methyl methacrylate and lauryl methacrylate. -

However, graft polymers containing polymer segments having less than about 20 repeating monomer units are useful for many purposes, but graft polymers having at least about 20 repeating monomer units in the various polymer segments are preferred.

Although, as shown, the graft polymers mentioned herein are characterized by a wide variety of physical properties, depending on the monomers used in their preparation, and also the molecular weights of the various polymer segments contained in each graft polymer, all of these graft polymers are useful as tackifiers.

These films can be used as nutrient wrapping material, painters' protective suits, protective wrappers for merchandise displayed for sale, and other such purposes.

The invention is further illustrated by the following examples. In each case, all raw materials must be pure and care must be taken to ensure that the reagent mixtures remain dry and free from impurities. All parts and percentages, unless expressly stated otherwise, are parts by weight and percentages by weight.

Example 1

To a solution of one drop of diphenylethylene at 10 ° C is added portionwise a 12% solution of tert-butyllithium in pentane until the pink color persists, with the addition of a further 30 ml (0.0U mol) of t-butyllithium solution followed by 312 ml. g (3.0 moles) of styrene.

The temperature of the polymerization mixture is maintained at U0 ° C for 30 minutes, after which the reactive polystyrene is terminated by treatment with 8 ml (0.08 mol) of vinyl 2-chloroethyl ether. The polymer formed precipitates upon addition of the benzene solution to methanol, and the polymer is isolated by filtration. Its average molecular weight, osmometrically determined in jbf ^ rjff ^ as, is 7200 IT 57267 (theor .: 7870) and the molecular weight distribution is very narrow, i. Mv / Μη is less than 1.06.

Example 2

Preparation of polystyrene terminated with vinyl chloroacetate.

To a solution of one drop of diphenylethylene in 2500 ml of cyclohexane at U0 ° C is added portionwise a solution of 12- $ sec-butyllithium in cyclohexane until the pink color persists, adding a further 18 ml (0.02¾ mol) of sec-butyllithium, and then 312 g (3.0 moles) of styrene. The temperature of the polymerization mixture is maintained at L0 ° C for 30 minutes, after which the reactive polystyrene is protected by treatment with 8 ml (0.0i * 0 moles) of diphenylethylene, and then terminated by treatment with 6 ml (0, 05 moles) of vinyl chloroacetate. The resulting polymer is blended by adding a cyclohexane solution to methanol and the polymer is isolated by filtration. It has an average molecular weight, determined osmometrically in the vapor phase, of 12,000 (theor .: 13265), and a very narrow molecular weight distribution, i. Mv / Mn is less than 1.06.

Example 3

Preparation of epichlorohydrin-terminated polystyrene.

A benzene solution of reactive polystyrene is prepared according to Example 1 and the termination is performed by treating the solution with 10 g (0.10 moles) of epichlorohydrin. The resulting terminated polystyrene is precipitated with methanol and isolated by filtration. Its molecular weight, determined osmometrically in the vapor phase, is 8660 (theor .: 7757) and its average molecular weight distribution is very narrow.

Example ¾ ^ Preparation of vinyl chloroacetate terminated poly (alpha-methylstyrene).

To a solution of 357 g (3.0 moles) of N-methylstyrene in 2500 ml of tetrahydrofuran is added dropwise a solution of 12- $ tert-butyllithium in pentane until the pink color persists. An additional 15.0 mL (0.03 moles) of tert-butyllithium solution is then added, resulting in a bright red coloration of the solution. The temperature of the mixture is then lowered to -80 ° C, and after the mixture has been at this temperature for 30 minutes, 5.6 ml of diphenylethylene are added. The resulting mixture is poured into 5.0 ml (0.0¾ mol) of vinyl chloroacetate and the poly (σ <· -methylstyrene) thus terminated is precipitated with methanol and isolated by filtration. Its average molecular weight, determined osmometrically in the vapor phase,

't' I

18 57267 is 1U28O (Theor .: 12065) and the molecular weight distribution is very narrow.

Example 5

Preparation of poly (-methylstyrene) terminated with allyl chloride.

To a solution of k72 g (1.0 mol) of ύ <-methylstyrene in 2500 ml of tetrahydrofuran is added dropwise a 2% strength solution of n-butyllithium in hexane until the pink color persists. An additional 30 ml of this n-butyllithium solution is added to give a bright red color. The temperature of the mixture is then lowered to -80 ° C, and after 30 minutes at this temperature, 1.5 g (0.06 mol) of allyl chloride are added. The red color disappears almost immediately, indicating that the reactive polymer is terminated. The resulting colorless solution is poured into methanol to save terminated poly (methylstyrene) having an average molecular weight in the vapor phase as determined osmometrically by 11,000 (theoretical: 12,300).

Example 6

Preparation of methacrylic chloride terminated polystyrene.

To a solution of 0.2 ml of diphenylethylene in 2.5 ml of benzene is added dropwise a 12- # n-butyllithium hexane solution until the pink-brown color persists. An additional 2k mL (0.031 moles) of this n-butyllithium solution is added, followed by U16 g (0.0 moles) of styrene to give an orange solution. The temperature is kept at U0 ° C at all times by cooling from the outside and adjusting the rate of styrene addition. After the addition of the entire amount of styrene, the temperature is maintained as such for 30 minutes and then lowered to 20 [deg.] C., after which b, k g (0.1 mol) of ethylene oxide are added, whereby the solution becomes colorless. The reactive polystyrene is terminated by reacting it with 10 ml (0.1 mol) of methacrylyl chloride. The average molecular weight of the polymer obtained (as determined osmometrically in the vapor phase) is 10,000. The methacrylic chloride used in the above process can be replaced with acrylic chloride to give an acrylic acid ester end group in the polystyrene chain.

Examples 1-6 illustrate the preparation of terminated reactive polymers. These are used as starting materials in the process of Examples 7-1 for the preparation of inoculum polymers. Terminated reactive polymers are present in the seed copolymers as side chains, with the polymerizable end group of the terminated reactive polymer terminating in the body of the seed copolymer as part of the whole.

Example 7

Preparation of graft polymer from polystyrene and ethyl acrylate terminated with vinyl 2-chloroethyl ether.

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To a solution of 18 g of octylphenoxy-polyethoxyethanol (emulsifier) in 300 g of deionized water is added, with vigorous stirring, a solution of 30 g of the polystyrene product of Example 1 and 70 g of ethyl acrylate. The resulting dispersion is purged with nitrogen and then heated with stirring at 65 ° C, after which 0.1 g of ammonium persulfate is added to initiate polymerization. 200 g of ethyl acrylate and 0.5 g of a 2% aqueous solution of ammonium persulphate are then added portionwise over 3 hours, the temperature being kept at δ5 ° C at all times. The resulting graft polymer emulsion is cast on a glass plate and allowed to air dry at room temperature to form a flexible self-supporting film. - The film is shown to have uniform polystyrene segments by extraction with cyclohexane, which dissolves polystyrene a ', leaving no residue from the cyclohexane extract on evaporation.

Example 8

Preparation of graft polymer from vinyl chloroacetate terminated poly (-x - methylstyrene) and butyl acrylate.

A solution of 50 g of high molecular weight poly (o <-methylstyrene terminated with vinyl chloroacetate with an average molecular weight of 12,600 and 50 g of butyl acrylate in 1 kg of toluene is purged with nitrogen at 70 ° C and then 1 g of azo The temperature is maintained at 70 ° C for 2k hours to give a graft spheron solution from which a film is cast on a glass plate.The dry film is slightly sticky and is found to contain polystyrene segments by extraction with cyclohexane and evaporation into a cyclohexane extract.

Example 9

Preparation of graft polymer from epichlorohydrin-terminated polystyrene and isobutylene.

To a solution of 20 g of high molecular weight polystyrene terminated with epichlorohydrin and having an average molecular weight of 10,000 in 1 liter of toluene at 70 ° C is added 80 g of isobutylene. Slowly add 1 x 5 mL of boron-trichloride-ethyl ether complex maintaining the temperature at 7070 ° C throughout. The polymerization occurs upon addition of the catalyst and ends almost immediately after the entire amount of catalyst has been added. The graft polymer formed is recovered by evaporating the toluene and washing the residual solid with methanol.

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Example 10

Preparation of graft polymer from epichlorohydrin-terminated polystyrene and isobutylene.

To 1,000 ml of methyl chloride at -70 ° C is added 10 g of epi-chlorohydrin-terminated high molecular weight polystyrene having an average molecular weight of 10,000. To this solution, kept at -70 ° C, is added continuously and dropwise the solution. with 2 g of aluminum chloride in 400 ml of methyl chloride and 90 g of isobutylene. The time required for these additions is one hour, and after this time the polymerization is substantially complete. The graft polymer formed is isolated by evaporating off the methylene chloride.

Example 11

Preparation of graft polymer from high molecular weight polystyrene and ethyl acrylate terminated with methacrylyl chloride.

A mixture of 21 g of methacrylyl-terminated high molecular weight polystyrene having an average molecular weight of 10,000 and prepared according to Example 6, 2 g of ethyl acrylate and 0.035 g of azo-bis-isobutyronitrile is prepared at room temperature and kept under nitrogen for 18 hours. 67 ° C. The resulting product is a tough, opalescent material that can be modified at 160 ° C to give a clear, tough, transparent sheet.

Example 12

Preparation of graft polymer from high molecular weight poly (ofc-methylstyrene) and ethylene terminated with allyl chloride.

A solution of 20 g of high molecular weight poly (O (methylstyrene) terminated with allyl chloride) having an average molecular weight of 27,000 in 100 ml of cyclohexane is prepared and 5.5 .mu.l of a 0.645 molar solution of diethylaluminum chloride in hexane is added to this solution. and 2 ml of vanadium oxychloride, and then ethylene is pressed into the vessel until a pressure of 200 KPa is introduced, this system is gently stirred for about one hour at 30 [deg.] C., after which the polymer precipitates from solution, is collected by filtration and pressed into a thin transparent film. is tough and flexible.

Claims (12)

2i 57267 A graft polymer which can be used in the manufacture of films and which has a backbone and associated side chains, characterized in that a) the side chains have a rather narrow molecular weight distribution between 5,000 and 50,000 and consist of an anionic polymerization initiator having an alkali metal alkyl, a residue, at least 20 polymerized monomer units, the monomer is anionically polymerized and the monomer is styrene or γ-methylstyrene, or a mixture thereof, and a termination group having a copolymerizable vinyl end group containing up to 6, A halogen containing 6 carbon atoms of vinyl ester of an alkanoic acid, or an allyl halide, a methylallyl halide, an acrylyl halide or a methacyllyl halide, and optionally further comprising a protective agent with a lower alkylene oxide or 1,1-diphenylethylene, and b) and at least one ethylenically unsaturated backbone monomer of ethyl acrylate, butyl acrylate or isobutylene, the side chains being located at regular intervals in the backbone and having at least 20 repeating backbone monomer units therebetween. Graft polymer according to Claim 1, characterized in that the residue of the anionic polymerization initiator is a secondary butyl group. Graft polymer according to Claim 1, characterized in that the preservative is an ethyleneoxy group. The graft polymer according to claim 1, characterized in that the anionically polymerizable monomer is styrene, the terminating group is -CH 2 CH 6 -O-CHOH 4, and the backbone monomer is ethyl acrylate. Graft polymer according to Claim 1, characterized in that the anionically polymerizable monomer is? -Methylstyrene, the termination group is -CH 2 -CO-O-CH 3 CH 2 and the backbone monomer is butyl acrylate. The graft polymer according to claim 1, characterized in that the anionically polymerizable monomer is O (-methylstyrene), the termination group is -CH 2 -CH = CH 2, and the backbone monomer is ethylene. The graft polymer according to claim 1, characterized in that the anionically polymerizable monomer is styrene, the protecting agent is ethylene oxide, the termination group is -QO-C = CHp, and the backbone monomer is ethyl acrylate. ch3 22 572 67 Θ. Process for the preparation of a graft polymer according to claim 1, characterized in that a living polymer is prepared by polymerizing in an inert solvent an anionically polymerizable, ethylenically unsaturated monomer of styrene or Of-methylstyrene or a mixture thereof in the presence of having a molecular weight of 5,000 to 50,000 and a narrow molecular weight distribution, reacting the resulting monofunctional living polymer, which may be protected with lower alkylene oxide or 1,1-diphenylethylene, with a vinyl haloalkyl ether having an alkyl group containing up to 6 carbon atoms, or up to 6 carbon atoms halogen with vinyl ester of alkanoic acid, or with allyl halide, methallyl halide, acrylic halide or methacryl halide to form a macromolecular monomer, having a copolymerizable vinyl end group, followed by copolymerizing the resulting copolymerizable vinyl end group with an ethylenically unsaturated backbone monomer having ethyl acrylate, butyl acrylate, at least one of the following, wherein a mixture of two or more of said isomer, units of an anionically polymerizable monomer, and wherein the side chains are substantially evenly spaced in the backbone with at least about 20 backbone monomer units therebetween. Process according to Claim 8, characterized in that the anionic polymerization initiator is sec-butyllithium. Process according to Claim 8, characterized in that the preservative is ethylene oxide. Process according to Claim 8, characterized in that the anionically polymerizable monomer is styrene, the terminating agent is vinyl chloroacetate and the backbone monomer is ethyl acrylate. Process according to Claim 8, characterized in that the anionically polymerizable monomer is o (-methylstyrene), the terminating agent is vinyl chloroacetate and the backbone monomer is butyl acrylate. Process according to Claim 8, characterized in that the anionically polymerizable monomer is 0 ("methylstyrene, the terminating agent is allyl chloride and the backbone monomer is ethylene. 1H). Process according to Claim 8, characterized in that the anionically polymerizable monomer is styrene, is methacrylic chloride and the backbone is ethyl acrylate ...... <* 23 57267