Process for preparing a hyperbranched polymer, hyperbranched polymer, use thereof, mixture and composition based thereon

UKRAINE

(19) and A (11) 85166 (13) C2

(51) IPC (2006)

C08C 63 / 00C08C 81 / 00C08C 85 / 00C08B 87 / 00C08B 101/00

MINISTRY OF EDUCATION SCIENCE OF UKRAINE

STATE DEPARTMENT OF INTELLECTUAL PROPERTY

DESCRIPTION

TO THE INVENTORY PATENT

(54) WAY OF RECEIVING A PRESERVED POLYMER, A NON-DEPENDENT POLYMER, IONIZATION, COMPOSITION AND COMPOSITION ON ITS BASIS

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(21) 20041210877

(22) May 30, 2003

(24) Jan 12, 2009

(86) PCT / ЕР03 / 05785, 30.05.2003

(31) 02077106.9

(32) May 29, 2002

(33) EP

(46) Jan 12, 2009, BUL No. 1,2009

(72) CEDERGARD NILS DAN ANDERS, STOLTERIC MICHAEL

(73) TATE END LAYLING PABLIC LIMITED COMPANY

(56) from 2002/002242 A1.03.01.2002

of 5 434 241 and July 18, 1995

EP 0 761 712 A, 12.03.1997

out of 5,470,944 A on November 28, 1995

(57) 1. A method of producing a super-branched polymer having an average molecular weight of at least 30000 and having more than one central branch point, each of which is joined by three or more beams, i.e. polymeric chains, said rays may include additional spin points, through which additional branching and / or stitching is performed,

wherein said method comprises combining a first formuler having at least three functional end groups and a second prepolymer having at least two functional end groups, wherein said functional end groups of the first prepolymer are capable of reacting with a dehydration condensation with said functional end groups of the second formylformer , as a result of the reaction of dehydration condensation between the end groups in prepolymers in such a way that the functional end groups of the first prepolymer in the reaction of dehydration condensation with the functional end groups of the second polymer during the ongoing polymerization.

2. The method of claim 1, wherein the cross-linked polymer is capable of biodegradation and / or hydrolysis.

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3. The method of claims. 1 or 2, where the cross-linked polymer is a poly (hydroxycarboxylic) acid.

4. The method of claim 3, wherein the branched polymer is an acid (lactic) acid.

5. The method according to any one of the preceding claims, the dender-branched polymer has an average mass molecular weight of at least 500,000.

6. The method according to any one of the preceding claims, the dender-branched polymer has an average mass molecular weight not exceeding 1000000.

7. The method according to any of the preceding claims, the deacidification condensation droplet is carried out in a melt, or at least partially in a solid state.

8. The method according to any one of the preceding claims, the denatured polymer is obtained without the use of an organic solvent.

9. The method according to any one of the preceding claims, the first and / or second prepolymer being a polypeptide (hydroxycarboxylic acid) having an average mass molecular weight of at least 500.

10. The method according to any one of the preceding claims, the first and / or second prepolymer is a poly (hydroxycarboxylic acid) having an average mass molecular weight not exceeding 500000.

11. The method according to any one of the preceding claims, wherein the functional end groups of the first and / or second polymer are independently selected from hydroxy or carboxyl groups.

12. The method according to any one of the preceding claims, the combination of the dereaction is carried out between more than two form polymers.

13. The method according to any one of the preceding claims, wherein at least one of the prepolymers is obtained as a result of the polycondensation of one or more amino acids, or as a result of polycondensation of the hydroxy acids, wherein said hydroxy acids are most preferably selected from lactic acid and glycolic acid.

iA (11) 85166 (13) C2

σ>

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14. The method according to any one of the preceding claims, wherein at least one of the prepolymers is prepared by a polymerization mechanism with the disclosure of a cycle of:

- one or more cyclic esters, preferably I_, I_-lactide, û, û-lactide, racemic an anti-oxidant, meso-lactide and / or glycolid, is -caprolactone;

- cyclic carbonates, preferably trimethylene-zinc and / or

- cyclic amides, mainly caprolactam.

15. The method according to any of the preceding claims, wherein at least one of the prepolymers is obtained by reacting a reaction between its monomer and / or oligomers having the terminal hydroxy, carboxy, cyano, amido, epoxy and / or anhydride Late Groups.

16. The method of any one of the preceding claims, which optionally includes a cross-linking step and / or a modification phase in the end groups.

17. A super-branched polymer, which is a polymer having two or more central branch points, each of which has three or more beams, i.e., polymeric chains, wherein said beams may include additional points of the branching through which additional straightening and / or stitching is performed, and which has a mean ovo molecular mass of at least 30,000,

wherein said branched polymer is obtained by means of any of the preceding claims.

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18. A super-branched polymer according to claim 17, which is capable of biodegrading and / or hydrolysis of complex ether groups.

19. A super-branched polymer according to claim 17 or 18, which is a copolymer containing block, statically distributed, alternating or grafted structures.

20. A mixture of branched polymer according to any one of the preceding claims. 17-19 and impurities, selected from fillers, strengthening impurities, plasticizers, stabilizers, coloring pigments, mastic for forms, antipyrens and combinations of two or more of these impurities.

21. Polymeric composition containing two or more branched polymers in any of the steps. 17-19.

22. The polymer composition of claim 21, further comprising an impurity according to claim 20.

23. Application over branched polymer forgotten from pp. 17-19 in films, molded tubes, fibers, particles, gels, dispersions or solutions for packaging materials, coatings, adhesives, chewing gums, electronic components, or in medical applications.

24. Application over branched polymer forgotten from pp. 17-19 for modification of shock-absorbing materials, increase in deformation heat resistance, plasticization, reinforcement, increase in compatibility, or manipulation of the stability of one or more polymer compositions (compositions).

The invention relates to a method for obtaining a branched polymer, in particular, an overly-feminine biodegradable and / or hydrolyzed poly mers, characterized by an average mass molecular weight of at least 30,000, and the methods for producing them.

The term "super-branched" is known among facsimiles in the field; in this document, the term -this term envisages the inclusion of polymers having one or more central atoms as a branch of the branch, to which two or more polymer chains are formed, formed by respective repeating monomer units, i.e., rays. These rays include additional points of the branching, ensuring the availability of additional branching and / or sewing in the course of continuous polymerization.

It is widely known that the production of polymers with high molecular weight, in particular, by-li (hydroxycarboxylic acid), such as, for example, poly (lactic acid), is not possible due to the direct reaction of dehydration condensation. As a result of equilibrium between the reaction participants in the reaction mixture Polymer is produced with a low molecular weight, which often dislodges not meeting the requirements of the standard of mechanical properties in many applications. The commercial interest in solving this problem is growing in the course of awareness of environmental problems, and there were described several approaches to obtaining a polymer,

such as poly (hydroxycarboxylic acid), with a high molecular weight.

EP-A-0572675 describes a method for obtaining decomposable polymers based on (hydroxycarboxylic acids) with high molecular weight by the mechanism of the reaction of dehydration condensation. Work ЕР-А-07106^L.4 describes a method for obtaining polymers based on a (hydroxy) acid according to the mechanism of the reaction of dehydrogenation condensation and subsequent introduction of a (hydroxy acid) by reaction (s) into a molecule of an aspirate, which is selected from the group consisting of polyisothiazole compounds, anhydrides of many basic acids, cyclic complexes of imines, cyclic simple isomers, aromatic hydroxycarboxylic acids, polyamino compounds, multi-atomic alcohols, epoxy compounds, polyfunctional aziridine derivatives, lactams, lactones or diethylene glycolypes chloroformates However, the described methods require the use of at least one organic solvent, thus giving a negative impact in terms of the impact on the environment. In addition, at another stage of the reaction of the solvent, it is necessary to dry the drafts obtained during the reaction of dehydration condensation, for example, using drying agents in order to achieve the desired result in the form of effective removal from the reaction medium. Alternatively, in the course of the reaction, you can add a fresh, succinic organic solvent that is extremely palatable.

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both from the point of view of protecting the surrounding area and from an economic point of view. Another drawback of the use of organic solvents in the reaction of dehydration condensation is that the resulting polymer should be extracted from the solvent, usually using a non-solvent polymer, and dried. These stages lead to unnecessary labor costs, take away a lot of time and usually reduce the output for used inputs, further reducing the benefits of the way from the point of view of industrial sales and protection of the environment.

Source IZ-A-5434241 describes a method for producing a poly (lactic acid) comprising poly-condensation of lactic acid in the presence of a polyhydroxyl compound having at least four hydroxyl groups leading to the production of a polymer, which is defined as a star-shaped ny The resulting poly (lactic acid) is characterized by a higher molecular weight in comparison with the polymer obtained by the methods of dehydration, which are commonly used, but these known methods are characterized by the presence of a clearly defined limit relative to the molecular weight obtained. If the polyhydroxyl compound is used in large quantities, then the polymer will have the terminal hydroxyl groups, and the dehydrogenation condensation reaction can not continue, which in this way results in low molecular weight polymerization. On the other hand,

The work of EP-A-0792901 describes copolymers on the basis of linear aliphatic complex polyesters with a molecular weight, sufficiently high for practical use, resulting from the dehydration condensation of aliphatic dicarboxylic acid and aliphatic diol in the presence of an aliphatic monohydroxycarboxylic acid.

The work of IZ-A-5470944 describes the production of co-expandable polymers on the basis of (lactic acid) with high molecular weight due to the sewing of telecellar polymers based on poly (lactic acid) with a low molecular weight, using diisocyanates, bis-epoxides , bis-oxazolines or complex bis-ortho esters.

EP-A-0829503 describes a dispersed polymer and a method for producing a dispersed polymer with outputs less than 90%, wherein the polymer comprises hydroxycarboxylic acid (A), a polyfunctional central compound, which is carboxylic acid and / or an anhydride thereof having three or more functional groups, or a hydroxyl-vial of a compound having three or more hydroxyl groups, (B) and a polyfunctional compound having more than one functional group, (C), and is obtained by means of a dehydration condensation reaction. In the preferred embodiments, organic ro-factor is used, at least for some

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the stages of obtaining, which, as previously described in this document, has several negative implications both from the point of view of the protection of the surrounding environment and from an economic point of view. In addition, according to EP-A-0829503, all compounds, i.e., A, B, and C, are preferably added at one and the same time, which in this way results in a reaction that is not controlled, although it is possible to obtain a high molecular weight polymer ma-soyu Other variants of realization are also described, although for them there is no possibility of any exact control of reaction chemistry.

However, the inventors of the present invention unexpectedly found that super-branched polymers with a high molecular weight can be improved by the method of obtaining a reaction of dehydration condensation at high yields, with an improved degree of control of the reaction chemistry for a polymer obtained by using certain central functional compounds. Polymers characterized by a high molecular weight are defined in this document as a measure of the average mass molecular weight, which is at least 3,000,000 mol / mol, more preferably at least 5,000,000 mol / mol. The upper limit of the median mass is not limited to the mass of the molecule, but it is preferably at most 1,000,000. The methods according to the present invention include the combination of a first prepolymer having at least three functional end groups, with a second prepolymer, which has at least two functional end groups, due to the reaction of dehydration condensation between the final groups of the polymers. Improvements are, for example, in the following:

1. The amount of rays and / or the molecular mass of functionalized prepolymers can be precisely regulated by selecting the central initiating compound and / or its amount, thereby, desirably affecting the properties of the super-branched polymer resulting, in particular, from the poly (hydroxycarboxylic acid).

2. Extremely branched copolymers, for example, block or statistical copolymers, can be recovered and controlled in a precise manner, which can be used, for example, to provide a poly-hydrophobic and hydrophilic moiety.

3. The number of functional end groups, whichnot necessarily be used for conductingfurther chemical reactions, in the super-branchedpolymer can easily be brought to the desired level.

4. A super-branched polymer with a high molecular weight can be obtained with high outputs without the use of organic solvents or crosslinking compounds, which is beneficial from the point of view of environmental protection, as well as economically speaking.

It has been found that according to the method of the present invention it is possible to obtain biodegradable and / or hydrolyzed polymers, in particular, by-line (hydroxycarboxylic acid), such as poly (lactic) acid. From the point of view of environmental protection, bio-dispersing and / orhydrolyzed polymers are advantageous, since such polymers do not contribute to contamination on-

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environment, and they can also be used in biological systems, for example, in medical devices.

The reaction of dehydration condensation is predominantly carried out in the melt at a temperature sufficiently high to remove from the reaction medium received water. However, the temperature of the reaction is important to withstand less than 250 ° C, and more importantly less than 230 ° C, in order to prevent dehydration condensation from passing thermal decomposition and / or other adverse reactions. To remove water more efficiently, usually use reduced pressure and / or intermediate gas in the form of an inert gas. However, the present invention does not impose any special restrictions on how the method of dehydration condensation will be implemented.

In the general case, in the reaction of dehydration condensation, an appropriate quantity of a catalyst known in the state of the art is used, and in this embodiment neither the catalyst or the combination of catalysts to use, nor when the catalyst is added, no special restrictions are imposed. Typical catalysts include inorganic and organic metal compounds such as, for example, δη, Zn, Re, AI, and the like, acids such as, for example, trifluoromethanesulfonic acid, p-toluenesulfonic acid and the like. The amount of catalyst in any wayany restrictions are not imposed until the katalizator will satisfy the requirement of its original purpose, which is to increase the speed of the reaction. Usually added from 0.001 to 1% (by weight), and more often from 0.01 to 1% (wt.

The method of the invention makes it possible to obtain polymers of high molecular weight without the need to resort to the use of an organic solvent due to the binding properties of the reaction mixture. However, if desired, a solution such as alcohols, esters, ethers, carbon-hydrogen or halogenated solvents can be used. Preferably said first and / or said second prepolymer is a poly (hydroxycarboxylic acid) and characterized by an average molecular weight molecular weight of at least 500, and preferably at most> 50000, most preferably at most 500000.

Functional end groups in said first and / or second second prepolymer are independently selected from the functional groups suitable for participating in the condensation reaction, for example, form polymers with terminal hydroxy, carboxylic, cyano, amido, epoxy and / or anhydride groups.

The functional end groups of said first and / or said second prepolymers are preferably selected independently from hydroxy or carboxyl groups.

Thus, in accordance with a preferred embodiment of the invention, there is provided a biodegradable and / or hydrolyzable polymer comprising a poly (hydroxycarboxylic acid) polymer (PheRuoI) I, having three or more phy

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end-groups, for example, groups of carboxylic acids or hydroxyl groups, prepolymer-based poly (hydroxycarboxylic acid) (Pge-RoIT2) having two or more functional end groups, for example, carboxylic acid groups or hydroxyl groups, and a dehydration reaction of the condensation of said prepolymers ( Thus, it results in the production of a highly branched poly (hydroxycarboxylic acid) with a high molecular weight according to the present invention.

According to the present invention, the use of any carboxylic acid known at the state-of-the-art technique and having three or more reactive groups of carboxylic acid, including carboxylic acids such as, for example, 1, 3,5-trimethyl-1,3,5-cyclohexanedicarboxylic acid, 1,2,3-

propanetricarboxylic acid, 1,2,3,4-

cyclopentane tetracarboxylic acid, 1,2,4,5-benzene tetracarboxylic acid, 1,2,3,4-butantetracarboxylic acid and 1,2,3,4,5, bicyclohexanexacarboxylic acid.

In accordance with the present invention, for the preparation of a star-shaped prepolymer with terminal hydroxyl groups (PheRoIut1), any alcohol known at the current level of technology, having three or more reactive hydroxyl groups, including such alcohols as, for example, trimethylolethane , trimethylolpropane, butantriol, floroglucin, erythritol, pentaerythrito or dipentaerythrite. Optionally, it is possible to use alcoholic derivatives of sugars naturally occurring in the form of mono-, di- or tris-chardids of hexose or pentose or maltitol, sorbitol, mannitol, xylitol, inositol, and the like.

According to the present invention, in order to obtain a linear or star-shaped prepolymer with the terminal groups of carboxylic acid (PheRoIut2), it is desirable to use any carboxylic acid, at the present state of the art, and having two or more reactive groups of carboxylic acid, including carboxylic acids such as oxalic acid, malonic acid, amber acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, pumileic acid, cork acid, azelaic acid, 1,3,5-trimethyl-1, 3,5-cyclohexantrine 1,2,3-propanetricarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,3,4-butantetracarboxylic acid and 1,2,3 , 4,5,6-cyclohexanexacarboxylic acid.

According to the present invention, for the preparation of a linear or star-shaped prepolymer with terminal hydroxyl groups (PheRoIut2), it is possible to use any alcohol known in the state of the art technology and having two or more reactive hydroxyl groups, including such alcohols as, for example, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, trimethylolethane, trimetholinopropane, butanethriol, floroglucin, erythrite, pentaerythritol or dipentaerythritis. Optional possible use of alcohol derivatives of sugars,

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occurring in nature, in the form of mono-, di- or trisaccharides of hexose or pentose, or of maltitol, sorbitol, mannitol, xylitol, inositol, and the like.

In accordance with the foregoing, the central functional compounds can be reacted with hydroxycarboxylic acid to form a hydrochloric acid-based hydrochloric acid prepolymer modified by finite groups. Eventually, this hydroxycarboxylic acid prepolymer, modified by the finite grout, can be sewn from another prepolymer on the base of hydroxycarboxylic acid, modified in the final groups, and obtain a super branched polymer with a high molecular weight. As described above, this method can be realized and without the use of crosslinkers or solvents.

Alcohols and carboxylic acids having two or more functional hydroxyl groups or groups of carboxylic acids in the present invention are called initiating compounds, since the data of the compound determine the final molecular weight, as well as the final groups of the prepolymers PheRoIuTi and PheRoYuT2, even though the initiation of the reaction necessarily occurs with the participation of said compound, which is an alcohol and / or carboxylic acid. An initiating compound can be used individually or in the form of a mixture with one or more other initiating compounds bows with the samefunctional groups. If the initiating compound exists in different stereoforms, such as, for example, inositol that has nine stereoisomers, then one individual isomer can be used individually or can be used by mixing isomers.

It should be understood that the functional compounds used as initiating compounds of the present invention should not be a single compound of a small number of compounds having hydroxyl groups or carboxylic acid groups mentioned in this document as examples, but they may also include other compounds having hydroxyl groups or groups of a carboxylic acid or compounds having other initiating groups such as, for example, amido, amino, epoxy, cyano, nitro, sulfano, mercapto, siloxy or phosphorogypsum.

The hydroxycarboxylic acid which can be used in the present invention is a carbonic acid having a hydroxyl group in the molecule, including, for example, lactic acid, glycolic acid, 4-hydroxy-acetic anhydrous and 6-hydroxy-propionic acid. Hydroxycarboxylic acid can be used individually or in combination with other hydroxycarboxylic acid (acid). If the hydroxycarboxylic acid exists in different stereophages, such as, for example, malic acid, then one individual isomer or a mixture of isomers may be used individually.

In an attractive embodiment of the method of the present invention, the coupling reaction is carried out between more than two prepolymers, for example, as described in Example 7.

At least one of the prepolymers is preferably obtained by polycondensation of one or several amino acids, or of polycondensation of hydroxy acids, wherein said hydroxy acids are preferable

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but are selected from lactic acid, hydroxypropionic acid, hydroxy-fatty acid and glycolic acid, for example as described in Example 8.

In yet another preferred embodiment, at least one of the prepolymers is provided with a cyclic opening polymerization induction, for example, from a ring-like structure of dimers of hydroxycarboxylic acids such as, for example, lacquer, glycolide, or from other ring-shaped complex esters, such as lactones, such as β-propylactone, δ-valerolactone, ε-caprolactone, and co-salactones, such as those described in ro-bot IZ-D-3072680, preferably cyclic complex esters selected from I_, I_-lactide, YSCH-lactide, racemic lactide, meso-lactide and / or glycolid, ε-caprolactone; or from another type of ring-like esters, such as cyclic carbonates, preferably trimethylene carbonate, or with cyclic amides, preferably caprolactam.

Ring-shaped ester, ethers on an ester of a complex ester or amide can be used individually or in combination with other ring-like esters. If ring-shapedcomplete ether exists in various stereoforms, for example, lactide, then it is possible to use an in isolation one isomer or a mixture of isomers.

The invention does not impose any particularlimits on how it is possible to polymerize with the disclosure of the cycle, and possible use of any method known in the state of the art, such as, for example, polymerization in the extruder, provided that only the necessary functional end groups, essential for carrying out the reaction of dehydration condensation of the prepolymeter to obtain, thus, a super-branched polymer. Polymerization with the disclosure of the cycle is carried out promptly in the melt, ensuring the motility of the appropriate mixing during the reaction, in the presence of an appropriate amount of a catalyst known in the art. Characteristic analyzers include inorganic and organiccompounds of metals, such as, for exampleHell, Zn, Zn, Re, AI and the like, acids such as, for example, trifluoromethanesulfonic acid, p-

toluene sulfonic acid, and the like. The number of catalyst in no special way is unlimited, unless the catalyst or a mixture of tallizers will fulfill its initial purpose, which is to increase the speed reaction. Typically, from 0.001 to 1% (by weight), and more often from 0.01 to 1% (by mass) of a catalyst, based on the number of reagents, is used.

In addition, the invention relates to overgrown feminine polymers obtained by the method described above; said polymer preferably hasbiocarbonyl and / or hydrolyzed complexorganic groups. In a particular embodiment, the ultrasonic polymer in accordance with the invention is a copolymer consisting of block, statistically distributed or grafted alternating current circuits, while each of them ensures its advantages, such as the nature of decomposition, compatibility, impact resistance and so on, that is, a specific structure.

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The properties of the polymers that are synthesized by the method of the present invention may additionally be brought into line with the properties of the foregoing use, followed by the admixture of a mixture of one or more polymers of the invention and one or more house-shocks selected, for example, from fillers, reinforcing ( reinforcing) impurities, plastifiers, stabilizers or other impurities similar to coloring pigments, lubricants for forms, fire retardants and the like, and combinations of two or more matte materials erials

Excipients used may be of an inorganic or organic nature, such as magnesium carbonate and calcium, kaolin, tricalcium phosphate, talc, wood fiber, apple fiber, zein, gluten and casein in any available pharma or form. In the present invention, preferred organic natural fillers are used.

The reinforcing impurities used may have an inorganic nature, such as metallic or glass mustache, fibers, hollow fibers, non-woven or woven materials. Examples of reinforcing impurities of organic origin may be fibers, non-woven or woven materials of natural fibers, similar to fibers of flax, hemp, jute, frames, cotton or any type of artificial fibers or hollow fibers.

Suitable plasticizers, such as complex ethers of mono- and polycarboxylic acids, polymeric acid esters, polyalkyl esters, glycerol-ester ethers and glycolic ethers, can be used, for example, individually or in the form of mixtures with other plasticizers.

Examples of acceptable stabilizers are anti-oxidants and deactivators of catalysts. Examples of impurities are nucleation agents, coloring pigments, lubricants for forms, antistatic impurities, impurities that improve printing qualities, antipyreens.

In the field (hydroxycarboxylic acid) or under chaspololymerization, or later, you can also addadditional components, such as medical-purpose components, conditioning additives, anti-starches and acceptors.

The invention further provides a polymeric mixture comprising two or more branched-chain poly-mers of the invention, optionally in combination with the above-mentioned admixture.

Due to the improved control of the chemical composition and microstructure of the cross-branched polymer of the present invention, the physical properties of the polymer can be accurately varied within the wide range. As a result, it is easy to get materials that, for example, will be strong and hard-me, soft and flexible, sticky and so on. For such universal ultrafilm polymers, the specialist in the field can provide a wide range of applications and variants of use. However, no special restrictions on the addendum is not imposed, unless the properties of the mentioned polymer will adequately respond to the properties required in the application. Such an application, for example, can exist in the packagingindustry where the predominant hard material.In the result, for example, the synthesis of copolymer-

Rho, which combines polymers with high values ​​of Td and low Td with a block or statistical distribution of monomer units, hyper-branched polymer can also be obtained in such a way that it demonstrates the corresponding properties in applications, for example, desirable adhesive properties, m 'quality and / or elasticity. In addition, materials such as hydrophilic blocks and hydrophobic blocks suitable for use, such as gel or dispersion, can be obtained as a result of block or multiblock copolymerization. Due to the large number of functional endpoints, the superlarge-tangled poly (hydroxycarboxylic acid) can also be used with profit in medical applications, such as, for example, biomaterials with bio-logically active molecules that are chemically or physically linked to the polymer. Extremely branched (hydroxycarboxylic acid), for example, for use in medical supplements, can, in addition, be obtained by using an initiating compound that has a positive effect on the specific biological medium in which the polymer is used. Another advantageous addition may also be, for example, the use in mixtures with other polymeric materials.

The highly branched polymer corresponding to the wine-making process, the above-described mixture or composition can be advantageously used in films, molded beads, fibers, particles, gels, dispersions or routines for packaging materials, coatings, adhesives, chewing gums, components of electronic devices or, as indicated above, in medicalapplications. The super-branched polymer corresponding to the invention, the above-described mixture or composition may also be advantageously used to modify impact strength, increase heat resistance, plasticization, reinforcement, increase compatibility, or manipulate the stability of one or more polymer compositions (compositions).

In the following, the invention is further explained by means of the following non-limiting examples and figures, wherein:

FIG. 1 shows a schematic representation of examples of prepolymers used in the present invention, i.e., PheRoIuTi and Pge-RoITu2. For greater clarity in the star-shapedpolymer, only two repeatinglines in each beam are depicted.

FIG. 2 is a schematic representation of a branched poly (hydroxycarboxylic acid) produced by dehydration condensation of said prepolymers of the present invention. For greater clarity in the super-branched poly (hydroxycarboxylic acid), only shown several repeating units. The central functional compounds (C and C in Figs. 1 and 2) are a compound containing the reactive groups indicated in various embodiments of the invention. R & apos; & apos; in Figs. 1 and 2 are aliphatic groups of the linker of the repeating polymer in such a way, forming a repeating link by line (hydroxycarboxylic acid) from the corresponding mono-dimensional link of the present invention. P and P 'may or may not be one and the same aliphatic-

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the group η and t in FIG. 1 represent a number of repetitive lobes in the prepolymer and may or may not be one and the same integer of the 13th number.

3 shows the dependence of the average mass molecular mass on the time of polymerization of the reaction between the prepolymer from experiment No. 5 and the prepolymer from experiment No. 10.

4 shows the dependence of the average mass molecular mass on the time of polymerization of the reaction between the prepolymer from Example 1 of Experiment No. 9 and various prepolymers from Example 1: Experiment No. 1 (a), Experiment No. 2 (□) and Experiment No. 4 (A).

5 shows the dependence of the average mass molecular weight of the block copolymer on the time of polymerization in the reaction between the prepolymer from example 1 of experiment No. 7 and the prepolymer from example 2 of experiment No. 13.

Examples

Reactions of dehydration condensation are carried out using a module of a laboratory rotary generator, equipped with a thermostated oil bath, a vacuum device and an inlet vent for inert gas. Reactions to the mechanism for liming with the disclosure of the cycle were carried out in the atmosphere of the atmosphere in the mixer No. 50 Ε with electrical heating. Reactions on the mechanism of the polymerization with the disclosure of the cycle were additionally (albeit necessarily) carried out in round glass glassware in an inert atmosphere using a laboratory mixer mixer and a thermostatically controlled oil bath for heating to the desired polymerization temperature. With all chemical manipulations, purifications and syntheses, standard laboratory methods are used.

The amount of added monomer (hydroxycarboxylic acid or ring-shaped ester of hydroxycarboxylic acid) and the initiating compound having a carboxylic acid group or

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hydroxyl groups were determined in accordance with standard methods of polymerization on the basis of molecular calculations, aiming to obtain a certain molecular mass in synthesized prepolymers.

For the measurement of molecular mass, a device for GPC (gel permeation chromatography) was used. The composition of the copolymer was determined by the method of NMR analysis (nuclear magnetic resonance). Differential scanning calorimetry (DSC) was used to measure the thermophysical properties. The analyzes were carried out in accordance with standard methods known in the modern level of technology.

Example 1. Obtaining of prepolymers by the mechanism of reaction of dehydration condensation

Different hydroxycarboxylic acids (acid) (see Table 1) containing free water initiating a carboxylic acid or hydroxyl groups and 0.1% (wt) of 2-ethylhexanoate of tin (II) , loaded in a round bottom flask and heated by stirring in the module of the rotary evaporator under reduced pressure to remove free water from the reaction mixture and the oligomerization of hydroxycarbonytic acid. After removing the calculated amount of free water and proceeding with oligomerisation, the molten rotor evaporator was purified with acetone, and even gradually reduced the pressure to the minimum milligram shown in Table 1 and continued the reaction of dehydration condensation at 180 ° C. for a period of time indicated in Table 1. After the reaction was terminated, the polymerization products were cooled and stored in ambient conditions until analysis and use for subsequent sewing reactions. The conditions in the reaction of dehydration condensation and the characteristics of form polymers are also shown in Table 1.

Conditions of reactions, molecular weight and its distribution for prepolymers obtained by the mechanism of the reaction of dehydration condensation

Table 1

<tr><td><p>No. Experiment</p></td><td><p>Hydroxy-carbonic acid</p><p>acid</p></td><td><p>Initiating compound</p></td><td><p>Limit time (h)</p></td><td><p>Minimum p (mbar)</p></td><td><p>M ™</p><p>(g / mol)</p></td><td><p>Mk / Mp</p></td></tr><tr><td><p>1</p></td><td><p>I-lactic acid</p></td><td><p>1,4-butanediol</p></td><td><p>8</p></td><td><p>12</p></td><td><p>2500</p></td><td><p>1.84</p></td></tr><tr><td><p>2</p></td><td><p>I-lactic acid</p></td><td><p>Glycerol</p></td><td><p>8</p></td><td><p>25</p></td><td><p>3700</p></td><td><p>1.66</p></td></tr><tr><td><p>3</p></td><td><p>I-lactic acid</p></td><td><p>Glycerol</p></td><td><p>18</p></td><td><p>14</p></td><td><p>4600</p></td><td><p>1.92</p></td></tr><tr><td><p>4</p></td><td><p>I-lactic acid</p></td><td><p>Pentaerythritol</p></td><td><p>8</p></td><td><p>14</p></td><td><p>2400</p></td><td><p>2.07</p></td></tr><tr><td><p>5^and</p></td><td><p>I-lactic acid</p></td><td><p>Inosite</p></td><td><p>9</p></td><td><p>20</p></td><td><p>4700</p></td><td><p>2.02</p></td></tr><tr><td><p>6^and</p></td><td><p>I-milk - acid</p></td><td><p>Inosite</p></td><td><p>10</p></td><td><p>18</p></td><td><p>4500</p></td><td><p>1.86</p></td></tr><tr><td><p>7</p></td><td><p>I-lactic acid</p></td><td><p>Amber Acid</p></td><td><p>14</p></td><td><p>25</p></td><td><p>3800</p></td><td><p>2,18</p></td></tr><tr><td><p>8</p></td><td><p>I-lactic acid</p></td><td><p>Decanidioic acid</p></td><td><p>13</p></td><td><p>17</p></td><td><p>3600</p></td><td><p>4.29</p></td></tr><tr><td><p>9</p></td><td><p>I_-lactic acid</p></td><td><p>1,2,3,4,5,6-cyclohexane-hexacarboxylic acid</p></td><td><p>8</p></td><td><p>20</p></td><td><p>2000</p></td><td><p>2.71</p></td></tr><tr><td><p>10</p></td><td><p>I_-lactic acid</p></td><td><p>1,2,3,4,5,6-cyclohexane-hexacarboxylic acid</p></td><td><p>21</p></td><td><p>Atmosphere</p></td><td><p>1000</p></td><td><p>2.14</p></td></tr><tr><td><p></p></td><td><p>Glycolic acid</p></td><td><p>Glycerol</p></td><td><p>5</p></td><td><p>30</p></td><td><p>-</p></td><td><p>-</p></td></tr><tr><td><p>12^and</p></td><td><p>Glycolic acid / І_-</p><p>lactic acid</p></td><td><p></p></td><td><p>10</p></td><td><p>30</p></td><td><p>1000</p></td><td><p>2.36</p></td></tr>

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In the reaction, 0.2% (w / w) of 2-ethylhexanoate of tin (II) was used.

^BIn the reaction to remove the formed water, an auxiliary gas-argon was used.

^withThe prepolymer is not soluble in a solvent used to determine the molecular weight. In the analysis

By the DSC method, the values ​​of Tt were obtained, which is approximately equal to 180 ° C.

Statistical copolymer 54/46 (mol / mol).

Example 2. Preparation of prepolymers by the mechanism of polymerisation with the disclosure of the cycle

The mo-number, the initiating compound and 0.05% (w / w) of 2-ethylhexanoate of tin (II) were loaded into the pre-heated reaction capacity (170 ° C.) in an inert atmosphere. After the end of

The legs of a given polymerization time polymerization stopped, the polymer was cooled and stored in conditions of the environment to conduct analyzes and use in subsequent reactions of stitching. Characteristics of prepolymers demonstrated in Table 2.

Molecular weight and its distribution for prepolymers obtained by the mechanism of polymerization with the disclosure of the cycle

Table 2

<tr><td><p>Experiment number</p></td><td><p>Monomer</p></td><td><p>Initiating compound</p></td><td><p>M »(g / mol)</p></td><td><p>M »/ Mn</p></td></tr><tr><td><p>13</p></td><td><p>ε-caprolactone</p></td><td><p>Pentaerythritol</p></td><td><p>10300</p></td><td><p>1.17</p></td></tr><tr><td><p>14</p></td><td><p>ε-caprolactone</p></td><td><p>Pentaerythritol</p></td><td><p>6700</p></td><td><p>1.43</p></td></tr><tr><td><p>15</p></td><td><p>Racemic Lactide</p></td><td><p>Floroglyucine</p></td><td><p>33800</p></td><td><p>1.69</p></td></tr><tr><td><p>16</p></td><td><p>Racemic Lactide</p></td><td><p>Inosite</p></td><td><p>16400</p></td><td><p>1.30</p></td></tr><tr><td><p>17</p></td><td><p>Racemic Lactide</p></td><td><p>Dipentaerythritol</p></td><td><p>21600</p></td><td><p>1.18</p></td></tr><tr><td><p>18</p></td><td><p>B, B-lactide</p></td><td><p>Pentaerythritol</p></td><td><p>31700</p></td><td><p>1.45</p></td></tr><tr><td><p>19 ^</p></td><td><p>ε-caprolactone / B, B-lactide</p></td><td><p>Pentaerythritol</p></td><td><p>10200</p></td><td><p>1.24</p></td></tr><tr><td><p>20s</p></td><td><p>ε-caprolactone / B, B-lactide</p></td><td><p>Pentaerythritol</p></td><td><p>10500</p></td><td><p>1.41</p></td></tr><tr><td><p>21</p></td><td><p>ε-caprolactone / racemic lactide</p></td><td><p>Pentaerythritol</p></td><td><p>22600</p></td><td><p>1.35</p></td></tr>

^andPolymer obtained from the company ZOIUAU.

^ı Block copolymer obtained by the mechanism of step polymerization.^withIn polymerization, 0.1% (w / w) of 2-ethylhexanoate of stannous (II) was used.

³ Statistical copolymer.

Example 3. Dependence of the increase of molecular weight on the time of polymerization

59.95 g of prepolymer with terminal hydroxyl groups from experiment No. 5 and 12.68 g of a prepolymer with end-groups of carboxylic acid from experiment No. 10 were loaded into a round-bottomed column and heated at 180 ° C. with stirring in a modulus of a rotary evaporator. The pressure was gradually reduced to a minimum value equal to 3 mbar, and the passage of the dehydration condensation reaction was monitored, depending on the increase in mass of the mass of the molecule from the time of the molding. Within 10 hours, a rigid polymer of poly (hydroxycarboxylic acid) was obtained - with an average mass molecular weight exceeding 200,000 g / mol. 3 shows the dependence of the average mass molecular mass from the time of the field of erization.

Example 4. Effect of various initiating compounds

A known amount of (40-50 g) prepolymer with terminal groups of carboxylic acid from experiment # 9 and three different prepolymers with terminal hydroxyl groups were loaded into a round bottom column and heated to 180 ° C. with stirring in the modula of the rotary evaporator. Three different prepolymers with end hydroxyl groups that were used were:

(a) prepolymer from experiment No. 1,

(b) prepolymer from Experiment No. 2 and

(c) prepolymer from experiment No. 4.

Pressure was gradually reduced to a minimum value equal to 30 mbar, and the passage of the reaction of dehydration condensation was monitored, depending on the increase in the average molecular weight of the molecule from the time of polymerization. In all experiments used 100% (by mass) of prepolymer with final hydroxyl groups in the calculation of namas of prepolymer with the terminal groups of carbonic acid. The dependence of the average mass molecular weight on the time of polymerization when the forp-polymer is bound to the carboxylic acid terminal groups under the influence of various prepolymers with the terminal hydroxyl groups is demonstrated in FIG. 4 (forequalimers with terminal hydroxyl groups from the excipient No. 1 (o) , experiment number 2 (□) and

experiment number 4 (Δ)).

Example 5. Adjustment of the content of hydroxyl end groups in the sewing reaction

59.95 g of prepolymer with terminal hydroxyl groups from experiment No. 6 and 12.68 g of a prepolymer with end-groups of carboxylic acid from experiment No. 10 were loaded into a round-bottomed column and heated at 180 ° C. with stirring in a modulus of a rotary evaporator. The pressure was gradually reduced to a minimum value of 14 mbar and the reaction of the dehydration con-

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the dangers were monitored according to the content of the final chemical reactions, from the time of polymerization (tab-groups of the OH-group available for follow-up 3).

Table 3

The dependence of the content of the end-groups of -OH in the poly (hydroxycarboxylic acid) from the time of polymerization

<tr><td><p>Polymerization time (h)</p></td><td><p>The content of the finite groups is OH (% (mole))^and</p></td></tr><tr><td><p>0</p></td><td><p>6.9</p></td></tr><tr><td><p>2</p></td><td><p>6.1</p></td></tr><tr><td><p>4</p></td><td><p>5.7</p></td></tr>

^and Determined by the NMR method analysis.

Example 6. Obtaining of a branched block copolymer

40.00 g of prepolymer with terminal hydroxyl groups from experiment No. 13 and 40.00 g of a prepolymer with end-groups of carboxylic acid from experiment No. 7 were loaded into a round-bottomed column and heated at 180 ° C. with stirring in a modulus of a rotary evaporator. The pressure was gradually reduced to a minimum value of 20 mbar, and the passage of the dehydration condensation reaction was monitored, depending on the increase in the mass molecular weight of the block copolymer from the time of polymerization (FIG. 5). After 18 hours, a high-modulus block copolymer with an average weight molecular weight equal to 69,000 g / mol was obtained.

EXAMPLE 7 Preparation of a super-branched static copolymer

40.00 g of prepolymer from experiment No. 12 and 40.00 g of prepolymer with end-groups of carbonic acid from experiment No. 7 were loaded into a round-bottom flask and heated at 180 ° C. with a pe-stir in the module of the rotary evaporator. The pressure was gradually reduced to a minimum value of 30 mbar, and the reaction of dehydration condensation was carried out for 16 hours. After that during 15 hours at 20 mbar in module ro-turn evaporator additionally performed reaktsiyumizh 10,92h and 16,38h resulting polymer forpoli-mayor of the end hydroxyl groups of the Expo rymentu №20, receiving resilient and flexible over-branched statistical copolymer schoharakteryzuyetsya a Td of 8 ° C and an average weight molecular weight of up to 51100 g / mol.

Example 8. Carrying out of the partition-coupled reaction in a solid state

24.05 g of powdered prepolymer with terminal hydroxyl groups from experiment No. 11 and 56.18 g of the prepolymer with the terminal groups of carboxylic acid from experiment No. 8 loaded the round bottom flask and heated at 180 ° C. by stirring in the module of the rotary evaporator. The pressure was reduced stepwise to a minimum value of 20 mbar, and the reaction of dehydration condensation was carried out for 33 hours, producing a rigid block copolymer consisting of more hydrophilic glycol units and less hydrophilic lactoid units. Block-copolymer was dissolved in a solvent used for determinations of molecular weight, due to the presence of glycol blocks. According to the analysis of the DSC method for a sample purified using chloroform, a wide bimodal peak of melting in the range of 161 ° -198 ° C was found,

Example 9. Preparation of crosslinked (hydroxycarboxylic acid)

40,00 g of prepolymer with terminal hydroxyl groups from experiment No. 4 and 40,00 g of a prepolymer with end-groups of carboxylic acid from experiment No. 9 were loaded into a round-bottomed column and heated at 180 ° C. with stirring in a modulus of a rotary evaporator. The pressure was gradually reduced to a minimum value of 30 mbar and the dehydration condensation reaction was carried out for 22 hours. The resulting cross-linked poly-mercury was characterized by a high viscosity of the melt and not dissolved in conventional organic solvents such as chloroform.

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Computer layout V. Matselio Signature Circulation 28 copies.

Ministry of Education and Science of Ukraine

State Department of Intellectual Property, st. Uritskogo, 45, Kyiv, Ukraine, 03680

State Enterprise "Ukrainian Institute of Industrial Property", st. Glazunova, 1, m. Kiv - 42, 01601