GB2198442A - Copolymers of acrylic acid or methacrylic acid or their alkaline metal salts - Google Patents
Copolymers of acrylic acid or methacrylic acid or their alkaline metal salts Download PDFInfo
- Publication number
- GB2198442A GB2198442A GB08723640A GB8723640A GB2198442A GB 2198442 A GB2198442 A GB 2198442A GB 08723640 A GB08723640 A GB 08723640A GB 8723640 A GB8723640 A GB 8723640A GB 2198442 A GB2198442 A GB 2198442A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acid
- metal salts
- copolymers
- acrylic acid
- alkaline metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- 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
- 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
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
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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)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
i - 4 2198442 Copolymers of acrylic or methacrylic acid or oil their
alkaline metal salts The invention Dertains to copolymers 011 acrylic or meth- their alkaline metal salts ivith macromono- acrylic acid or of mners based on oligourethanes which are able to absorb large amounts of water and are therefore suitable as materials removing water or for applications as a gel in the swollen state.
Materials of natural origin, as nonlaoven cellulose or cotton fibers, or natural and synthetic spongy materials so far are L U U $. -1 mostly used as the materials absorbing water mainly for hygienic and iniedicall purposes in the production of tissues, powders, and the li-lre. However, these materials have a li-lited absorption capacity and cannot absorb sufficient amounts of water or bodv 'I--i(iui-ds.
!his is why materials were recently proposed which are based on water soluble polymiers and copolymers -with their solubility practically completely suppressed by crosslin',...:ino by means of' I- C> crosslinking agents which are compounds containing two or Tore reacItive functional groups (e.g. unsaturated linlkages, epoxide 11 - v groups, etc. Another way how to suppress -l,,L-4e L.Y Ls 1 J c pop- ,o-cement c' hydrophilic, groups with 1.1 -il the part.Lal rep. L _CrOUDS0 C) - u--h materials were obt-ained, for example, by copolymerizate or f acrylic ac; ycol me'Uhac.-yla-'U ---ono Ld with ethylene gl, m.e'L.acryl-ic acid with divinylbenzene (U.S. Paten-L no. 4,37Q,,8,,'c') (1983), Czeehoslovn-',. Patent no. 185,863 (1978)), scrylamide with li,Nlal.',ylidene-bis-acryla.riide or with ethylene glycol diaerylate or divinylbenzene (Japanese Fatent no. 68 23,468), 11 11 by the crosslinking reaction of N-hydroxyacrylamide using a W light energy at low temperature (Japanese Ilatent, 69 C=.
by copolymerization of polyol methacrylate with unsaturated acids or monor-ners containing basic groups in the presence of C) 11 ethylene Elyeol diacrylate, methylene-bis-aci.ylamide or divinylbenzene (Japanese Patent no. 73 25,749), or by copolymeri- ion of unsaturated carboxylic acJ.ds or sulfonic acids with Za L, - - -j- -L pol.val'n-,lene dscrylate or poly(ethylere glycol) dig!-ici-dy! 1Patent, n,--. 2,061,725 (1082) is also _known. the preparation of a copolymer c--'L ethylene, vin-71 ester (e.g. vinyl acetate) and acrylic ester (e.g. methyl C, acrylate) with divinylbenzene, which is in tne -following step W - A saponi-fied (japanese Ilatuent no. 78 1C4,691). Also polysaccha- 11 ke) gra-f-Led, with acrylo- -,:rches, cellulose, and Lile rides (SU- 1-, k J gh s orpll cn ni'-,le cive by a WiLh n, --- -- c, - - c E'ormed by the di---cgrafting f Coolyi,,ers of pol,7sacc ardes - - 111 k, tent no. 82 38,80Q with --cryli-c or methacrylic acid (Japanese Pat pol:l(vn-,,lelcohol) -,od-i-'."5-ed with sodium salt. of acrylLc cr Met- hacr-,lic acid (Ger-man Patenll, (FIERS) no. 2,935,712 (10.80)) are - lar proper-'-U- als wit s m Jes.
ilc),,,;ever. the above mentioned mGteri-als had nu--erous problems in their practical application, above all an insu--,'oicier-lu tion capacity 'or water or body liquids, and also t-he sorp-'L. L ration r.-,.ethods for some of them are rather complicated. Long- 5JS terM ap.:!-'Ca-'Lions o_ soze o_f these materl- in. the swollen 9 L L state, i.e. in the fo m Of gel, led to the destruction o' their structure as a consequence of poor stability.
The objective of this invention, which overcomes the above said shortcomings, is a copolymer of acrylic acid or methacrylic acid or of their alkaline metal salts with m--cromonomers based on oligourethanes carrying unsaturated groups of the acrylate and/ or methacrylate type at one or both ends of chain, the chemical structure of which corresponds to the general formula I X H 10 -R - OC ONII-LR 1 NHC 01 n OCH2CH2Lxju--C;=k;K2 (i) or the general formula II C5 X X 1 i CH ---u-jjuuut-i2CH20CONIMI1TIZ.CO[OROCOIMRIITIC 0] CC; H O-C=CH- (!I) 2 n 2U '2 Lk; 4 where RI-Js the residue Of the used aliphatic, aromatic or alid,-iisocyana'te, R is the residue cf.' a lo,.,;-molecular-weight aliDhatic diol with, 2-4 carbon atoms, X is IHI or WII 3 and n = 2-40, whereas the= composition is given by the ratio of 0.5 wit. part-s to 10 wt. parts Of the macrorrionomer to 100 wt. parts of acrylic acid or methacrylic acid or their alkaline metal salts.
A.suitable diisocyanate from the aliphatic derivatives is -b-ylenedJisocyanate, Lro-m -he aromatic deriyatives p-phe- hexamet 11 n,ylenedJA.-3socian,-2'ue, 2,zl-tolyleredi-isocs,--na-'Le, "-, 6-'Lolyleredi--isocyanate(or their M.'Xture), lened'lisocyanate, and fProm. the aliphat-..Le-aroma"il-ic derivatives 4,41-me'Lhylene-bis(phenyli-socyanate) and 4,41-o-thylene-bis(phenylisocyanate). The difunctional oligourethane is formed by a polyaddition reaction in the presence of - 4 diols as are ethylene glycol, propylene glycol, 1,2-propane- v diol, 1,4-butanediol, and diethylene glycol (3-oxa-1,5-pentanediol).
Oligourethane with one or two terminal vinyl groups is prepared either sequentially, i.e. diisocyanate is first ali L. lowed to react witIlkydroxyallkyi acrylate or hydro_-:7al';_-yl Methacrylate and,after this reaction is cor.,pleted, the addition with the corresponding diol is carried out. The reaction may be also realized in one stage, where both hydroxy compounds, i.e. mono hyd=xy d--_h_YdI2ox-y c or.-poi:-nds, reac t with diisocyanate at 4 e s e tim.e. Hydroxyal]kyl ester acts as a terminator in both c as e s.
Preparation of these macromonomers based on olicoureth-!--nes h an unsaturated group of or methacrylate L,er:i-4nated wii, U U W t J no.
7 - d - - L - -- ,,pe 3-1 cne bol - s dese-'bed J- U.S. Satent 4,58--.,3,,:.L (1986): ( C-zechoslovak Patent no. 223,409 (1983).
---e ca,2c-.., o absorb wa er or body licuid and indirecul, a!--o -che mechanical strength of gels in swollen state depend of the cool,.,.,ner com-one-n-"1s. Accordino- to C> on the --:-'orme:, or latter property, the ratio is chosen in the rec.on of C.5 tO 10 Wt. Parts Of the macromono mer to iCC parts off acrylic acid or methaerylic acid or SOCIUM- or salts.
j;-ei,zc-,tcn reGc-' -ch r.lay be carried out ,.-e couo. o n a s su -e+ or init- tion b.7 G!! s7ener211, hods usinG initiators 14a sys' c-=s nduc,iE the radcal cooolymerJza-Lion, for exam le j -1 - L - - - L, '1 7 -eio.,.ride, cumene hydroperoxide, cyclohlexanol peroxide, --- - - - -,:1_ di,cet.y- peroxide, d-J-+.er-L,-butyl peroxide, diisopropyl peroxo- 1 carbonate, azo-tis-isobutyronitrile, potassium or ammonium diperoxodisulfatel or their combinations with reducing agents, e.g. sodium thiosulfLate, ascorbic acid, hydroxyacetone, and metal ions as Fe 2+ or Cu+. The reaction nay be carried out either in the absence of a solvent (in bulk) or in its presence, i.e. in water, alcohols, ketones, or aprolk-sic solvents as dimethylformahiide or N-methylpyrrolidone, or in their mixtures with water.
