WO2013077831A1 - Watersoluble linear copolymer - Google Patents
Watersoluble linear copolymer Download PDFInfo
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- WO2013077831A1 WO2013077831A1 PCT/UA2012/000052 UA2012000052W WO2013077831A1 WO 2013077831 A1 WO2013077831 A1 WO 2013077831A1 UA 2012000052 W UA2012000052 W UA 2012000052W WO 2013077831 A1 WO2013077831 A1 WO 2013077831A1
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- Prior art keywords
- hydrogen
- amide
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- 229920005684 linear copolymer Polymers 0.000 title description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 150000001408 amides Chemical class 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001577 copolymer Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 241000699700 Ondatra zibethicus Species 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims 2
- ZRKLEAHGBNDKHM-UHFFFAOYSA-N N,n'-diallyl-2,3-dihydroxysuccinamide Chemical compound C=CCNC(=O)C(O)C(O)C(=O)NCC=C ZRKLEAHGBNDKHM-UHFFFAOYSA-N 0.000 claims 1
- 235000013847 iso-butane Nutrition 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 abstract description 13
- 239000004952 Polyamide Substances 0.000 abstract description 6
- 229920002647 polyamide Polymers 0.000 abstract description 6
- 229920002521 macromolecule Polymers 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004429 atom Chemical group 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000009396 hybridization Methods 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 230000009878 intermolecular interaction Effects 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 description 13
- MTPJEFOSTIKRSS-UHFFFAOYSA-N 3-(dimethylamino)propanenitrile Chemical compound CN(C)CCC#N MTPJEFOSTIKRSS-UHFFFAOYSA-N 0.000 description 8
- 239000004160 Ammonium persulphate Substances 0.000 description 8
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 235000019395 ammonium persulphate Nutrition 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- ZRKLEAHGBNDKHM-HTQZYQBOSA-N (2r,3r)-2,3-dihydroxy-n,n'-bis(prop-2-enyl)butanediamide Chemical compound C=CCNC(=O)[C@H](O)[C@@H](O)C(=O)NCC=C ZRKLEAHGBNDKHM-HTQZYQBOSA-N 0.000 description 4
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 4
- 229960002477 riboflavin Drugs 0.000 description 4
- 235000019192 riboflavin Nutrition 0.000 description 4
- 239000002151 riboflavin Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 241001365789 Oenanthe crocata Species 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000140 heteropolymer Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/38—Amides
- C08F222/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
Definitions
- the invention belongs to the chemistry of high molecular substances more specifically to the synthetic high molecular substances, the chain of which can be hydrophilic 3D matrix arising due to H-linkages that emerge between the amide and carboxylic groups of polyamides and provide the possibility to keep the water environment.
- netlike or cross-linked polymers the chains of which are connected by the covalent connections with the creation of the single space structure - polymer net.
- the characteristic properties of netlike polymers are the absence of viscous-flow state and little solubility in any solvent. Netlike polymers swelled in the solvent are called gels.
- Solubility of polymers and their chemical stability depend on the peculiarities of the structure, presence of branching, cross-linkages, length of macromolecule and other factors.
- Cellulose is a known watersoluble cross-linked dipolymer. It has three dimensional structure formed with the help of acrylamide or acrylamide and acrylate linked through the divinyl monomer that is used in the composition and has water and group of salts (see, patent US4051086).
- Watersoluble cross linked dipolymer which has the three dimensional structure (see, patent JP6227328) formed on the basis of ammonium acrylate and linking agent is also known.
- the aim of the development work is the creation of watersoluble linear heterochain dipolymer on account of low-energetic connections of monomers, that create it, which is hydrophilic 3D matrix that keeps water environment and gives it watersolubility, increases fluidity and reduces its chemical stability.
- watersoluble linear heterochain dipolymer has the general formula:
- Ri can be atom of hydrogen or alkyl CH3,
- R 2 can be COOH, CONH 2) (CH 3 )-COOH depending on the kind of vinyl monomer,
- R3 is atom of hydrogen or OH group, depending on the kind of divinyl monomer
- R 4 can be (CH2-CHR3) or (CH 2 -CHR 3 -CH 2 ),
- R5 can be (CH 2 ) or (CH(OH)) 2, depending on the kind of divinyl monomer.
- DATD diallyltartardi
- the homopolymer gets the structure of heteropolymer (polyamide) with the different physical-chemical properties.
- Polyamides are the heterochain polymers, in which in the main chain of macromolecule the amide groups -CO-NH- are present.
- Carbon-chain polymers with the side amide groups -CO-NH 2 for example polyacrylamide, do not belong to the polyamides.
- Amide section of the molecule is unique according to its structure properties and according to the peculiar intermolecular interactions. Due to the hybridization of nitrogen, carbon and hydrogen atoms in the amine group, this section is almost flat. What is also important is that the hydrogen, connected with the nitrogen atom and oxygen atom in carbon groups are able to create the strong hydrogen linkage.
- the cross-cross-linked net of polymer is not created. Therefore the macromolecule of the substance is hydrophilic 3D matrix which arises on the account of H-linkages between the amide and carboxyl groups of polyamide, which keeps water environment.
- H-linkages are approximately 20 times less strong than covalent. Unlike the usual chemical linkages, H-linkage arises not as a result of single-stage synthesis using the radical linking agent but is created under the correspondent artificial circumstances.
- the distinctive feature of the H-linkages is comparatively low strength, its energy is almost one order less than the energy of covalent chemical linkage for example.
- DATD ⁇ , ⁇ '-diallyltartardiamide
- Watersoluble linear heterochain dipolymer is illustrated by the examples. On the figure 1 the structure of watersoluble linear heterochain dipolymer with the mentioning of the H-linkages between the amide and carboxyl groups is graphically represented in general view.
- the substances in the general view are received by two step polymerization in water environment with the initiating agents of polymerization.
- the following substances can be used as the initiating agents of the first grade of polymerization:
- DMAPN Dimethylaminopropionitrile
- Ammonium persulphate (APS) (NH. 2S2O8
- Target dipolymer on the basis of methyl-acrylic acid and BISAM was received by two step polymerization in water environment with the initiating agents of polymerization.
- the preproduct was scoured with distilled water, after that the homogenization was performed mechanically (under the ultraviolet lamp) adding drop by drop water solution of riboflavin - this way the second step of polymerization was performed.
- Target dipolymer on the basis of methyl-acrylic acid and (DATD) was received by two step polymerization in water environment with the initiating agents of polymerization.
- the preproduct was scoured with distilled water, after that the homogenization was performed mechanically (under the ultraviolet lamp) adding drop by drop water solution of riboflavin - under these circumstances the second step of polymerization was performed.
- Target dipolymer on the basis of acrylamide and BISAM was received by two step polymerization in water environment with the initiating agents of polymerization.
- the preproduct was scoured with distilled water, after that the homogenization was performed mechanically (under the ultraviolet lamp) adding drop by drop water solution of riboflavin - under these circumstances the second step of polymerization was performed.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Medicinal Preparation (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention concerns watersoluble linear heterochain dipolymer having the general formula: (-CH2-CR1R2)n-(R4-NHCO-R5-NHCO-R4)m where R1 can be atom of hydrogen or alkyl CH3, R2 can be COOH, CONH2, (CH3)-COOH depending on the kind of vinyl monomer, R3 is atom of hydrogen or OH group, depending on the kind of divinyl monomer, R4 can be (CH2-CHR3) or (CH2-CHR3-CH2), R5 can be (CH2) or (CH(OH))2, depending on the kind of divinyl monomer, m and n - interrelationships between the vinyl and divinyl monomers, herewith the correlation m/n is within 10 to 100, herewith the sections of the chain in which amide groups -CO-NH- are present, are connected with the similar sections through the H-linkages between the amide and carboxyl groups. Such a substance belongs to polymer of a new structure with different physical- chemical properties. Amide section of the molecule is unique according to its structural properties and according to peculiar intermolecular interactions. Due to the hybridization of nitrogen, carbon and hydrogen atoms in the amine group, this section is almost flat. What is also important is that the hydrogen, connected with the nitrogen atom and oxygen atom in carbon groups are able to create the strong hydrogen linkage. Besides in the mentioned substance the cross-cross-linked net of polymer is not created. Therefore the macromolecule of the substance is hydrophilic 3D matrix which arises on the account of H-linkages between the amide and carboxyl groups of polyamide, which keeps the water environment.
Description
WATERSOLUBLE LINEAR COPOLYMER
The invention belongs to the chemistry of high molecular substances more specifically to the synthetic high molecular substances, the chain of which can be hydrophilic 3D matrix arising due to H-linkages that emerge between the amide and carboxylic groups of polyamides and provide the possibility to keep the water environment.
In the variety of polymer systems one can distinguish netlike or cross-linked polymers, the chains of which are connected by the covalent connections with the creation of the single space structure - polymer net. The characteristic properties of netlike polymers are the absence of viscous-flow state and little solubility in any solvent. Netlike polymers swelled in the solvent are called gels.
But the unique properties of the polymer group that provide the possibility to keep water environment and unusual sensibility to external conditions (pH, solvent content, temperature) attract the interest of the researchers. The creation of membranes with the controlled penetration, carriers of treatment preparations and their direct transport, new fillers, work at the new types of robots, plant growing in the new nutritional solutions - all these are possible due to the unique properties of such substances.
Quite a lot of substances on the basis of cross-linked polyacrylamide are developed and used nowadays. They are received usually from the following elements: acrylamide and methylene-bis-acrylamide in which the linear chains of polyacrylamide as carbochain homopolymer are connected by methylene-bis- acrylamide by the strong covalent connections, in other words cross-linked by the methylene-bis-acrylamide with the creation of 3D net, centers of which keep water. These are the chemically stable substances with the little solubility and small indexes of swelling under the normal conditions.
Because of the peculiarities of their structure these substances have the steady character (as their 3D net is based on the strong covalent connections).
For example (patent RU2301814):
As a result one can come to the conclusion that the high cross-linking by the cross-linker of 3D net of homochain polyacrylamide, restrict the swelling and fluidity in the solvent and lead to such a negative property as tixotropy. As a result these substances have the general properties: swell only during 80-100 hours at high temperatures (for example RU2301814), which points out on the cross-cross-linked polyacrylamide with branched structure.
These properties of polymers as solubility, ability to thick flow, stability, high sensibility to the creation of covalent chemical connections between the macromolecules (the so called cross-linking).
Solubility of polymers and their chemical stability depend on the peculiarities of the structure, presence of branching, cross-linkages, length of macromolecule and other factors.
Cellulose is a known watersoluble cross-linked dipolymer. It has three dimensional structure formed with the help of acrylamide or acrylamide and acrylate linked through the divinyl monomer that is used in the composition and has water and group of salts (see, patent US4051086).
Upper boarder line of the swelling of known watersoluble cross-linked dipolymer is restricted by the low values, besides strictly linked and three dimensional structure restricts its fluidity. Copolymer is characterized by the long termed chemical stability, which is undesirable in some practical cases.
Watersoluble cross linked dipolymer which has the three dimensional structure (see, patent JP6227328) formed on the basis of ammonium acrylate and linking agent is also known.
Upper boarder line of the swelling of known watersoluble cross-linked dipolymer is restricted by the low values, besides strictly linked and three dimensional
structure restricts its fluidity. Copolymer is characterized by the long termed chemical stability, which is undesirable in some practical cases.
The aim of the development work is the creation of watersoluble linear heterochain dipolymer on account of low-energetic connections of monomers, that create it, which is hydrophilic 3D matrix that keeps water environment and gives it watersolubility, increases fluidity and reduces its chemical stability.
To fulfill this aim watersoluble linear heterochain dipolymer has the general formula:
(-CH2-CRiR2)n-(R4-NHCO-R5-NHCO-R4)m
in which
Ri can be atom of hydrogen or alkyl CH3,
R2 can be COOH, CONH2) (CH3)-COOH depending on the kind of vinyl monomer,
R3 is atom of hydrogen or OH group, depending on the kind of divinyl monomer,
R4 can be (CH2-CHR3) or (CH2-CHR3-CH2),
R5 can be (CH2) or (CH(OH))2, depending on the kind of divinyl monomer.
m and n - interrelationships between the vinyl and divinyl monomers, herewith the correlation m/n is within 10 to 100,
herewith the sections of the chain in which amide groups -CO-NH- are present, are connected with the similar sections through the H-linkages between the amide and carboxyl groups.
Such a substance belongs to the polymer of new structure, that can be referred to the watersoluble dipolymers, that can be received in a way of copoiymerization of vinyl monomers of group of ethylene carboxylic acid CH2=CH-COOH and its derivatives (methyl-acrylic acid (2-methylpropene acid) CH2=C(CH3)-COOH, acrylamide (CH2=CH-CO-NH2), methylmethacrylate (CH2=C(CH3)-COOCH3, and divinyl monomers that have in their content amide groups (-CO-NH-) Ν,Ν'- diallyltartardiamide (DATD) -CH2=CH-CH2-NH-CO-CH(OH)-CH(OH)-CO-NH-CH2- CH=CH2, BISAM (C2H3-CO-NH-CH2-CO-NH-C2H3) into the linear dipolymer. After the copoiymerization as a consequence of the receiving the amide groups -CO-NH- by the main chain, the homopolymer gets the structure of heteropolymer (polyamide) with the different physical-chemical properties.
Polyamides are the heterochain polymers, in which in the main chain of macromolecule the amide groups -CO-NH- are present. Carbon-chain polymers with the side amide groups -CO-NH2, for example polyacrylamide, do not belong to the polyamides.
Amide section of the molecule is unique according to its structure properties and according to the peculiar intermolecular interactions. Due to the hybridization of nitrogen, carbon and hydrogen atoms in the amine group, this section is almost flat. What is also important is that the hydrogen, connected with the nitrogen atom and oxygen atom in carbon groups are able to create the strong hydrogen linkage.
Besides in the mentioned substance the cross-cross-linked net of polymer is not created. Therefore the macromolecule of the substance is hydrophilic 3D matrix which arises on the account of H-linkages between the amide and carboxyl groups of polyamide, which keeps water environment.
H-linkages are approximately 20 times less strong than covalent. Unlike the usual chemical linkages, H-linkage arises not as a result of single-stage synthesis using the radical linking agent but is created under the correspondent artificial circumstances.
The distinctive feature of the H-linkages is comparatively low strength, its energy is almost one order less than the energy of covalent chemical linkage for example.
These exactly linkages provide the big swelling and watersolubility of the mentioned substance.
In some variants of realization of watersoluble linear heterochain dipolymer the vinyl monomers are chosen from the group of ethylene carboxylic acid CH2=CH- COOH and its derivatives (methylacrylic acid (2-methylpropene acid) CH2=C(CH3)- COOH,
and acrylamide (CH2=CH-CO-NH2)
or methylmethacrylate (CH2=C(CH3)-COOCH3
The usage of the mentioned peculiarities in dipolymer additionally increases the swelling of the target substance.
In some variants of realization of watersoluble linear heterochain dipolymer the vinyl monomers are chosen from the group of Ν,Ν'-diallyltartardiamide (DATD)-CH2 = CH-CH2-NH -CO-CH(OH)-CH(OH)-CO-NH-CH2-CH=CH2, BISAM (C2H3-CO-NH-CH2- CO-NH-C2H3).
The usage of the mentioned peculiarities in dipolymer additionally increases the solubility of the target substance.
Watersoluble linear heterochain dipolymer is illustrated by the examples. On the figure 1 the structure of watersoluble linear heterochain dipolymer with the mentioning of the H-linkages between the amide and carboxyl groups is graphically represented in general view.
The substances in the general view are received by two step polymerization in water environment with the initiating agents of polymerization. The following substances can be used as the initiating agents of the first grade of polymerization:
Tetramethylethylenediamine (TEMED) C6Hi6N2 - (CH3)2 -CH2-CH2-N(CH3)2,
Dimethylaminopropionitrile (DMAPN) C5H10N2 - (CH3)2N-CH2-CH2-CN,
Ammonium persulphate (APS) (NH. 2S2O8
6,7-Dimethyl-9-(D-1 -ribitil) - isoalloxazine (riboflavin) C17H20N4O6
Example 1
Target dipolymer on the basis of methyl-acrylic acid and BISAM was received by two step polymerization in water environment with the initiating agents of polymerization.
Polymerization was performed according to the following scheme.
To receive 100 ml of solution which contains 5 weight percent of polymethyl- acrylic acid, 5 ml of methyl-acrylic acid (MAA) were used, BISAM 0,009 g was taken as a divinyl monomer in an amount of 1 section for 100 sections of polymethyl-acrylic acid. Water solution of ammonium persulphate (APS) (0,5 g) and small quantity of dimethylaminopropionitrile (DMAPN) were added. The received solution was mixed and left for 45 minutes. After that primarily synthesized preproduct was taken out of the glass and comminuted.
The preproduct was scoured with distilled water, after that the homogenization was performed mechanically (under the ultraviolet lamp) adding drop by drop water solution of riboflavin - this way the second step of polymerization was performed.
Example 2.
Target dipolymer on the basis of methyl-acrylic acid and (DATD) was received by two step polymerization in water environment with the initiating agents of polymerization.
To receive 100 ml of solution which contains 5 weight percent of acrylic acid, 5 ml of acrylic acid (AA) were used, Ν,Ν'-diallyltartardiamide (DATD) 0,65 g was taken
as a divinyl monomer in an amount of 1 section for 80 sections of acrylic acid. Water solution of ammonium persulphate (APS) (0,5 g) and small quantity of dimethylaminopropionitrile (DMAPN) were added. The received solution was mixed and left for 45 minutes at room temperature. After that primarily synthesized preproduct was taken out of the bottle and comminuted.
The preproduct was scoured with distilled water, after that the homogenization was performed mechanically (under the ultraviolet lamp) adding drop by drop water solution of riboflavin - under these circumstances the second step of polymerization was performed.
Example 3.
Target dipolymer on the basis of acrylamide and BISAM was received by two step polymerization in water environment with the initiating agents of polymerization.
To receive 100 ml of solution which contains 4 weight percent of acrylamide, 4 g of acrylamide (AA) were used, BISAM 0,08 g was taken as a divinyl monomer in an amount of 1 section for 50 sections of acrylamide. Water solution of ammonium persulphate (APS) (0,5 g) and small quantity of dimethylaminopropionitrile (DMAPN) were added. The received solution was mixed and left for 45 minutes. After that primarily synthesized preproduct was taken out of the bottle and comminuted.
The preproduct was scoured with distilled water, after that the homogenization was performed mechanically (under the ultraviolet lamp) adding drop by drop water solution of riboflavin - under these circumstances the second step of polymerization was performed.
Claims
1. Watersoluble linear heterochain dipolymer of general formula:
(-CH2-CR1R2)n-( 4-NHCO-R5-NHCO-R4)m
where
Ri can be atom of hydrogen or alkyl CH3,
R2 can be COOH, CONH2, (CH3)-COOH depending on the kind of vinyl monomer,
R3 is atom of hydrogen or OH group, depending on the kind of divinyl monomer,
R4 can be (CH2-CHR3) or (CH2-CHR3-CH2),
R5 can be (CH2) or (CH(OH))2, depending on the kind of divinyl monomer, m and n - interrelationships between the vinyl and divinyl monomers, herewith the correlation m/n is within 10 to 100,
herewith the sections of the chain in which amide groups -CO-NH- are present, are connected with the similar sections through the H-linkages between the amide and carboxyl groups.
2. Watersoluble linear heterochain dipolymer according to claim 1 , where the vinyl monomers were chosen from the group of ethylene carboxylic acid CH2=CH- COOH or its derivatives (methyl-acrylic acid (2-methylpropane acid) CH2=C(CH3)- COOH, and acrylamide (CH2= CH-CO-NH2) or methylmethacrylate (CH2=C(CH3)- COOCH3.
3. Watersoluble linear heterochain dipolymer according to claim 1 , where the vinyl monomers were chosen from the group of Ν,Ν'-diallyltartardiamide (DATD) -
CH2=CH-CH2-NH-CO-CH(OH)-CH(OH)-CO-NH-CH2-CH=CH2, BISAM (C2H3-CO-NH- CH2-CO-NH-C2H3).
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MX2014006227A MX346741B (en) | 2011-11-24 | 2012-05-23 | Watersoluble linear copolymer. |
| AU2012341101A AU2012341101B2 (en) | 2011-11-24 | 2012-05-23 | Watersoluble linear copolymer |
| US14/360,800 US9365668B2 (en) | 2011-11-24 | 2012-05-23 | Watersoluble linear copolymer |
| JP2014543457A JP6266527B2 (en) | 2011-11-24 | 2012-05-23 | Water-soluble copolymer |
| BR112014012554A BR112014012554A2 (en) | 2011-11-24 | 2012-05-23 | water soluble linear copolymer |
| CN201280057472.XA CN103958574B (en) | 2011-11-24 | 2012-05-23 | Water-soluble linear copolymer |
| CA2856497A CA2856497A1 (en) | 2011-11-24 | 2012-05-23 | Watersoluble linear copolymer |
| EA201400608A EA201400608A1 (en) | 2011-11-24 | 2012-05-23 | SOLUBLE IN WATER LINEAR COPOLYMER |
| EP20120730284 EP2782954A1 (en) | 2011-11-24 | 2012-05-23 | Watersoluble linear copolymer |
| IN1053MUN2014 IN2014MN01053A (en) | 2011-11-24 | 2014-05-30 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| UAU201113857U UA67354U (en) | 2011-11-24 | 2011-11-24 | Water-soluble linear hetero-chain dipolymer |
| UAU201113857 | 2011-11-24 |
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| Publication Number | Publication Date |
|---|---|
| WO2013077831A1 true WO2013077831A1 (en) | 2013-05-30 |
Family
ID=48470146
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/UA2012/000052 WO2013077831A1 (en) | 2011-11-24 | 2012-05-23 | Watersoluble linear copolymer |
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| Country | Link |
|---|---|
| US (1) | US9365668B2 (en) |
| EP (1) | EP2782954A1 (en) |
| JP (1) | JP6266527B2 (en) |
| KR (1) | KR101345191B1 (en) |
| CN (1) | CN103958574B (en) |
| AU (1) | AU2012341101B2 (en) |
| BR (1) | BR112014012554A2 (en) |
| CA (1) | CA2856497A1 (en) |
| CL (1) | CL2014001368A1 (en) |
| CO (1) | CO6990744A2 (en) |
| CZ (1) | CZ2012316A3 (en) |
| EA (1) | EA201400608A1 (en) |
| IN (1) | IN2014MN01053A (en) |
| MX (1) | MX346741B (en) |
| UA (1) | UA67354U (en) |
| WO (1) | WO2013077831A1 (en) |
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| US4658000A (en) * | 1983-08-16 | 1987-04-14 | Reanal Finomvegyszergyar | Polyacrylamide adhesive for fixing the sorbent layers of overpressured, one-and multilayer-chromatographic plates and a process for the preparation thereof |
| US5055521A (en) * | 1987-06-04 | 1991-10-08 | Atochem | Agent for rendering compatible at least two incompatible thermoplastic polymers, process for the preparation and thermoplastic alloys obtained therefrom |
| JPH06227328A (en) | 1993-02-03 | 1994-08-16 | Oki Electric Ind Co Ltd | Electronic control unit for automobile |
| US20040068071A1 (en) * | 2001-02-23 | 2004-04-08 | Heinz Hoff | Thermoplastic block copolymers consisting of polyalkyl(meth)acrylate and polyamide segments and the use thereof |
| RU2301814C2 (en) | 2000-08-25 | 2007-06-27 | Контюра С.А. | Polyacrylamide hydrogel and employment thereof as endoprosthesis |
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| CH643569A5 (en) * | 1980-03-21 | 1984-06-15 | Isaflex Ag | METHOD FOR PRODUCING WASSERAUSTAUSCHENDEM, non-toxic POLYMER MATERIAL BASED ON ACRYLAMIDE / N, N'-methylenebisacrylamide. |
| SE9203646L (en) | 1992-12-03 | 1994-05-24 | Eka Nobel Ab | Chiral adsorbents and their preparation as well as compounds on which the adsorbents are based and their preparation |
| JPH0966300A (en) * | 1995-08-31 | 1997-03-11 | Mitsui Toatsu Chem Inc | Flocculation treatment agent for cement-containing waste sludge |
| JPH11315123A (en) * | 1998-05-01 | 1999-11-16 | Sumitomo Chem Co Ltd | Tartramide-based copolymer, its production and detergent containing the same copolymer |
| JP2000239378A (en) | 1998-12-25 | 2000-09-05 | Mitsui Chemicals Inc | Production of water-absorbing resin |
| JP4389008B2 (en) * | 1999-11-09 | 2009-12-24 | 独立行政法人産業技術総合研究所 | Organogel composite spherical inorganic porous particles and method for producing the same |
| CN1465405A (en) * | 2002-06-03 | 2004-01-07 | 吉林富华医用高分子材料有限公司 | Method for making medical aquogel |
-
2011
- 2011-11-24 UA UAU201113857U patent/UA67354U/en unknown
-
2012
- 2012-02-08 KR KR1020120012886A patent/KR101345191B1/en not_active IP Right Cessation
- 2012-05-14 CZ CZ20120316A patent/CZ2012316A3/en unknown
- 2012-05-23 CA CA2856497A patent/CA2856497A1/en not_active Abandoned
- 2012-05-23 EA EA201400608A patent/EA201400608A1/en unknown
- 2012-05-23 EP EP20120730284 patent/EP2782954A1/en not_active Withdrawn
- 2012-05-23 US US14/360,800 patent/US9365668B2/en not_active Expired - Fee Related
- 2012-05-23 MX MX2014006227A patent/MX346741B/en active IP Right Grant
- 2012-05-23 WO PCT/UA2012/000052 patent/WO2013077831A1/en active Application Filing
- 2012-05-23 AU AU2012341101A patent/AU2012341101B2/en not_active Ceased
- 2012-05-23 BR BR112014012554A patent/BR112014012554A2/en not_active IP Right Cessation
- 2012-05-23 CN CN201280057472.XA patent/CN103958574B/en not_active Expired - Fee Related
- 2012-05-23 JP JP2014543457A patent/JP6266527B2/en not_active Expired - Fee Related
-
2014
- 2014-05-23 CL CL2014001368A patent/CL2014001368A1/en unknown
- 2014-05-30 IN IN1053MUN2014 patent/IN2014MN01053A/en unknown
- 2014-06-24 CO CO14136083A patent/CO6990744A2/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4051086A (en) | 1976-03-25 | 1977-09-27 | Hercules Incorporated | Absorption rate of absorbent polymers by treating with glyoxal |
| US4658000A (en) * | 1983-08-16 | 1987-04-14 | Reanal Finomvegyszergyar | Polyacrylamide adhesive for fixing the sorbent layers of overpressured, one-and multilayer-chromatographic plates and a process for the preparation thereof |
| US5055521A (en) * | 1987-06-04 | 1991-10-08 | Atochem | Agent for rendering compatible at least two incompatible thermoplastic polymers, process for the preparation and thermoplastic alloys obtained therefrom |
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| US20040068071A1 (en) * | 2001-02-23 | 2004-04-08 | Heinz Hoff | Thermoplastic block copolymers consisting of polyalkyl(meth)acrylate and polyamide segments and the use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2014006227A (en) | 2015-03-06 |
| CN103958574A (en) | 2014-07-30 |
| KR20130057925A (en) | 2013-06-03 |
| MX346741B (en) | 2017-03-29 |
| EA201400608A1 (en) | 2014-12-30 |
| BR112014012554A2 (en) | 2017-06-06 |
| UA67354U (en) | 2012-02-10 |
| KR101345191B1 (en) | 2013-12-27 |
| CO6990744A2 (en) | 2014-07-10 |
| US20150038661A1 (en) | 2015-02-05 |
| CZ2012316A3 (en) | 2013-06-19 |
| EP2782954A1 (en) | 2014-10-01 |
| JP6266527B2 (en) | 2018-01-24 |
| AU2012341101A1 (en) | 2014-06-12 |
| IN2014MN01053A (en) | 2015-05-15 |
| US9365668B2 (en) | 2016-06-14 |
| JP2014533768A (en) | 2014-12-15 |
| CA2856497A1 (en) | 2013-05-30 |
| CL2014001368A1 (en) | 2015-01-23 |
| CN103958574B (en) | 2016-09-28 |
| AU2012341101B2 (en) | 2016-08-25 |
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