WO2015138561A1 - Polyurethane adhesives for reverse osmosis modules - Google Patents
Polyurethane adhesives for reverse osmosis modules Download PDFInfo
- Publication number
- WO2015138561A1 WO2015138561A1 PCT/US2015/019882 US2015019882W WO2015138561A1 WO 2015138561 A1 WO2015138561 A1 WO 2015138561A1 US 2015019882 W US2015019882 W US 2015019882W WO 2015138561 A1 WO2015138561 A1 WO 2015138561A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- adhesive composition
- composition according
- polyol
- adhesive
- reverse osmosis
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 224
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 223
- 239000004814 polyurethane Substances 0.000 title claims abstract description 73
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 73
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 299
- 229920005862 polyol Polymers 0.000 claims abstract description 80
- 150000003077 polyols Chemical class 0.000 claims abstract description 80
- 239000004014 plasticizer Substances 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000004359 castor oil Substances 0.000 claims abstract description 16
- 235000019438 castor oil Nutrition 0.000 claims abstract description 16
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 16
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 15
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 15
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 14
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 11
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 239000003921 oil Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 229920005903 polyol mixture Polymers 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims description 25
- 150000002009 diols Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000003549 soybean oil Substances 0.000 claims description 12
- 235000012424 soybean oil Nutrition 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 9
- 235000019198 oils Nutrition 0.000 claims description 9
- 239000013008 thixotropic agent Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical class OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 125000005591 trimellitate group Chemical group 0.000 claims description 6
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical class C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 claims description 5
- LXODQLXKQIJVNK-UHFFFAOYSA-N 2-(2-benzoyloxypropoxy)propyl benzoate Chemical class C=1C=CC=CC=1C(=O)OC(C)COC(C)COC(=O)C1=CC=CC=C1 LXODQLXKQIJVNK-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 229910052570 clay Inorganic materials 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 239000000454 talc Substances 0.000 claims description 5
- 229910052623 talc Inorganic materials 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 4
- 235000021317 phosphate Nutrition 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 125000005498 phthalate group Chemical class 0.000 claims description 4
- 235000013772 propylene glycol Nutrition 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- 229940015975 1,2-hexanediol Drugs 0.000 claims description 3
- 229940031723 1,2-octanediol Drugs 0.000 claims description 3
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 3
- YSRSBDQINUMTIF-UHFFFAOYSA-N decane-1,2-diol Chemical compound CCCCCCCCC(O)CO YSRSBDQINUMTIF-UHFFFAOYSA-N 0.000 claims description 3
- SITULKFUBJXOJH-UHFFFAOYSA-N diheptyl hexanedioate Chemical compound CCCCCCCOC(=O)CCCCC(=O)OCCCCCCC SITULKFUBJXOJH-UHFFFAOYSA-N 0.000 claims description 3
- WIYAGHSNPUBKDT-UHFFFAOYSA-N dinonyl hexanedioate Chemical compound CCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCC WIYAGHSNPUBKDT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 claims description 3
- AVIYEYCFMVPYST-UHFFFAOYSA-N hexane-1,3-diol Chemical compound CCCC(O)CCO AVIYEYCFMVPYST-UHFFFAOYSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- KHLCTMQBMINUNT-UHFFFAOYSA-N octadecane-1,12-diol Chemical compound CCCCCCC(O)CCCCCCCCCCCO KHLCTMQBMINUNT-UHFFFAOYSA-N 0.000 claims description 3
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 150000003890 succinate salts Chemical class 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- -1 salt ions Chemical class 0.000 description 12
- 125000005442 diisocyanate group Chemical group 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003204 osmotic effect Effects 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 235000012222 talc Nutrition 0.000 description 4
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- CVPZXHCZKMFVOZ-UHFFFAOYSA-N [4-(benzoyloxymethyl)cyclohexyl]methyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(CC1)CCC1COC(=O)C1=CC=CC=C1 CVPZXHCZKMFVOZ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 2
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
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- YCZJVRCZIPDYHH-UHFFFAOYSA-N ditridecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCCC YCZJVRCZIPDYHH-UHFFFAOYSA-N 0.000 description 2
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000012466 permeate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- HDDLVZWGOPWKFW-UHFFFAOYSA-N trimethyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound COC(=O)CC(O)(C(=O)OC)CC(=O)OC HDDLVZWGOPWKFW-UHFFFAOYSA-N 0.000 description 2
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- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
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- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- FEXQDZTYJVXMOS-UHFFFAOYSA-N Isopropyl benzoate Chemical compound CC(C)OC(=O)C1=CC=CC=C1 FEXQDZTYJVXMOS-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- RYEVPEDOQVMHIY-UHFFFAOYSA-N N=C=O.N=C=O.CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1 Chemical compound N=C=O.N=C=O.CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1 RYEVPEDOQVMHIY-UHFFFAOYSA-N 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- FGPCETMNRYMFJR-UHFFFAOYSA-L [7,7-dimethyloctanoyloxy(dimethyl)stannyl] 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)O[Sn](C)(C)OC(=O)CCCCCC(C)(C)C FGPCETMNRYMFJR-UHFFFAOYSA-L 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- ROPXFXOUUANXRR-BUHFOSPRSA-N bis(2-ethylhexyl) (e)-but-2-enedioate Chemical compound CCCCC(CC)COC(=O)\C=C\C(=O)OCC(CC)CCCC ROPXFXOUUANXRR-BUHFOSPRSA-N 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- RSRICHZMFPHXLE-AATRIKPKSA-N bis(2-methylpropyl) (e)-but-2-enedioate Chemical compound CC(C)COC(=O)\C=C\C(=O)OCC(C)C RSRICHZMFPHXLE-AATRIKPKSA-N 0.000 description 1
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 229940099371 diacetylated monoglycerides Drugs 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- JJXNVYMIYBNZQX-UHFFFAOYSA-N diphenyl (2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 JJXNVYMIYBNZQX-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- UOBSVARXACCLLH-UHFFFAOYSA-N monomethyl adipate Chemical compound COC(=O)CCCCC(O)=O UOBSVARXACCLLH-UHFFFAOYSA-N 0.000 description 1
- DHRXPBUFQGUINE-UHFFFAOYSA-N n-(2-hydroxypropyl)benzenesulfonamide Chemical compound CC(O)CNS(=O)(=O)C1=CC=CC=C1 DHRXPBUFQGUINE-UHFFFAOYSA-N 0.000 description 1
- FGTVYMTUTYLLQR-UHFFFAOYSA-N n-ethyl-1-phenylmethanesulfonamide Chemical compound CCNS(=O)(=O)CC1=CC=CC=C1 FGTVYMTUTYLLQR-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 235000015205 orange juice Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- UDKSLGIUCGAZTK-UHFFFAOYSA-N phenyl pentadecane-1-sulfonate Chemical compound CCCCCCCCCCCCCCCS(=O)(=O)OC1=CC=CC=C1 UDKSLGIUCGAZTK-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- WCLDITPGPXSPGV-UHFFFAOYSA-N tricamba Chemical compound COC1=C(Cl)C=C(Cl)C(Cl)=C1C(O)=O WCLDITPGPXSPGV-UHFFFAOYSA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- TUUQISRYLMFKOG-UHFFFAOYSA-N trihexyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCOC(=O)CC(C(=O)OCCCCCC)(OC(C)=O)CC(=O)OCCCCCC TUUQISRYLMFKOG-UHFFFAOYSA-N 0.000 description 1
- AMMPRZCMKXDUNE-UHFFFAOYSA-N trihexyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCOC(=O)CC(O)(C(=O)OCCCCCC)CC(=O)OCCCCCC AMMPRZCMKXDUNE-UHFFFAOYSA-N 0.000 description 1
- APVVRLGIFCYZHJ-UHFFFAOYSA-N trioctyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCCCOC(=O)CC(O)(C(=O)OCCCCCCCC)CC(=O)OCCCCCCCC APVVRLGIFCYZHJ-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-VBJOUPRGSA-N triricinolein Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC)COC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-VBJOUPRGSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Definitions
- the instant invention generally relates to polyurethane adhesives. More specifically, the instant invention relates to polyurethane adhesives used for fabricating reverse osmosis (RO) modules.
- RO reverse osmosis
- Reverse osmosis is the process of forcing a solvent from a region of high solute concentration through a semipermeable membrane to a region of low solute concentration. The process is done by applying a pressure in excess of the osmotic pressure.
- Reverse osmosis has numerous applications, including, but not limited to, the separation of pure water from seawater and brackish waters where seawater or brackish water is pressurized against one surface of the membrane, causing transport of salt-depleted water across the membrane and emergence of potable drinking water from the low-pressure side.
- Other applications of reverse osmosis include concentrating food liquids, e.g., orange juice, production of maple syrup, and production of hydrogen.
- spiral wound cartridges There are typically two types of semipermeable membrane configurations used for reverse osmosis: spiral wound cartridges and hollow core.
- the membranes have a dense layer in the polymer matrix where the separation of solute from solvent occurs. In most cases, the membrane is designed to allow only solvent (such as water) to pass through this dense layer, while preventing the passage of solutes (such as salt ions).
- spiral wound cartridges include adhesives to seal the interstices or voids in the membrane, which prevents leakage of feed fluid to the permeate collection tube. In a particular example, as discussed in U.S. Patent No.
- the adhesive can be applied to an upstream surface of a membrane material in locations where a downstream surface has been treated that flow therethrough is prevented.
- the adhesive can be applied in other locations of the membrane material as required by the structure and/or application the membrane is utilized in, such as, for example, folds of the membrane, along longitudinal edges, a downstream surface, and the like.
- the fully-cured adhesive Since the cartridge is subjected to high water pressure, the fully-cured adhesive must be strong and durable. If the hardness of the fully-cured adhesive is too low, then the pressure of the water can cause failure of the adhesive bond, and ultimately the failure of the cartridge. However, if the hardness of the fully-cured adhesive is too high then the adhesive can become brittle and also cause failure.
- the hardness of the adhesive can be measured on the Shore hardness scale, and the methods of taking such measurements are known in the art. Further, it is noted that the tensile strength of a fully-cured adhesive is used as a measure of suitability of the adhesive in a reverse osmosis module.
- a further characteristic of a successful adhesive is the ability of the adhesive to penetrate the membrane material in order to establish a sufficient adhesive bond.
- Osmotic blistering which results in side seal leakage and end seal leakage (often referred to as “veining” or “lightning bolt” failure) of the feed fluid to the permeate collection tube.
- Osmotic blistering may also encourage bacterial growth and may also cause dimensional change of the membrane, making it difficult to remove and replace.
- Osmotic blistering is exacerbated by the use of alkaline cleaning fluids, such as, for example, sodium hydroxide solution, which are frequently used in the industry.
- alkaline cleaning fluids such as, for example, sodium hydroxide solution
- the present invention is believed to be an answer to the need of providing an adhesive that is durable in reverse osmosis applications and is resistant to alkaline fluids.
- the adhesive composition of the present invention surprisingly reduces or eliminates osmotic blistering and veining and lightning bolt failures often exhibited in known adhesive compositions.
- the adhesive compositions of the present invention also minimizes the width of the bond line used in the reverse osmosis module application while demonstrating improved rheology, viscosity and flow control as compared to known adhesive compositions.
- the invention is directed to an adhesive composition suitable for reverse osmosis modules, the adhesive composition comprising: (I) from about 65 wt to 99 wt of a polyurethane composition based on a total wt of the adhesive composition, the polyurethane composition comprising: (A) an isocyanate group-containing pre-polymer comprising a reaction product of (i) castor oil or a derivative thereof; and (ii) a polyisocyanate; and (iii) optionally a second polyol; and (B) an isocyanate-reactive polyol mixture comprising: (i) a polybutadiene polyol; and (ii) a urethane catalyst; and (iii) optionally the second polyol; and (II) from about 1 wt to about 35 wt of a plasticizer based on the total wt of the adhesive composition, wherein the adhesive composition is essentially free from diluent oils and solvents.
- a further aspect of the invention is directed to an adhesive composition suitable for reverse osmosis modules, the adhesive composition comprising: (I) from about 65 wt to about 99 wt of a polyurethane composition, based on a total weight of the adhesive composition, the polyurethane composition comprising: (A) an isocyanate group-containing pre-polymer comprising a reaction product of (i) castor oil or a derivative thereof; and (ii) a polyisocyanate; and (B) an isocyanate-reactive polyol mixture comprising: (i) polybutadiene polyol; (ii) a urethane catalyst; and (iii) a secondary polyol; and (II) from about 1 wt to about 35 wt of a plasticizer, based on the total wt of the adhesive composition, wherein the adhesive composition is essentially free from diluents oils and solvents, further wherein a tensile strength of the adhesive composition when fully cured is at
- a further aspect of the invention is directed to a reverse osmosis module comprising an adhesive composition according to any of the adhesive compositions described herein.
- Still a further aspect of the invention is directed to a method of constructing a reverse osmosis module, the method comprising: applying an adhesive composition to at least a portion of a membrane present in the reverse osmosis module, the adhesive composition according to any of the adhesive compositions described herein.
- FIG. 1 is a perspective drawing of a reverse osmosis module having a membrane with an adhesive composition applied thereto.
- the invention is directed to an adhesive composition that includes a polyurethane composition and a plasticizer.
- the adhesive composition is essentially free from diluent oils and solvents.
- the term "essentially free” as used herein means the composition contains unavoidable levels but no more.
- Diluent oils and solvents are not part of the adhesive composition and the term "diluent oils and solvents" refer to compositions that do not include the polyurethane adhesive, i.e., they are not reacted with the polyisocyanate in the adhesive composition, and include, but are not limited to hydrocarbons, e.g., petroleum spirits, kerosene, mineral oils and vegetable oils such as corn oil, canola oil, and olive oil.
- the adhesive composition can be used, for example, in a reverse osmosis module and the inventors have surprisingly found that adhesive compositions according to the embodiments herein reduces or eliminates osmotic blistering and leakage in reverse osmosis modules.
- the adhesive composition includes a two-part polyurethane composition (hereinafter referred to as a "polyurethane composition") and a plasticizer.
- the adhesive composition includes from about 65 wt.% to about 99 wt.% of the polyurethane composition (or any amount in between) and from about 1 wt.% to about 35 wt.% plasticizer (or any amount in between) based on the total wt.% of the adhesive composition. It is contemplated that other amounts of the polyurethane composition may be present in the adhesive composition, such as, for example, the polyurethane may be present in an amount between about 75 wt. % and 99 wt. % or any amount in between, based on the total weight of the adhesive composition.
- the polyurethane may be present in an amount between about 85 wt. % and 99 wt. % or any amount in between, based on the total weight of the adhesive composition.
- the plasticizer may be present in the adhesive composition in and amount between about 1 wt. % and 35 wt. % or any amount in between, based on the total weight of the adhesive composition. In one example, the plasticizer may be present in the adhesive composition in an amount between about 20 wt. % and about 30 wt. % or any amount in between, based on the total weight of the adhesive composition.
- the polyurethane composition used in the adhesive composition includes part (A), which is an isocyanate group-containing pre-polymer comprising a reaction product of castor oil or a derivative thereof and a polyisocyanate and optionally a second polyol; and part (B), which is an isocyanate-reactive polyol mixture comprising a polybutadiene polyol and a urethane catalyst and optionally the second polyol.
- Part (A) and part (B) of the polyurethane composition can be mixed together in any manner known in the art, including, but not limited to hand mixing, static mixing, and dynamic mixing. It is also noted that part (A) can be added to part (B) or vice versa, or, in the alternative, part (A) and part (B) can be simultaneously added to the same vessel.
- the castor oil i.e., ricinoleic acid triglyceride, present in the isocyanate group-containing pre-polymer of part (A) is a renewable raw material that is widely commercially available. It is noted that a derivative of castor oil includes any polyol derived from castor oil, which includes a hydrolysis product, an ethoxylated product, a transesterfied product, or an esterfied product, or a polyamide product.
- the polyisocyanate used to prepare the prepolymer of part (A) of the polyurethane composition is any compound having at least two isocyanate moieties.
- Diisocyanates can be exemplified by 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (4,4'- MDI), 2,4'-diphenylmethane diisocyanate (2,4'- MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'- dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4- phenylene diisocyanate, toluene diisocyanate, butane- 1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, naphthylene diisocyanate, m
- diisocyanate hydrogenated xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1 ,3-bis(isocyanatomethyl)cyclohexane, methyl- cyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, 2,4,6-triisopropylbenzene diisocyanate, isopropylidene bis(4-cyclohexylisocyanate), and mixtures thereof .
- Exemplary mixtures of diisocyanates include mixtures of 4,4'-MDI and 2,4-MDI.
- the polyisocyanate used to prepare the part (A) prepolymer can also be a polyisocyanate prepared, for example, by reacting a diisocyanate with a diisocyanate-reactive compound such as a polyol e.g., a diol or polyamine, e.g., a diamine.
- a diisocyanate-reactive compound such as a polyol e.g., a diol or polyamine, e.g., a diamine.
- Exemplary polyisocyanates used to prepare the part A prepolymer include polymeric forms of MDI.
- the polyisocyanate used to prepare the part (A) prepolymer can also be a carbodimide-modified diisocyanate, e.g. , a carbodiimide- modified MDI.
- the polyisocyanate used to prepare the prepolymer of part (A) has an isocyanate (NCO) content that varies from
- the isocyanate (NCO) content of the part (A) prepolymer varies from 5% to 25% (mass percent). In another embodiment, the isocyanate (NCO) content of the part (A) prepolymer varies from 10% to 20% (mass percent), and more preferably between 13% to 19% (mass percent) as measured by ASTM D2572.
- the part (A) prepolymer of the polyurethane composition may contain a second polyol.
- the optional second polyol in part (A) of the polyurethane composition is any polyol (i.e., a compound having more than one hydroxyl group appended thereto) that can react with an isocyanate group.
- the second polyol is preferably chosen from a group of polyols having a molecular weight of less than about 600.
- the second polyol is chosen from a group of polyols having a molecular weight of between about 80 and about 300.
- the second polyol is chosen from a group of polyols having a molecular weight of between about 80 and about 200.
- the second polyol is chosen from a group of polyols having a molecular weight of between about 300 and about 600.
- second polyols examples include glycols, i.e., diols containing a 1,2 dihydroxy group such as ethylene glycol or propylene glycol and derivatives thereof, and glycerol or glycerin and derivatives thereof.
- second polyols include polypropylene glycol and
- the second polyol is a diol having from 3 to 20 carbon atoms. In another embodiment, the second polyol is a diol having 4 to 12 carbon atoms. In a further embodiment, the second polyol is a diol having 5 to 10 carbon atoms.
- diols examples include, but are not limited to: 2-ethyl-l,3-hexanediol; 1,2-propanediol; 1,3-butanediol; 2,2,4-trimethyl-l,3-pentanediol, 1,12-octadecanediol; 1,2-hexanediol; 1,2- octanediol; and 1,2-decanediol.
- second polyols include a tetrol such as pentaerythritol.
- the second polyol can be a polyether polyol prepared from either ethylene oxide and/or propylene oxide optionally reacted with another polyol such as glycol or glycerol.
- the polybutadiene polyol of part (B) of the polyurethane composition is a low molecular weight, hydroxyl terminated homopolymer of butadiene.
- polybutadiene polyols include, but are not limited to, liquid hydroxyl terminated polymers of butadiene sold under the names Poly bd ® R-45HTLO and Poly bd ® R-20LM, both commercially available from Cray Valley USA, LLC, Exton, PA, USA, as well as under the name HyproTM 2800X95 HTB, commercially available from CVC Thermoset Specialties, Moorestown, NJ, USA .
- the urethane catalyst of part (B) of the polyurethane composition maybe any urethane catalyst.
- urethane catalysts include tin catalysts such as dialkyl tin dialkanoates, for example, Fomrez catalyst UL-28 (dimethyltin dineodecanoate), which provides very short gel and tack-free times as well as good solubility in polyurethane systems.
- urethane catalysts include, but are not limited to: stannous octoate, commercially available as Dabco ® T-9 from Air Products, AUentown, PA, USA; organotin, commercially available as Dabco ® 131 from Air Products, AUentown, PA, USA; 1,4-diazabicyclooctane, available as Dabco ® Crystalline Catalyst from Air Products, AUentown, PA, USA; n-cetyl-n,n- dimethylamine, available as Dabco ® B-16 from Air Products, AUentown, PA, USA; dibutyltin dilaurate, available as Dabco ® T-12 from Air Products, AUentown, PA, USA; dibutyltin diacetate, available as MetacureTM T-l catalyst from Air Products, AUentown, PA, USA; a blend of zinc neodecanoate, bismuth neodecanoate and neo
- the optional second polyol that may be used in part (B) of the polyurethane composition includes the same second polyols as described in relation to part (A) above. It is contemplated that if the part (A) and part (B) of the polyurethane composition both include the second polyol, the second polyol may be the same or different.
- Either or both part (A) and part (B) of the polyurethane composition may also include a defoamer.
- a defoamer is added in an amount between about 0.01 and about 0.1 wt. % to part (A).
- a defoamer is added in an amount between about 0.01 and about 0.1 to part (B).
- a defoamer is added in an amount between about 0.005 and about 0.05 to part (A) and in an amount between about 0.005 and about 0.05 to part (B).
- the defoamer utilized in either or both part (A) and part (B) of the polyurethane composition may be any defoamer that is known in the art.
- the defoamer is a silicone based defoamer, such as, for example, an alkyl aryl silicone polymer-based antifoaming additive, commercially available as SF8843 from Momentive Performance Materials Holdings LLC, Columbus, OH, USA.
- the defoamer is a silicone free defoamer, such as a isoparaffin based defoamer, such as, for example, BYK 054, available from BYK USA, Inc., Wallingford, CT, USA.
- the viscosity of part (A) of the polyurethane composition is at least 600 cps. In one embodiment, the viscosity of part (A) of the polyurethane composition is between about 600 cps and about 50,000 cps, including any value therebetween. In another embodiment, the viscosity of part (A) of the polyurethane composition is between about 10,000 cps and about 50,000 cps, including any value therebetween. In a further embodiment, the viscosity of part (A) of the polyurethane composition is between about 20,000 cps and about 40,000 cps, including any value therebetween. In yet a further embodiment, the viscosity of part (A) of the polyurethane composition is between about 30,000 cps and about 35,000 cps, including any value
- part (A) of the polyurethane composition is measured after all of the components of part (A) are combined.
- the viscosity of part (B) of the polyurethane composition is at least 600 cps. In one embodiment, the viscosity of part (B) of the polyurethane composition is between about 600 cps and about 50,000 cps, including any value there between. In another embodiment, the viscosity of part (B) of the polyurethane composition is between about 1,000 cps and about 50,000 cps, including any value therebetween. In a further embodiment, the viscosity of part (B) of the polyurethane composition is between about 1,000 cps and about 40,000 cps, including any value therebetween. In yet a further embodiment, the viscosity of part (B) of the polyurethane composition is between about 1,000 cps and about 30,000 cps, including any value therebetween.
- the polyurethane composition of the adhesive composition can contain any ratio or amount of part (A) and part (B).
- the polyurethane composition contains about 10 wt. % to about 90 wt. % of part (A) and about 10 wt. % to about 90 wt. % of part (B).
- Other examples are contemplated wherein the polyurethane composition contains about 20 wt. % to about 80 wt. % of part (A) and about 20 wt. % to about 80 wt. % of part (B); 30 wt. % to about 75 wt. % of part (A) and about 25 wt. % to about 70 wt.
- the polyurethane composition contains about 50 wt. % part (A) and about 50 wt. % part (B), i.e., part (A) and part (B) are mixed in a 1: 1 ratio.
- the second polyol is optional in part (A) and part (B) of the polyurethane composition. It is contemplated that neither part (A) nor part (B) of the polyurethane composition may include the second polyol. It is also contemplated that either one or both of part (A) and part (B) may include the second polyol. In one embodiment of the polyurethane composition, part (A) or part (B) includes at least 4 wt. % of the second polyol based on a total wt. % of part (A) and part (B). In another embodiment of the polyurethane composition, part (A) or part (B) includes at least 6 wt.
- part (A) or part (B) includes at least 10 wt. % of the second polyol based on a total wt. % of part (A) and part (B).
- part (A) and part (B) of the polyurethane composition has between about 4 wt. % to about 30 wt. % of the second polyol based on a total wt. % of part (A) and part (B).
- the adhesive composition also includes a plasticizer.
- the plasticizer is added to part (B), and then part (B) containing the plasticizer is mixed with part (A).
- the plasticizer is added to part (A) and then part (A) containing the plasticizer is mixed with part (B).
- the plasticizer is added both in part (A) and part (B) and then mixed together to form the polyurethane composition.
- the plasticizer can be any plasticizer capable of being used in an adhesive composition. Suitable plasticizers include, but are not limited to, azelates, sebacates, maleates, succinates, phthalates, adipates, dicarboxylic/tricarboxylic ester-based plasticizers, phosphates, trimellitates, glutarates, citrates, dipropylene glycol dibenzoates, diethylene glycol dibenzoates, epoxidized soybean oil, esters of soybean oil or combinations of any of the foregoing plasticizers. In one embodiment, the plasticizer has a maximum water content of 0.04 wt. % based on the total weight of the plasticizer.
- phthalate-based plasticizers include, but are not limited to: bis(2-ethylhexyl) phthalate, diisononyl phthalate, di-n-butyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, do-n-octyl phthalate, diisooctyl phthalate, diethyl phthalate, diisobutyl phthalate, dioctyl phthalate, diundecyl phthalate, and di-n-hexyl phthalate.
- trimellitates include, but are not limited to: trimethyl trimellitate, tri-(2- ethylhexyl)trimellitate, tri-(n-octyl, n-decyl) trimellitate, tri-(heptyl, nonyl) trimellitate, n-octyl trimellitate.
- adipates, glutarates, dicarboxylic acids, phosphates, sebacates, and maleates include, but are not limited to: 1, 2-benzene dicarboxylic acid, polyester glutarate, o- isopropylphenyl diphenyl phosphate, tri-n-butyl citrate, dialky diether glutarate, bis(2- ethylhexyl)adipate, dioctyl adipate, polyester adipate, dimethyl adipate, monomethyl adipate, diisodecyl adipate, diisononyl adipate, bis(2-ethylhexyl)sebacate, bis(2-ethylhexyl)azelainate, tri(2-ethylhexyl)trimellitate, di(C7-9-alkyl) adipate, butyl fumarate, diisobutyl fumarate, bis(2- ethylhe
- esters of soybean oil include methyl soyate, ethyl soyate and propyl soyate.
- benzoates include, but are not limited to: l-[2-(benzoyloxy)propoxy]propan-2-yl benzoate, commercially available as BenzoflexTM from Eastman Chemical Company, Kingsport, TN, USA.
- plasticizers include, but are not limited to: dioctyl terephthalate, 1,2- cyclohexane dicarboxylic acid diisononyl ester, epoxidized vegetable oils, alkyl sulphonic acid phenyl ester, N-ethyl toluene sulfonamide (ortho and para isomers), N-(2-hydroxypropyl) benzene sulfonamide, N-(n-butyl)benzene sulfonamide, tricresyl phosphate, tributyl phosphate, glycols/polyethers, organophosphates, triethylene glycol dihexanoate, tetraethylene glycol diheptanoate, polymeric plasticizers, polybutene, acetylated monoglycerides, alkyl citrates, triethyl citrate, acetyl triethyl citrate, tributyl citrate
- Suitable commercially available plasticizers also include diisodecyl phthalate, sold as
- Jayflex DIDP from Exxon Mobil Chemical, Houston, TX, USA.
- Other acceptable phthalate plasticizers include other JayflexTM plasticizers from Exxon Mobil Chemical, Houston, TX, USA, (such as, for example, Jayflex DOP), the DIOCTYLTM, SANTICIZER ® , and DIBUTYLTM plasticizers commercially available from Monsanto, St. Louis, Missouri, USA, and the
- Preferred plasticizers have low volatility, such as long chain, branched phthalates (e.g. , ditridecyl phthalate, di-L-nonyl phthalate and di-L-undecyl phthalate).
- Useful dibenzoates are available as BENZOFLEX ® 9 88, BENZOFLEX ® 50 and BENZOFLEX ® 400 commercially available from Velsicol Chemical Corporation, Rosemont, IL, USA.
- Soybean oil is commercially available under the trade name FLEXOLTM EPO, from Dow Chemicals, DE, USA.
- the polyurethane composition and the plasticizer may be combined or mixed in any manner acceptable to form the adhesive composition, which includes, but is not limited to, hand mixing, static mixing, and dynamic mixing. It is noted that the polyurethane composition may be added to the plasticizer, or vice versa, or alternatively, the polyurethane composition and plasticizer may be simultaneously added to a vessel to form the adhesive composition.
- the adhesive composition may include a filler, or a rheology modifier preferably being a thixotropic agent ("thixotrope(s)") or a combination thereof, which may be added to part (A) and/or part (B) of the polyurethane composition.
- the filler may be any suitable filler known in the art, including, but not limited to talc, calcium carbonate, barium sulfate, magnesium hydroxide, clay, mica, titanium dioxide, or any combination of the foregoing.
- the rheology modifier includes all synthetic and natural anti-sagging additives from BYK Additives/Elements Specialties, Wallingford, CT, USA, along with primary amine-terminated polyether compounds.
- Primary amine-terminated polyether compounds include, but are not limited to
- polyoxypropylene amine having a molecular weight from about 110 or 200, to preferably about 500 (although molecular weights up to about 2000 are suitable) and an amine functionality of about 2 to 3, preferably about 2.
- Such primary amino-terminated polyethers are manufactured and sold by Huntsman Corporation, Salt Lake City, UT, under the name Jeffamine.
- Particularly preferred is Jeffamine D-230, which is a polyoxypropylene glycol terminated with primary amines and having an amine functionality of 2 and a molecular weight of about 230.
- Crosslinking in the adhesive composition can be further accelerated by adding a hydroxyl- containing tertiary amine such as diisoproponol amine commercially available as QUADROL by BASF Corp., Germany.
- Thixotropy develops rapidly when part (A) and part (B) of the polyurethane composition are mixed together in the presence of such amines.
- Thixotropic agents include, but are not limited to, inorganic additives and can include, for example, fumed silica, amorphous silicon dioxide, clays, bentonites, talcs, and the like, and combinations thereof.
- the adhesive composition When the polyurethane composition and the plasticizer are combined to form the adhesive composition, the adhesive composition typically has an initial mix viscosity of at least about 10,000 cps.
- the term "initial mix” as used in "initial mix viscosity” refers to the viscosity of the adhesive composition when both parts (A) and (B) of the polyurethane and the plasticizer are first mixed together.
- the initial mix viscosity of the adhesive composition is between about 10,000 cps and about 40,000 cps, including any value therebetween.
- the initial mix viscosity of the adhesive composition is between about 10,000 cps and about 25,000 cps, including any value therebetween.
- the initial viscosity of the adhesive composition is between 20,000 cps and about 35,000 cps, including any value therebetween. In another example, the initial viscosity of the adhesive composition is between 30,000 cps and 40,000 cps, including any value therebetween. While certain ranges of initial mix viscosity are provided above, it is contemplated that the initial mix viscosity of the adhesive composition can be any value higher than 20,000 cps. The initial mix viscosity can range from 5000 cps to 70,000 cps based on the processing requirements.
- the adhesive compositions should be flexible in order to penetrate the interstices and voids in the membrane of a reverse osmosis module, but also should be strong enough to result high pressures to which the membrane is subjected to use thereof.
- the adhesive composition is applied to the membrane of the reverse osmosis module.
- the adhesive composition is cured after application to the membrane.
- An example reverse osmosis module 10 is illustrated in FIG. 1, wherein the adhesive composition 12 is shown applied to at least a portion of a membrane 14.
- the example shown in FIG. 1 is only used for illustration purposes and is not meant to be limiting to the scope of the present invention.
- the adhesive composition can be cured through room temperature curing or heat curing. When the adhesive composition is fully cured, the adhesive will have certain properties that help impart beneficial characteristics to the adhesive composition when used in a reverse osmosis module.
- the adhesive composition typically has a Shore hardness of greater than about 20A when fully cured. In another example, the adhesive composition has a Shore hardness of at least about 30A when fully cured, while in another example the adhesive composition has a Shore hardness of at least about 40 A when fully cured. In yet a further example, the adhesive composition has a Shore hardness of at least about 35D when fully cured. In a further example, the adhesive composition has a Shore hardness of between 35D and 80D when fully cured. In another example, the adhesive composition has a Shore hardness of between 60A and 80D.
- the adhesive composition When fully cured, the adhesive composition should have tensile strength of greater than 100 psi, preferably greater than 500 psi. In another example, the adhesive composition has a tensile strength of greater than 1,000 psi, preferably greater than 2,000 psi when fully cured. The tensile strength can be measured by, for example, the Instron Tensiometer. It is contemplated that the adhesive composition can be applied to a desired membrane using any technique known in the art to apply such adhesives. For example, the adhesive composition may be applied to a membrane of a reverse osmosis module using any commercially available coater, such as a slot die coater. The adhesive composition may be applied as a layer having any desired thickness. In one example, the adhesive composition is applied in a layer of about 0.2 to about 4 mil thick, although other thicknesses can be applicable.
- Embodiment 1 An adhesive composition suitable for reverse osmosis modules, the adhesive composition comprising:
- A an isocyanate group-containing pre-polymer comprising a reaction product of (i) castor oil or a derivative thereof; and (ii) a polyisocyanate; and (iii) optionally a second polyol; and
- an isocyanate-reactive polyol mixture comprising: (i) a polybutadiene polyol; and (ii) a urethane catalyst; and (iii) optionally the second polyol; and
- the adhesive composition is essentially free from diluent oils and solvents.
- Embodiment 2 The adhesive composition according to embodiment 1, wherein an initial mix viscosity of the adhesive composition is at least 10,000 cps.
- Embodiment 3 The adhesive composition according to any one of the preceding embodiments, wherein the initial mix viscosity of the adhesive composition is between about 10,000 cps and about 40,000 cps.
- Embodiment 4 The adhesive composition according to any one of the preceding embodiments, wherein the initial mix viscosity of the adhesive composition is between about 30,000 cps and about 40,000 cps.
- Embodiment 5. The adhesive composition according to any one of the preceding embodiments, wherein the initial mix viscosity of the adhesive composition is between about 20,000 cps and about 35,000 cps.
- Embodiment 6 The adhesive composition according to any one of the preceding embodiments, wherein the initial mix viscosity of the adhesive composition is between about 10,000 cps and about 25,000 cps.
- Embodiment 7 The adhesive composition according to any one of the preceding embodiments, further comprising a Shore hardness of greater than about 20A when fully cured.
- Embodiment 8 The adhesive composition according to any one of the preceding embodiments, further comprising a Shore hardness of at least about 30A when fully cured.
- Embodiment 9 The adhesive composition according to any one of the preceding embodiments, further comprising a Shore hardness of at least about 40A when fully cured.
- Embodiment 10 The adhesive composition according to any one of the preceding embodiments, further comprising a Shore hardness between 60A and 80D when fully cured.
- Embodiment 11 The adhesive composition according to any of embodiments 1-6 and 9-10, further comprising a Shore hardness of at least about 35D when fully cured.
- Embodiment 12 The adhesive composition according to any one of embodiments 1- 6 and 9-10, further comprising a Shore hardness between 35D and 80D when fully cured.
- Embodiment 13 The adhesive composition according to any one of the preceding embodiments, wherein a tensile strength of the adhesive composition is greater than about 100 psi.
- Embodiment 14 The adhesive composition of any one of the preceding
- a tensile strength of the adhesive composition is at least 1,000 psi when fully cured.
- Embodiment 15 The adhesive composition of any one of the preceding
- a tensile strength of the adhesive composition is at least 2,000 psi when fully cured.
- Embodiment 16 The adhesive composition according to any one of the preceding embodiments, wherein either part (A) or part (B) comprises at least 4 wt of the second polyol based on a total weight percent of part (A) and part (B).
- Embodiment 17 The adhesive composition according to any one of the preceding embodiments, wherein either part (A) or part (B) comprises at least 6 wt. % of the second polyol based on a total weight percent of part (A) and part (B).
- Embodiment 18 The adhesive composition according to any one of the preceding embodiments, wherein either part (A) or part (B) comprises at least 10 wt. % of the second polyol based on a total weight of part (A) and part (B).
- Embodiment 19 The adhesive composition according to any one of the preceding embodiments, wherein the second polyol is chosen from a group of polyols having a molecular weight less than about 600.
- Embodiment 20 The adhesive composition according to any one of the preceding embodiments, wherein the second polyol is a polyol having a molecular weight between 80-300 Daltons.
- Embodiment 21 The adhesive composition according to embodiment 20, wherein the second polyol is a diol.
- Embodiment 22 The adhesive composition according to embodiment 19 wherein the second polyol is selected from the group consisting of 2-ethyl-l,3-hexanediol; 1,2- propanediol; 1,3-butanediol; 2,2,4-trimethyl-l,3-pentanediol, 1,12-octadecanediol; 1,2- hexanediol; 1,2-octanediol; and 1,2-decanediol.
- the second polyol is selected from the group consisting of 2-ethyl-l,3-hexanediol; 1,2- propanediol; 1,3-butanediol; 2,2,4-trimethyl-l,3-pentanediol, 1,12-octadecanediol; 1,2- hexanediol; 1,2-octanediol; and 1,2-decaned
- Embodiment 23 The adhesive composition according to embodiment 19, wherein the second polyol is a polypropylene glycol or a polytetramethylene ether glycol.
- Embodiment 24 The adhesive composition according to any one of the preceding embodiments, wherein at least one of part (I) (A) and part (I)(B) further comprise a filler, a thixotropic agent or a combination thereof.
- Embodiment 25 The adhesive composition according to embodiment 24, wherein at least one of part (I) (A) and part (I)(B) comprise a filler selected from the group consisting of talc, calcium carbonate, barium sulfate, magnesium hydroxide, clay, mica, titanium dioxide, and combinations thereof.
- a filler selected from the group consisting of talc, calcium carbonate, barium sulfate, magnesium hydroxide, clay, mica, titanium dioxide, and combinations thereof.
- Embodiment 26 The adhesive composition according to embodiment 24, wherein part (I)(B) of the adhesive composition further comprises a thixotropic agent.
- Embodiment 27 The adhesive composition according to embodiment 26, wherein the thixotropic agent is selected from the group consisting of fumed silica, amorphous silicon dioxide, talc, clay and combinations thereof.
- Embodiment 28 The adhesive composition according to any one of the preceding embodiments, wherein part (I) of the adhesive composition includes between about 10 wt. % and about 90 wt. % of part (A) based on the total weight of part (I) and between about 10 wt. % and about 90 wt. % of part (B) based on the total weight of part (I).
- Embodiment 29 The adhesive composition according to any one of the preceding embodiments, wherein part (I) of the adhesive composition includes between about 20 wt. % and about 80 wt. % of part (A) based on the total weight of part (I) and between about 20 wt. % and about 80 wt. % of part (B) based on the total weight of part (I).
- Embodiment 30 The adhesive composition according to any one of the preceding embodiments, wherein part (I) of the adhesive composition includes between about 30 wt. % and about 70 wt. % of part (A) based on the total weight of part (I) and between about 30 wt. % and about 70 wt. % of part (B) based on the total weight of part (I).
- Embodiment 31 The adhesive composition according to any one of the preceding embodiments, wherein part (I) of the adhesive composition includes about 50 wt. % of part (A) based on the total weight of part (I) and about 50 wt. % of part (B) based on the total weight of part (I).
- Embodiment 32 An adhesive composition suitable for reverse osmosis modules, the adhesive composition comprising:
- an isocyanate-reactive polyol mixture comprising: (i) polybutadiene polyol; (ii) a urethane catalyst; and (iii) a secondary polyol; and
- the adhesive composition is essentially free from diluents oils and solvents, further wherein a tensile strength of the adhesive composition when fully cured is at least 1,000 psi, and a Shore hardness of the adhesive composition when fully cured is between about 35D and about 75D.
- Embodiment 33 The adhesive composition according to any one of the preceding embodiments, wherein the plasticizer is selected from the group consisting of azelates, sebacates, maleates, succinates, phthalates, adipates, dicarboxylic/tricarboxylic ester-based plasticizers, phosphates, trimellitates, glutarates, citrates, dipropylene glycol dibenzoates, diethylene glycol dibenzoates, epoxidized soybean oil, esters of soybean oil, and combinations thereof.
- the plasticizer is selected from the group consisting of azelates, sebacates, maleates, succinates, phthalates, adipates, dicarboxylic/tricarboxylic ester-based plasticizers, phosphates, trimellitates, glutarates, citrates, dipropylene glycol dibenzoates, diethylene glycol dibenzoates, epoxidized soybean oil, esters of soybean oil, and combinations thereof.
- Embodiment 34 The adhesive composition according to any one of the preceding embodiments, wherein the plasticizer is selected from the group consisting of dipropylene glycol dibenzoates, diethylene glycol dibenzoates, epoxidized soybean oil, esters of soybean oil, diheptyl adipate, dioctyl adipate, dinonyl adipate, and combinations thereof.
- the plasticizer is selected from the group consisting of dipropylene glycol dibenzoates, diethylene glycol dibenzoates, epoxidized soybean oil, esters of soybean oil, diheptyl adipate, dioctyl adipate, dinonyl adipate, and combinations thereof.
- Embodiment 35 A reverse osmosis module comprising an adhesive composition according to any one of the preceding embodiments.
- Embodiment 36 A reverse osmosis module comprising an adhesive composition according to embodiment 32.
- Embodiment 37 A method of constructing a reverse osmosis module, the method comprising:
- an adhesive composition to at least a portion of a membrane present in the reverse osmosis module, the adhesive composition according to any one of embodiments 1-32.
- Embodiment 38 A method of constructing a reverse osmosis module, the method comprising:
- Adhesive compositions according to one or more of the foregoing embodiments are further discussed in the Examples provided below.
- Table 1 Chemical Used & Trade Names:
- Table 2 provides the components for part (A) and part (B) of the polyurethane composition and the plasticizer of the adhesive composition in Examples I- II, which are adhesive compositions according to the invention. Table 2 also provides the components for Examples III- IV (comparative adhesive compositions). In Examples I- IV, part (B) of the polyurethane composition does not include a second polyol.
- Parts (A) and (B) of the adhesive compositions in Examples I-IX are synthesized according to the following procedures.
- a sample of the isocyanate group-containing pre-polymer of part (A) is analyzed to determine NCO content according to ASTM D 2572.
- additional castor oil is added and reacted under vacuum at a temperature between about 80°C to about 85°C for 2 hours to lower the NCO content to the target NCO value, i.e. 5% to 25% (mass percent) NCO content. If the calculated NCO content is lower than the target value, extra diisocyanate is added to increase the NCO content. The NCO content is determined again to ensure the NCO content is within the target value prior to use.
- part (B) of the polyurethane composition does not include a second polyol and a thixotrope.
- Each of the adhesive compositions in Examples I-IV is synthesized by blending the polybutadiene diol, plasticizer and defoamer in a vessel for 30 minutes. Water is then stripped from the mixture so that the water content of the mixture is less than 0.04 wt. %. The catalyst is then added and the mixture is stirred between 40 and 45 minutes to result in a homogenous mixture.
- part (B) of the polyurethane composition includes a second polyol and a thixotrope.
- Each of the adhesive compositions in Examples VI-IX is synthesized by blending the polybutadiene diol, plasticizer and defoamer in a vessel for 30 minutes. Water is then stripped from the mixture so that the water content of the mixture is less than 0.04 wt. %.
- the second polyol, secondary diol EH diol is added to, and blended with, the mixture after it is stripped of water so that the water content is 0.04 wt. % or less.
- the catalyst is then added to the mixture at room temperature and mixed followed by the thixotrope.
- the thixotrope is added to the mixture at room temperature and is mixed between 40 minutes and 45 minutes until a homogenous mixture is obtained.
- Table 2 Examples I-IV Example Example Example Example Example Example Example Example Example Example
- Part B wt. % wt. % wt. % wt. % wt. %
- Table 3 provides the components for part (A) and part (B) of the polyurethane composition and the plasticizer of the adhesive composition in Examples V-IX, which are adhesive compositions according to the invention.
- part (B) of the polyurethane composition does include a second polyol.
- Table 3 Examples V-IX
- Part B wt. % wt. % wt. % wt. % wt. % wt. %
- Second polyol % amount in B x
- the initial viscosity of Part A+ Part B is measured immediately after mixing.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
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Priority Applications (5)
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CN201580025242.9A CN106471087B (en) | 2014-03-12 | 2015-03-11 | Polyurethane adhesive for reverse osmosis modules |
CA2942481A CA2942481C (en) | 2014-03-12 | 2015-03-11 | Polyurethane adhesives for reverse osmosis modules |
KR1020167028311A KR102339480B1 (en) | 2014-03-12 | 2015-03-11 | Polyurethane adhesives for reverse osmosis modules |
EP15712752.3A EP3116929A1 (en) | 2014-03-12 | 2015-03-11 | Polyurethane adhesives for reverse osmosis modules |
JP2016557044A JP6584423B2 (en) | 2014-03-12 | 2015-03-11 | Polyurethane adhesive for reverse osmosis module |
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US201461951741P | 2014-03-12 | 2014-03-12 | |
US61/951,741 | 2014-03-12 |
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PCT/US2015/019882 WO2015138561A1 (en) | 2014-03-12 | 2015-03-11 | Polyurethane adhesives for reverse osmosis modules |
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EP (1) | EP3116929A1 (en) |
JP (1) | JP6584423B2 (en) |
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JP2021183702A (en) * | 2017-02-28 | 2021-12-02 | 第一工業製薬株式会社 | Polyurethane resin composition for sealing and sealed article |
US11647768B2 (en) | 2020-11-11 | 2023-05-16 | International Business Machines Corporation | Pretreated clay composition and process for selective removal of planar molecules from solutions |
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CA2982120C (en) * | 2015-04-09 | 2023-08-15 | Elantas Pdg, Inc. | Polyurethane adhesives for reverse osmosis modules |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4842736A (en) | 1988-09-06 | 1989-06-27 | Desalination Systems, Inc. | Spiral wound membrane |
JPH0657236A (en) * | 1992-08-11 | 1994-03-01 | Yokohama Rubber Co Ltd:The | Intimate mixture for sealing cable joint |
JP2006096912A (en) * | 2004-09-30 | 2006-04-13 | Yokohama Rubber Co Ltd:The | Two-pack curable type polyurethane resin composition |
US7303675B2 (en) | 2002-06-21 | 2007-12-04 | Ge Osmonics, Inc. | Blister protection for spiral wound elements |
CN102850989A (en) * | 2012-09-26 | 2013-01-02 | 贵阳时代沃顿科技有限公司 | Two-component polyurethane adhesive and preparation method thereof |
CN102911636A (en) * | 2012-09-26 | 2013-02-06 | 贵阳时代沃顿科技有限公司 | Double-component polyurethane adhesive, preparation method and application thereof |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4865735A (en) * | 1988-02-18 | 1989-09-12 | Caschem, Inc. | Amine containing polyurethane compositions for separatory devices |
JP2007224078A (en) * | 2006-02-21 | 2007-09-06 | Nippon Polyurethane Ind Co Ltd | Polyurethane resin-forming composition for sealant used for hollow fiber membrane module, and sealant for hollow fiber membrane module using the composition |
-
2015
- 2015-03-11 EP EP15712752.3A patent/EP3116929A1/en active Pending
- 2015-03-11 WO PCT/US2015/019882 patent/WO2015138561A1/en active Application Filing
- 2015-03-11 CA CA2942481A patent/CA2942481C/en active Active
- 2015-03-11 JP JP2016557044A patent/JP6584423B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4842736A (en) | 1988-09-06 | 1989-06-27 | Desalination Systems, Inc. | Spiral wound membrane |
JPH0657236A (en) * | 1992-08-11 | 1994-03-01 | Yokohama Rubber Co Ltd:The | Intimate mixture for sealing cable joint |
US7303675B2 (en) | 2002-06-21 | 2007-12-04 | Ge Osmonics, Inc. | Blister protection for spiral wound elements |
JP2006096912A (en) * | 2004-09-30 | 2006-04-13 | Yokohama Rubber Co Ltd:The | Two-pack curable type polyurethane resin composition |
CN102850989A (en) * | 2012-09-26 | 2013-01-02 | 贵阳时代沃顿科技有限公司 | Two-component polyurethane adhesive and preparation method thereof |
CN102911636A (en) * | 2012-09-26 | 2013-02-06 | 贵阳时代沃顿科技有限公司 | Double-component polyurethane adhesive, preparation method and application thereof |
Non-Patent Citations (4)
Title |
---|
DATABASE WPI Week 199413, Derwent World Patents Index; AN 1994-107050, XP002739991 * |
DATABASE WPI Week 200629, Derwent World Patents Index; AN 2006-278636, XP002739990 * |
DATABASE WPI Week 201349, Derwent World Patents Index; AN 2013-H60054, XP002739993 * |
DATABASE WPI Week 201376, Derwent World Patents Index; AN 2013-H30636, XP002739992 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021183702A (en) * | 2017-02-28 | 2021-12-02 | 第一工業製薬株式会社 | Polyurethane resin composition for sealing and sealed article |
JP7219797B2 (en) | 2017-02-28 | 2023-02-08 | 第一工業製薬株式会社 | Polyurethane resin composition for encapsulation and encapsulant |
US11647768B2 (en) | 2020-11-11 | 2023-05-16 | International Business Machines Corporation | Pretreated clay composition and process for selective removal of planar molecules from solutions |
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EP3116929A1 (en) | 2017-01-18 |
CA2942481A1 (en) | 2015-09-17 |
CA2942481C (en) | 2023-01-17 |
JP6584423B2 (en) | 2019-10-02 |
JP2017510678A (en) | 2017-04-13 |
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