Cyclo copolymers
United States Patent n91 Sackmann et al.  
 [ 1 Apr. 8, 1975 1 CYCLO COPOLYMERS [75] Inventors: Gunter Sackmann, Leverkusen;  
 Gunter Kolb, Cologne- Stammheim, both of Germany [73] Assignee: Bayer Aktiengesellschaft,  
 Leverkusen. Germany [22] Filed: Jan. 11, I973 [21] Appl. No.: 322,709  
 Related U.S. Application Data [63] Continuation-impart of Ser. No. 176.390, Aug. 18,  
 1971, abandoned.  
 [56] References Cited UNITED STATES PATENTS 2.995.535 8/1961 Gethins 260/235 OTHER PUBLICATIONS Chem. Abst., 67, 44912m.  
 Primary ExaminerChristopher A. Henderson Attorney, Agent, or FirmConno11y and Hutz [5 7] ABSTRACT The invention relates to a process for the production of cyclocopolymers. characterised in that compounds of the general formula 1 in which R and R may be identical or different and mean H. CH3. C1 or Br; and X means where R means hydrogen, an aliphatic or aromatic radical, are copolymerised with unsaturated compounds of the general formula 2 R R on M5 6):  
 in which n is 1 4; R is H. CH or CI-I -CH; Y is OH or NH and R and R may be identical or different and mean hydrogen or (C -C )-a1kyl,  
 preferably in equimolar amounts. and possibly with the use of further unsaturated compounds which are copolymerisable with compounds of the formula 1 and to copolymers obtainable by the process of the inven- Hon.  
 &#39;1 Claim, N0 Drawings 1 CYCLO COPOLYMERS CROSS REFERENCE TO RELATEDAPPLICATION This application is a continuation-in-part of now abandoned Ser. No. 176,390 as filed Aug. 18, 1971.  
  It is known to radical-polymerise unsaturated carboxylic acid anhydrides. With the use of large amounts of catalyst, the homopolymerisation of unsaturated carboxylic acid anhydrides yields only polymers of a comparatively low molecular weight. (cf R. W. Lenz, Organic Chemistry of Synthetic High Polymers, Interscience Publishers N.Y., 1967, page 389).  
  If, on the other hand, the radical polymerisation of allyl compounds, such as eg allyl alcohol, is attempted, virtually no polymeric substance is obtained (cf U.S. Pat. No. 2,541,155).  
  Surprisingly, it has now been found that unsaturated cyclic compounds of the general formula 1 in which R and R may be identical or different and mean H, CH Cl or Br, and X means -O- OI -N&#34; where R is hydrogen, an aliphatic or aromatic radical, can be copolymerised with unsaturated compounds of the general formula 2 CH2 c (t n r in which n means 1 4; R is H, CH or CH OH; Y is OH or NH and R and R may be identical or different and mean hydrogen, or (C C )-alkyl, optionally in the presence of further unsaturated compounds which are copolymerisable with compounds of the formula 1, to form high-molecular cyclo copolymers.  
  The subject-matter of the present invention therefore comprises a process for the production of cyclo copolymers, which is characterised in that compounds of the general formula 1 are copolymerised with unsaturated compounds of the general formula 2, preferably in equimolar amounts, and optionally with the use of further unsaturated compounds which are copolymerisable with compounds of the formula I.  
  The unsaturated compounds of the general formula 1 comprise, for example, maleic acid anhydride, monochloro-, dichloro-, monobromoand dibromo-maleic acid anhydride, maleic acid-imide, maleic acid N- methyland -N-phenyl-imide and citraconic acid anhydride.  
  Compounds of the general formula 2 are, for example, allyl alcohol, methallyl alcohol, allylamine, methal- 2 lylamine, 2-methylene-propane-diol-l,3, l-buten-4-ol l-penten-S-ol and 1,1-dimethyl-allyl alcohol.  
  Examples of further unsaturated compounds which are copolymerisable with compounds of the formula 1 are allyl compounds and methallyl compounds of the general formula 3 in which R is hydrogen or methyl; Z is halogen, isocyanato, OCOR or OR where R means the radical of an aliphatic, cycloaliphatic or aromatic hydrocarbon with l to 18 preferably 1 to 8 carbon atoms.  
  In particular, the following allyl compounds may be mentioned by way of example: cyclic acroleinacetale, allyl chloride, 2-chloropropene, allyl acetate, allyl octeate, allyl cyanide, allyl isocyanate, allyl methyl ether, allyl butyl ether, allyl phenyl ether, allyl cyclohexyl ether.  
  The corresponding methallyl compounds are also suitable.  
  Monomers which impart self-cross-linking properties to the cyclo copolymers, such as N-methoxymethylallyl-urethane, may also be used.  
  Moreover, the following unsaturated compounds which are copolymerisable with compounds of the formula l are suitable: vinyl compounds, e.g., unsaturated ethers such as vinyl methyl ether, vinyl butyl ether, isopropenyl ethyl ether; unsaturated esters, such as vinyl acetate or 1,3-diacetoxy-2methylene-propane, vinyl aromatic compounds, such as e.g., styrene, a-methylstyrene, p-chlorostyrene or p-methoxystyrene; divinyl compounds, such as e.g., divinyl ether and divinylsulphone; vinylidene compounds, such as e.g., vinylidene chloride and vinylidene fluoride.  
  In addition, mono and polyolefines, such as ethylene, propylene, l-butene, 2-butene, isobutylene, diisobutylene, triisobutylene, tetraisobutylene, cyclopentene, cyclohexene, butadiene and isoprene are also suitable as further unsaturated compounds which are copolymerisable with compounds of the formula 1.  
  In the process according to the invention, the compounds of the formula 1 as well as those of the formula 2 and the unsaturated compounds which are copolymerisable with compounds of the general formula 1 and are mentioned above, can be used individually or in combination with each other.  
 The polymerisation can be carried out in bulk, with.  
 the use of a solvent which is inert towards the reaction components, in a non-aqueous emulsion or suspension, v  
 or also as precipitation polymerisation. Polymerisation in inert solvents, such as dioxane, tetrahydrofuran, acetone and methyl ethyl ketone, aromatic hydrocarbons, such as benzene, toluene and xylene, and ethyl acetate, is preferred.  
 The polymerisation temperature depends on the catalyst system used. It preferably ranges from 20C to The polymerisation can be initiated by heating, by illumination with actinic light or by&#39; the addition of radical-forming substances, such as e.g. peroxides, hydroperoxides, H 0 percarbonates, perborates, peracetic acid or peracetates, persulphates, azo compounds such as azobisisobutyronitrile, as well as redox catalysts.  
  The usual regulators for influencing the molecular weight may be added to the polymerisation for influencing the molecular weight, such as long-chain alkyl mercaptans, diisopropylxanthogen disulphide, nitro compounds and similar compounds.  
  The compounds of the general formulae 1 and 2 are preferably used in equimolar amounts for the cyclo copolymerisation. If, in addition, there are used the aforesaid further unsaturated compounds which are copolymerisable with compounds of the formula 1, the amounts of the latter have to be such that the sum total of these compounds and of those of the general formula 2 is equimolar to the sum total of the compounds of the general formula 1. The preferred reaction moreover is carried out by using 25 Mol-percent of the compounds of the general formula 2 wherein R is H or CH Y is OH, R and R is H and n is 1, 25 Mol-percent of the aforesaid further unsaturated compounds being copolymerisable with compounds of the formula 1 and having molecular weights less than 219, and 50 M01- percent of the sum total of the compounds of the general formula 1 wherein X means O.  
  A process which is formally similar to the claimed process and which is disclosed in the U.S. Pat. No. 3 51 1 820, is using 2-phenyl-substituted allyl alcohol and allyl alcohol derivatives. But owing to the phenyl substituents of the allyl components, this process is not comparable with the process of the present invention; therefore the copolymers obtainable by this process have a high degree of insolubility in organic solvents (see U.S. Pat. No. 3,511,820, column 4 lines 51/56) which the products of the present invention do not have.  
  When, for example, maleic acid anhydride, on the one hand, and e.g., allyl or methallyl alcohol, on the other hand, are used, the claimed process, surprisingly, leads to high-molecular cyclo copolymers which are soluble because they are not cross-linked.  
  As can be seen from the spectroscopic findings which indicate the presence of carboxyl and lactone groups and the absence of C=C double bonds and cyclic carboxylic acid anhydride groupings, it is highly probable that the copolymer of maleic acid anhydride and allyl alcohol contains the following recurrent structural unit of the formula 4:  
 CH-CH I 1 COOH c=o It follows that the copolymerisation proceeds as an intramolecular cyclo copolymerisation, i.e., with simultaneous or consecutive ring opening and ring closure reactions.  
  This transcyclisation between compounds of the formulae 1 and 2, which proceeds before or after the copolymerisation or synchronously with the latter and, presumably, like other lactone formations or ester formations (cf. E. Muller, Neuere Anschauungen der Organischen Chemie, Springer-Verlag 1957, pages 175 and 264-267), according to an ionic mechanism, fails to occur to the extent to which the aforesaid unsaturated compounds which are copolymerisable with comsist, at least partially, preferably at least 50 percent, re-  
 ferred to the sum of the equivalents in the polymer chain derived from the corresponding unsaturated cyclic compounds of the general formula 1, of structural units of the formula 5 coonc \O/ CH2 CH R in which R and R may be identical or different and mean hydrogen, methyl or halogen, preferably chlorine and/or bromine, and R is hydrogen or methyl.  
  The products obtained by the preferred reaction of 50 Mol-percent of compounds of the formula 1 wherein X means O, 25 Mol-percent of at least one compound of formula 2 wherein R is H or CH Y is OH, R and R is H and n is 1, and 25 Mol-percent of at least one of the aforesaid further unsaturated compounds being copolymerisable with the compounds of the formula 1 and having molecular weights less than 219, are characterized by having 50 percent, referred to the sum of the equivalents in the polymer chain derived from the corresponding unsaturated cyclic compounds of the general formula 1, cyclic lactone structures of the type of formula 5.  
  The copolymers of the present invention are therefore quite different from the terpolymers disclosed in the U.S. Pat. No. 2 995 535 which have reactive hydroxyl groups as well as carboxylic groups, the former 0f which are particularly esterified with fatty acids. Moreover, the molar ratio of the amounts of the copolymerisable monomers is quite different from that of the instant process; in the copolymerisation process disclosed in the U.S. Pat. No. 2 995 535 the sum of the amounts of the allyl alcohol compounds and of the vinyl monomers (styrene) is not equimolar to the amount of the copolymerisable dibasic unsaturated acids or acid derivatives.  
 These new cyclocopolymers prepared according to the invention can be dissolved in numerous organic solvents, such as e.g., acetone, tetrahydrofuran, dimethyl formamide, dimethyl sulphoxide, to a satisfactory extent, i.e., to give an at least 10 percent by weight solution, and they can also be made water-soluble by salt formation.  
  The new compounds areproducts with interesting properties which are due to the carboxyl groups, on the one hand, and to the lactone rings, on the other hand. The carboxyl groups impart to the cyclo copolymers according to the invention a strong polarity giving these compounds access to important technical fields of application. By neutralising the carboxyl groups with organic or inorganic bases, there are obtained watersoluble high-molecular compounds with an unusually wide spectrum of application. Obviously, it is possible to branch or cross-link the cyclo copolymers by reacting the carboxyl groups with the conventional bior polyfunctional compounds, such as diamines, polyamines, polyepoxides, polyisocyanates etc. The lactone rings impart to the cyclo copolymers outstanding solu-. bility and an excellent compatibility with numerous tion of pigment dispersions and of microporous foil material, and as polishingagent for synthetic floor coverings. Moreover the products of the instant invention have excellent adhesiveness to different supports, espenatural and synthetic materials. 5 cially metals, e.g. copper, and are therefore useful as The said properties may be varied in almost any way photo laquers. by grafting other radical-polymerisable monomers on EXAMPLES 1 20 to the cycle copolymers according to the invention by known methods, preferably in the presence of radical Equimolar amounts of the starting monomers and the formers. l0 initiator, in amounts of 0.02 10.0 percent by weight On account of these very interesting properties, the are dissolved in the solvent concerned, and the resulcyclo copolymers have a very wide spectrum of applitant solution is transferred to reaction vessels whick cation. By way of example, there may be mentioned the have been heated and rinsed with nitrogen. These are use as varnish, adhesive, coating agent for various subtightly sealed under nitrogen and heat d t h Strates Such as Wood, P p metal, leather, yn he i quired temperature. When the polymerisation is complastics, impregnating agent, textile auxiliary, finishing pleted, the polymer can be precipitated by adding the or plasticising g protective l id and mulsifier, resultant viscous solutions dropwise to an excess or thickening agent, coupling agent, mo ded ar BleS, ether or low-boiling petroleum ether. The precipitatec foam or also as film or foil, as agent for improving the white powdery polymers are subsequently dried in 2 s t u as hair t ng g s lectrophoretvacuum drier at 60C until the weight remains conically applicable primers or varnishes, for the preparastam,  
 Example Starting lnitiator Solvent Temperature Yield [-nldl/g monomer l maleic acid- AJBN dioxane 70C 0.315  
  anhydride (MA) allyl alcohol 2 MA AJBN benzene 70C allyl alcohol 3 MA AJBN dioxane 60C almost allyl alcohol quantitative 4 cyclohcxyl tetrahydro- C percarbonate furan 5 acetone 30C 55.071 6 cyclohexylacetone 1 5C percarbonate/ p-dimethyl toluidinc 7 MA AJBN dioxane 70C l00.07r  
  methallyl alcohol 8 AJ BN acetone C 90.571 9 cyclohexyl acetone 30C l 00.07:  
  percurbonate l0 AJBN dioxan 70C l00.0&#39;/t 0.228 l l lauroyl acetone 15C peroxide/pdimethyltoluidine l2 cyclohcxyl acetone 15C percarhonate/ p-dimethyltoluidine 13 AJBN dioxan 70C 96.571 0.241 14 A] BN dioxan 70C 100.071 15 MA AJBN dioxan 70C 66.57:  
  2-methylene propane diol- 1.3 l6 AJ BN dioxan C 17 AJBN DMF 60C l8 cyclohcxyl acetone 30C 63.771  
  percarhonate 19 MA AJBN dioxane 70C 72. W1  
  l-buten-4-ol 20 MA AJBN dioxane 70C isoprenc alcohol AJBN Azohisisohutymnitrile isoprene alcohol S-hytIroxy-3mtethyl-huten- EXAMPLES 21 28 Equimolar amounts of maleic acid anhydride and the copolymerisation components are intimately mixed by. stirring in an autoclave, and the stated amount of initiator is then added. The mixture is heated to polymerisation temperature under nitrogen. When the polymerisation is completed, the autoclave is opened and the product obtained dissolved in a solvent. The polymers are then precipitated in the form of colourless powders by adding these solutions dropwise to an excess of ether or petroleum ether; they are then dried in a vacuum at 60C until the weight remains constant.  
 prene alcohol The yields range from 20 to 98% EXAMPLES 29 46 In each case, maleic acid anhydride and two copolymerisation components are dissolved in a solvent together with the initiator. The amount of the two comonomers is chosen in such a way that their sum total is equivalent to the amount of maleic acid anhydride. This solution is introduced into a dry four-neck Exam le Startin monomer initiator Solvent Tem p g p flask which is fitted with stirrer, reflux condenser, inter- 21 MA AJBN 120C nal thermometer as well as with inlet and outlet for ni- 22 gm i AJBN trogen and WhlCl&#39;l has been rinsed Wlth nitrogen, and it ally] alcohol is stirred at the reaction temperature until the Y o 23 if :lcohol AJBN 60C polymerisation is completed. The resultant product 1s 24 MA AJBN then added dropwise to an excess of ether or low- 25 methallyl 8150M] AJBN 60C boiling petroleum ether whereupon the polymer is pre- 26 MA AJBN cipltated in the form of a colourless powder. This 15 filpropane diol-l,3 tered off and dried in a vacuum at 60C for 48 hours.  
 Example Starting monomer lnitiator Solvent Temperature Conversion [1;] dl/g 29 MA AJBN dioxane 70C 95.0%  
  ally] alcohol ally] acetate 30 MA AJBN dioxane 70C ally] alcohol ally] chloride 3] MA AJBN dioxane 70C 86.57:  
  ally] alcohol ally] ethyl ether 32 MA AJBN dioxane 70C 56.]?!  
  ally] alcohol diisobutylene 33 MA AJBN dioxane 70C 81.37!  
  allyl alcohol cyclopentene I 34 MA AJBN dioxane 70C ally] alcohol l-butene 35 MA AJBN dioxane 70C 89.27!  
  methallyl alcohol allyl acetate 36 MA cyclohcxyl acetone 30C SL071 0.288  
  methallyl alcohol percarhonate ally] acetate 37 MA AJBN dioxane 70C l00.07l 0.]8]  
  methallyl alcohol methallyl acetate 38 MA AJBN dioxane 70C 85.7%  
  methallyl alcohol ally] chloride 39 MA AJBN dioxane 70C 95.771  
  methallyl alcohol diisobutylene 40 MA AJBN dioxane 70C 93.6%  
  methallyl alcohol cyclopentene 4] MA AJBN dioxane 70C 97.5% 0.238  
  methallyl alcohol l-hutene 42 MA AJBN dioxane 70C 0.68]  
  methally] alcohol styrene 43 MA AJBN dioxane 70C 0.2 II  
  methallyl alcohol vinyl acetate 44 MA AJBN dioxane 70C methallyl alcohol vinyl isohutyl ether 45 MA AJBN dioxane C 68.971  
  methylcnepropane-dioll.3 allyl alcohol 46 MA AJBN dioxane 70C Z-methylenepropanc-dioll .3 l.3-diacetoxy- Z-methylenepropane Citraconic acid anhydride and the copolymerisation components are dissolved in equimolar amounts in the solvent, and the initiator is then added. The reaction mixture is transferred to pressure bottles which are tightly sealed under nitrogen. The reaction is then carried out at a constant temperature with continuous shaking in a roller cabinet. Finally, the resultant solution is stirred into an excess of ether, and the colourless precipitate is filtered off. It is then dried in a vacuum at 60C for 48 hours.  
  The reactions without a solvent are carried out analogously. The reaction product is finally diluted with acetone and the polymer is precipitated by stirring the mixture into an excess of ether.  
 Example Starting monomer Initiator Solvent Temp.  
 48 AJBN dioxane 70C 49 AJBN 70C 50 AJBN 70C l AJBN 100C The yields are lower throughout than those obtained with the use of maleic acid anhydride.  
 We claim:  
  1. A polymer which is soluble in acetone, tetrahydrofuran, dimethylformamide and dimethylsulphoxide to an extent yielding a solution containing 10 percent by weight or more of said polymer and which is watersoluble in the form of its salt, said polymer having an average molecular weight of 5,000 to 100,000 and having a lactone structure of the formula R R2 R3 I CH C -C (I:  
 COOH E 0 CH wherein R and R are the same or different and are selected from the group consisting of hydrogen, methyl, chlorine and bromine and R is hydrogen or methyl, said polymer being produced by the process which consists of copolymerizing a first monomer of the formula wherein R is as aforesaid in equimolar amounts at a temperature between 20 and 200C.