!.'U has been Droved earlier that the copolymerization of co=ercial lowmolecullar-weight monomers 1^--hydroxj-e-ALhyl methacrylate, h.-jdro--z--, ye'tlhy--, acrylate, hydroy-yprop,1 acrylate, and N-vinylpyrrolidone with the macromonomer of the oligourethane type is a prerequisite of a relatively higli m-echanical strength o--!' the resultin.7 products in swollen state U.15. Patent no.
!Z::; 11 L -I 4,,,..5o5t2--36 (1198-7 1 ((-'zec,l,.osioia'-s- P-Patent. no. 250c.39). IL Lurned 'ha' this enect occurs also -n the case c' coDol-,,m.eriza-io.-,i oul t U U -1 - - 11 -1 J_ 0 - U o--:-' acr,,,!--'c or acid or their al'21-aline m.etIal salts, Itr: 'I U a c c. 0 di m, '1 1 -L - .h-Lch ex-ri-Ib- ec.,..a.-.ical sturength even after swe'ling -1 Go U I- ', t w ' -led Y 0 - 35, '00 9 of v, _. t, i _. d i s t 11 - 10 OW their. original weight, i.e. if' the content of solids was 1-0.286c,. The swelling capacity of these highly swelling malerials was W - the crushed (ground) copolymer determined by placing 0.5 iss 0- C) W to 7 -i. -,; ----- - - 1_) on -1-ne 1-10-1-1 -. of a, m-e2su-Jne. cyllinder and overcasting he volume of gel was read w d ii s t 1 c d t, e r o t h e m a r', hours of after, 4-4 1 standJnr-- and divided b.v 0.5 (or multiplied W T1h-e result multiplied by 1C0 gave the capacit in percdn', L - j As ffollows fro-m above description and from the appended examoles, the method J"or iDrodaci-ng these copolymners is easy - 0 a-d does not -f-rom usual procedures.
Example 1
Preparation of ol--ouret,'-,,-.ne (r.--CA-o.,.nonomer) with molecular 1:
w e i g1ht 23C.0 A glass 'Kettle with volume 1000 ml equipped with a thermo- te reflux condenser with a calciu.. chloride seal, st a (1 m nle-t, A'- of nitrogen, and thermometer was charged with 82.4 M1 of he:came',,h,,lenediisocyanate (content of NCO of theory), 9.15 mi of 2-lydroxvethyl methacrylate, and 1.5 9 of tetrabutyl e r h e a 't, i n cz, t o 5 0 il L C for 22 hours with. stirring under -10 ---o2-en, o-O was add n 1 11 -L 11 1-1) ed followed, af-er homogenization, by 53 g of 2,21-oxy(diethanol) (diethylene gglycol) dissolved in 300 i-al of d-ime'ihylforma:.,iide in the presence of 4.5 =71 of le-'Lra"Du,-,yl tin. TI-e Ilixture was allowed to react', for L U + the product.,,.as then precipitated by pouring, the Jnto E "I of distilled water under stirrins.
1. -L - U U L -- - P S U 1 L, - C) - t le-'-. -n overni-ht at ambient, tle=.7.era- ---hwater, and dried in vacuum to the -she, w, u L, 1 ' c, --,,rle=ayer was charged with 50 9 offreshly -c-d acryllic n-ciu -cromonomer 'ncsed on ol c-o- -) g 0 2: EI - - C-- 1 - - a n d' to -ixed. an electromagnetic stirrer and distributed into 8 -;ol.i,nes of 10 m! each, which were first flushed i with- i-i'uroEe-rl. The ampoules viere sealed and the copolymeriza- tion re-ct-on carri. - 1 L d out i-', t-,'70 -Qtoc,-,es: first for 20 hours 7 - at labor@-'Qory temperalouze (the main part of reaction was completed wit- hin about 3 hours), then for 16 hours at 40 OC. The product was re-noved from ampoules, ground in a cross mill, and 0.05 M sodium hydroxide (NaOIH).
overcast with 12,500 ml oL Liquid above the swollen gel was decanted after 24 hours and the gel w3s washed twice with 10,000 ml of distilled water. The last portion of wa' L I Ler (pH 6-5) was decanted, the gel was substantially deswelled by additoon off 500 ml of-C ethanol while its grainy structure remained preserved, filtered, and dried 0 in a vacuum oven at 40 C. The resulting powdered product swelled lume Q--'Ler overcastin- of 1 g with distilled water to the vo.
C) of 210 ml.
E-:aM-D1e 3 Preparation oJE' oligourethane (macromonomer) based on d-J-.he.nyl- isoc 1-e with 11 2SCO methane dl janat n The glass kettle specified in example 1 was charged with g of 4,41-.---h le-rie-bis-(plier,,71isocyana'Le) 440 g Of C> dime'Lh,-,il--;'orma.-.,i-ide, and 4.68 g of 2-h57drorje-.t-h-yl methacrylate ur. ed under nitrogen to 50 0 C t-,-d '-e-+ (HEMA l i e m i x- t. e s h e a t, - - 11 L'-, at ithis 'Lemperature for 2 hours. AI, mi.xture of 15.26 g of diethylene glycol (DEG) and 8.47 9 of 1,4-butanediol (BD) was then. added and the reaction was continued for another 4 hours.
r-I.., Ihe used rattio of starting components:
C) j=: DEG: BD = 1.0: 0.15: 0.6: 0.4.
A-te:, the react5on -,.;as completed, the react5o.n innixture was P. U.L U L, -- - cooled to ambient temperature and the product was precipitated A under vi.,-,orous stirring into 1C. 1 of distilled water and -worked out similarly as in example 1. A--5"ter drying, 86 g of the powde- of theory) -Ith = 2,870 (determined red zi,-,cro,-,.onomer (0 W-; 'v-n Jj the method o2 end groups by means o:- was obtained.
Example 4
A glass flask equipped with a stirrer, inlet of nitrogen, and thermometer was charged with 10 g of freshly distilled acrylic acid, 50 m]- of 31.11 aqueous sodium hydroxide (NaOH), and O.C2 z of the macromonomer with LI 2870 prepared accordinc n t to example 3. The reaction mixture was then homogenized and bubbled through with nitrogen and M5 ml of a 1-i; aqueous 1 C- - s o 1 u 'L i o n o S 0 and 0.25 nl of a 6-% aqueous solution 2 2 8 -.4 0 Of was added. Temperature was increased to 40 c under stirring and maintained for 6 hours. The reaction product'.,Nas Yjashed with 5c-o' aqueous ethanol and dried at reduced pressure and 50 0 C for 24r hours. T1hie absorption of distilled water amounted to 311000 %.
Example 5 Model tampons - verification for medical purposes A copolymerization product according to example 2 in the crushed form in auantities of c. 0.1 g (with an accuracy of 0.001 g) was packed into bags made from unglued cellulose paper stock, which otherwise are used as tea bags.
After filling, the bags were closed with an aluminium foil tape, weighed and immersed into 1) distilled water 2) saline containing 0.9 mass % 'iaci 3) blood plasma.
An empty bag, also closed with Al foil, was used as a control sample in the same procedure.
After 24 h the bags were removed and weighed, and the following sorption capacities (in mass %) were determined:
distilled water 10 700 saline 860 blocd plasma 1 070 1 CLADISS:
CO-OlyMerS OL -,CryliC acid or methaerylic acid or tlneir al'-n-,al-ine metal salts with a mDcromono.-ner based on oligourethane terminated at one or'both ends of the chain with an unsaturated and/ group of the acrylate or- methecrylate type, Lhe chermical structure of which corresponds to the general --,'or:pula i X i S [O-R-OCOIITL-rR 1 CC H-CII20CO-C =C H d 2 or Genterp! formula!I X 1 -100CH IIMCOEO-R-OCOTH-RliTH,'%',0 OCH C-lc34^Uuu-U=CH ii U h2 --U 2 C F2 OC' n 2 4 2 ---Pa low-nolecular-weigh+ all i o 1 i-,jhere R is the residue o. -Pha'-c d- with. 2 to 4 carbon atoms R' is the residue of an al c 1 arom.e.'L,ic, or allpIL--1a-'tlic-a romatic diisocyanate, 'X'I is H or CH13 and n = 2 to 40,,.,,-hereas their co-mnposition is Siven by the ratio of 0.5 to 10 il,.,e-igh't, parts of the macromonomer. to 1 or th ir alkaline DarItS Of aCl-yLiC acid or z,.,zethecryl-ic acir 1 -1 e 1 - r.
rne- tal salts.
T
Claims (1)
- 2. Copolymer of acrylic acid or methacrylic acid or their alkaline saltsas claimed in Claim 1 substantially as described in any of the examples disclosed herein.er copies may be obtained from The Patent Office, Published 1988 at The Patent Office, State House, 65,71 High o1born, Londan WC1R 4TP. Furth Wes Branch. St Mary Cray. Orpington Kent BRs 311D Printed by MWtiplex techniques ltd. St Mary Cray. Kent. Corf 1187
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS867492A CS263644B1 (en) | 1986-10-16 | 1986-10-16 | Copolymers of acrylic or methacrylic acid or alkalic metal salts thereof |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8723640D0 GB8723640D0 (en) | 1987-11-11 |
| GB2198442A true GB2198442A (en) | 1988-06-15 |
| GB2198442B GB2198442B (en) | 1990-05-30 |
Family
ID=5424164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8723640A Expired - Fee Related GB2198442B (en) | 1986-10-16 | 1987-10-08 | Copolymers of acrylic or methacrylic acid or of their alkaline metal salts |
Country Status (5)
| Country | Link |
|---|---|
| AT (1) | ATA272387A (en) |
| CS (1) | CS263644B1 (en) |
| DE (1) | DE3735141A1 (en) |
| FR (1) | FR2605324B1 (en) |
| GB (1) | GB2198442B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4015085C2 (en) * | 1990-05-11 | 1995-06-08 | Stockhausen Chem Fab Gmbh | Crosslinked, water-absorbent polymer and use for the manufacture of hygiene articles, for soil improvement and in cable sheathing |
| DE4020780C1 (en) * | 1990-06-29 | 1991-08-29 | Chemische Fabrik Stockhausen Gmbh, 4150 Krefeld, De | |
| DE4026239A1 (en) * | 1990-08-18 | 1992-02-20 | Hoechst Ag | COPOLYMERISATE CONTAINING CARBOXYL GROUPS, THEIR PRODUCTION AND THEIR USE AS THICKENERS |
| JP3045422B2 (en) * | 1991-12-18 | 2000-05-29 | 株式会社日本触媒 | Method for producing water absorbent resin |
| DE69922962T2 (en) * | 1998-06-15 | 2006-01-05 | Union Carbide Chemicals & Plastics Technology Corp., Danbury | IN ALKALI SOLUBLE THICKENERS FOR LATEX |
| DE10114382A1 (en) * | 2001-03-23 | 2002-09-26 | Beiersdorf Ag | Moisture-absorbing material used for plasters, medical fixings, wound coverings and bandages comprises adhesive matrix of silicon, gel former and optionally silicone resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4584354A (en) * | 1981-04-17 | 1986-04-22 | Ceskoslovenska Akademie Ved Of Prague | Graft copolymers and the method of their preparation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4514552A (en) * | 1984-08-23 | 1985-04-30 | Desoto, Inc. | Alkali soluble latex thickeners |
| IT1177161B (en) * | 1984-11-12 | 1987-08-26 | Resem Spa | ETHYLENICALLY UNSATURATED MONOMER POLYMERS MODIFIED WITH OLIGOURETHANE AND WATER DISPERSIONS OBTAINED FROM THEM |
-
1986
- 1986-10-16 CS CS867492A patent/CS263644B1/en unknown
-
1987
- 1987-10-08 GB GB8723640A patent/GB2198442B/en not_active Expired - Fee Related
- 1987-10-14 AT AT0272387A patent/ATA272387A/en not_active Application Discontinuation
- 1987-10-15 FR FR878714253A patent/FR2605324B1/en not_active Expired
- 1987-10-16 DE DE19873735141 patent/DE3735141A1/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4584354A (en) * | 1981-04-17 | 1986-04-22 | Ceskoslovenska Akademie Ved Of Prague | Graft copolymers and the method of their preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2198442B (en) | 1990-05-30 |
| CS749286A1 (en) | 1988-09-16 |
| DE3735141A1 (en) | 1988-04-21 |
| FR2605324B1 (en) | 1989-12-01 |
| CS263644B1 (en) | 1989-04-14 |
| ATA272387A (en) | 1991-11-15 |
| GB8723640D0 (en) | 1987-11-11 |
| FR2605324A1 (en) | 1988-04-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |