AP834A - Process to prepare foam from high internal phase emulsions. - Google Patents
Process to prepare foam from high internal phase emulsions. Download PDFInfo
- Publication number
- AP834A AP834A APAP/P/1998/001303A AP9801303A AP834A AP 834 A AP834 A AP 834A AP 9801303 A AP9801303 A AP 9801303A AP 834 A AP834 A AP 834A
- Authority
- AP
- ARIPO
- Prior art keywords
- emulsion
- water
- high internal
- phase
- internal phase
- Prior art date
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 135
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000006260 foam Substances 0.000 title description 37
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000003860 storage Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 7
- 229920006254 polymer film Polymers 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 58
- 239000000178 monomer Substances 0.000 description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 239000004094 surface-active agent Substances 0.000 description 25
- -1 olefin halides Chemical class 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 239000003999 initiator Substances 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 239000008346 aqueous phase Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 235000002639 sodium chloride Nutrition 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 239000007762 w/o emulsion Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000223 polyglycerol Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000001593 sorbitan monooleate Substances 0.000 description 3
- 235000011069 sorbitan monooleate Nutrition 0.000 description 3
- 229940035049 sorbitan monooleate Drugs 0.000 description 3
- 229920002554 vinyl polymer Polymers 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
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000004147 Sorbitan trioleate Substances 0.000 description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 2
- 150000001361 allenes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000019337 sorbitan trioleate Nutrition 0.000 description 2
- 229960000391 sorbitan trioleate Drugs 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NULRZTYFHXTPTH-MXTXEKNZSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C)SC([C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO)SCC Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C)SC([C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO)SCC NULRZTYFHXTPTH-MXTXEKNZSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- XFBSDJUKJYOLAG-OCYQJKLISA-N [(2r,3r,4s,5r)-6-oxo-2,3,4,5-tetra(prop-2-enoyloxy)hexyl] prop-2-enoate Chemical compound C=CC(=O)OC[C@@H](OC(=O)C=C)[C@@H](OC(=O)C=C)[C@H](OC(=O)C=C)[C@@H](OC(=O)C=C)C=O XFBSDJUKJYOLAG-OCYQJKLISA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910001385 heavy metal Chemical class 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/283—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum a discontinuous liquid phase emulsified in a continuous macromolecular phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/14—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length
- B29C39/16—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length between endless belts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/20—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
- B29C44/32—Incorporating or moulding on preformed parts, e.g. linings, inserts or reinforcements
- B29C44/321—Incorporating or moulding on preformed parts, e.g. linings, inserts or reinforcements the preformed part being a lining, e.g. a film or a support lining
- B29C44/3215—Folding devices for the lining
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/20—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
- B29C44/32—Incorporating or moulding on preformed parts, e.g. linings, inserts or reinforcements
- B29C44/334—Filling the preformed spaces or cavities
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/028—Foaming by preparing of a high internal phase emulsion
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0504—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being aqueous
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
A process is provided for curing a high internal phase emulsion to form a porous crosslinkcd polymeric material, comprising the steps of: forming a high internal phase emulsion having at least one curable phase; providing a continuous strip of polymeric film wherein the polymeric film is incompatible with each of the phase of emulsion; placing at least a portion of the emulsion continuously on the polymer film; closing the polymeric film around the emulsion; spiraling the emulsion in the polymeric film onto a spool, wherein the spool rotates about an essentially vertical axis for storage of the emulsion during curing; and curing the emulsion within the polymeric film on the spool. Apparatuses to perform this process arc also disclosed.
Description
PROCESS TO PREPARE FOAMS FROM HIGH INTERNAL PHASE EMULSIONS
This invention relates to a process to prepare foam compositions from high internal phase emulsions wherein the non-internal phase is a polymerizable composition. ΙΚιΚεχώηριΚΔρΚ
Polymeric foams can be generally classified as 10 either closed-cell foams or as open-cell foams. Open-cell foams can be used as a matrix to contain various liquids and gases. They are suitable for various applications such as, for example, use in wipes and diapers, as carriers and ion fig exchange resins. For some of these applications, it is 15 desirable to have porous crosslinked polymer blocks which have a very low density and a high capacity of absorbing and retaining liquids. Such high absorption capacity, low density, porous polymer blocks can be prepared by polymerizing a specific type of water-in-oil emulsion known as high internal phase emulsion having relatively small amounts of a continuous oil phase and relatively greater amounts of an internal water phase.
Such high absorption capacity, low density, foams are prepared by a process disclosed in U.S. Pat. No.
4,522,953 by polymerizing and crosslinking monomers in the continuous oil phase of a high internal phase water-in-oil KA emulsion with a polymerization initiator such as potassium persulfate. Generally, these high internal phase water-inoil emulsions contain at least 90 weight percent of a water phase as the internal phase. The high ratio water-in-oil emulsions are formed by combining the oil phase with water under moderate shear. In order to obtain this high internal phase water-in-oil emulsion, a surfactant is used to stabilize the emulsion. It is also advantageous to incorporate an electrolyte into the aqueous phase. The amount and type of electrolyte, along with the amount and type of surfactant, effects the pore size, and wicking ability of the cured foam.
AP/P/ 9 8 / 0 1 3 0 3
APO00834
Foams prepared from high internal phase emulsions are generally cured at temperatures of forty to seventy degrees centigrade for periods of several hours.. In a laboratory scale, this is easily accomplished. Scale up to a reasonable commercial scale is a signifi-cant challenge. Curing and handling individual tubs of emulsion and foam would be slow and labor intensive.
U.S. Pat. No. 5,250,576, issued to Des Marais et al. on October 5, 1993, 5,198,472, issued to Des Marais et al. on March 30, 1993, and 5,149,720, issued to Des Marais et al. on September 22, 1992, disclose a continuous process to prepare a high internal phase emulsion for curing into foam compositions, but the emulsions are continuously poured into polymerization containers and cured in the individual containers. Thus, preparation of the emulsion in a continuous fashion is known, but curing remains a slow and labor intensive operation.
It is therefore an object of the present invention to provide a method to prepare foams from of high internal phase emulsions wherein the method can be readily automated and operated on a large scale.
In another aspect, it is an Object of the present invention to provide an apparatus wherein emulsions can be cured in large volumes.
Description of the.....Invention
-7*| According to the present invention, a process for curing a high internal phase emulsion to form a porous crosslinked polymeric material is provided, the process comprising the steps of:
forming a high internal phase emulsion having at least one curable phase; providing a continuous strip of polymeric film wherein the polymeric film is incompatible with each of'the phase of emulsion; placing at least a portion of the emulsion continuously on the polymer film; closing the polymeric film around the emulsion; spiraling the emulsion in the· polymeric film onto a spool, wherein the spool rotates about an essentially vertical axis for storage of
AP/P/ 9 8 / 0 1 3 0 3
AP Ο Ο Ο 8 3 4 the emulsion during curing; and curing the emulsion within the polymeric film on the spool.
In another aspect of the present invention, apparatuses capable of performing this method are also claimed.
This method provides for continuous curing of an emulsion, and therefore is more readily scaled up to commercial operations .
Brief Description of the Drawings 10 FIG. 1 is a schematic drawing of on embodiment of the present invention.
FIG. IA is a cross section of emulsion in a polymeric film of FIG. 1.
FIG. 2 is a top view of the embodiment of the 15 present invention of FIG. 1.
Detailed Description of the Preferred Embodiments
An emulsion according to the present invention is produced by forming a first curable water-in-oil high internal phase emulsion by gradually adding and mixing an aqueous solution optionally containing an electrolyte into a monomer solution (oil phase) containing a mixture of polymerizable monomers and a surfactant. A poly-merization initiator is added either in the monomer solution or the aqueous solution before mixing or after formation of the emulsion depending on the desired process conditions. The curable water-in-oil high internal phase emulsion is then cured (polymerized and crosslinked) by heating the emulsion at a temperature of at least about 25°C for a time effective to cure the monomers.
The mixture of polymerizable monomers generally contains one or more vinyl monomers and one or more crosslinking agents. Various monomers may be used in the preparation of the foams, provided the monomers can be dispersed in or form an oil phase of a water-in-oil high internal phase emulsion (oil-soluble) and have a polyerizable vinyl group. Suitable vinyl monomers include, for example, monoalkenyl arene monomers such as styrene, aAP/P/ 9 8 / 0 1 3 0 3
APO 0 0 8 3 4 methylstyrene, chloromethylstyrene, vinyl-thylbenzene and vinyl toluene; acrylate or methacrylate esters such as 2ethylhexyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, n-butyl meth-crylate, lauryl methacrylate, and isodecyl methacrylate; conjugated diolefins such as butadiene, isoprene, and piperylene; allenes such as allene, methyl allene and chloroallene; olefin halides such as vinyl chloride, vinyl fluoride and polyfluoro-olefins; and mixtures thereof.
Suitable crosslinking agents can be any multifunctional unsaturated monomers capable of reacting with the vinyl monomers. The crosslinking agents contain.at least two functional groups. The functionality can be, for example, vinyl groups, acrylate groups and meth-acrylate groups. Multifunctional unsaturated cross-inking monomers include, for example, difunctional unsaturated crosslinking monomers such as divinylbenzene, diethylene glycol dimethacrylate, 1,3-butanediol dimeth-acrylate, and allyl methacrylate and tri-, tetra- and . penta-functional unsaturated crosslinking monomers such as trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate, glucose pentaacrylate, glucose diethylmercaptal pentaacrylate, and sorbitan triacrylate; and poly-functional unsaturated crosslinking monomers such as polyacrylates (eg. sucrose per(meth)acrylate and cellulose (meth)acrylate). Crosslinking monomers are typically present in each emulsion in an amount of from about 2 weight percent to about 70 weight percent, preferably from about 5 weight percent to about 40 weight percent based on the total monomer mixture. Some of these crosslinking monomers can be incorporated as a noncrosslinked monomer as long as at least about 2 weight percent of the crosslinking monomers are crosslinked.
Divinylbenzene is a preferred crosslinking monomer, and is typically available as a mixture with ethylstyrene in proportions of about 55:45 by weight. These
AP/P/ 9 8 / 0 1 3 0 3
APO00834 proportions can be modified so as to enrich the oil phase with one or the other component. Generally, it is advantageous to enrich the mixture with ethylstyrene which simultaneously reducing the amount of styrene in the monomer blend. The preferred ratio of divinylbenzene to ethyl styrene is from about 30:70 to 55:45, and most preferably from about 35:65 to about 45:55, by weight. The inclusion of higher levels of ethylstyrene imparts greater toughness without increasing the Ts of the resulting copolymer to the degree that styrene does.
Suitable polymerization initiators can be watersoluble or oil-soluble. Water-soluble initiators include, for example, persulfates such as potassium or sodium persulfate and various redox systems such as ammonium persulfate together with sodium metabisulfite. Oil soluble (monomer soluble) initiators include, for example, azo compounds such as azobisisobutyro-nitrile; and peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, alkylperoxycarbonates such as di-2-ethylhexyl peroxydicarbonate and di(sec-butyl)peroxydi-carbonate and alkyl-peroxycarboxylates such as t-butyl peroxy isobutyrate, 2,5-dimethyl-2,5-bis(2,3-ethy1-hexanoylperoxy) hexane, and t-butyl peroctoate. The preferred water-soluble polymerization initiator is potassium persulfate and the preferred oil-soluble polymerization initiators are W alkylperoxycarbonates and alkyl-peroxycarboxylates for fast curing time.
Most preferable alkylperoxycarbonates are branched at the l-carbon position and most preferable alkylperoxycarboxyl-ates are branched at the a-carbon position and/or l-carbon position. These branched alkylperoxycarbonate peroxide can be represented by the formula:
AP/P/ 9 8 / 0 1 3 0 3 s
AP Ο Ο Ο 8 3 4
Λ' Ο ! y
R'-C-O-q-O can be represented by the where R1 is independently Cx to C16 hydrocarbons or hydrogen in which at least two of the R1 are hydrocarbon groups.
The preferred branched alkyl carboxylate peroxide formula:
R2
I
-—C-R2
Ρ' O r O , I ϊ y
Rl-C-c-0-0--C /7=0,1 where R1 and R2 are independently Cl to C16 hydrocarbon groups or hydrogen in which at least two of the R1 or R2 are hydrocarbon groups. Preferably at least two of both R1 and R2 are hydrocarbon groups. Hydrocarbon groups can be alkyl, alkenyl or aryl groups.
The water-soluble initiators and/or oil-soluble tj initiators should be present in an effective amount to cure (polymerize and to crosslink) the monomers so that the monomers are substantially polymerized and cross-linked prior to significant diffusion of monomers between the two emulsions. Typically the initiator can be present from about 0.005 to about 15 weight percent based on the monomers. The initiators can be introduced with the oil phase or the aqueous phase before or after formation of the high internal phase emulsion.
A water-soluble initiator such as potassium persulfate can be added to the aqueous solution before forming the emulsions or-to the emulsions. An oil-soluble
AP/P/ 9 8 / 0 1 3 0 3
f...- A V/*
A
W?
APO 0 0 8 3 4 initiator can be added to the monomer solution or an advanced monomer solution or to the emulsion. Addition of a polymerization initiator to an high internal phase waterin-oil emulsion is described in U.S. Pat. No. 5,210,104, the disclosure of which is herein incorporated by reference. The initiator added to the emulsion can optionally be blended into the emulsion by any blending technique such as, for example, static mixer or a pin mixer at a low shear rate, to form a curable water-in-oil high internal phase emulsion. The rate of shear must be high enough to blend the initiator but low enough not to allow the emulsion to coalesce or liquify.
Conveniently, the initiators can be added to the oil phase (monomer phase) or aqueous phase prior to formation of the emulsion. Alternatively, at least a portion of the monomer solution can be advanced (partially polymerized) in the presence of an effective amount of an advancement initiator or by a free-radical-producing radiation source to produce an advanced monomer component prior to formation of the emulsion to reduce curing time.
To form a stable high internal phase emulsion requires that a surfactant be included in the emulsion. Such surfactant must be soluble in the oil phase used to form the emulsion. The surfactant may be nonionic, cationic, anionic or amphoteric provided the surfactant or combination of surfactants are effective to form a stable high internal phase emulsion. Preferred types of surfactants that can be used include sorbitan fatty acid esters, polyglycerol fatty acid esters, polyglycerol fatty acid esters, polyoxyethylene fatty acids and esters. In particular, sorbitan fatty acid esters such as sorbitan monolaurate (SPAN® 20), sorbitan monooleate (SPAN® 80), and combinations of sorbitan trioleate (SPAN® 85), and sorbitan monooleate. One such surfactant combination is the combination of sorbitan monooleate and sorbitan trioleate in a weight ration greater than or equal to about 3:1, more preferably about 4:1. Another acceptable surfactant in
AP/P/ 9 8/01303
TRIODAN® 20 which is a polyglycerol ester available from Grindsted and EMSORB 252 which is a sorbitan sesquioleate available from Henkel.
Between about one and about thirty percent by 5 weight of surfactant, based on the monomers in the oil phase, is generally sufficient, with higher oil to water ratios and higher mixing and curing temperatures generally requiring more surfactant than lower oil to water ratios and temperatures.
The type of surfactant used, in making the high internal phase emulsions that are to be polymerized is important in forming water-in-oil high internal phase emulsion and the final properties of the polymerized foams obtained. The surfactants are typically added to the monomer phase (oil phase).
The amount of surfactant system must be such that a water-in-oil high internal phase emulsion will form. Generally, the surfactant system is present in an amount effective to form a water-in-oil high internal phase emulsion. Preferably, the surfactant system can be present in concentrations of from about 0.1 to about 40 weight il.
percent, more preferably about one to about thirty weight percent based on the monomers of the particular emulsion. When saccharide fatty acid esters are used as a component of the surfactant the saccharide fatty acid surfactants are -.k’ preferably present from about 0.1 weight percent to about weight percent, more preferably from about 0.1 to about 25 weight percent based on the monomers. When sorbitan fatty acid esters are used as a component of the surfactant the sorbitan fatty acid ester surfactants are preferably present from about 2 weight percent to about 36 weight percent, more preferably from about 5 weight percent to about 25 weight percent based on the monomers.
The relative amounts of the aqueous phase containing water and an electrolyte and monomer phase containing monomers and surfactants used to form the high internal phase emulsions are a factor in determining the
AP/P/ 9 8 / 0 1 3 0 3
APOΟ 0 8 3 4 structural, mechanical and performance properties of the resulting polymeric foam phases. The ratio of water and oil in the emulsions can influence the density, cell size, and specific surface area of the foam phase. To form a polymeric foam phase with suitable density and high absorption capacity, the water-in-oil high internal phase emulsions typically contain as the internal phase, at least about 90 weight percent of water, based on the emulsion, corresponding to a water to oil weight ratio of at least about 9:1, more preferably at least about 95 weight percent of water, most preferably at least about 97 weight percent of water, corresponding to a water to oil weight ratio of
-- at least about 33:1.
• 7./
The internal aqueous phase preferably contains a water-soluble electrolyte to stabilize the emulsion and to make the foam more water wettable. Suitable electrolytes include inorganic salts (monovalent, divalent, trivalent or mixtures thereof), for example, alkali metal salts, alkaline earth metal salts and heavy metal salts such as halides, sulfates, carbonates, phosphates and mixtures thereof. Such electrolyte includes, for example, sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, lithium chloride, magnesium chloride, calcium chloride, magnesium sulfate, aluminum chloride and mixtures thereof. Mono- or di-valent salts with monovalent anions such as halides are ® preferred.
The formation of a water-in-oil high internal phase emulsion is dependent on a number of factors such as the monomers used, water to oil ratio, type and amount of
0 surfactant used, mixing conditions, presence and the amount of water-soluble electrolyte. It.has been found that by adding a quaternary salt to a primary surfactant such as sorbitan fatty acid ester or saccharide fatty acid ester, a stable emulsion can be formed and high water to oil ratio can be achieved resulting in high fluid absorption capacity foams.
AP/P/ 9 8 / 0 1 3 0 3
APO 0 0 8 3 4
The formation of a water-in-oil emulsion is described in U.S. Pat. No. 4,522,953, and U.S. Pat. No. 5,149,720, the disclosures of which are incorporated herein by reference. In general, to form the water-in-oil emulsion, the water can be mixed in any way up to a water to oil ratio of about 4:1. An oil-in-water emulsion may result if the water was , added all at once beyond a water to oil ratio of about 4:1. Typically, the water is therefore added gradually with a moderate rate of shear. A small capacity mixer such as a paint mixer with a shear rate of at least about 5 s'1, preferably at least about 10 s'1 can be used to mix the water-in-oil emulsion. A larger mixer equipped with an impeller with a shear rate of at least about 10 s*1 or a pin gap mixer with a shear rate of at least about 50 s'1, preferably at least about 100 s _1can also be used. If the shear rate is too low, the water-inoil· emulsion may revert to a oil-in-water emulsion. It is desirable to at least have a water to oil ratio of about 9:1, preferably at least about 19:1, more preferably at least about 30:1 for a high absorbency capacity foam.
A high internal phase emulsion can be prepared in batches or continuously. To form the high internal phase emulsion in batches, the emulsion is formed in a vessel or a container by gradually adding an aqueous phase to a monomer mixture and/or advanced monomer mixture under a pj moderate rate of shear until the desired water to oil ratio is reached.
An individual high internal phase emulsion can be prepared continuously by initially preparing a preformed
0 emulsion of approximately the same character as the desired emulsion by the method described above, then introducing into the preformed emulsion, both the aqueous phase and/or the oil phase in such proportions so as to produce the desired emulsion at a desired rate of production of emulsion. The emulsified mass is maintained in a state of continuous shear sufficient to reduce the effective viscosity of the mass near to that of the introduced phase
AP/P/ 9 8 f u 1 3 0 3
APO 0 0 8 3 4 but not above the inherent shear stability point of the desired emulsion. The prepared emulsion is then withdrawn at the desired rate.
The aqueous phase and the monomer phase for the 5 batch process and the continuous process can be introduced in a mixing vessel by an aqueous stream or a monomer stream, respectively, through one or more inlets. The streams can be combined prior to or after entering the mixing vessel then mixed in such a way to produce the desired emulsion.
The mixing vessel is any container in which the high internal phase emulsion is made regardless of the type of mixer or mixer head used.
The emulsion is preferably polymerized and cured at a temperature within the range of about 25°C to about
90°C, as long as the emulsion is stable at the curing temperature. · Alternatively, a multiple-step process as described in U.S. Pat. No. 5,189,070 issued February 23, 1993, the disclosure of which is herein incorporated by reference, can also be used. In the multi-step process the emulsion is pre-cured at a temperature of less than about 65°C until the emulsion has a Rheometrics dynamic shear modulus of greater than about 500 pascal, (lightly gelled, having a consistency like a jelly or a gelatin referred to as gel) , then cured at a temperature of above about 70°C for a time effective to cure the gel. The cure can be as high as about 175°C under a pressure sufficient to prevent the aqueous phase from boiling.
The emulsions can be heated, for example, by hot water, hot air, steam, electron beam radiation (EBR), radio frequency (RF), microwave or ohmic heating. The emulsions should be cured until the desired properties are obtained. Typically, to obtain a cured foam, the emulsions should be cured for at least about 8 hours, at 60°C or at least about 1 hour at 60°C then 3 hours at a temperature of above about 70°C. Generally, the extent of reaction after curing Is at least about 85% of the monomers, preferably at least about 90%, more preferably at least about 95% (i.e.,
AP/P/ 9 8 / 0 1 3 0 3
II
APO Ο ο 8 3 4 less than about 5% of free monomers), most preferably at least about 99% (i.e., less than about 1% of free monomers) in order to obtain good properties.
In the practice of the present invention, the 5 emulsion may be formed in batches or continuously, but the emulsion is placed on a continuous polymer film continuously in order to have a relatively continuous curing of the emulsion. The polymeric film is preferably polyproplyene, but could be another material that does not adhere to the cured emulsion, and does not cause the emulsion to break at the surface of the film. Polypropylene is convenient because it has these properties, is readily formed into a film, is inexpensive and can be recycled.
After being placed on a continuous film, the film is closed around the emulsion. The film can be simply laid over the emulsion in an overlapping fashion, or edges of the film can be interlocked with a mechanical closing zip-lock. Alternatively, the film edges can be sealed together using, for example, a heat seal or adhesive. A continuous tube of
0 the emulsion in . the film is therefore created. This continuous film is then more easily cured and handled after curing. The film is then preferably removed from outside of the cured emulsion, and the cured emulsion is then further processed, by for example, slicing the emulsion into thinner pieces, removing water and drying the emulsion.
The emulsion could be placed on the continuous sheet in a thickness such that slicing of the resultant cured foam to thinner sheets is not necessary. If a relatively thin sheet of emulsion is cured on the continuous sheet so that slicing is not necessary, the continuous sheet could be a material that adheres to the cured foam, and the continuous sheet could then function as a backing sheet to the foam. Slicing of the cured foam could also be avoided by layering films and emulsion repeadily, so that a significant thickness, for example four inches, of emulsions could be cured at one time, and then separated by pulling apart film sheets between the layers. In some end-uses, it
AP/P/ 9 8/01303 could bo beneficial to have such backing sheet be impervious to liquids. For example, having the impervious backing sheet impervious to liquids could be useful in a diaper.
Referring now to FIGS. 1, IA, and 2, an embodiment 5 of the present invention is shown schematically. Emulsion 1 is placed in a film 2. The film is initially on a roll 3, and is pulled off the roll in as a doubled sheet. The doubled sheet is spread by spreading rollers 4, to provide a vertical pocket 5 for the emulsion. The film could alternatively be on a single layer roll, and doubled to form a pocket by guiding rollers or wires. The emulsion is placed in the pocket by, for example, a distribution manifold 6. A tank 7 is provided for either holding an emulsion made by a batch process or for holding a volume of emulsion that is being prepared continuously. The emulsion can be pumped by pump 8 . through recycle piping 11 to a static mixer 9 with a slip stream of emulsion being routed through a control valve 10 to the distribution manifold 6.
The film 2 is provided with an interlocking seal along the edges of the film, with a bead 12 on one edge and a locking edge 13 along the other edge. After the emulsion is placed in the vertical pocket 5, the edges are locked by a zipper fitting 14. The emulsion in the locked film is then wrapped onto a spool 15 for curing. Multiple spools
15 can be provided so that when one spool is full, the
KK emulsion loaded onto that spool can be cured and another spool can be used to store the emulsion that is being place, at that time, onto the continuous polymeric sheet 2. Changing spools can be accomplished, for example, by providing two clamps to seal a section of the sealed film that contains the polymer, and cutting the film between the clamps. The spools can be rotatable to enable the spools to pull the emulsion filled film along.
The pocket formed by the spreader rollers can be,
5 for example, four inches wide and four feet high. A pocket of this dimension can hold the emulsion with a reasonable thickness of polypropylene film. When a spool is filled
AP/P/ 9 8 / 0 1 3 0 3
APO Ο Ο 8 3 4 with emulsion filled film, a stiff band or a series of stiff bands can be placed around the outer most film pocket, and this stiff band will hold the outer most film pocket nearly vertical on the spool. It is preferably that the spool have a diameter of at least 85 feet in order to accommodate a significant volume of emulsion.
After the emulsion is cured, the cured emulsion can be unwrapped from the spool and further processed by, for example, slicing the cured emulsion into thinner slices, removing water, rinsing, and drying the cured emulsion.
These foams can be optionally post-cured to improve the foam properties. Post-curing of 'the foam can be carried out by heating the foams to a temperature of above about 75°C, preferably greater than 90°C by steam, hot air or other heating source. Such heating may be performed in a heat exchanger, oven, over heated rollers, hot water, hot air, steam, electron beam radiation (EBR), radio frequency (RF), microwave or ohmic heating or by other means.
Once the curing and/or post-curing process is completed, the water incorporated in the foam may be removed or squeezed out, dried by heat or flashed by lowering the pressure to a suitable level to evaporate the remaining liquid to give the desired degree of dryness in the product foam. These drying techniques will preferably be used after the desired state of cure is developed in the foam material.
The foams of the present invention may be washed prior to, after or between drying stages (removing at least a portion of the water) to yield an absorbent block which is especially useful for the absorption of liquids.
Typically, these foams are washed to reduce the electrolyte content of the foam with a solvent such as, for example, an alcohol, a low concentration electrolyte solution .(lower concentration than the water phase) such as 1% calcium
5 chloride solution or deionized water. The washed foams can be conveniently dried by squeezing the water and/or solvent out of the foams and air or heat drying.
Claims (3)
1. A process for curing a high internal phase emulsion to form a porous crosslinked polymeric material, the process comprising the steps of:
forming a high internal phase emulsion having at least one curable phase;
providing a continuous strip of polymeric film wherein the polymeric film is incompatible with each of the phases of the emulsion;
placing at least a portion of the emulsion continuously on the polymeric film;
closing the polymeric film around the emulsion;
spiraling the emulsion in the polymeric film onto a spool, wherein the spool rotates about an essentially vertical axis for storage of the emulsion during curing; and curing the emulsion within the polymeric film on the spool.
2. The process of claim 1 further comprising the step of dewatering the cured emulsion as it is removed from the spool after the emulsion is cured.
3. The process of claim 1 wherein the continuous polymeric sheet is effective to function as a backing sheet that is impervious to liquids adhered to the cured emulsion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/591,991 US5670101A (en) | 1996-01-26 | 1996-01-26 | Process to prepare foams from high internal phase emulsions |
| PCT/US1997/001118 WO1997027240A2 (en) | 1996-01-26 | 1997-01-24 | Process to prepare foams from high internal phase emulsions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AP9801303A0 AP9801303A0 (en) | 1998-09-30 |
| AP834A true AP834A (en) | 2000-05-10 |
Family
ID=24368803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| APAP/P/1998/001303A AP834A (en) | 1996-01-26 | 1997-01-24 | Process to prepare foam from high internal phase emulsions. |
Country Status (28)
| Country | Link |
|---|---|
| US (1) | US5670101A (en) |
| EP (1) | EP0876423B1 (en) |
| JP (1) | JP2000504050A (en) |
| KR (1) | KR19990082022A (en) |
| CN (1) | CN1064979C (en) |
| AP (1) | AP834A (en) |
| AT (1) | ATE190635T1 (en) |
| AU (1) | AU705532B2 (en) |
| BG (1) | BG102643A (en) |
| BR (1) | BR9707190A (en) |
| CA (1) | CA2244175A1 (en) |
| CZ (1) | CZ228498A3 (en) |
| DE (1) | DE69701448T2 (en) |
| EA (1) | EA001383B1 (en) |
| EE (1) | EE9800220A (en) |
| ES (1) | ES2144843T3 (en) |
| GR (1) | GR3033398T3 (en) |
| HU (1) | HUP0101266A3 (en) |
| IL (1) | IL125443A0 (en) |
| IS (1) | IS4801A (en) |
| NO (1) | NO983409L (en) |
| NZ (1) | NZ331100A (en) |
| OA (1) | OA10817A (en) |
| PL (1) | PL327993A1 (en) |
| PT (1) | PT876423E (en) |
| SK (1) | SK101598A3 (en) |
| TR (1) | TR199801436T2 (en) |
| WO (1) | WO1997027240A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002537460A (en) | 1999-02-22 | 2002-11-05 | ザ、プロクター、エンド、ギャンブル、カンパニー | Continuous curing method from HIPE to HIPE foam |
| US6204298B1 (en) | 1999-02-22 | 2001-03-20 | The Procter & Gamble Company | Processes for the rapid preparation of foam materials from high internal phase emulsions at high temperatures and pressures |
| JP4749642B2 (en) | 1999-09-08 | 2011-08-17 | 株式会社日本触媒 | Method for producing porous crosslinked polymer |
| US6573305B1 (en) * | 1999-09-17 | 2003-06-03 | 3M Innovative Properties Company | Foams made by photopolymerization of emulsions |
| US6395792B1 (en) * | 1999-10-12 | 2002-05-28 | Nippon Shokubai Co., Ltd. | Method for production of porous cross-linked poymer |
| US6406648B1 (en) * | 1999-11-02 | 2002-06-18 | The Procter & Gamble Company | Method of making shaped foam implements |
| WO2001038404A1 (en) * | 1999-11-19 | 2001-05-31 | Nippon Shokubai Co., Ltd. | Method for production of porous cross-linked polymer material |
| US6274638B1 (en) * | 1999-11-19 | 2001-08-14 | Nippon Shokubai Co., Ltd. | Method for production of porous cross-linked polymer material |
| JP4601812B2 (en) * | 1999-12-13 | 2010-12-22 | 株式会社日本触媒 | Method for producing porous crosslinked polymer |
| AU1736501A (en) | 1999-12-13 | 2001-06-18 | Nippon Shokubai Co., Ltd. | Method for production of porous cross-linked polymer |
| US6299808B1 (en) | 2000-06-05 | 2001-10-09 | The Dow Chemical Company | Continuous process for polymerizing, curing and drying high internal phase emulsions |
| US6730712B2 (en) | 2000-10-25 | 2004-05-04 | Nippon Shokubai Co., Ltd. | Method of manufacturing porous cross-linked polymer sheet |
| JP4628579B2 (en) * | 2001-04-17 | 2011-02-09 | 株式会社日本触媒 | Method for producing porous crosslinked polymer |
| US8426670B2 (en) * | 2001-09-19 | 2013-04-23 | Nippon Shokubai Co., Ltd. | Absorbent structure, absorbent article, water-absorbent resin, and its production process and evaluation method |
| GB0406981D0 (en) | 2004-03-27 | 2004-04-28 | Eastman Kodak Co | Ink receiving material |
| US7608070B2 (en) | 2004-09-30 | 2009-10-27 | Kimberly-Clark Worldwide, Inc. | Foam-based fasteners |
| US7640637B2 (en) | 2005-11-01 | 2010-01-05 | Kimberly-Clark Worldwide, Inc. | Methods to modify the fibrous landing layer of a foam based fastener and products made from the same |
| US20110160321A1 (en) | 2009-12-30 | 2011-06-30 | Steven Ray Merrigan | Reduction of unpolymerized monomers in high internal phase emulsion foam |
| US20120108692A1 (en) | 2010-10-27 | 2012-05-03 | John Collins Dyer | Preparation of foam materials derived from renewable resources |
| CN117801358B (en) * | 2024-03-01 | 2024-05-17 | 华东理工大学 | A porous polymer based on a polymerizable deep eutectic solvent and a preparation method thereof |
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| US5149720A (en) * | 1991-08-12 | 1992-09-22 | The Procter & Gamble Company | Process for preparing emulsions that are polymerizable to absorbent foam materials |
| US5358974A (en) * | 1993-07-29 | 1994-10-25 | Shell Oil Company | Process for preparing low density porous crosslinked polymeric materials |
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| FR1599874A (en) * | 1968-11-29 | 1970-07-20 | ||
| US3768937A (en) * | 1972-04-30 | 1973-10-30 | Toyo Tire & Rubber Co | Apparatus for continuously producing a snythetic polymer foamed mass having square cross section |
| DE2343294C3 (en) * | 1973-08-28 | 1980-03-20 | Bayer Ag, 5090 Leverkusen | Composite materials and processes for their manufacture |
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1996
- 1996-01-26 US US08/591,991 patent/US5670101A/en not_active Expired - Fee Related
-
1997
- 1997-01-24 ES ES97903088T patent/ES2144843T3/en not_active Expired - Lifetime
- 1997-01-24 CZ CZ982284A patent/CZ228498A3/en unknown
- 1997-01-24 AP APAP/P/1998/001303A patent/AP834A/en active
- 1997-01-24 JP JP9527017A patent/JP2000504050A/en active Pending
- 1997-01-24 CN CN97192502XA patent/CN1064979C/en not_active Expired - Fee Related
- 1997-01-24 AU AU17088/97A patent/AU705532B2/en not_active Ceased
- 1997-01-24 PT PT97903088T patent/PT876423E/en unknown
- 1997-01-24 TR TR1998/01436T patent/TR199801436T2/en unknown
- 1997-01-24 EE EE9800220A patent/EE9800220A/en unknown
- 1997-01-24 IL IL12544397A patent/IL125443A0/en unknown
- 1997-01-24 WO PCT/US1997/001118 patent/WO1997027240A2/en not_active Ceased
- 1997-01-24 DE DE69701448T patent/DE69701448T2/en not_active Expired - Fee Related
- 1997-01-24 KR KR1019980705742A patent/KR19990082022A/en not_active Withdrawn
- 1997-01-24 PL PL97327993A patent/PL327993A1/en unknown
- 1997-01-24 BR BR9707190-0A patent/BR9707190A/en not_active Application Discontinuation
- 1997-01-24 NZ NZ331100A patent/NZ331100A/en unknown
- 1997-01-24 AT AT97903088T patent/ATE190635T1/en not_active IP Right Cessation
- 1997-01-24 EA EA199800660A patent/EA001383B1/en not_active IP Right Cessation
- 1997-01-24 EP EP97903088A patent/EP0876423B1/en not_active Expired - Lifetime
- 1997-01-24 CA CA002244175A patent/CA2244175A1/en not_active Abandoned
- 1997-01-24 HU HU0101266A patent/HUP0101266A3/en unknown
- 1997-01-24 SK SK1015-98A patent/SK101598A3/en unknown
-
1998
- 1998-07-21 BG BG102643A patent/BG102643A/en unknown
- 1998-07-21 IS IS4801A patent/IS4801A/en unknown
- 1998-07-23 NO NO983409A patent/NO983409L/en not_active Application Discontinuation
- 1998-07-24 OA OA9800121A patent/OA10817A/en unknown
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2000
- 2000-05-11 GR GR20000401086T patent/GR3033398T3/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5149720A (en) * | 1991-08-12 | 1992-09-22 | The Procter & Gamble Company | Process for preparing emulsions that are polymerizable to absorbent foam materials |
| US5358974A (en) * | 1993-07-29 | 1994-10-25 | Shell Oil Company | Process for preparing low density porous crosslinked polymeric materials |
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