GB2084585A - The Preparation of High Molecular Weight Hydrophilic Polymer Gels - Google Patents
The Preparation of High Molecular Weight Hydrophilic Polymer Gels Download PDFInfo
- Publication number
- GB2084585A GB2084585A GB8030899A GB8030899A GB2084585A GB 2084585 A GB2084585 A GB 2084585A GB 8030899 A GB8030899 A GB 8030899A GB 8030899 A GB8030899 A GB 8030899A GB 2084585 A GB2084585 A GB 2084585A
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- United Kingdom
- Prior art keywords
- process according
- radical
- gel
- polymer
- hydrophilic polymer
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- 229920001477 hydrophilic polymer Polymers 0.000 title claims abstract description 10
- 239000000499 gel Substances 0.000 title abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 229920006163 vinyl copolymer Polymers 0.000 claims abstract description 6
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- -1 amine salt Chemical class 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- USFMMZYROHDWPJ-UHFFFAOYSA-N trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical class CC(=C)C(=O)OCC[N+](C)(C)C USFMMZYROHDWPJ-UHFFFAOYSA-N 0.000 claims description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 4
- 239000007863 gel particle Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 11
- 239000003999 initiator Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 239000004160 Ammonium persulphate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 235000019395 ammonium persulphate Nutrition 0.000 description 3
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- QMYCJCOPYOPWTI-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;hydron;chloride Chemical compound Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QMYCJCOPYOPWTI-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 229920003118 cationic copolymer Polymers 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- QYCVBOXNHNZFKO-UHFFFAOYSA-N ethylideneazanide Chemical compound [CH2]C=[N] QYCVBOXNHNZFKO-UHFFFAOYSA-N 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- AIUAMYPYEUQVEM-UHFFFAOYSA-N trimethyl(2-prop-2-enoyloxyethyl)azanium Chemical compound C[N+](C)(C)CCOC(=O)C=C AIUAMYPYEUQVEM-UHFFFAOYSA-N 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
-
- 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
Abstract
A hydrophilic polymer gel can be prepared by polymerising the monomer or monomers of said polymer in an aqueous medium together with a compatible organic solvent and vinyl copolymer comprising 5 to 95 mol% of units of the general formula: <IMAGE> and, correspondingly, 95 to 5 mol% of recurring units of the formula: <IMAGE> in which R1 and R3 independently represent hydrogen or lower alkyl, R2 represents an alkyl group of at least 8 carbon atoms, and Y represents a hydrophilic radical or a quaternisable radical such as a pyridino or imidazolino radical. The method for the preparation of such gels prevents adherence of the gel particles together and so enables the complete drying of the gels.
Description
SPECIFICATION
The Preparation of High Molecular Weight Hydrophilic Polymer Gels
This invention relates to the preparation of high molecular weight hydrophilic polymer gels.
The preparation of high molecular weight hydrophilic polymer especially polyacrylamide, gels by bathwise polymerisation of aqueous monomer solution under adiabatic conditions has been known for some time. In general, the gels contain 25 to 40% by weight of solid, the remainder being water. The removal of the iatter has been effected by treatment with an organic solvent and this naturally adds to the cost as well as introducing a hazard element into the process. Alternatively, it is possible to dry these gel materials with hot air but the difficulty with this procedure is that as the gel dries and disintegrates, because of the sticky nature of the latter, the particles tend to adhere together thus making complete drying extremely difficult and, in many cases, almost impossible.There is, therefore, a need for a process which enables one to obtain gel particles which have little or no tendency to stick to one another and which, therefore, can be dried by hot air.
According to the present invention there is provided a process for the preparation of a hydrophilic polymer gel which comprises polymerising the monomer or monomers in an aqueous medium together with a compatible organic solvent and an organic vinyl copolymer as defined below. The organic vinyl copolymers used in the process of the present invention comprise 5 to 95 mol % of units of the general formula:
and correspondingly, 95 to 5 mol % of recurring units of the formula::
in which R, and R3 independently represent hydrogen or lower alkyl i.e. of 1 to 4 carbon atoms, preferably methyl, R2 represents an alkyl group of at least 8 carbon atoms, typically stearyl, and Y represents a hydrophilic radical or a quaternisable radical, in particular H, OOH or an alkali metal ammonium or amine salt thereof, a heterocyclic radical such as a pyridino or imidazolino radical, or a radical of the formula:
in which x is 1 to 4, preferably 2 to 4, R5 and R6 and R7 are independently lower alkyl radicals or hydrogen and X represents an anion, typically a chloride, methyl sulphonate, ethyl sulphonate or T sulphate anion, e.g. -COC2H4N(C2H5)2. In addition, Y may also represent --CONH,.
The copolymers used in the process of the present invention are thus vinyl addition type polymers. The correct balance of hydrophilic to hydrophobic groups in the polymer chain is important.
This balance can be achieved by using a mixture of a long chain fatty ester, typically of acrylic or methacrylic acid such as stearyl methacrylate or acrylate and a generally water-soluble monomer such as acrylic or methacrylic acid or methacryloyloxyethyltrimethyl ammonium salt, typically the metho sulphonate in the specified molar proportions. Of course, the cationic esters can be either in quaternised form or in the form of a salt such as the hydrochloride.
A preferred copolymer for use in the process of the present invention is derived from stearyl methacrylate and dimethyl amino ethyl methacrylate, typically prepared in a mol ratio of 1:1.25. This copolymer is typically used either after neutralisation with hydrochloric acid or after quaternisation with dimethylsulphate although, of course, it can be used as the free amine.
The molecular weight of the copolymers is generally from 1,000 to 500,000, preferably 1,000 to 15,000.
The copolymers used in the process may be prepared using conventional methods such as addition polymerisation, typically in organic solvents such as paraffinic or organic solvents or chlorinated solvents such as tetrachloroethylene.
As indicated above, the preparation of the gels is carried out in an aqueous medium in the presence of a compatible organic solvent. By "compatible" is meant an organic solvent which does not react with any of the materials present in the reaction medium. The organic solvent is preferably one which forms an azeotrope with water, especially one forming an azeotrope at 60 to 1000C. Typical organic solvents include perchloroethylene, hexane, white spirit, benzene, toluene and xylene although, of course, they must be compatible with the copolymer.
The monomer or monomers to be polymerised are generally present in the aqueous medium at a concentration from 1 5 to 90%, preferably 25 to 75% by weight. The pH of the solution can vary within a wide range but is typically from 2 to 8.5, especially from 6 to 8.5. The polymerisation can be carried out under either adiabatic or isothermal conditions; it is typically conducted at a temperature from 10 to 11 00C, more particularly from 10 to 900 C. The polymerisation is generally assisted with the use of conventional initiators including redox, persalt, and azo type initiators such as azobisisobutyronitrile, azobiscyanovaieric acid, ammonium persulphate and 2,2-azobis(2-amidinopropane) hydrochloride.
The concentration of initiator depends on the nature of the initiator. Azo initiators are conveniently used in an amount up to 2,000, for example 10 to 2,000, more particularly 500 to 1,000, ppm by weight (based on the weight of the monomer present). For per salts the concentration is generally 20 to 200, especially 50 to 100, ppm by weight and for ferrous ammonium sulphate typically 1 to 100, preferably 5 to 50, ppm by weight.
The process of the present invention is of general applicability enabling one to obtain gels of hydrophilic polymer. The invention is, however, particularly valuable for the preparation of acrylamide polymer gels. The term "acrylamide polymer" is intended to cover not only acrylamide homopolymers but also acrylamide copolymers containing other monomer units.
Suitable comonomers include acrylic and methacrylic acid, quaternised amino alkyl acrylates and methacrylates, as well as quaternised vinyl nitrogen-containing heterocyclic compounds. Specific monomers are:
(a) acrylic acid or alkali metal salts or amine salts thereof,
(b) diethylaminoethylacrylate or dimethylaminoethyl methacrylate quaternised with dimethyl sulphate or methyl chloride,
(c) methacrylamidopropyl trimethyl ammonium chloride,
(d) vinyl pyridine or vinyl imidazoiine quaternised with dimethyl sulphate or methyl choride. Other hydrophilic polymers which can be prepared in gel form include homopolymers of the monomers specified in paragraphs (b), (c) and (d) above.
It is a surprising feature of the present invention that the cationic copolymers used to assist the production of the gels can be used to prepare anionic as well as cationic acrylamide polymers.
The process of the present invention enables one to obtain polymers having a high molecular weight, generally of the order of 1 x 106 and molecular weights as much as 1 xl 07 or more can be obtained.
Once the polymerisation is complete the gel is generally broken down into particles of the desired size, typically not more than about 0.5 cm. In general, they can readily be dried in hot air without sticking together and, in this connnection, it should be noted that the organic solvent present, particularly when it forms an azeotrope with water, assists in the drying process. Further, in contrast to prior proposals where the solvent is used to dewater the gel, the solvent used need not be toxic and/or inflammable. The dried material can then be ground if desired.
The following examples further illustrate the present invention:
Example 1
0.6 Kg of acrylic acid were dissolved in 5.76 litres of de-ionised water. The pH was adjusted to 6.0 with caustic soda solution, cooling being applied to keep the temperature below 300 C. 2.4 Kg of acrylamide were dissolved in this solution and a final pH adjustment to 7.2 was carried out. 0.16 Kg of a 56% active solution in white spirit of a copolymer of stearyl methacrylate/dimethylaminoethylmethacrylate (1/1.25 mol ratio; molecular weight about 5,000) were stirred in.The temperature at this stage was 1 20C. The solution was purged with nitrogen for 20 minutes and 80 ml of methanol, 50 ppm of ammonium persulphate, 600 ppm of 2,2'-azobis (2 amidino propane) hydrochloride and 25 ppm of ferrous ammonium sulphate were added in that order (all quantities of initiator being based on the monomer). The initiators were added as dilute aqueous solutions. The temperature rose to 900 C.
The polymerisation was carried out in a well insulated steel vessel which retained sufficient heat to complete the polymerisation.
The gel was broken down into particles of less then 0.5 cm in size. The particles showed no tendency to re-adhere to each other when squeezed in the hand or put under a 1 Kg weight. A wax-like fee was imparted to the material. Drying was effected in a laboratory scale hot air drier to a moisture content of 10%.
The material produced possessed excellent solubility and had a molecular weight of 8.5 million as measured by intrinsic viscosity.
Example 2
A solution of 3 Kg acrylamide in 7 Kg of dionised water was prepared using the same stearyl methacrylate copolymer as in Example 1. The pH of the solution was adjusted to 5.0 using hydrochloric acid. Polymerisation was carried out adiabatically as in Example 1.
The resultant gel when disintegrated showed excellent non-adhesive properties and the gel particles could be hot air dried directly to give a moisture content of 12%. The polymer was solubie in water and had a molecular weight of 5 million.
Example 3
A solution of 3.75 Kg of acrylamide in 9.5 litres of de-ionised water was prepared. 5.0 kg of 75% solution of acryloyloxyethyl trimethylammonium methosulphate was added. 1 Kg of a 25% solution in hexane of a stearyl methacrylate/diethylaminoethyl acrylate copolymer (1:1.25 mole ratio) was added with stirring. 200 gm of dimethyl sulphate was added and stirred for 10 minutes. The solution was purged for 20 minutes with nitrogen foliowed by the addition of 0.5 Kg methanol, 25 ml of a 5% ammonium persulphate solution and 30 ml of a 1% ferrous ammonium sulphate solution (in the order given). A rapid exotherm to 1 050C occurred in 2 minutes with the emission of steam. The final solids content of the gel block was 70%. This was cut up to small particles which were non-sticky and which were hot air dried to 12% moisture to yield water soluble polymer.
Example 4
The procedure of Example 1 was repeated except the stearyl-methacrylate copolymer was replaced by a copolymer of acrylic acid and stearyl methacrylate (mole ratio 1.3:1) in hexane. The polymerisation followed a similar course and yielded a gel which, after disintegration, showed no tendency to re-adhere.
Claims (11)
1. A process for preparing a hydrophilic polymer gel which comprises polymerising the monomer or monomers of said polymer in an aqueous medium together with a compatible organic solvent and vinyl copolymer comprising 5 to 95 mol % of units of the general formula:
and, correspondingly, 95 to 5 mol of recurring units of the formula:
in which R, and R3 independently represent hydrogen or lower alkyl, R2 represents an alkyl group of at least 8 carbon atoms, and Y represents a hydrophilic radical or a quaternisable radical such as pyridino or imidazolino radical.
2. A process according to claim 1 for preparing an acrylamide polymer (as hereinbefore defined) gel.
3. A process according to claim 1 or 2 in which R, and R3 independently represent hydrogen or methyl.
4. A process according to any one of claims 1 to 3 in which R2 represents stearyl.
5. A process according to any one of claims 1 to 4 in which Y representsOH,COOH or an alkali metal, ammonium or amine salt thereof, -CONH2, a pyridino or imidazolino radical or a radical of the formula:
in which x is 1 to 4, R5, Re and R7 are independently lower alkyl or hydrogen and X represents an anion.
6. A process according to any one of the preceding claims in which the vinyl copolymer is derived from stearyl acrylate or methacrylate and acrylic or methacrylic acid or methacryloyloxyethyltrimethyl ammonium salt.
7. A process according to claim 6 in which the vinyl copolymer is derived from stearyl methacrylate and dimethylaminoethyl methacrylate in a mole ratio of about 1 :1.25.
8. A process according to any one of the preceding claims in which the organic solvent is perchloroethylene, hexane, white spirit, benzene, toluene orxylene.
9. A process according to any one of the preceding claims for preparing a gel of a polymer having a molecular weight of at least 1 xl 106.
10. A process according to claim 1 substantially as hereinbefore described.
11. A hydrophilic polymer gel whenever prepared by a process as claimed in any one of the preceding claims.
New Claims or Amendments to Claims filed on 25th May 1981
Superseded Claims
New or Amended Claims: Claims 1-11 1 filed after date of application on 25/5/81.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8030899A GB2084585B (en) | 1980-09-25 | 1980-09-25 | The preparation of high molecular weight hydrophilic polymer gels |
| SE8105599A SE8105599L (en) | 1980-09-25 | 1981-09-22 | PREPARATION OF HYDROPHILIC POLYMER GELS WITH HIGH MOLECULE WEIGHT |
| IT24077/81A IT1139468B (en) | 1980-09-25 | 1981-09-22 | PREPARATION OF HIGH MOLECULAR WEIGHT HYDROPHILE POLYMER GELS |
| DE19813137524 DE3137524A1 (en) | 1980-09-25 | 1981-09-22 | METHOD FOR PRODUCING HIGH MOLECULAR HYDROPHILIC POLYMER GELS |
| JP56148912A JPS5785812A (en) | 1980-09-25 | 1981-09-22 | Manufacture of high molecular hydrophilic polymer gel |
| FR8117945A FR2490649B1 (en) | 1980-09-25 | 1981-09-23 | PROCESS FOR PREPARING A HIGH MOLECULAR WEIGHT HYDROPHILIC POLYMER GEL |
| ES505753A ES505753A0 (en) | 1980-09-25 | 1981-09-24 | PROCEDURE TO PREPARE A HIGH MOLECULAR WEIGHT HYDROPHILIC POLYMER GEL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8030899A GB2084585B (en) | 1980-09-25 | 1980-09-25 | The preparation of high molecular weight hydrophilic polymer gels |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2084585A true GB2084585A (en) | 1982-04-15 |
| GB2084585B GB2084585B (en) | 1983-11-30 |
Family
ID=10516271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8030899A Expired GB2084585B (en) | 1980-09-25 | 1980-09-25 | The preparation of high molecular weight hydrophilic polymer gels |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5785812A (en) |
| DE (1) | DE3137524A1 (en) |
| ES (1) | ES505753A0 (en) |
| FR (1) | FR2490649B1 (en) |
| GB (1) | GB2084585B (en) |
| IT (1) | IT1139468B (en) |
| SE (1) | SE8105599L (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2572671A1 (en) * | 1984-11-06 | 1986-05-09 | Dai Ichi Kogyo Seiyaku Co Ltd | PROCESS FOR THE PREPARATION OF HYDRO-SOLUBLE POLYMER GEL PARTICLES |
| EP0346834A2 (en) * | 1988-06-13 | 1989-12-20 | National Starch and Chemical Investment Holding Corporation | Process for the manufacture of polymers |
| GB2426977A (en) * | 2005-06-10 | 2006-12-13 | Nippon Paint Co Ltd | Cissing inhibitor for cationic electrodeposition |
| US9916931B2 (en) | 2014-11-04 | 2018-03-13 | Capacitor Science Incorporated | Energy storage devices and methods of production thereof |
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| US10340082B2 (en) | 2015-05-12 | 2019-07-02 | Capacitor Sciences Incorporated | Capacitor and method of production thereof |
| US20170301477A1 (en) | 2016-04-04 | 2017-10-19 | Capacitor Sciences Incorporated | Electro-polarizable compound and capacitor |
| US10347423B2 (en) | 2014-05-12 | 2019-07-09 | Capacitor Sciences Incorporated | Solid multilayer structure as semiproduct for meta-capacitor |
| WO2015175558A2 (en) | 2014-05-12 | 2015-11-19 | Capacitor Sciences Incorporated | Energy storage device and method of production thereof |
| JP2018511167A (en) | 2015-02-26 | 2018-04-19 | キャパシタ サイエンシス インコーポレイテッド | Self-healing capacitor and manufacturing method thereof |
| US9932358B2 (en) | 2015-05-21 | 2018-04-03 | Capacitor Science Incorporated | Energy storage molecular material, crystal dielectric layer and capacitor |
| US9941051B2 (en) | 2015-06-26 | 2018-04-10 | Capactor Sciences Incorporated | Coiled capacitor |
| US10026553B2 (en) | 2015-10-21 | 2018-07-17 | Capacitor Sciences Incorporated | Organic compound, crystal dielectric layer and capacitor |
| US10305295B2 (en) | 2016-02-12 | 2019-05-28 | Capacitor Sciences Incorporated | Energy storage cell, capacitive energy storage module, and capacitive energy storage system |
| US10153087B2 (en) | 2016-04-04 | 2018-12-11 | Capacitor Sciences Incorporated | Electro-polarizable compound and capacitor |
| US9978517B2 (en) | 2016-04-04 | 2018-05-22 | Capacitor Sciences Incorporated | Electro-polarizable compound and capacitor |
| US10395841B2 (en) | 2016-12-02 | 2019-08-27 | Capacitor Sciences Incorporated | Multilayered electrode and film energy storage device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1205748A (en) * | 1966-11-21 | 1970-09-16 | Michael Raymond Clarke | Thickened aqueous liquids |
| NO139410C (en) * | 1976-02-19 | 1979-03-07 | Sintef | PROCEDURE FOR THE MANUFACTURE OF LATEX |
| GB2039497B (en) * | 1979-11-20 | 1983-01-26 | Ici Ltd | Manufacture of polymer dispersions and coating compositions derived from them |
-
1980
- 1980-09-25 GB GB8030899A patent/GB2084585B/en not_active Expired
-
1981
- 1981-09-22 JP JP56148912A patent/JPS5785812A/en active Pending
- 1981-09-22 SE SE8105599A patent/SE8105599L/en not_active Application Discontinuation
- 1981-09-22 IT IT24077/81A patent/IT1139468B/en active
- 1981-09-22 DE DE19813137524 patent/DE3137524A1/en not_active Withdrawn
- 1981-09-23 FR FR8117945A patent/FR2490649B1/en not_active Expired
- 1981-09-24 ES ES505753A patent/ES505753A0/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2572671A1 (en) * | 1984-11-06 | 1986-05-09 | Dai Ichi Kogyo Seiyaku Co Ltd | PROCESS FOR THE PREPARATION OF HYDRO-SOLUBLE POLYMER GEL PARTICLES |
| EP0346834A2 (en) * | 1988-06-13 | 1989-12-20 | National Starch and Chemical Investment Holding Corporation | Process for the manufacture of polymers |
| EP0346834A3 (en) * | 1988-06-13 | 1991-05-29 | National Starch and Chemical Investment Holding Corporation | Process for the manufacture of polymers |
| GB2426977A (en) * | 2005-06-10 | 2006-12-13 | Nippon Paint Co Ltd | Cissing inhibitor for cationic electrodeposition |
| US9916931B2 (en) | 2014-11-04 | 2018-03-13 | Capacitor Science Incorporated | Energy storage devices and methods of production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2490649A1 (en) | 1982-03-26 |
| IT8124077A0 (en) | 1981-09-22 |
| ES8207561A1 (en) | 1982-09-16 |
| DE3137524A1 (en) | 1982-06-16 |
| FR2490649B1 (en) | 1986-06-13 |
| GB2084585B (en) | 1983-11-30 |
| JPS5785812A (en) | 1982-05-28 |
| SE8105599L (en) | 1982-03-26 |
| ES505753A0 (en) | 1982-09-16 |
| IT1139468B (en) | 1986-09-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |