GB1572219A – Acrylamide polymer hydrogels of reduced adhesiveness and their production
– Google Patents
GB1572219A – Acrylamide polymer hydrogels of reduced adhesiveness and their production
– Google Patents
Acrylamide polymer hydrogels of reduced adhesiveness and their production
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Info
Publication number
GB1572219A
GB1572219A
GB29363/77A
GB2936377A
GB1572219A
GB 1572219 A
GB1572219 A
GB 1572219A
GB 29363/77 A
GB29363/77 A
GB 29363/77A
GB 2936377 A
GB2936377 A
GB 2936377A
GB 1572219 A
GB1572219 A
GB 1572219A
Authority
GB
United Kingdom
Prior art keywords
acrylamide
polyethylene glycol
hydrogel
weight
acrylate
Prior art date
1976-01-09
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.)
Expired
Application number
GB29363/77A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Rayon Co Ltd
Nitto Chemical Industry Co Ltd
Original Assignee
Mitsubishi Rayon Co Ltd
Nitto Chemical Industry Co Ltd
Priority date (The priority date 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 date listed.)
1976-01-09
Filing date
1977-07-13
Publication date
1980-07-30
1976-01-09
Priority claimed from JP159976A
external-priority
patent/JPS5938242B2/en
1976-12-17
Priority claimed from JP15084776A
external-priority
patent/JPS5910694B2/en
1977-07-13
Application filed by Mitsubishi Rayon Co Ltd, Nitto Chemical Industry Co Ltd
filed
Critical
Mitsubishi Rayon Co Ltd
1980-07-30
Publication of GB1572219A
publication
Critical
patent/GB1572219A/en
Status
Expired
legal-status
Critical
Current
Links
Espacenet
Global Dossier
Discuss
239000000017
hydrogel
Substances
0.000
title
claims
description
33
229920002401
polyacrylamide
Polymers
0.000
title
claims
description
15
238000004519
manufacturing process
Methods
0.000
title
description
5
229920000642
polymer
Polymers
0.000
claims
description
52
229920001223
polyethylene glycol
Polymers
0.000
claims
description
49
239000002202
Polyethylene glycol
Substances
0.000
claims
description
48
HRPVXLWXLXDGHG-UHFFFAOYSA-N
Acrylamide
Chemical compound
NC(=O)C=C
HRPVXLWXLXDGHG-UHFFFAOYSA-N
0.000
claims
description
43
239000000178
monomer
Substances
0.000
claims
description
34
238000000034
method
Methods
0.000
claims
description
33
239000000243
solution
Substances
0.000
claims
description
18
239000007864
aqueous solution
Substances
0.000
claims
description
16
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
9
-1
dimethylaminohydroxypropyl
Chemical group
0.000
claims
description
9
239000000203
mixture
Substances
0.000
claims
description
8
229920003169
water-soluble polymer
Polymers
0.000
claims
description
7
BAPJBEWLBFYGME-UHFFFAOYSA-N
Methyl acrylate
Chemical compound
COC(=O)C=C
BAPJBEWLBFYGME-UHFFFAOYSA-N
0.000
claims
description
6
229920002554
vinyl polymer
Polymers
0.000
claims
description
6
239000003795
chemical substances by application
Substances
0.000
claims
description
4
229920001577
copolymer
Polymers
0.000
claims
description
4
125000000391
vinyl group
Chemical group
[H]C([*])=C([H])[H]
0.000
claims
description
4
SMZOUWXMTYCWNB-UHFFFAOYSA-N
2-(2-methoxy-5-methylphenyl)ethanamine
Chemical compound
COC1=CC=C(C)C=C1CCN
SMZOUWXMTYCWNB-UHFFFAOYSA-N
0.000
claims
description
3
NIXOWILDQLNWCW-UHFFFAOYSA-N
2-Propenoic acid
Natural products
OC(=O)C=C
NIXOWILDQLNWCW-UHFFFAOYSA-N
0.000
claims
description
3
NLHHRLWOUZZQLW-UHFFFAOYSA-N
Acrylonitrile
Chemical compound
C=CC#N
NLHHRLWOUZZQLW-UHFFFAOYSA-N
0.000
claims
description
3
JIGUQPWFLRLWPJ-UHFFFAOYSA-N
Ethyl acrylate
Chemical compound
CCOC(=O)C=C
JIGUQPWFLRLWPJ-UHFFFAOYSA-N
0.000
claims
description
3
CERQOIWHTDAKMF-UHFFFAOYSA-N
Methacrylic acid
Chemical compound
CC(=C)C(O)=O
CERQOIWHTDAKMF-UHFFFAOYSA-N
0.000
claims
description
3
GYCMBHHDWRMZGG-UHFFFAOYSA-N
Methylacrylonitrile
Chemical compound
CC(=C)C#N
GYCMBHHDWRMZGG-UHFFFAOYSA-N
0.000
claims
description
3
YIQOKWWBKOVYBX-UHFFFAOYSA-N
[3-(dimethylamino)-3-hydroxypropyl] 2-methylprop-2-enoate
Chemical compound
CN(C)C(O)CCOC(=O)C(C)=C
YIQOKWWBKOVYBX-UHFFFAOYSA-N
0.000
claims
description
3
229910052783
alkali metal
Inorganic materials
0.000
claims
description
3
125000002573
ethenylidene group
Chemical group
[*]=C=C([H])[H]
0.000
claims
description
3
FQPSGWSUVKBHSU-UHFFFAOYSA-N
methacrylamide
Chemical compound
CC(=C)C(N)=O
FQPSGWSUVKBHSU-UHFFFAOYSA-N
0.000
claims
description
3
RCLLINSDAJVOHP-UHFFFAOYSA-N
n-ethyl-n’,n’-dimethylprop-2-enehydrazide
Chemical compound
CCN(N(C)C)C(=O)C=C
RCLLINSDAJVOHP-UHFFFAOYSA-N
0.000
claims
description
3
PNJWIWWMYCMZRO-UHFFFAOYSA-N
pent‐4‐en‐2‐one
Natural products
CC(=O)CC=C
PNJWIWWMYCMZRO-UHFFFAOYSA-N
0.000
claims
description
3
150000003242
quaternary ammonium salts
Chemical class
0.000
claims
description
3
230000000379
polymerizing effect
Effects
0.000
claims
description
2
SJIXRGNQPBQWMK-UHFFFAOYSA-N
2-(diethylamino)ethyl 2-methylprop-2-enoate
Chemical compound
CCN(CC)CCOC(=O)C(C)=C
SJIXRGNQPBQWMK-UHFFFAOYSA-N
0.000
claims
2
DPBJAVGHACCNRL-UHFFFAOYSA-N
2-(dimethylamino)ethyl prop-2-enoate
Chemical compound
CN(C)CCOC(=O)C=C
DPBJAVGHACCNRL-UHFFFAOYSA-N
0.000
claims
2
239000002253
acid
Substances
0.000
claims
2
150000007513
acids
Chemical class
0.000
claims
2
150000001252
acrylic acid derivatives
Chemical class
0.000
claims
2
150000002734
metacrylic acid derivatives
Chemical class
0.000
claims
2
QHVBLSNVXDSMEB-UHFFFAOYSA-N
2-(diethylamino)ethyl prop-2-enoate
Chemical compound
CCN(CC)CCOC(=O)C=C
QHVBLSNVXDSMEB-UHFFFAOYSA-N
0.000
claims
1
NIXOWILDQLNWCW-UHFFFAOYSA-M
Acrylate
Chemical compound
[O-]C(=O)C=C
NIXOWILDQLNWCW-UHFFFAOYSA-M
0.000
claims
1
NRGNIRIWTPPPCH-UHFFFAOYSA-N
[3-(dimethylamino)-3-hydroxypropyl] prop-2-enoate
Chemical compound
CN(C)C(O)CCOC(=O)C=C
NRGNIRIWTPPPCH-UHFFFAOYSA-N
0.000
claims
1
239000007863
gel particle
Substances
0.000
description
34
238000006116
polymerization reaction
Methods
0.000
description
33
239000000499
gel
Substances
0.000
description
21
238000001035
drying
Methods
0.000
description
12
LYCAIKOWRPUZTN-UHFFFAOYSA-N
Ethylene glycol
Chemical compound
OCCO
LYCAIKOWRPUZTN-UHFFFAOYSA-N
0.000
description
9
125000000129
anionic group
Chemical group
0.000
description
7
IJGRMHOSHXDMSA-UHFFFAOYSA-N
Atomic nitrogen
Chemical compound
N#N
IJGRMHOSHXDMSA-UHFFFAOYSA-N
0.000
description
6
239000002245
particle
Substances
0.000
description
6
XLYOFNOQVPJJNP-UHFFFAOYSA-N
water
Substances
O
XLYOFNOQVPJJNP-UHFFFAOYSA-N
0.000
description
6
125000002091
cationic group
Chemical group
0.000
description
5
239000004698
Polyethylene
Substances
0.000
description
4
229920006317
cationic polymer
Polymers
0.000
description
4
230000000694
effects
Effects
0.000
description
4
229920000573
polyethylene
Polymers
0.000
description
4
239000000843
powder
Substances
0.000
description
4
HEMHJVSKTPXQMS-UHFFFAOYSA-M
Sodium hydroxide
Chemical compound
[OH-].[Na+]
HEMHJVSKTPXQMS-UHFFFAOYSA-M
0.000
description
3
QVGXLLKOCUKJST-UHFFFAOYSA-N
atomic oxygen
Chemical compound
[O]
QVGXLLKOCUKJST-UHFFFAOYSA-N
0.000
description
3
239000008367
deionised water
Substances
0.000
description
3
229910021641
deionized water
Inorganic materials
0.000
description
3
238000001125
extrusion
Methods
0.000
description
3
238000010528
free radical solution polymerization reaction
Methods
0.000
description
3
WGCNASOHLSPBMP-UHFFFAOYSA-N
hydroxyacetaldehyde
Natural products
OCC=O
WGCNASOHLSPBMP-UHFFFAOYSA-N
0.000
description
3
229910052757
nitrogen
Inorganic materials
0.000
description
3
229910052760
oxygen
Inorganic materials
0.000
description
3
239000001301
oxygen
Substances
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description
3
239000008188
pellet
Substances
0.000
description
3
229910001220
stainless steel
Inorganic materials
0.000
description
3
QAOWNCQODCNURD-UHFFFAOYSA-N
Sulfuric acid
Chemical compound
OS(O)(=O)=O
QAOWNCQODCNURD-UHFFFAOYSA-N
0.000
description
2
229920006322
acrylamide copolymer
Polymers
0.000
description
2
229920006318
anionic polymer
Polymers
0.000
description
2
230000015572
biosynthetic process
Effects
0.000
description
2
GZUXJHMPEANEGY-UHFFFAOYSA-N
bromomethane
Chemical compound
BrC
GZUXJHMPEANEGY-UHFFFAOYSA-N
0.000
description
2
NEHMKBQYUWJMIP-UHFFFAOYSA-N
chloromethane
Chemical compound
ClC
NEHMKBQYUWJMIP-UHFFFAOYSA-N
0.000
description
2
230000000977
initiatory effect
Effects
0.000
description
2
239000003505
polymerization initiator
Substances
0.000
description
2
239000011148
porous material
Substances
0.000
description
2
238000010298
pulverizing process
Methods
0.000
description
2
238000010926
purge
Methods
0.000
description
2
150000003839
salts
Chemical class
0.000
description
2
239000010935
stainless steel
Substances
0.000
description
2
239000000126
substance
Substances
0.000
description
2
238000011282
treatment
Methods
0.000
description
2
OJZJPJZINHWHAT-UHFFFAOYSA-N
2-(diethylamino)ethyl prop-2-enoate;2-(dimethylamino)ethyl prop-2-enoate
Chemical compound
CN(C)CCOC(=O)C=C.CCN(CC)CCOC(=O)C=C
OJZJPJZINHWHAT-UHFFFAOYSA-N
0.000
description
1
MTPJEFOSTIKRSS-UHFFFAOYSA-N
3-(dimethylamino)propanenitrile
Chemical compound
CN(C)CCC#N
MTPJEFOSTIKRSS-UHFFFAOYSA-N
0.000
description
1
DTSBYIWBBRRVIY-BJDJZHNGSA-N
Asp-Met-Met-Cys
Chemical compound
CSCC[C@@H](C(=O)N[C@@H](CS)C(=O)O)NC(=O)[C@H](CCSC)NC(=O)[C@H](CC(=O)O)N
DTSBYIWBBRRVIY-BJDJZHNGSA-N
0.000
description
1
239000004705
High-molecular-weight polyethylene
Substances
0.000
description
1
229920003171
Poly (ethylene oxide)
Polymers
0.000
description
1
229920000297
Rayon
Polymers
0.000
description
1
239000000654
additive
Substances
0.000
description
1
230000000996
additive effect
Effects
0.000
description
1
239000002998
adhesive polymer
Substances
0.000
description
1
230000002411
adverse
Effects
0.000
description
1
238000005054
agglomeration
Methods
0.000
description
1
230000002776
aggregation
Effects
0.000
description
1
150000001350
alkyl halides
Chemical class
0.000
description
1
150000003863
ammonium salts
Chemical class
0.000
description
1
KGBXLFKZBHKPEV-UHFFFAOYSA-N
boric acid
Chemical compound
OB(O)O
KGBXLFKZBHKPEV-UHFFFAOYSA-N
0.000
description
1
239000004327
boric acid
Substances
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
238000005520
cutting process
Methods
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description
1
230000001419
dependent effect
Effects
0.000
description
1
FBFVXSBCWUNIQI-UHFFFAOYSA-N
desmethoxymajusculamide C
Natural products
CN1C(=O)C(C(C)C)N(C)C(=O)CNC(=O)C(C(C)CC)N(C)C(=O)CNC(=O)C(C(C)CC)OC(=O)C(C)C(CC)NC(=O)C(C)NC(=O)C(C)(C)C(=O)C(C)NC(=O)C1CC1=CC=CC=C1
FBFVXSBCWUNIQI-UHFFFAOYSA-N
0.000
description
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detrimental effect
Effects
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description
1
150000008050
dialkyl sulfates
Chemical class
0.000
description
1
DENRZWYUOJLTMF-UHFFFAOYSA-N
diethyl sulfate
Chemical compound
CCOS(=O)(=O)OCC
DENRZWYUOJLTMF-UHFFFAOYSA-N
0.000
description
1
229940008406
diethyl sulfate
Drugs
0.000
description
1
VAYGXNSJCAHWJZ-UHFFFAOYSA-N
dimethyl sulfate
Chemical compound
COS(=O)(=O)OC
VAYGXNSJCAHWJZ-UHFFFAOYSA-N
0.000
description
1
238000010981
drying operation
Methods
0.000
description
1
238000007720
emulsion polymerization reaction
Methods
0.000
description
1
238000005516
engineering process
Methods
0.000
description
1
239000008394
flocculating agent
Substances
0.000
description
1
239000012530
fluid
Substances
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description
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238000005187
foaming
Methods
0.000
description
1
239000012634
fragment
Substances
0.000
description
1
230000007062
hydrolysis
Effects
0.000
description
1
238000006460
hydrolysis reaction
Methods
0.000
description
1
239000003999
initiator
Substances
0.000
description
1
INQOMBQAUSQDDS-UHFFFAOYSA-N
iodomethane
Chemical compound
IC
INQOMBQAUSQDDS-UHFFFAOYSA-N
0.000
description
1
229940102396
methyl bromide
Drugs
0.000
description
1
229940050176
methyl chloride
Drugs
0.000
description
1
USHAGKDGDHPEEY-UHFFFAOYSA-L
potassium persulfate
Chemical compound
[K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O
USHAGKDGDHPEEY-UHFFFAOYSA-L
0.000
description
1
238000012673
precipitation polymerization
Methods
0.000
description
1
230000005855
radiation
Effects
0.000
description
1
239000002964
rayon
Substances
0.000
description
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238000010008
shearing
Methods
0.000
description
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238000005507
spraying
Methods
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description
1
238000005728
strengthening
Methods
0.000
description
1
238000010557
suspension polymerization reaction
Methods
0.000
description
1
229920003002
synthetic resin
Polymers
0.000
description
1
239000000057
synthetic resin
Substances
0.000
description
1
239000002562
thickening agent
Substances
0.000
description
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238000005303
weighing
Methods
0.000
description
1
Classifications
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
C08J3/00—Processes of treating or compounding macromolecular substances
C08J3/12—Powdering or granulating
C08J3/124—Treatment for improving the free-flowing characteristics
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
C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
C08L33/24—Homopolymers or copolymers of amides or imides
C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
C08J2333/24—Homopolymers or copolymers of amides or imides
C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
C08L71/02—Polyalkylene oxides
Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y10S524/00—Synthetic resins or natural rubbers — part of the class 520 series
Y10S524/916—Hydrogel compositions
Description
PATENT SPECIFICATION ( 11) 1 572 219
b ( 21) Application No 29363/77 ( 22) Filed 13 Jul1977 ( 19), ( 44) Complete Specification Published 30 Jul 1980 ( 51) INT CL CO 8 L 33/26 (C 08 L 33/26 71/02) ( 52) Index at Acceptance C 3 L DF JB 1 C 3 W 210 C 3 Y F 585 ( 72) Inventors: HISAO OTANI AKIHISA FURUNO IWAO OHSHIMA ( 54) ACRYLAMIDE POLYMER HYDROGELS OF REDUCED ADHESIVENESS AND THEIR PRODUCTION ( 71) We, NITTO CHEMICAL INDUSTRY CO, LTD, No 5-1 Marunouchi, 1-Chome, Chiyoda-Ku, Tokyo, Japan and MITSUBISHI RAYON CO LTD, No 8, Kyobashi 2-Chome, Chuo-Ku, Tokyo, Japan, both Japanese Companies, do hereby declare the invention for which we pray that a Patent may be granted to us, and the method by
which it is to be performed, to be particularly described in and by the following statement: 5
This invention relates to acrylamide polymer hydrogels of reduced adhesiveness, and their production.
Water-soluble polymers such as polyacrylamide, partially hydrolyzed products of polyacrylamide, and cationic, anionic or nonionic copolymers containing acylamide (generically referred to herein as polymers derived from acrylamide have recently gained increasing 10 acceptance as paper strengthening agents, thickeners for use in papermaking and flocculating agents for treating water.
Various methods of polymerization, e g, as described in Encylopedia of Polymer Science and Technology, Vol 1, (John Wiley and Sons, Inc ( 1964)) and more specifically, methods such as aqueous solution polymerization (e g as described in U S Patent 3, 332,922), 15 emulsion polymerization (e g as described in U S Patent 3,284,393), suspension polymerization (e g as described in U S Patent 2,982,749), radiation polymerization (e g as described in U S Patent 3,477,932) or precipitation polymerization are known to prepare polymers, derived from acrylamide but the aqueous solution polymerization method has been most widely used because it is economical and easily affords highmolecular weight 20 polymers From the stand point of economy in polymerization, transportation or drying, it is desirable to start the polymerization with a high monomer concentration.
As the concentration of the monomer increases, however, the resulting polymer becomes an elastomeric gel having a higher viscosity, and is difficult to handle as a fluid A possible method for avoiding this difficulty would be one which comprises mincing such a high 25 viscosity elastomeric gel into coarse gel-particles, drying the particles using a rotary cylindrical dryer, a belt-type dryer or the like, and then finely pulverizing the dried particles thereby to produce a readily water-soluble powdery polymer that is easy to handle This method, however, has the disadvantage that because of the adhesiveness of the polymeric gel, its adhesion to other substances or to itself becomes exceedingly high, and this is a great 30 drawback in drying the polymeric hydrogel.
In order to solve this problem, U S Patent 3,905,122 discloses a method which comprises extruding a high-viscosity elastomeric gel through a perforated plate, forming mutually adhering small gel globules by cutting the gel before or after passing the gel through the perforated plate, and drying the aggregate with hot air while applying a shearing force This 35 method is successful to some extent, and hydrogels of anionic or nonionic polymers can be treated relatively well with this method Since, however, hydrogels of cationic polymers generally have a much higher adhesiveness than anionic or nonionic polymers, a reduction in the adhesion of the polymeric hydrogel particles to one another still cannot be achieved, and a good drying operation is difficult to perform 40 It has, however, now been found that polyethylene glycol added during the production of polymer derived from acrylamide or to the resulting hydrogel-like polymer markedly reduces the adhesiveness of water-soluble cationic polymers, derived from acrylamide and such polymers can be minced and dried without hardly any adhesion between the gel particles 45 1,572,219 It has also been discovered that when this technique is applied to the production of anionic or nonionic acrylamide polymers or copolymers, the adhesiveness of these types of polymeric gels is further reduced as compared with that obtained with conventional treatments of anionic or nonionic polymeric gels, and operability in pulverizing and drying such polymeric gels is also enhanced Moreover, a partial agglomeration of the polymeric gel particles within the dryer due to their adhesiveness is avoided, a problem which has been observed frequently in conventional techniques.
Accordingly, the present invention resides in one aspect in a method for reducing the adhesiveness of a hydrogel of a water-soluble polymer derived from acrylamide comprising solution polymerizing a high concentration aqueous solution of acrylamide or a monomeric 10 mixture containing acrylamide in the presence of polyethylene glycol having an average molecular weight of 300 to 1,000,000.
In a further aspect, the invention resides in a method for reducing the adhesiveness of a hydrogel of a water-soluble polymer derived from acrylamide, which comprises applying polyethylene glycol having an average moleculor weight of 300 to 1,000, 000 to the surface 15 of the hydrogel.
The polymer derived from acrylamide used in the methods described above must be substantially elastic, and have some degree of rigidity If the concentration of the starting monomer is too low at the time of polymerization, the resulting polymeric gel becomes soft and difficult to treat For example, when an acrylamide polymer having an average molecu 20 lar weight of about 8 million is desired, the lower limit of concentration of the starting monomer is about 18 % by weight.
Examples of suitable polymers derived from acrylamide for use in the above methods are polyacrylamide, partially hydrolyzed products of polyacrylamide, and water-soluble copolymers of acrylamide with any other vinyl or vinylidene monomers as comonomers 25 Examples of vinyl comonomers which can be used to prepare these acrylamide copolymers include cationic vinyl monomers such as diethylaminoethylacrylate dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate dimethylaminohydroxypropyl acrylate, dimethylaminohydroxypropyl methacrylate, or dimethylaminoethyl acrylamide; quaternary ammonium salts of cationic vinyl monomers 30 obtained by treatment with quaternizing agents, e g alkyl halides such as methyl chloride, methyl iodide, methyl bromide; dialkyl sulfates such as dimethyl sulfate, diethyl sulfate; nonionic monomers such as acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate or methacrylamide; anionic monomers such as acrylic acid, methacrylic acid, or salts of these e g, alkali metal salts or ammonium salts 35 A suitable molecular weight for the polymers derived from acrylamide is at least 1,000,000, preferably about 2,000,000 In the case of a cationic polymer pendant groups are present and, therefore, polymer derived from acrylamide having a molecular weight slightly lower than that of a nonionic or an anionic polymer can be employed Where a cationic monomer is used to produce the polymer derived from acrylamide, the comonomer 40 can be used in an amount of up to about 50 % by weight to the total weight of acrylamide and the comonomer However, where an anionic monomer is used, it is preferred to use less than about 50 % by weight Specifically, on considering the solubility of the final polymer product, for certain kinds of monomer the upper limit for the comonomer used is the maximum solubility which the comonomer itself possesses 45 With respect to the aqueous solution polymerization, suitable process conditions which can be used to produce the polymers derived from acrylamide can be easily selected by one skilled in the art For example, a 23 % aqueous solution of a monomer mixture comprising % of acrylamide by weight of the total monomer and 5 % of dimethylaminoethyl methacrylate by weight of the total monomer is subjected to adiabatic polymerization at a polymer 50 ization initiation temperature of 25 to 28 C using 2,2 ‘-azobis-2 amidinopropane hydrochloride as a polymerization initiator After about 2-3 hours, the polymerization temperatures reaches its maximum value (about 95 C) and the polymerization is complete, the resultant product being a raw rubber-like and adhesive polymer hydrogel In general a monomer concentration in the aqueous solution is a concentration of at least 18 % by weight 55 The polyethylene glycol used as the additive in the methods described above has an average molecular weight of 300 to 1,000,000, preferably 1,000 to 20,000 When polyethylene glycol having an average molecular weight of 300 to 1,000 is employed, a reduction in adhesiveness to some extent can be obtained However, the reduction effect in adhesiveness is best exhibited when the polyethylene glycol has an average molecular 60 weight of about 1,000 to 20,000 On the other hand, when polyethylene glycol (including polyethylene oxides in a broad sense) having a very high molecular weight (e g an average molecular weight of 1,000,000 or higher) is used, the effect of reducing the adhesiveness is substantially the same as in the case of using a polyethylene glycol having an average molecular weight of not more than 1,000 It has been found however that when this very 65 3 1,572,219 high-molecular-weight polyethylene glycol is used during the polymerization, the viscosity of the monomer solution increases because the polyethylene glycol dissolves in the solution prior to polymerization, and this adversely affects the polymerization operation.
When the polyethylene glycol is added during polymerization of an acrylamide-type monomer, the polyethylene glycol is dissolved in the aqueous solution of the monomer in 5 the required amount When the polyethylene glycol is to be applied directly to a hydrogellike polymer, a fine powder of the polyethylene glycol may be applied to the polymer, it being appreciated that polyethylene glycol having the above-specified molecular weight has the form of flakes at room temperature (about 20-300 C) Alternatively, an aqueous solution of the polyethylene glycol may be first formed and the solution then sprayed onto the 10 polymer.
It is to be appreciated that an aqueous solution of polyethylene glycol is not compatible with a hydrogel of a polymer, derived from acrylamide and with the passage of time, the polyethylene glycol tends to deposit on the surface of the polymer Hence, even if the polyethylene glycol is incorporated into the hydrogel-like polymer, the polyethylene glycol 15 gradually gathers on the surface of the polymer to coat the surface sufficiently to reduce the adhesiveness of the polymer.
The amount of the polyethylene glycol used is from 0 02 to 10 %, preferably 0 1 to 5 %, by weight based on the monomer solution or the polymeric hydrogel The specific amount used in each case varies slightly depending upon the period in time at which the addition is made 20 Thus, when the polyethylene glycol is added to the polymerization system prior to the polymerization, the amount added is 0 1 to 10 % by weight, but when the polyethylene glycol is applied, e g, by spraying onto the polymeric hydrogel, a sufficient effect can be achieved using a smaller amount, e g, not more than about 0 05 % by weight The reason a smaller amount can be used is unknown, but it is assumed to be that it is unnecessary to 25 actually incorporate the polyethylene glycol into the interior of the hydrogel.
For anionic polymers, nonionic polymers, or weakly cationic polymers containing less than about 20 % by weight of cationic monomer units, the effect achieved with the polyethylene glycol is sufficiently exhibited even when the polyethylene glycol is employed in an amount of as low as 0 05 to 0 2 % by weight based on the monomer solution or the 30 hydrogel On the other hand, medium to strongly cationic copolymers containing a higher ratio of cationic monomer units have increased adhesiveness, and therefore, small amounts of polyethylene glycol are not sufficient to reduce the adhesiveness of these types of polymers and the remaining adhesiveness is detrimental in subsequent handling of the polymer.
However, addition of polyethylene glycol in amount of 0 5 to 5 % by weight based on the 35 monomer solution or the hydrogel reduces the adhesiveness of such polymeric hydrogels to an extent such that the hydrogel can be minced and dried satisfactorily.
Accordingly, the amount of polyethylene glycol which is suitable is also dependent on the composition of the polymer derived from acrylamide but can readily be determined by one skilled in the art It should, however, be noted that excessive amounts of polyethylene 40 glycol not only reduce the quality of the polymer, but also foaming tends to occur when the polymer is dissolved in water.
The water-soluble hydrogel-like polymer derived frim acrylamide whose adhesiveness has been reduced in the manner described above can be formed into a dry powder by, for example, the method disclosed in U S Patent 3,905,122 cited above Even when the 45 polymer is transported and stored in the form of small hydrogel globules, the globules do not adhere to one another, and therefore can be formed into an aqueous solution at the desired use location.
The following Examples are given to illustrate the present invention in greater detail and in the Examples all parts, percents, ratios and the like are by weight unless otherwise 50 indicated.
EXAMPLE 1
17.5 kg of acrylamide, 0 92 kg of dimethylaminoethyl methacrylate, 300 g of 96 % sulfuric acid and 160 g of polyethylene glycol having an average molecular weight of 6250 55 were uniformly dissolved in deionized water in a 100-liter polymerization vessel whose interior was made of stainless steel, to form 80 kg of a monomer solution The solution was purged with nitrogen to remove oxygen sufficiently, and after adding 8 0 g of 1,2 ‘ -azobis-2 -amidinopropane hydrochloride as a polymerization initiator, polymerization at 280 C (starting temperature) in an adiabatic state was conducted The polymerization ended in 60 minutes, and the temperature of the polymer reached 95 ‘C at maximum due to the heat of polymerization After the polymerization, the top end plate of the polymerization vessel was removed, and the vessel was turned through 1800 to remove the polymer entirely The adhesiveness of the polymer gel to the polymerization vessel at this time was so slight that it could be neglected 65 1,572,219 1,572,219 The polymeric gel obtained ( 40 kg per batch) was passed through an extrusion mincer having a perforated plate with a pore diameter of 3 2 mm at its forward end and a cutter inside the mincer The resulting cord-like minced gel particles were dried in a rotary cylindrical hot air dryer having a diameter of 470 mm and a width of 560 mm The drying conditions were as follows: rotating speed of the drying drum: 4 5 rpm; flow rate of hot air 5 at the inlet: 0 6 m/sec; hot air temperature: 60 WC; and drying time: 300 minutes.
During the drying, the minced polymer gel was in the form of pellets with a diameter of several millimeters which were dried while flowing well in the drying drum Finally, dried pellets in a substantially cubic form which were extremely easy to handle were obtained.
The dried pellets were pulverized finely using a pulverizer to obtain a powdery polymer 10 The powdery polymer was soluble in water, and an aqueous solution of the polymer at a concentration of 1 % had a viscosity of 4,800 centipoises as determined by a Brookfield viscometer using a No 2 rotor at a speed of 6 rpm The powdery polymer had a moisture content of 7 9 %.
EXAMPLE 2 15
Polymerization was carried out under the same conditions as in Example 1 except that polyethylene glycol was not used, and then using the same procedure as in Example 1, cord-like minced gel particles were obtained.
Minced gel particles were spread on a stainless steel wire gauze, and an aqueous solution 20 of polyethylene glycol having a molecular weight of about 6,000 in the varying concentrations as shown in Table 1 below was sprayed onto the minced gel particles in an amount of 2 % by weight based on the weight of the cord-like minced gel particles.
kg of each of the resulting cord-like minced gel particles was dried under the same conditions as in Example 1 The results obtained are also given in Table 1 25 Table 1
Concentration of Conditions within Amount of PolyPolyethylene Glycol the Dryer ethylene Glycol (% by weight) (freedom from adhesion (% by weight gel) 30 of gel particles to one another) Excellent 0 4 10 Excellent 02 35 Good 0 1 2 Fair 0 04 1 Fair 0 02 0 Poor 0 40 Comparison 1) The adhesion of the gel particles to one another was evaluated on the following scale.
Excellent:Hardly any adhesion of the gel particles to one another and to the inside wall of the dryer was observed, and the flowability of the gel particles was excellent.
After drying, the gel particles became separate single particles.
Good: Some adhesion was observed between the fel particles and between the gel particles and the inside wall of the dryer.
Fair: A fairly high degree of adhesion was observed although the degree of adhesion Poor: was better than in the case of not employing polyethylene glycol.
Poor: About 80 % by weight of the gel particles within the dryer adhered to one 50 another Moreover, considerable labor was required to remove the dried gel particles which adhered to the inside wall of the dryer.
EXAMPLE 3 55
Using a 15-litre experimental polymerization vessel, oxygen was removed from a monomer solution ( 1000 g) of each of the compositions shown in Table 2 by purging the system with nitrogen, and after addition of 0 1 g of 2,2 ‘-azobis-2 amidinopropane hydrochloride, polymerization at 30 WC (starting temperature) in an adiabatic state was conducted.
The resulting polymer gel was comminuted using a small-sized extrusion mincer having a porous plate with a pore diameter of 4 mm and having a cutter inside the mincer The minced fragments of the polymer gel were spread on a synthetic resin net in a shelf-type hot air dryer, and dried at 60 WC for 15 hours The adhesion of the gel particles to one another during the period of time from mincing to drying was evaluated 65 L’ Table 2
2 3 Comparison Composition’ Acrylamide (g) DMAEMA (g) 96 %H 125 O, (g) Polyethylene Glygol (g) Average Molecular weight of Polyethylene Glycol Adhesion of Gel Particles to One Another Remarks 218 5 11.5 3.75 Extremely high 218 5 11.5 3.75 2.5 400 Somewhat high 218 5 218 5 11.5 11 5 3.75 3 75 2.5 5 0 1,500 1,500 Slight Scarcely none Polymerization Run 218 5 11.5 3.75 2.5 6,250 Scarcely none S 218 5 11.5 3.75 2.5 20,000 Scarcely none 218 5 11.5 3.75 2.5 1 million Somewhat high Viscosity of monomer solution increased The components were dissolved in deionized water so that the resulting solution weighed 1,000 g (hereinbelow the same).
Dimethylaminoethyl methacrylate (hereinbelow the same).
it 6 1,572,219 6 EXAMPLE 4
A monomer solution of each of the compositions shown in Table 3 below was polymerized in an adiabatic state using the same polymerization vessel as used in Example 3 under the conditions shown in Table 3 below.
The polymeric gels obtained were each minced and dried in the same way as in Example 3, and the adhesion of the gel particles to one another was evaluated in the same way The results are shown in Table 3.
Table 3
Polymerization Run Compa Compa Comparison 3 7 rison 4 8 9 rison 5 10 Composition Acrylamide (g) DMAEMA (g) DMMC (g) 96 %H 2504 (g) Polyethylene Glycol (g) Polymerization Initiation Temperature (o C) Amount of Initiator (ppm/monomer solution) Adhesion of Polymeric gel particles to one another Viscosity of a 1 % Aqueous Solution of Powdery Polymer (centipoises) Remarks 220 220 2.0 200 Some Scarcely none 2,300 2,150 No Ioc Nonionic Very high; crushed gel particles again agglomerated; (many aggregates of dried gel particles formed) (formation of powder ldifficult) 160 160 52 52 4.0 16 O 32 32 100 Some Scarcely what none high 350 400 Tertiary + Cationic 320 320 20.0 250 Scarcely none 250 Very high; crushed gel particles again agglomerated; (many aggregates of dried gel particles formed) (formation of powder difficult) 8,700 Quaternized catioc Quaternized -1 ctoi Methyl chloride quaternary salt of DMAEMA.
Having an average molecular weight of 6,250 2,2 ‘-Azobis-2-amidinopropane hydrochloride l 8 1,572,219 EXAMPLE S
23 kg of acrylamide, 0 6 kg of sodium hydroxide and 0 9 kg of boric acid were dissolved in deionized water to form 100 kg of a monomer solution The solution was divided into two 5 portions each weighing 50 kg These portions were each placed in an 80litre polymerization vessel, and 0 23 kg of polyethylene glycol having an average molecular weight of 4,000 was added to one portion Oxygen was removed sufficiently from both systems by purging with nitrogen, and at 250 C, 2 0 g of potassium persulfate and 2 0 g of dimethylaminopropionitrile were added as polymerization initators Both systems exhibited the same 10 polymerization behavior, and began to polymerize in about 10 minutes In about 90 minutes, the temperature reached 930 C at a maximum, whereupon the polymerization ended to afford hydrogels free from flowability The hydrogels were aged for 16 hours in an adiabatic state.
Then, the hydrogels were minced and dried in the same way as set forth in Example 1 15 About 200 % of the polymer gel particles obtained in the absence of polyethylene glycol adhered to one another and caked In contrast, hardly any caked portion in the polymer gel particles was obtained in the presence of polyethylene glycol Both of these polymers were hydrolyzed products of polyacrylamide with a hydrolysis ratio of about 14 mole C.
EXAMPLE 6 20
The nonionic polyacrylamide shown in Comparison 3 in Table 3 was prepared using a 10-litre stainless steel polymerization vessel on a scale of 6 kg All of the gel particles obtained were minced employing the same extrusion mincer as used in Example 1 to form a cord-like gel aggregate One kilogram-portions of the gel aggregate were each placed in a 25 polyethylene bags, and polyethylene glycol (molecular weight about 6,000) in the various amounts shown in Table 4 below was sprinkled in a powdery form onto the aggregates in the bags.
The cord-like gel aggregates, placed in the bags, were allowed to stand for one week, and then, the adhesion of the gel particles to one another was examined The results obtained 30 are shown in Table 4.
TABLE 4
Freedom of Amount of Polyethylene Adhesion of Gel Particles 35 Glycol Added to one Another (Weight So) Excellent 1 Excellent 0.5 Excellent 0.2 Good 0.02 Fair Poor 45 The adhesion of the gel particles was visually evaluated on the following scale.
Excellent:No aggregates Good: The gel particles were all separated by merely applying a light force from outside the bag.
Fair: The gel particles were all separated by merely applying a medium force from 50 outside the bag.
Poor: The gel particles formed a mass with apparently no boundary between the particles.
Note: The «medium force» and «light force» as used above is not critical but is generally expressed as follows 55 Medium forces: Grasping the bag, a pressure of about 5 to about 10 kg/cm 2.
Light force: Lightly shaking the bag.
Claims (1)
WHAT WE CLAIM IS:-
1 A method for reducing the adhesiveness of a hydrogel of a water-soluble polymer derived from acrylamide comprising solution polymerizing a high concentration aqueous 60 solution of acrylamide or a monomeric mixture containing acrylamide in the presence of polyethylene glycol having an average molecular weight of 300 to 1,000, 000.
2 A method as claimed in Claim 1, wherein the amount of the polyethylene glycol ranges from 0 02 to 10 % by weight, based on the weight of the aqueous solution of the monomer 65 1,572,219 9 1,572,219 9 3 A method as claimed in Claim 2, wherein the amount of the polyethylene glycol ranges from 0 1 to 5 % by weight, based on the weight of the aqueous solution of the monomer.
4 A method as claimed in any one of the preceding Claims, wherein the polymer derived from acrylamide is polyacrylamide, a partially hydrolyzed product of polyacrylamide, or a copolymer derived from acrylamide and another vinyl or vinylidene monomer copolymerizable therewith.
A method as claimed in Claim 4, wherein the comonomer is at least one member selected from dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminohydroxypropyl acry 10 late, dimethylaminohydroxypropyl methacrylate, dimethylaminoethyl acrylamide, quaternary ammonium salts of these acrylates or methacrylates, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, methacrylamide, acrylic acid, methacrylic acid and alkali metal salts of these acids.
6 A method for reducing the adhesiveness of a hydrogel of a water-soluble 15 acrylamide-type polymer, which comprises applying polyethylene glycol having an average molecular weight of 300 to 1,000,000 to the surface of the hydrogel.
7 A method as claimed in Claim 5, wherein the amount of the polyethylene glycol is 0.02 to 10 % by weight, based on the weight of the hydrogel.
8 A method as claimed in Claim 7, wherein the amount of the polyethylene glycol is 20 0.1 to 5 % weight based on the weight of the hydrogel.
9 A method as claimed in any one of Claims 6 to 8, including crushing the hydrogel prior to applying the polyethylene glycol thereto.
A method as claimed in any one of Claims 6 to 8, wherein the polyethylene glycol is applied in the form of an aqueous solution thereof 25 11 A method as claimed in any one of Claims 6 to 10, wherein the hydrogel polymer is polyacrylamide, a partially hydrolyzed product of polyacrylamide, or a copolymer derived from acrylamide and another vinyl or vinylidene monomer copolymerizable therewith.
12 A method as claimed in Claim 11, wherein the comonomer is at least one member selected from dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dieth 30 ylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminohydroxypropyl acrylate, dimethylaminohydroxypropyl methacrylate, dimethylaminoethyl acrylamide, quaternary ammonium salts of these acrylates of methacrylates, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, methacrylamide, acrylic acid, methacrylic acid and alkali metal salts of these acids 35 13 A method as claimed in any one of the preceding Claims, wherein the polyethylene glycol has an average molecular weight of 1,000 to 20,000.
14 A method as claimed in Claim 1 or Claim 6, for reducing the adhesiveness of a hydrogel of a water-soluble polymer derived from acrylamide substantially as hereinbefore described with reference to any one of the Examples 40 A hydrogel of a water-soluble polymer derived from acrylamide produced by a method as claimed in any one of the preceding Claims.
16 A hydrogel of a water-soluble polymer derived from acrylamide containing polyethylene glycol MARKS & CLERK, 45 Chartered Patent Agents, Alpha Tower, ATV Centre, Birmingham Bl 1 TT Agents for the Applicants 50 Printed for Her Majesty’s Stationery Office, by Croydon Printing Company Limited, Croydon Surrey, 1980.
Published by The Patent Office, 25 Southampton Buildings London, WC 2 A l AY,from which copies may be obtained.
GB29363/77A
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Legal Events
Date
Code
Title
Description
1980-10-29
PS
Patent sealed [section 19, patents act 1949]
1993-03-10
PCNP
Patent ceased through non-payment of renewal fee
Effective date:
19920713
