HK1195574A - Watersoluble linear copolymer - Google Patents

Description

Water-soluble linear copolymer

Technical Field

The present invention belongs to the chemistry of high molecular substances, more specifically synthetic high molecular substances, whose molecular chain may be a hydrophilic 3D matrix, said 3D matrix being caused by H bonds between amide and carboxyl groups of polyamines, and offers the possibility of maintaining an aqueous environment.

Background

In various polymer systems, reticulated or crosslinked polymers can be distinguished, the chains of which are covalently linked to form a single spatial structure-a polymer network. The characteristic properties of the network polymer are the absence of viscous state and the little solubility in any solvent. The network polymer swollen in the solvent is called a gel.

The unique property of the provision of polymeric groups to maintain an aqueous environment and a non-generic sensitivity to external conditions (pH, solvent content, temperature) has attracted the interest of researchers, the formation of membranes with controlled osmosis, the vehicles of therapeutic formulations and their direct transport, novel bulking agents, working on novel robots, the growth of plants in novel nutrient solutions-all of which are made possible by the unique properties of the substances.

Many crosslinked polyacrylamide based materials are now being developed and used. They are often obtained from the following elements: acrylamide and methylene-bis-acrylamide, in which the linear chain of polyacrylamide, which is a carbon chain homopolymer, is linked to methylene-bis-acrylamide through a strong covalent linkage, in other words, cross-linking with methylene-bis-acrylamide, forms a 3D network, the center of which holds water. These are chemically stable substances that have low solubility and a small swelling factor under normal conditions.

Due to their structural singularity, these substances have a stable character (since their 3D networks are based on strong covalent links).

For example (patent RU2301814):

it can therefore be concluded that the high crosslinkability of the crosslinker of the 3D network of homo-chain polyacrylamide limits the swelling and flowability in solvents and leads to negative properties such as thixotropy. As a result, these materials have such general properties: swelling (e.g. RU2301814) only occurs during 80 to 100 hours at high temperature, which is reflected in cross-linked polyacrylamides with a branched structure.

These properties of the polymer are solubility, ability to flow thickly, stability and high sensitivity to the formation of covalent chemical linkages between macromolecules, so-called cross-linking.

The solubility of polymers and their chemical stability are determined by the unusual nature of the structure, the presence of branching, crosslinking, the length of macromolecules and other factors.

Cellulose is a known water-soluble crosslinked biopolymer. It has a three-dimensional structure, is formed with the aid of acrylamide or acrylamide and acrylate, is linked by a divinyl monomer used in the composition, and has water and salt groups (see patent US 4051086).

The upper limit of swelling (upper binder line) of known water-soluble crosslinked biopolymers is limited by the lower limit (low value), and furthermore the linking is strictly carried out and its flowability is limited by the three-dimensional structure. Copolymers are characterized by long-term chemical stability, which is undesirable in some practical cases.

Water-soluble crosslinked dipolymers having a three-dimensional structure formed on the basis of ammonium acrylate and a crosslinking agent are also known (see patent JP 6227328).

The upper limit of the swelling of the known water-soluble crosslinked biopolymers is limited by the lower limit, and furthermore the linking is strictly carried out and the three-dimensional structure limits its flowability. Copolymers are characterized by long-term chemical stability, which is undesirable in some practical cases.

Disclosure of Invention

The aim of the research work is to form water-soluble linear heterochain dipolymers (dipolymers) which, based on the low-energy linkage of the monomers of the dipolymers, are hydrophilic 3D matrices which preserve the aqueous environment and confer water-solubility, increase fluidity and reduce their chemical stability.

To achieve this object, the water-soluble linear heterochain dipolymer has the general formula:

(-CH₂-CR₁R₂)_n-(R₄-NHCO-R₅-NHCO-R₄)_m

wherein

R₁May be a hydrogen atom or an alkyl group CH₃，

R₂According to the type of vinyl monomer, COOH, CONH₂、(CH₃)-COOH，

R₃Depending on the type of divinyl monomer is a hydrogen atom or an OH group,

R₄may be (CH)₂-CHR₃) Or (CH)₂-CHR₃-CH₂)，

R₅May be (CH) according to the type of divinyl monomer₂) Or (CH (OH))₂，

m and n-the correlation between the vinyl and divinyl monomers,

wherein the m/n ratio is within the range of 10 to 100,

the chain segment in which the amide group-CO-NH-is present is linked to a similar segment by an H bond between the amide group and the carboxyl group.

This substance belongs to a new structure that can be called the water-soluble biopolymerThe polymer of (a), which is obtainable in such a way that a vinyl monomer and a divinyl monomer are copolymerized into the linear dipolymer: the vinyl monomer is selected from acrylic acid CH₂(methacrylic acid (2-methacrylic acid) CH ═ CH-COOH and derivatives thereof₂＝C(CH₃) -COOH, acrylamide CH₂＝CH-CO-NH₂) Methyl methacrylate (CH)₂＝C(CH₃)-COOCH₃A divinyl monomer being a dipropenyl monomer N, N' -diallyltartramide (DATD) CH having in their content an amide group (-CO-NH-)₂＝CH-CH₂-NH-CO-CH(OH)-CH(OH)-CO-NH-CH₂-CH＝CH₂、BISAM(C₂H₃-CO-NH-CH₂-CO-NH-C₂H₃). After copolymerization, the result is an amide group-CO-NH-received by the main chain, the homopolymer giving the structure of the heteropolymer (polyacrylamide) different physico-chemical properties.

Detailed Description

Polyamides are heterochain polymers in which amide groups-CO-NH-are present in the main chain of the macromolecule. With pendant amide groups-CO-NH₂Carbon chain polymers such as polyacrylamides are not included in the polyamides.

The amide-based segment of the molecule is unique in terms of the structural properties of the molecule and in terms of peculiar intermolecular interactions. This segment is almost flat due to the hybridization of the nitrogen, carbon and hydrogen atoms in the amine group. It is also important that the hydrogen attached to the nitrogen and oxygen atoms in the carbon group (carbon group) is able to form a strong hydrogen bond.

Except as mentioned in the materials, no cross-linked network of polymers is formed. Thus, the macromolecule of the substance is a hydrophilic 3D matrix, which is due to hydrogen bonds between the amide and carboxyl groups of the polyamide, which maintains an aqueous environment.

The H bond is about 20 times less strong than the covalent bond. Unlike typical chemical bonds, H bonds are not caused as a result of a single-stage synthesis using a group linker, but are formed under a corresponding artificial environment.

H bonds are characterised by a low strength and almost a level lower energy than e.g. covalent chemical bonds.

It is these bonds that provide the material with great swelling and water solubility.

In some embodiments of achieving the water-soluble linear heterochain dipolymer, the vinyl monomer is selected from the group consisting of: acrylic acid CH₂(methacrylic acid (2-methacrylic acid) CH ═ CH-COOH and derivatives thereof₂＝C(CH₃)-COOH、

And acrylamide CH₂＝CH-CO-NH₂)

Or methyl methacrylate (CH)₂＝C(CH₃)-COOCH₃。

The use of said odd properties in the biopolymer additionally enhances the swelling of the target substance.

In some embodiments of achieving the water-soluble linear heterochain dipolymer, the vinyl monomer is selected from the group consisting of: n, N' -diallyl tartaric diamide (DATD) -CH₂＝CH-CH₂-NH-CO-CH(OH)-CH(OH)-CO-NH-CH₂-CH＝CH₂、BISAM(C₂H₃-CO-NH-CH₂-CO-NH-C₂H₃)。

The use of said odd properties in the bipolymer additionally improves the solubility of the target substance.

By way of example, water soluble linear heterochain dipolymers. On fig. 1, the structure of a water-soluble linear heterochain biopolymer with said H bond between an amide group and a carboxyl group is illustrated in a full view.

The substances in the overall view are obtained by a two-stage polymerization in an aqueous environment using polymerization initiators. The following may be used as initiators for the first stage polymerization:

tetramethylethylenediamine (TEMED) C₆H₁₆N₂-(CH₃)₂N-CH₂-CH₂-N(CH₃)₂

Dimethylaminopropionitrile (DMAPN) C₅H₁₀N₂-(CH₃)₂N-CH₂-CH₂-CN

Ammonium Persulfate (APS) (NH)₄)₂S₂O₈

6, 7-dimethyl-9- (D-1-ribosyl) -isoalloxazine (riboflavin) C₁₇H₂₀N₄O₆

Example 1

The target dipolymers based on methyl-acrylic acid and BISAM were obtained by two-step polymerization in an aqueous environment using a polymerization initiator.

The polymerization was carried out in the following manner.

To obtain 100ml of a solution containing 5% by weight of polymethacrylic acid, 5ml of methyl-acrylic acid (MAA) was used. 0.009g of BISAM was used as a dipropylene-based monomer in an amount of 1 part of 100 parts (section) polymethacrylic acid. An aqueous solution of Ammonium Persulfate (APS) (0.5g) and a small amount of Dimethylaminopropionitrile (DMAPN) were added. The resulting solution was mixed and left for 45 minutes. The preliminary synthesis preproduct was then removed from the glass vessel and comminuted.

The pre-product was washed (scour) with distilled water and then the second polymerization step was carried out in this way by motorized homopolymerization (under UV lamp) by dropwise addition of an aqueous solution of riboflavin (riboflavin).

Example 2

The target dipolymer based on methyl-acrylic acid (DATD) was obtained by a two-step polymerization in an aqueous environment using a polymerization initiator.

To obtain 100ml of a solution containing 5% by weight of acrylic acid, 5ml of Acrylic Acid (AA) were used, and 0.65g of Ν, Ν' -diallyltartramide (DATD) was used as the dipropenyl monomer in an amount of 1 part of 80 parts of acrylic acid. An aqueous solution of Ammonium Persulfate (APS) (0.5g) and a small amount of Dimethylaminopropionitrile (DMAPN) were added. The resulting solution was mixed and left at room temperature for 45 minutes. The preliminary synthesis preproduct was then removed from the bottle and comminuted.

The pre-product was washed with distilled water and then the homopolymerization was motorized (under uv lamp) by adding dropwise an aqueous solution of riboflavin (riboflavin) -in these cases the polymerization of the second step was carried out.

Example 3

The target dipolymer based on acrylamide and BISAM was obtained by two-step polymerization in aqueous environment using a polymerization initiator.

To obtain 100ml of a solution containing 4% by weight of acrylamide, 4g of acrylamide (AA) was used, and 0.08g of BISAM was used as a dipropylene monomer in an amount of 1 part of 50 parts of acrylamide. An aqueous solution of Ammonium Persulfate (APS) (0.5g) and a small amount of Dimethylaminopropionitrile (DMAPN) were added. The resulting solution was mixed and left for 45 minutes. The preliminary synthesis preproduct was then removed from the bottle and comminuted.

The pre-product was washed with distilled water and then the homopolymerization was motorized (under uv lamp) by adding dropwise an aqueous solution of riboflavin (riboflavin) -in these cases the polymerization of the second step was carried out.

Claims (3)

1. A water-soluble linear heterochain dipolymer having the general formula:

(-CH₂-CR₁R₂)_n-(R₄-NHCO-R₅-NHCO-R₄)_m，

wherein

R₁May be a hydrogen atom or an alkyl group CH₃，

R₂According to the type of vinyl monomer, COOH, CONH₂、(CH₃)-COOH，

R₃According to diethylThe type of alkenyl monomer is a hydrogen atom or an OH group,

R₄may be (CH)₂-CHR₃) Or (CH)₂-CHR₃-CH₂)，

R₅May be (CH) according to the type of divinyl monomer₂) Or (CH (OH))₂，

m and n-the correlation between the vinyl and divinyl monomers,

wherein the m/n ratio is within the range of 10 to 100,

the chain segment in which the amide group-CO-NH-is present is linked to a similar segment by an H bond between the amide group and the carboxyl group.

2. The water-soluble linear heterochain dipolymer of claim 1, wherein the vinyl monomer is selected from the group consisting of: acrylic acid CH₂(methacrylic acid (2-methacrylic acid) CH-COOH or a derivative thereof₂＝C(CH₃) -COOH and acrylamide CH₂＝CH-CO-NH₂) Or methyl methacrylate (CH)₂＝C(CH₃)-COOCH₃。

3. The water-soluble linear heterochain dipolymer of claim 1, wherein the vinyl monomer is selected from the group consisting of Ν, Ν' -diallyl-tartrate (DATD) -CH₂＝CH-CH₂-NH-CO-CH(OH)-CH(OH)-CO-NH-CH₂-CH＝CH₂、BISAM(C₂H₃-CO-NH-CH₂-CO-NH-C₂H₃) Group (d) of (a).