DE1084919B - Process for the block copolymerization of olefinically unsaturated compounds - Google Patents

Description

GERMAN

The invention relates to a new process for the production of block copolymers which is so directed can be that it can easily be a polymer with any desired molecular weight and any composition can be obtained from any number of sequences of any different monomeric units is composed.

According to the invention, a new and improved polymerization process for making various Types of linear block copolymers created, whereby the individual blocks can have any length. The conversion of the monomer to the desired polymer takes place almost quantitatively with minimal formation of undesirable By-products.

According to the invention, the new mixed block or poly-block polymers are produced by a process for polymerisation Obtained olefinically unsaturated compounds, which is characterized in that one unsaturated polymerizable compound in the presence of a polymer with at least one negatively charged ao NEN carbon end group, which in one of the poly block polymerization previous process stage has been prepared, polymerized.

The new process uses an "active polymer" as a polymerization initiator, which is at least

a negatively charged carbon atom has j c - I,

which can transfer its electrons to a monomer and thereby the polymerization of the monomer starts. The preparation of these active polymers used according to the invention as polymerization initiators is not the subject of the invention.

The polymeric polymerization promoter can be any particular polymeric product made in accordance with the invention. A polymer which has been prepared by the polymerization of a polyunsaturated hydrocarbon with conjugated double bonds and an addition compound of alkali metal and a polycyclic aromatic compound or other suitable initiator of anionic polymerization in an inert medium can also be used as a promoter. For best results, the polymerization * 5 in solution in an inert medium is carried out in complete absence of water and oxygen, at below 0 ⁰ C, although temperatures up to 60 ° C are still within the scope of the invention. You can z. B. easily steer the process so that two-block polymers, three-block polymers and other multiple-block polymers with any number of repetitive sequences of the individual monomers are formed.

The monomers which according to the invention can easily be produced by processes for block copolymerization olefinically unsaturated compounds

Applicant:

Polymer Corporation Limited,
Sarnia, Ontario (Canada)

Representative: Dipl.-Ing. K.-A. Brose, patent attorney,
Pullach near Munich, Wiener Str. 1/2

Claimed priority:
V. St. v. America 17 February 1956

Michael M. Szwarc, Syracuse, NY (V. St. Α.),
has been named as the inventor

polymerize the polymeric polymerization promoter let, are the acyclic and alicyclic compounds with 4 to about 12 carbon atoms per molecule, in which have at least one aliphatic unsaturated center in conjugation with a second unsaturated center stands. The second unsaturated center can be an aromatic nucleus, a carbonyl group, a nitrile group or be an ethylene double bond. The monomers that are polymerized by the process of the invention, are unsaturated compounds conjugated with one or a combination of the following unsaturated Types:

C = C -

-C = C-C-

-C = C-C ^

-C = C-C = C-

-C = C-C = C-

The unsaturated aliphatic moiety that each monomer must have according to the invention may be Be acetylene bond (see formula 5), preferably acts

009 549/443

3 4

it is an ethylene double bond (—X = C -), metal addition compound react. That is why im as shown in the above structures (1) to (4). generally a concentration ratio of moles of the

Typical representatives of suitable monomers, the polyalkali metal compounds of which are used as starters for moles of unsaturated carbon, are unsaturated hydrogen such as 0.02: 1 to 0.00001 maintained.
Hydrocarbons, such as styrene, lower alkyl derivatives of 5 Bring sodium and naphthalene in a ge-Styrpls, such as methylstyrene, butadiene, 2-methylbutadiene, suitable solvents such as tetrahydrofuran and (isoprene), 2,3-dimethylbutadiene, 1,3-pentadiene and a temperature of about -80 ⁰ C with each other to cyclopentadiene; furthermore unsaturated compounds with reaction, the result is a compound that has the following heteroatoms (oxygen and nitrogen), such as a methyl structure: Na®-naphthalene ³ . If you bring this acrylate, acrylonitrile and methacrylonitrile. The invention io connection z. B. with styrene together under the is not limited to these specific examples, since the reaction conditions described, a negatively charged styrene molecule is also formed by other unsaturated compounds of the above transfer of the negative charge from naphthalene to the mentioned classes such as certain halogen-substituted styrene, the derivatives can be polymerized. then as a polymerization initiator the formation of a styrene

The polymerization process according to the invention is 15 homopolymeric with a negatively charged Kohlenim generally below 6O ⁰ C carried out, whereby also atom activated in the terminal. The alkali metal at temperatures down to - 120 ⁰ C can be worked. addition compound is made at the moment of their contact. It has been found that the best results are consumed at temperature with the styrene. In this way, many temperatures between 0 and 100 ⁰ C can be achieved. The linear molecules formed by polystyrene, all of which have a negative range between -65 and -90 ° C, are particularly charged and therefore do not react with one another preferably. Within this preferred temperature range. After all of the styrene has been used up, the reaction is extremely rapid and yields a product made up of many polystyrene units, each with an almost 100% conversion in a few seconds. a negative charge on the terminal carbon

The monomeric and the polymeric polymerization substance atom, which is only maintained if components are preferably in a suitable 25 the polystyrene remains in an inert medium. That organic solvents brought together. The polystyrene thus produced can polymerize any solvent must under the reaction conditions one of the monomers mentioned, such as butadiene or isoprene remain liquid, must not start with the to be polymerized and methacrylate, to a block copolymer, Monomers still with the polymerization promoter in which the polystyrene polymerization promoter to the react and must have a sufficiently relieving effect. 30 polymer of the added monomers is bound. Liquids particularly preferred as reaction media. It turned out that the and solvents are aliphatic mono- and polyethers made of block polymers that consist of only one type of one from low freezing point, e.g. B. tetrahydrofuran, monomeric hydrocarbon are also built up Dioxane, dimethyl and diethyl glycol ethers and their carry a negative charge and therefore also in the Mixtures. 35 able to act as polymerization promoters for formation

To block copolymers of high molecular weight from block polymers with higher molecular weight It is important that polymerization promoters act. The method according to the invention can then and monomers in an inert medium, i.e. in Ab- for the production of block polymers with any Essence of oxygen, air, water, acidic substances molecular weight and any number of consequences or other hydrogen-transferring compounds, 40 different or repeating monomeric substances Alcohols. This will be used on unity. The concentration of the mono-simple Way achieved by the fact that the reaction meren with respect to the polymeric Polymerisationsin an evacuated reaction vessel or in the presence of a promoter can be changed relatively strongly, of nitrogen and monomers and solvents In general, however, the weight ratio varies are used, which are 45 polymeric! Polymerization promoter to monomers tion zone were cleaned and dried. such as 1: 0.01 to 1: 100, preferably such as 1: 0.1 to 1:10.

The method of preparation for the polymeric polymeric stage process used in the process according to the invention can be regarded as a multi-stage process in which the first cation promoter is known. Thereafter, un-step in the known formation of the active polymer, saturated hydrocarbons such as styrene, butadiene and 50 the second and subsequent stages in the addition of isoprene, with a catalytic amount of the addition of the mentioned monomers to that in the first stage compound an alkali metal and a polycyclic produced reaction product consists in order to polymerize in this way aromatic compound in an inert atmosphere continuously a polymer with a corresponding. The latter reaction will preferentially build up molecular weight. As already mentioned above, at a temperature below 0 ° C and in a well-dissolving 55, the only solvent required in each stage of the polymerization process, such as the above-mentioned aliphatic polymerization initiator that is required in the previous ether, is carried out. It is important that the latter is the polymers produced in the stage. The method must be adapted to the reaction so that the polymeric reaction be conducted so that the polymeric initiator does not tion product is not, oxygen or comes with water with any of these additions in contact, there is the other substance into contact, the negative 60 negative Charge of the polymerization promoter neutrali-charge of the polymer produced can neutralize. can savor. But once the desired product is typical of the polycyclic aromatic compounds in terms of molecular weight or composition, which were formed with alkali metals (lithium, potassium, this desired product and sodium) may be converted into addition compounds during the isolation of this desired product and the polymerization product oxygen, water, alcohol , are naphthalene, phenanthrene and anthracene. 65 etc. have access. The following scheme is in no way intended to limit the invention to a polymerization promoter with a relative, but is only intended to obtain the better high degree of polymerization, e.g. B. serve between understanding. In the following equations, SOOOO and approximately 100,000 monomeric units, let mean (S ») ⁹ and ³ (S _m ) ' ³ the active polystyrene, which is the monomeric, unsaturated hydrocarbon by reaction of the styrene with the addition compound, preferably in a very small amount the alkali 70 the alkali metals and a polycyclic aromatic

5 6

Compound under the conditions described is ent- using active polystyrene as a polymer. S, I and B mean styrene, isoprene and sationspromotor, respectively. An evacuated reaction flask similar to butadiene. borrowed that in example 1 was with 31.6 cm ³ Tetrahydro- ® (S _n ) ^e + (m + k) B ■ -> - ^& {B _m ) (S _n ) (Bj.) * ³ ... etc . (6) ^{charged furan} , which contained 6.1 g of freshly distilled styrene, ς, 0, π, ς, m, o, ₇ > 5. The solution was then prepared by placing the [U _n ) -t-OTß -MS _B ^ ß _m j- [/) reaction flask in a dry ice-acetone cold mixture [S _n ) (B _m ) ^ü + ^ S -> - (S ") (B _m ) (S ^) " ³ (8) _{cooled to} _8o ° C. To the cold styrene solution was added [S _n ) (B _m ) [S _p ) ^e + rB -> - (S _n ) [B _m ) (S ₃ ,) (B _1. ) - ¹ ... etc. (9) thereupon 8.9 cm ^{3 of} tetrahydrofuran, the 0.00037 mol (S _n ) (B _m ) ^e + φΐ - + - [S _n ) [B _m ) (Ip) ^e (10) the addition compound of sodium and naphthalene (S _n ) (B _m ) (l _p ) ^Q + rB ^ (S _n ) (B _m ) (IJ (B _r ) © ... etc. ^{contained 10.} The reaction was completed in a few Se- ^{1 M MW} \ n) \ m) Kv) \ π ^{at -8O 0} C. Then 6.4 g of methyl methacrylate where n, m, k, p and r denote integers. Added. Again, the reaction was completed in a few seconds at -80 ° C. The entire reaction mixture shows that the process was a very one then poured into excess methanol, simple method of generation 12.0 g of a solid white polymer precipitated out of block copolymer, merisates with any recurring consequences. The following examples are in no way intended to be methacrylate. The polymeric product would represent a limitation in methyl, but serve only to dissolve the ethyl ketone, and then excess was in better understanding of the invention. Each of these glacial acetic acid was poured, and the entire polymer game was again separated out in a glass reaction vessel. Product (12 g) separated out. On the other hand, under anhydrous conditions and in air, if homopolymeric polystyrene and homoexclusion by using anhydrous solvents polymeric methyl methacrylate in methyl ethyl ketone and freshly distilled monomers; Solvent and dissolved and then poured into glacial acetic acid, only the homopolymeric reactants were released by smashing glass polystyrene, while the homopolymeric methyl ampoules placed in the glass reaction vessel, methacrylate remained in solution. This shows that this is done in order to avoid the entry of air into the reaction zone. Polymers produced in accordance with Example 2

Block copolymer of styrene and methyl methacrylate

Example 1 _{un (} jn ^ ht _e j _ne mixture of the corresponding homopoly-

A) Was an evacuated glass reaction flask of 30 mer.

about 200 ml capacity was 53 cm ³ Example 3
Tetrahydrofuran charged, the 9.2 g freshly distilled

Contained styrene. The solution was then cooled to -80 ° C by introducing this example. This example shows the preparation of a block mix of the reaction flask in a dry ice-acetone cold bath polymer made of styrene and isoprene. Then 7.5 cm ^{3 of} tetrahydro- 35 of active polyisoprene were used as a polymerization promoter,
furan, which contained 0.00041 mol of the addition compound from an evacuated reaction flask as in Example 1 sodium and naphthalene (Na® — Naphthalin®), was charged with 30 cm ^{3 of} tetrahydrofuran, which 3.6 g were added to the cold solution. The reaction contained freshly distilled isoprene at -80 ° C. The contents of the flask after a few seconds, ie after about 5 seconds, then was cooled to -8O ⁰ C. Thereupon one gave up. The viscosity of the reaction mixture was determined by ^{the method at 40 5 cm 3 of} tetrahydrofuran containing 0.0003 mol of addition room temperature (approximately 22 ° C.) by the falling ball compound of sodium and naphthalene, with a measurement of 1.2 seconds . cold isoprene solution. The color of the solution became almost

B) The tetrahydrofuran solution of the polystyrene immediately turned brownish-red, and the reaction was held in an inert atmosphere, that is to say it was complete for a few seconds without admission. While maintaining the water and moisture, and cooled to -80 ° C, 45 temperature of -80 ° C were added to the reaction mixture, whereupon 7.7 g of freshly distilled styrene and another 5.7 g of styrene, the color of the solution Immediately 56 cm ^{3 of} tetrahydrofuran were added. The reaction turned from brownish red to light red. The reaction was complete in a few seconds at 80 ° C. The viscosity mixture was then poured into excess methanol of the reaction mixture, measured at room temperature, with 8.5 g of a white solid polymer precipitating by the falling ball method as in part A) of this example. This yield corresponds to a 95% yield and was determined to be 14 seconds. The reaction mixture, conversion of the combined amounts of isoprene and styrene, was then poured into excess methanol, the polymeric product being collected on a filter, 16.9 g of polystyrene precipitated. This yield represents and dissolved in toluene. In the 25-fold dilution results in a 100 ° / _o owned sales of monomer to polymer! the toluene solution with isooctane showed neither a cloud, calculated on the combined amounts of styrene from 55, nor the formation of a precipitate. Gave part A) and part B) of this example. The polystyrene, but on the other hand the same isooctane is produced in the process of part A) of this example, in excess of a solution of homopolymeric poly there is therefore enough activity to add the additional styrene styrene and homopolymeric isoprene in toluene, so part B is different ) to polymerize this example. Which is made up of the homopolymeric polystyrene. If the binding of the active polystyrene to the added styrene 60 reaction product of this example were a mixture of, in its function as a polymerization promoter, homopolymeric polystyrene and homopolymeric polystyrene were proven by the fact that the viscosity was that in isoprene, so the homopolymeric polystyrene part B) would have been obtained Solution increased, although isooctane precipitated to upright. This demonstrated that the constant original polystyrene was maintained - that the polymeric product of this example was a block concentration of an additional amount of solvent copolymer.

was admitted. "..,. ■

^{5 6} Example 4

Example 2 This example shows the production of a block poly

This example demonstrates the preparation of a merizate from isoprene and styrene using a

Block copolymer of styrene-methyl methacrylate 70 of active polystyrene as a polymerization promoter.

An evacuated reaction flask as in Example 1 was charged with 4 cm ^{3 of} tetrahydrofuran containing 3 g of styrene. The solution was then cooled to -80 ° C. Then 5 cm ^{3 of} tetrahydrofuran containing 0.0003 mol of the addition compound of sodium and naphthalene were added. The color of the resulting solution immediately turned bright red. After the reaction had ended in a few seconds, 3 g of isoprene were added. The color of the solution turned brownish red almost instantaneously with the addition of the isoprene, and it was found that almost simultaneously with the addition of the isoprene, the viscosity of the solution increased considerably. The solution was then brought to room temperature and poured into excess methanol, 8 g of a solid white polymer precipitating out.

Example 5

This example shows the production of a poly block polymer from butadiene, styrene and isoprene.

An evacuated flask with a capacity of 200 ml was charged with 8 cm ^{3 of} tetrahydrofuran containing approximately 6 g of butadiene. The solution was cooled to -80 ° C., whereupon 5 cm ^{3 of} tetrahydrofuran containing 0.0002 mol of the addition compound of sodium and naphthalene were added. After about 10 seconds, the reaction is completed, and about 5 g of styrene, dissolved in an additional 12 cm ³ of tetrahydrofuran, were added at -8O ⁰ C, the color of the reaction mixture was almost bright red immediately. About 6 g of isoprene in 15 cm ^{3 of} tetrahydrofuran were then added at -80 ° C., and the color of the solution immediately turned brownish-red. In each reaction stage the viscosity of the reaction medium increases remarkably. The reaction is continued with the addition of butadiene, styrene and isoprene in reverse order. A polymer with a correspondingly increased molecular weight was produced after each addition of a monomer. Once a block polymer of the desired composition and molecular weight has been achieved, the reaction product is precipitated by pouring it into methanol or another suitable agent.

Generally speaking, the block copolymers of this invention compared improved properties with the homopolymers derived from the monomers that make up the block polymer composed, and they are preferably used as a substitute for these homopolymers or as additives to these to improve properties such. B. the strength. In addition, the block copolymers are This invention valuable binders for bonding layers of the individual homopolymers. So z. B. the block copolymer of styrene and isoprene, prepared according to the process in Examples 3 and 4, to be used, a layer of homopolymer polystyrene on a layer of homopolymer polyisoprene to glue. The block polymers can also be used to emulsify various organic liquids use.

The polymers of the invention are particularly suitable ^ß o as a durable, flexible coatings for manufactured articles and metal surfaces and can be applied to these in solution by the conventional coating methods. The polymers of this invention show their greatest solubility at room temperature in aromatics such as toluene and xylene and in aromatic and aliphatic ketones such as methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone and acetone.

The polymers produced according to the invention can be used in various end products, such as films and sheets

of various thicknesses, at temperatures between room temperature and 232 ° C by extrusion and deep-drawing processes. They can also be compression molded, to be precise at pressures between approximately 70 to 700 kg / cm ² in the temperature range given above.

Claims (16)

Patent claims: A process for the production of mixed block polymers or polyblock polymers from olefinically unsaturated compounds, characterized in that an unsaturated polymerisable compound is polymerised in the presence of a polymer having at least one negatively charged carbon end group which has been produced in a process stage preceding the polyblock polymerisation. 2. The method according to claim 1, characterized in that the polymer with at least one negatively charged carbon end group such is used, which by polymerization of a polyunsaturated hydrocarbon in the presence of an alkali metal and a polycyclic aromatic compound in a liquid reaction medium with exclusion of water and oxygen has been made. 3. The method according to claim 1 and 2, characterized in that below 60 ° C is polymerized. 4. The method according to claim 1, characterized in that the unsaturated polymerizable compound an aliphatic olefinic hydrocarbon having 4 to 12 carbon atoms is used. 5. The method according to claim 1, characterized in that the unsaturated polymerizable compound Butadiene is used. 6. The method according to claim 1, characterized in that that 2-methylbutadiene is used as the unsaturated polymerizable compound. 7. The method according to claim 1, characterized in that the unsaturated polymerizable compound 2,3-dimethylbutadiene is used. 8. The method according to claim 1, characterized in that the unsaturated polymerizable compound an aromatically substituted ethylene is used. 9. The method according to claim 8, characterized in that the unsaturated polymerizable compound Styrene is used. 10. The method according to claim 1, characterized in that the unsaturated polymerizable compound one is used which has a conjugated system of at least one ethylene double bond and a carbonyl group. 11. The method according to claim 10, characterized in that the unsaturated polymerizable compound Methyl methacrylate is used. 12. The method according to claim 1 and 2, characterized in that polymerized below 0 ° C will. 13. The method according to claim 12, characterized in that the unsaturated polymerizable compound Styrene and, as a polymer with a negatively charged carbon end group, homopolyisoprene is used. 14. The method according to claim 12, characterized in that the unsaturated polymerizable compound Isoprene and homopolystyrene is used as a polymer with a negatively charged carbon end group will. 9 10 15. The method according to claim 14, characterized in 17. The method according to claim 14, characterized in that as a polymer with a negative, that as unsaturated polymerizable cargo Carbon end group homopolybutadiene bond methyl methacrylate is used is used. 16. The method according to claim 14, characterized in 5 characterized in that the unsaturated polymerizable encryption I ⁿ contemplated publications: bond butadiene is used. U.S. Patent Nos. 2,146,447, 2,181,771. ® 009 549/443 6.60