CN1153181A - Preparation of polymer powders which are redispersible in aqueous medium - Google Patents
Preparation of polymer powders which are redispersible in aqueous medium Download PDFInfo
- Publication number
- CN1153181A CN1153181A CN 96122881 CN96122881A CN1153181A CN 1153181 A CN1153181 A CN 1153181A CN 96122881 CN96122881 CN 96122881 CN 96122881 A CN96122881 A CN 96122881A CN 1153181 A CN1153181 A CN 1153181A
- Authority
- CN
- China
- Prior art keywords
- polyelectrolyte
- monomer
- aqueous
- aqueous medium
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920000642 polymer Polymers 0.000 title claims abstract description 97
- 239000012736 aqueous medium Substances 0.000 title claims abstract description 41
- 239000000843 powder Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title description 21
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 67
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 64
- 238000001035 drying Methods 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 40
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 87
- 238000000034 method Methods 0.000 claims description 69
- 239000000463 material Substances 0.000 claims description 59
- 239000000178 monomer Substances 0.000 claims description 57
- 239000006185 dispersion Substances 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- 239000002612 dispersion medium Substances 0.000 claims description 12
- 238000010494 dissociation reaction Methods 0.000 claims description 12
- 230000005593 dissociations Effects 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 9
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 8
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229920003002 synthetic resin Polymers 0.000 claims description 4
- 239000000057 synthetic resin Substances 0.000 claims description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000002421 finishing Substances 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- 239000004922 lacquer Substances 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- 238000009156 water cure Methods 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims 1
- 150000001734 carboxylic acid salts Chemical class 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 description 31
- -1 halogen ion Chemical class 0.000 description 30
- 238000006116 polymerization reaction Methods 0.000 description 26
- 238000007046 ethoxylation reaction Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- 239000003995 emulsifying agent Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 22
- 230000006641 stabilisation Effects 0.000 description 20
- 238000011105 stabilization Methods 0.000 description 20
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 13
- 238000005507 spraying Methods 0.000 description 12
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 11
- 239000000084 colloidal system Substances 0.000 description 11
- 230000001681 protective effect Effects 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 125000002091 cationic group Chemical group 0.000 description 10
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 229920000447 polyanionic polymer Polymers 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 6
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- YBXHSDOJCKEVRI-UHFFFAOYSA-N C(=C)C=1NC=CN1.CC1(CC(C(=O)O)=CC=C1)C(=O)O Chemical compound C(=C)C=1NC=CN1.CC1(CC(C(=O)O)=CC=C1)C(=O)O YBXHSDOJCKEVRI-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 235000015278 beef Nutrition 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 230000002427 irreversible effect Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000009288 screen filtration Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000003760 tallow Substances 0.000 description 5
- 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 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000012874 anionic emulsifier Substances 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000006174 pH buffer Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Chemical group 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical group OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 101100450591 Human adenovirus B serotype 3 PVIII gene Proteins 0.000 description 2
- 101100294463 Human adenovirus E serotype 4 L2 gene Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 150000001408 amides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 230000003750 conditioning effect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 2
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
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- 239000012875 nonionic emulsifier Substances 0.000 description 2
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- QXIQCNFSNJEMOD-UHFFFAOYSA-N 3-hydroxybutan-2-yl prop-2-enoate Chemical compound CC(O)C(C)OC(=O)C=C QXIQCNFSNJEMOD-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical group CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 244000007853 Sarothamnus scoparius Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- WPVUEFCKVDDXSM-UHFFFAOYSA-N [2-(6-methylheptyl)phenyl] hydrogen sulfate Chemical compound CC(C)CCCCCC1=CC=CC=C1OS(O)(=O)=O WPVUEFCKVDDXSM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- RMXVHZFHSKRNJN-UHFFFAOYSA-N chlorourea Chemical compound NC(=O)NCl RMXVHZFHSKRNJN-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- DUYAAUVXQSMXQP-UHFFFAOYSA-N ethanethioic S-acid Chemical compound CC(S)=O DUYAAUVXQSMXQP-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002243 precursor Substances 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
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000001040 synthetic pigment Substances 0.000 description 1
- UWNNZXDNLPNGQJ-UHFFFAOYSA-N tert-butyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(C)(C)C UWNNZXDNLPNGQJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
Polymer powders which are redispersible in an aqueous medium are prepaed by drying an aqueous polymer dispersion whose polymer particle dispersed in the aqueous medium have a positive or a negative electric surface charge, with the addition of a water-soluble polyelectrolyte as a drying assistant, the electric charge of the polyion being opposite to the electric surface charge of the diperse polymer particles.
Description
The present invention relates to a kind of method for preparing redispersible polymer powder in aqueous medium, it prepares by the aqueous polymer dispersion that drying is added with drying aids, and the dispersive polymer particles has the plus or minus surface charge in this dispersion aqueous medium.
The invention still further relates to the redispersible polymer powder in water that obtains by this method, the purposes of these powder (for example as the additive in the inorganic adhesive or the tackiness agent of synthetic resins), and the aqueous polymer dispersion of these powder of preparation that contains the polyelectrolyte of adding.
Aqueous polymer dispersion (latex) is the system of extensively understanding for people, and its disperse phase is a spherical ball of string (being polymer particles) that is formed by the polymer chain that interwinds basically.Polymer particles typically have a diameter from 10-1000nm.Situation during as the polymers soln solvent flashing, aqueous polymer dispersion has the tendency that forms polymeric film after the volatilization of water base dispersion medium, so they can be used as base-material, tackiness agent and coating and use (they are especially favourable as the application of the high inside coating of the tackiness agent of synthetic resins and pigment content).
The most important factor of impact polymer water dispersion character is the size that is present in polymer particles in the dispersion disperse phase.The character of aqueous polymer dispersion, especially the glossiness of viscosity or its film depends on the particle diameter of dispersive polymer particles, or or rather, depend on that (for identical polymkeric substance, the film that little polymer particles forms generally has high glossiness for the size distribution of dispersive polymer particles; Wide size distribution generally makes the viscosity of aqueous polymer dispersion lower; The dispersion of little polymer particles, general higher to the bounding force of pigment, or the like).
But the defective that aqueous polymer dispersion is used is its preparation and uses and generally do not carry out in same place.Transportation from the preparation place to the place to use means the polymkeric substance that not only will transport the unique component of final formation polymeric film, but also will additionally transport the dispersion medium water that all can obtain easily throughout.In addition, aqueous polymer dispersion can only join in the place to use and improve the latter in the mineral binder bond, otherwise this binding agent just can solidify before use.
Therefore a kind of desirable form of any aqueous polymer dispersion is exactly the polymer powder of redispersible it when adding water.
Adding the water polymer powders redispersible generally obtains by drying of aqueous polymer dispersions.The example of this drying means has freeze-drying and spray-drying process.A kind of method in back is to be sprayed to polymeric dispersions in one hot gas flow and to carry out drying, and it is particularly conducive to the mass production powder.Be used for exsiccant gas and preferably and the super-dry device that circulates (for example with reference to EP-A262326 or EP-A407889) by the dispersion of being sprayed.
Though with polymers soln drying completely reversibility normally, but by the shortcoming of the polymer powder of drying of aqueous polymer dispersions preparation be add behind the water their redispersion ability generally may be not exclusively satisfactory, the polymer particles size distribution that forms during redispersion is general different with (the initial particle size distribution) of initial water dispersion.
This is because different with polymers soln, aqueous polymer dispersion is formed not to be thermodynamic stable system.It generates the interface that bigger secondary particulate (for example condensation product) reduces polymkeric substance and dispersion medium by the combination of less primary fine particles.Add dispersion agent in the disperse phase in the aqueous medium, can in considerable time, prevent the generation of two atomic grains.
The most common situation is, dispersion agent be can stable dispersion polymkeric substance/water base dispersion medium interface material.They are normally water miscible, can be divided into two big classes: a) protective colloid; B) emulsifying agent.The latter can be divided into again: a) anionic emulsifier; B) cationic emulsifier; C) nonionic emulsifier.The stabilization effect of protective colloid mainly is because protective colloid surrounds the dispersed polymeres particulate, and it is carried out space and/or electrostatic shielding.Their relative molecular weight is usually above 1500.They can the chemistry or only physical connection on the dispersed polymeres particulate.
Relative molecular weight is that less than the reason of the stabilization effect of 1500 emulsifying agent because they have amphipathic structure (polarity part-nonpolar part), they can reduce the interfacial tension at polymkeric substance/water base dispersion medium interface usually.If polarity partly is cationic group, then be called cationic emulsifier.If polarity partly is the anionic group, then be called anionic emulsifier.In polarity partly is under the situation of non-ionic type, then to be called nonionic emulsifier.Different with protective colloid, emulsifying agent can form micella in water.In addition, their feature is, at 25 ℃ and 1atm, when reaching micelle-forming concentration, they can reduce at least 25% with the surface tension of water.For anionic emulsifier, suitable counter ion is basic metal, alkaline-earth metal and ammonium ion.The suitable especially counter ion of cationic emulsifier is OH
-, halogen ion and NO
3 -
In the aqueous polymer dispersion with the cationic emulsifier stabilization, the polymer particles that forms disperse phase correspondingly has positive surface charge.Aqueous polymer dispersion with the anionic emulsifier stabilization contains the polymer particles with negative surface charge.The same with protective colloid, emulsifying agent also can the chemistry or only physical connection on the dispersed polymeres particulate.Certainly, also can use protective colloid and emulsifying agent to come the stabilization of polymers water dispersion simultaneously.
The other method of surface charge is provided is to mix the ionizable component in this polymkeric substance in order to be scattered in polymer particles in the aqueous medium.This is meant the compound that (for example) is such, α for example, and β-monoethylenically unsaturated carboxylic acid, it can form the pH value by changing aqueous medium electric charge or become ion at dissociation in water.If the dispersed phase polymer of aqueous polymer dispersion is directly to prepare (primary dispersion body) by the monomer free radical water emulsion polymerization with at least one ethylenically unsaturated group, the surface of dispersed polymeres particulate also may have the plus or minus electric charge that is produced by radical polymerization initiator so.Suitable molecular weight regulator (for example referring to JP-A7/53728) is another source of electric charge.Under the situation of secondary polymerization thing dispersion, polymkeric substance preparation (for example using radical polymerization, polycondensation or addition polymerization method) in solution usually, and be subsequently converted to aqueous polymer dispersion.Similarly, required surface charge can be produced by the initiator of selecting, conditioning agent and (under situation about transforming) dispersion agent.
The dispersed phase polymer particulate of aqueous polymer dispersion has and negative still have positive surface charge and can be determined by the electrophoretic mobility of measuring them by ordinary method.Most aqueous polymer dispersions have the polymer particles (aqueous polymer dispersion of anionic stabilization) that the surface has negative charge.They are the same with the aqueous polymer dispersion of cationic stabilization, are as known in the art all.
But in the drying process of aqueous polymer dispersion, the separating effect of dispersion agent is no longer enough usually, and forms irreversible secondary granule to a certain extent, that is, secondary granule remains unchanged in the redispersion process.Influence the performance of the aqueous polymer dispersion that redispersion obtains unfriendly.
Known have a kind of like this material, when being added to it in the aqueous polymer dispersion, can being suppressed at and forming irreversible secondary granule in the drying process.These materials are referred to as drying aids.They are well-known, and spraying drying auxiliary agent particularly is because spraying drying has promoted the formation of irreversible secondary granule to a certain extent.Simultaneously, drying aids has suppressed the formation of adhered polymer layer on dry wall in spray-drying process, thereby has improved the productive rate of polymer powder.
According to TIZ-Fachberichte109 No.9 (1985), 698et seq., the drying aids that uses all is water miscible at present, and they form a kind of matrix in drying process, and the water-insoluble primary polymer particulate that is surrounded by dispersion agent is embedded in this matrix.Matrix is surrounded and has been protected the primary polymer particulate, prevents to form irreversible secondary granule (being generally the aggregate of 50-250 μ m), and it comprises a large amount of primary fine particles that separated by drying aids matrix.Redispersion is in water the time, and this matrix is dissolved again, can form the primary polymer particulate that is surrounded by dispersion agent when initial basically again.In most cases, also in the reversible secondary granule that forms, add finely divided caking inhibiter (as finely divided silica powder), separating redispersible aggregate, with prevent (for example) in storage process they owing to gravity pressure lumps.
Germany applies for that openly DAS2238903 and EP-A576844 recommend to use poly-(N-vinyl pyrrolidone) as such drying aids.The water-soluble alkali of the multipolymer of EP-A78449 recommendation use 20-70wt (weight) % vinyl pyrrolidone and 30-80wt% vinyl-acetic ester, the condenses of naphthene sulfonic acid/formaldehyde and/or alkaline earth salt and their mixture are as drying aids.EP-A601518 recommends to use the drying aids of polyvinyl alcohol as the polyacrylic acid ester aqueous dispersion of anionic stabilization.U.Rietz recommends to use the drying aids of polyvinyl alcohol as aqueous polymer dispersion in Chemie u.Technologie makromolekularer Stoffe (FH-Texte FH Aachen) 53. (1987), 85.
EP-A467 103 relates to a kind of method for preparing redispersible polymer powder in aqueous medium, and it comprises, at 50-80mol (mole) the unsaturated list of % olefinic or dicarboxylic acid and the 20-50mol%C that add as drying aids
3-C
12Behind alkene and/or the cinnamic multipolymer, with the aqueous polymer dispersion spraying drying of anionic stabilization.
EP-A629650 recommends to use and contains the polymkeric substance of olefinic unsaturated sulfonic acid polymerized unit as the drying aids in the spraying drying of the aqueous polymer dispersion of anionic stabilization.
But the defective of the drying aids of prior art is that their performances in the drying of aqueous polymer dispersions process can not be entirely satisfactory.Particularly, in aqueous medium, during redispersion, can not reach initial polymer particles Particle Distribution (for example referring to TIZ-Fachberichte, 109No.9 (1985), 699) usually.When the dispersion of redispersion was filtered, the amount of residual condensation product can show this point on the filter.
JP-A7/53728 relates to a kind of spray drying process of aqueous polymer dispersion of ionic stabilization, it to the water dispersion that wherein adds water-insoluble finely divided inorganics particulate as drying aids, carry out drying afterwards, the surface charge of inorganics particulate is opposite with the surface charge polarity of dispersed polymeres particulate.Described inorganics particulate by electrostatic adhesion on the dispersed polymeres particulate, thereby in the drying process of aqueous polymer dispersion, form a protective layer, this patent claims that it promptly can improve redispersible, can prevent bonding again.Though proved the anti stick effect in an embodiment, do not proved that redispersible is enhanced.The shortcoming of JP-A7/93728 method is that the diameter of finely divided inorganics particulate must mate with the diameter of polymer particles.So just produced difficulty, particularly wanted under the situation of dry superfine dispersive aqueous polymer dispersion and aqueous polymer dispersion has under the situation that very wide particle diameter distributes.
EP-A262326 relates to a kind of particular spray drying means of aqueous polymer dispersion, and it attempts not use drying aids to carry out drying.But aspect the redispersible of the polymer powder that makes, this method can not be entirely satisfactory equally.
The object of the invention provides a kind of method for preparing redispersible polymer powder in aqueous medium, it comprises, the aqueous polymer dispersion drying of drying aids will be added with, the polymer particles that this dispersion is scattered in the aqueous medium has the plus or minus surface charge, and this method does not have the various shortcoming of prior art method.
We have found that, this purpose is reached by the method that the present invention prepares redispersible polymer powder in aqueous medium, it comprises, the aqueous polymer dispersion drying of drying aids will be added with, the polymer particles that this dispersion is scattered in the aqueous medium has the plus or minus surface charge, wherein, in aqueous polymer dispersion to be dried, add polyelectrolyte as drying aids, the mode that this polyelectrolyte can be dissociated into polyion and counter ion is dissolved in this water base dispersion medium, and the electric charge of polyion is opposite with the surface charge polarity of dispersed polymeres particulate.
According to R mpp Chemie Lexikon PI-S, Thieme Verlag, the 9th edition (1992) 3526 pages, " polyelectrolyte " means such base polymer, it has the group that can carry out ionic dissociation in aqueous medium, these groups can be the part of polymer chain or the substituting group on it, the group that can carry out ionic dissociation must be abundant, make that this polymkeric substance of disassociation form is solvable fully in water, promptly polyelectrolyte is dissociated into polyion and corresponding counter ion in aqueous medium.Polyelectrolyte mainly is divided into poly-acid and poly-alkali two classes.During disassociation, poly-acid loses proton and forms polyanion.The disassociation of poly-acid in aqueous medium can promote that form the aqueous solution of poly-hydrochlorate, that is, the common counter ion of polyanion is alkalimetal ion (Na by add alkali in aqueous medium
+, K
+, Li
+, Rb
+, Cs
+), alkaline-earth metal ions is (as Ca
2+, Mg
2+), H
+Ion, NH
4 +Ion and be different from NH
3The ammonium ion of amine.
Poly-alkali contains the ion precursor group, for example can combine last proton with acid-respons and the salifiable group of shape.Replacing protonated another kind of method is alkylation.The common counter ion of the polycation that forms is halogen ion (Cl
-, Br
-, I
-), CO
3 2-, SO
4 2-, CH
3-OSO
3 -And CH
3-CH
2-OSO
3 -Polyion (positively charged ion and negatively charged ion) can be an inorganic polymer, also can be organic polymer.According to the present invention, be preferably based on the polyelectrolyte of organic polymer.The number-average molecular weight that is applicable to polyelectrolyte of the present invention for example is 1000-3 * 10
6Or higher or 2000-5 * 10
5, or 5000-10
5, or 7500-50000 or 10000-25000.
Polyelectrolyte and preparation thereof are as known in the art (for example referring to US-A3205187; US-A 4038233; EP-A246580; EP-A544158; EP-A629650; EP-A467103; Oosawa, Polyelektrolytes, New York:Marcel Dekker 1971; Deng)
Their solubleness in water under 25 ℃ and 1atm is general 〉=1g/100g water, often 〉=10g/100g water and usually 〉=25g/100g water.
The polyelectrolyte that the present invention uses can be with very easy mode, obtained by the monomer radical polymerization with at least one ethylenically unsaturated group.The most important thing is, treat that at least a portion of polymerization single polymerization monomer has the group that can carry out ionic dissociation in aqueous medium.Based on the total amount for the treatment of polymerization single polymerization monomer, have the amount of monomer that in aqueous medium, can carry out the group of ionic dissociation be generally at least 5wt%, often for 10wt% at least or at least 20wt% or at least 40wt%, as a rule for 60wt% at least, be generally 80wt% or 90-100wt% at least.
For polycation type polyelectrolyte, having the suitable monomer that can carry out the group of ionic dissociation in aqueous medium is the monomer with quaternary nitrogen atom (quaternary ammonium salt).Its example has:
-Shi (I) compound
A in the formula
N Be Cl
-, Br
-, I
-, SO
4 2-, CO
3 2-, CH
3-OSO
3 -Or CH
3-CH
2-OSO
3 -,
R
1-R
5Be C independently of each other
1-C
20Alkyl, phenmethyl or H, and
N is 1 or 2;
-Shi (II) compound
In the formula
X is NH or O,
R
4Be H or C
1-C
20Alkyl,
R
5Be C
1-C
20Alkylidene group,
R
1, R
2And R
3Be C independently of each other
1-C
20Alkyl,
B
N Be Cl
-, Br
-, I
-, SO
4 2-, CO
3 2-, CH
3-OSO
3 -Or CH
3-CH
2-OSO
3 -, and
N is 1 or 2;
-Shi (III) compound
In the formula
R
1-R
6Be H or C independently of each other
1-C
20Alkyl, but one of them is-CH=CH
2,
C
N Be Cl
-, Br
-, I
-, SO
4 2-, CO
3 2-, CH
3-OSO
3 -Or CH
3-CH
2-OSO
3 -, and
N is 1 or 2;-Shi (IV) compound
In the formula
D
N Be Cl
-, Br
-, I
-, SO
4 2-, CO
3 2-, CH
3-OSO
3 -Or CH
3-CH
2-OSO
3 -, and
N is 1 or 2.
For polyanion type polyelectrolyte, have and can carry out the monomeric of ionic dissociation group and be exemplified as:
-C
3-C
6α, the salt of β-monoethylenically unsaturated carboxylic acid (particularly an alkali metal salt and ammonium salt);
-vinyl sulfonic acid and salt thereof (particularly an alkali metal salt and ammonium salt);
-vinyl sulfonic acid and salt thereof (particularly an alkali metal salt and ammonium salt);
-formula V compound
R in the formula
1And R
2C respectively does for oneself
1-C
10Alkylidene group, X are O or NH, and E
Be alkalimetal ion, NH
4 +Or (alkaline-earth metal ions)
1/2-Shi (VI) compound
R in the formula
1, R
2And R
3C respectively does for oneself
1-C
3Alkyl, R
4Be C
1-C
5Alkylidene group, X are O or NH, and F
Be alkalimetal ion, NH
4 +Or (alkaline-earth metal ions)
1/2-Shi (VII) and (VIII) compound
In the formula
R
1Be C
1-C
5Alkyl, and
G
Be alkalimetal ion, NH
4 +Or (alkaline-earth metal ions)
1/2
Generally, the monomeric salt that has sulfonic acid group and contain at least one ethylenically unsaturated group is particularly suitable for preparing polyanion type polyelectrolyte.Alkalimetal ion is Li particularly
+, Na
+, K
+, Rb
+Or Cs
+Alkaline-earth metal ions is Ca particularly
2+Or Mg
2+
Having the monomeric suitable comonomer that can carry out the group of ionic dissociation in aqueous medium is all other monomers with at least one ethylenically unsaturated group.They are known as nonionic monomers hereinafter.They for example are: alkene (C particularly
3-C
12Alkene), as ethene or propylene; Vinyl-arene is as vinylbenzene, α-toluene styrene, chloro styrene or Vinyl toluene; Vinyl alcohol and C
1-C
18The ester of alkane carboxylic acid is as vinyl-acetic ester, propionate, vinyl propionate, vinyl laurate and stearic acid vinyl ester; α, β-monoethylenically unsaturated monocarboxylic (preferred C
3-C
6, as vinylformic acid and methacrylic acid) and C
1-C
12, preferred C
1-C
8, C most preferably
1-C
4The methyl esters of the ester of alkanol, particularly vinylformic acid and methacrylic acid, ethyl ester, positive butyl ester, isobutyl ester, the tert-butyl ester and 2-ethylhexyl; Has the α of 6 carbon atoms at the most, β monoethylenically unsaturated dicarboxylic acid (as fumaric acid, methylene-succinic acid and toxilic acid) and C
1-C
12, preferred C
1-C
8, C most preferably
1-C
4The diester of alkanol is as dimethyl maleate or n-butyl maleate; Above-mentioned α, the nitrile of β-monoethylenically unsaturated carboxylic acid and acid amides are as vinyl cyanide and acrylamide; And conjugation C
4-C
8Diolefine is as 1,3-butadiene and isoprene.But, also can use other comonomer, for example: vinylamide, as N-vinyl pyrrolidone, N-caprolactam, N-vinyl formamide, N-vinyl acetamide or N-methyl-N-vinyl acetamide; Hydroxyalkyl wherein has the acrylic acid hydroxy alkyl ester and the hydroxyalkyl methacrylate of 2-4 carbon atom, as (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate; Polyoxyethylene glycol (methyl) acrylate with 2-50 ethylene oxide unit; C
1-C
18The allyl ester of alkane carboxylic acid; And the N-vinyl lactam shown in the formula (IX)
R in the formula
1Be C
3-C
8Alkylidene group.
The Raolical polymerizable of the polyelectrolyte that uses among preparation the present invention is preferably in the solution and carries out.The example of suitable solvent is water, methyl alcohol, ethanol, Virahol and other lower alcohol, also can use other organic solvent.Polyreaction usually with the miscible solvent of water in carry out.Based on the amount for the treatment of polymerization single polymerization monomer, polyreaction is generally carried out in the presence of the 0.1-2wt% radical initiator.Polymerization temperature is generally 40-100 ℃.
Radical initiator can use: superoxide, as hydrogen peroxide or peroxy-disulfuric acid and salt (alkali metal salts or ammonium salt) thereof, and organo-peroxide, as t-butyl hydroperoxide, cross two carbonic acid, two cyclohexyls, dibenzoyl peroxide, dilauroyl peroxide, cross the PIVALIC ACID CRUDE (25) tert-butyl ester and cross (2 ethyl hexanoic acid) tert-butyl ester.Certainly also can use azo-compound, as 2,2 '-azo two (2-methylbutyronitrile), 2, the two isobutyl dintrile, 2 of 2 '-azo, two (2-amidine propane) hydrochlorides and 2 of 2 '-azo, 2 '-azo two (2, the 4-methyl pentane nitrile) perhaps comprises the oxidation-reduction trigger system of superoxide and reductive agent such as formaldehyde sodium sulfoxylate.Polymerization temperature is depended in the selection of initiator.The molecular weight of polyelectrolyte can be controlled by adding molecular weight regulator by known way.Shi Yi conditioning agent is lower alcohol (it can be used as solvent simultaneously) especially.But, also can use other compound that is usually used in this purpose as molecular weight regulator, for example: sulphur compound, as 2 mercapto ethanol, butyl sulfhydryl, lauryl mercaptan, Thiovanic acid, thiol-acetic acid or thiolactic acid; Perhaps halogen compound is as tetracol phenixin.Generally speaking, treat that the polymeric monomer is added in the polymerization reactor continuously with the solution form in the solvent usually, feed rate is the conversion rate of polyreaction.Polyelectrolyte solution by drying forms can separate polyelectrolyte.But, in the methods of the invention, also can directly use the polyelectrolyte solution that obtains.
In the methods of the invention, importantly to avoid the cohesion of polymeric dispersions, can condense usually when in the aqueous polymer dispersion of anionic (cationic) stabilization, adding polycation type (polyanion type) polyelectrolyte.This can take following measure to be avoided cohesion, not that polyelectrolyte or its solution stirring are added in the aqueous polymer dispersion, but conversely aqueous polymer dispersion is stirred in the solution that is added to polyelectrolyte (referring to US-A5045576, US-A4038233, US-A3205187 and EP-A305039).Generally speaking, need the polyion total amount of electric charge of polyelectrolyte be higher than in and the required quantity of electric charge of polymer particles all surfaces electric charge (opposite polarity of this surface charge and polyion) in the aqueous polymer dispersion.
The inventor's electrophoresis studies show that; the polyanion of polyelectrolyte solution (polycation) by electrostatic adhesion on cationic (anionic) polymer particles surface; and under the excessive situation of polyion total amount of electric charge; make the reversing of polymer particles surface charge; promptly; opposite with the conventional drying auxiliary agent of prior art; in the methods of the invention; the disperse phase stage that can be in aqueous medium; just on the polymer particles of anionic (cationic) stabilization, form another kind of polycation (polyanion) type protective layer; this protective layer prevents to form irreversible secondary granule in the drying process of aqueous polymer dispersion; and particularly because their water dissolvable makes polymer powder have the perfect redispersible of being close in aqueous medium.Repeatedly change polarity successively by the polyion that uses the ionic charge alternating polarity to change, can form the very big protective layer of variation in thickness scope in a suitable manner.Adopt the method (at the finely divided insoluble inorganics particulate of polymer particles surface applied) of JP-A7/53728 at last, in final drying, can obtain in aqueous medium, having excellent redispersible, the polymer powder of anti stick again simultaneously.
By electrophoresis research, the variation of monitoring polymer microparticle surfaces charge polarity in detail.Based on the dispersive polymkeric substance, the add-on of polyelectrolyte makes the charge polarity on polymer particles surface change when just reaching its maximum value, and redispersible is best.
The present invention adopts spray-drying process to come drying of aqueous polymer dispersions usually, the temperature in T of hot blast
IBe 100-200 ℃, preferred 120-160 ℃, the temperature out T of hot blast
oBe 30-90 ℃, preferred 50-70 ℃.The spraying of aqueous polymer dispersion in hot blast for example can be adopted single mouth shower nozzle or spray broom or rotating disk.Usually use cyclopneumatic separator or filter that polymer powder is separated.The aqueous polymer dispersion of spraying and hot gas flow are preferably with the parallel mode charging.
For this reason, one embodiment of this invention comprises uses these polyelectrolyte to make drying aids, be mixed with the polymerized unit of nonionic monomers in this polyelectrolyte, the second-order transition temperature of the high-molecular weight homopolymer of this nonionic monomers (neutral temperature, ASTM D3418-82) is higher than 50 ℃.
As previously mentioned, the relative molecular weight that is used for the present invention's polyelectrolyte can change in wide range.It is its K value in 25 ℃ the aqueous solution that of the molecular-weight average of polyelectrolyte measures.The K value is the relative viscosity value of measuring according to the method that is similar to DIN53726.Herein, it based on the velocity of flow of neat solvent and the velocity of flow that contains the solution of a certain amount of polyelectrolyte (also referring to Cellulose chemie, 13 (1932), 58-64, and Kirk-Othmer, Encyclopedia of Chemical Technology, Vol.23, the 967-968 page or leaf).High K value is corresponding to high molecular-weight average.
According to the present invention, suitable polyelectrolyte is 0.1wt% at polyelectrolyte content, be that K value in the solution of solvent is 20-350, preferred 30-200 with the NaCl aqueous solution of 0.5M.Other polyelectrolyte that is suitable for is 1%wt at polyelectrolyte content, be that K value in the solution of solvent is 15-150, preferred 25-120 with water.
An advantage of the inventive method is that the polymer particles surface mainly is an electrostatic interaction with the avidity of polyion.Therefore, the chemical constitution of the inventive method and dispersed polymeres is irrelevant.Generally speaking; before adding polyelectrolyte; be used for the stabilization of polymers water dispersion disperse phase charged particle carrier and dispersive polymkeric substance not only physical connection but also chemistry to be connected be favourable (for example, being grafted on positively charged ion or the cationic protective colloid and the chemistry connection by free radical water emulsion polymerization).
Another advantage of the inventive method is that the particle diameter of the polyelectrolyte of adding needn't mate with the particle diameter of dispersive polymer particles in the aqueous polymer dispersion.It is this aqueous polymer dispersion 25 ℃ transmittance (the LT value is used white light, and light path is 2.5cm, and the solid content of aqueous polymer dispersion is diluted to 0.01wt%, measures with respect to pure water) that of polymer particles median size measures.
On the principle, the inventive method promptly can be used for the primary polymer water-dispersion of dry ionic stabilization, secondary polymerization thing water dispersion that again can dry ionic stabilization.
The inventive method be used for dry its mould second-order transition temperature≤50 ℃ or≤25 ℃ or≤0 ℃ aqueous polymer dispersion particularly advantageous.The second-order transition temperature of dispersive polymkeric substance is general 〉=-60 ℃ or 〉=-40 ℃ or 〉=-20 ℃.
This means that the inventive method is applicable to dry following aqueous polymer dispersion, its dispersive polymkeric substance is made of following monomer radical polymerization:
-70-100wt% vinylformic acid and/or methacrylic acid and C
1-C
12The ester of alkanol and/or vinylbenzene, perhaps
-70-100wt% vinylbenzene and/or divinyl, perhaps
-40-100wt% vinylchlorid and/or vinylidene chloride, perhaps
-40-100wt% vinyl-acetic ester, propionate and/or ethene.
In other words, the inventive method is suitable for the aqueous polymer dispersion of dry ionic stabilization, and its dispersive polymkeric substance is obtained by the monomer radical polymerization with at least one ethylenically unsaturated group, and described monomer for example is: alkene, for example ethene; Vi-ny l aromatic monomers is as vinylbenzene, alpha-methyl styrene, chloro styrene or Vinyl toluene; Halogen ethene and vinylidene halide are as vinylchlorid and vinylidene chloride; Vinyl alcohol and C
1-C
18The ester of monocarboxylic acid, as vinyl-acetic ester, propionate, vinyl propionate, vinyl laurate and vinyl stearate acid, and commercially available monomer VEOVA
(VEOVA X is the trade(brand)name of Shell company to 9-11, is vinyl carboxylates, is also referred to as Versatic
X acid); By the α that contains 3 to 6 carbon atoms, β-monoene belongs to unsaturated list and dicarboxylic acid (especially vinylformic acid, methacrylic acid, toxilic acid, fumaric acid and methylene-succinic acid) is generally 1 to 12, is preferably 1 to 8, is preferably 1 to 4 the formed ester of alkanol with carbon number, especially the methyl esters of vinylformic acid and methacrylic acid, ethyl ester, positive butyl ester, isobutyl ester and 2-ethylhexyl, dimethyl maleate or n-butyl maleate; α, the nitrile of β-monoethylenically unsaturated carboxylic acid is as vinyl cyanide; And C
4-C
8Conjugated diolefine is as 1,3-butadiene and isoprene.These monomers are main monomer, and to treat polymeric monomer total amount, their whole consumptions surpass 50wt%.Self-polymerization forms the monomer with high water miscible homopolymer, and they often carry out copolymerization as modified monomer, and the consumption of modified monomer is no more than 50wt%, is generally 0.5 to 20wt%, is preferably 1 to 10wt%, to treat the monomeric total amount of polymeric.
The monomeric example of this kind comprises the α of 3 to 6 carbon atoms, β-monoene belongs to unsaturated list and dicarboxylic acid and acid amides thereof, for example vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, acrylamide and Methacrylamide, with vinyl sulfonic acid and its water-soluble salt, and the N-vinyl pyrrolidone.The monomer of intrinsic strength that is commonly used to improve the aqueous polymer dispersion film to treat the monomeric total amount of polymeric, is generally 0.5 to 10wt% generally only with a small amount of participation copolymerization.This class monomer often contains epoxy group(ing), hydroxyl, N-methylol or carbonyl or at least two unconjugated unsaturated double-bonds.Their example comprises: the α of 3 to 10 carbon atoms, and the pure formed ester of the N-hydroxyalkyl amide of β-monoethylenically unsaturated carboxylic acid and itself and 1 to 4 carbon atom, for example N hydroxymethyl acrylamide and N-methylol methacrylamide are particularly preferred; The monomer that contains two vinyl contains the monomer of two vinylidenes and contains the monomer of two alkenyls.Dibasic alcohol and α, the formed diester of β monoethylenically unsaturated carboxylic acid (wherein preferably vinylformic acid and methacrylic acid) is particularly suitable.The monomeric example that contains two non-conjugated ethylenical unsaturated double bonds has aklylene glycol diacrylate and dimethacrylate, as glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate and propylene glycol diacrylate, Vinylstyrene, methacrylic vinyl acetate, vinyl acrylate, allyl methacrylate(AMA), allyl acrylate, diallyl maleate, diallyl fumarate, methylene-bisacrylamide, vinylformic acid cyclopentadiene ester or triallyl chlorourea acid esters.Methacrylic acid and acrylic acid hydroxyl-C
1-C
8-alkyl ester is especially suitable, as the hydroxyl ethyl ester of vinylformic acid and methacrylic acid, positive hydroxypropyl acrylate or positive hydroxy butyl ester, and the acetoacetoxy ethyl ester of diacetone-acryloamide(DAA) and vinylformic acid and methacrylic acid for example.Except that the monomer that contains unsaturated double-bond, also can carry out copolymerization on a small quantity as the molecular weight regulator of uncle's lauryl mercaptan or 3-mercaptopropyl trimethoxysilane, its consumption is generally 0.01 to 2%, to treat polymeric monomer total amount.
When the dispersed phase polymer of aqueous polymer dispersion to be dried is formed by following monomer radical polymerization, adopt the inventive method especially favourable:
A) 80 to 100wt% at least aly be selected from vinylbenzene, alpha-methyl styrene, Vinyl toluene, by the α of 3 to 6 carbon atoms, β-monoethylenically unsaturated carboxylic acid and 1 to the formed ester of the alkanol of twelve carbon atom, divinyl and 1 to the monomer of the vinyl ester of the alkane carboxylic acid of twelve carbon atom and allyl ester and
B) 0 to 20wt% other monomer that contains at least one ethylenically unsaturated group.
Possible monomer A for example is n-butyl acrylate, 2-EHA, methyl methacrylate and vinylbenzene.
Possible monomers B is acrylamide, Methacrylamide, vinylformic acid, vinyl cyanide, methacrylonitrile, 2-acrylamido-2-methyl propane sulfonic acid, vinyl pyrrolidone, Hydroxyethyl acrylate, vinylformic acid hydroxyl methyl esters, Propylene glycol monoacrylate, Rocryl 410, quaternized vinyl imidazole, (methyl) vinylformic acid N, N-dialkylaminoalkyl ester, N, N-dialkylaminoalkyl (methyl) acrylamide, (methyl) vinylformic acid trialkyl ammonium alkyl ester and trialkyl ammonium alkyl (methyl) acrylamide.
Described in the suitable protective colloid of stabilization disperse phase and/or the example of emulsifying agent such as the DE-A4213 965, polymerization starter also can be referring to DE-A4213965.In the methods of the invention, based on the volume of aqueous polymer dispersion, the solid content of aqueous polymer dispersion to be dried is generally 10-75%, is generally 20-65%, especially is 30-50%.
Should be understood that at last, except polyelectrolyte, the present invention also can use known other drying aids (as homopolymer of polyvinyl alcohol, Polyvinylpyrolidone (PVP), naphthene sulfonic acid/formaldehyde condensation products, Phenylsulfonic acid/formaldehyde condensation products, 2-acrylamido-2-methyl propane sulfonic acid etc.).Equally also can use caking inhibiter, as finely divided silica, it adds in spray-drying process, is used for preventing that polymer powder from luming at storage process.
The redispersible polymer powder in aqueous medium that the inventive method obtains is suitable for use as binding agent, lacquer, finishing agent, tackiness agent, coating (especially for paper) and the additive for synthetic resin of water cure material after adding entry, described in EP-A629650.
Embodiment
The preparation of the aqueous polymer dispersion DA-DF of anionic stabilization I. to be dried
General preparation method:
At first in polymerization reactor, add the mixture of following material and be heated to 90 ℃:
150g water,
5.6g concentration is that the ethoxylation of 20wt% is to isooctyl phenol (ethoxylation
Degree: 25, emulsifying agent) the aqueous solution,
0.48g concentration is the sulfate hemiester of the ethoxylation of 35wt% to isooctyl phenol
The aqueous solution of sodium salt (ethoxylation degree: 25, emulsifying agent),
3.9g concentration is the aqueous formic acid of 10wt%,
1.7g sodium bicarbonate, the pH buffer reagent and
3.4g concentration is the polyacrylamide solution of 20wt%, protective colloid.
Keeping temperature is 90 ℃, and metering adds material 1 continuously in this mixture in 2 hours, begins simultaneously with the adding of material 1 but separate adding material 2 in 2.5 hours on the space.Then with reaction mixture 90 ℃ of restir 120 minutes, be cooled to 60 ℃ afterwards.After adding the 1.1g t-butyl hydroperoxide in the 5.5g water, keeping temperature is 60 ℃, adds the solution of 0.6g formaldehyde sodium sulfoxylate in 15g water in 1 hour, continues to stir 0.5 hour at 60 ℃ then.Stir and finish after 15 minutes this mixture to be cooled to 25 ℃, and be the ammonia soln neutralization of 10wt% with 3.5g concentration.At last, be the screen filtration of 250 μ m with the aperture, after the filtration, measure the pH (electrode) of solid content, LT value and water base dispersion medium.The results are shown in table 1.
Material 1: the water miscible liquid of following component
560g monomer mixture A to F,
8.4g concentration is that the ethoxylation of 20wt% is to isooctyl phenol (ethoxylation
Degree: 25, emulsifying agent) the aqueous solution,
11.5g concentration is that the ethoxylation of 35wt% is to isooctyl phenol sulfate hemiester sodium
The aqueous solution of salt (ethoxylation degree: 25, emulsifying agent) and
162.9g water.
Material 2: be dissolved in the 3.3g Sodium persulfate in the 90g water.
The composition of monomer mixture A to F is also listed in the table 1.
Table 1
| The dispersion that forms | The composition of monomer mixture | Solid content (wt%) | The LT value | ??pH | ??Fox ??Tg ?(℃) |
| ????DA | 219.2gn-BA；252.0gS； ?11.2gAM；????5.6gMAM； | ???55.3 | ????8 | ??8.7 | ????7 |
| ????DB | 347.2gn-BA；196.0gS； ?11.2gAM；????5.6gMAM； | ???55.6 | ????9 | ??8.2 | ????-6 |
| ????DC | 403.2gEHA；140.0gS； ?11.2gAM；???5.6gMAA； | ???54.9 | ???12 | ??8.7 | ???-28 |
| ????DD | ?291.2gn-BA；252gS； ??11.2gAM；????5.6gMAA； | ???56.0 | ????5 | ??5.1 | ?????8 |
| ????DE | 291.2gn-BA；252gS； ?11.2gAM；????5.6gAA； | ???56.0 | ????5 | ??5.1 | ?????8 |
| ????DF | 291.2gn-BA；292gS； ?11.2gMAM；???5.6gAA； | ???55.4 | ???17 | ??4.8 | ?????6 |
The n-BA=n-butyl acrylate; The AM=acrylamide; The EHA=2-EHA; AA=vinylformic acid; The MAM=Methacrylamide; The MAA=methacrylic acid; S=vinylbenzene;
Tg
Fox(℃): the second-order transition temperature that uses the dispersed polymeres of Fox Equation for Calculating.According to Fox (T.G.Fox, Bull.Am.Phys.Soc. (Ser.II) 1 (1956), 123 and Ullmanns Encyklop die der technischenChemie, Vol.19, the 4th edition, Verlag Chemie, Weinheim (1980), 17,18 pages), the calculating formula of the second-order transition temperature of multipolymer is:
1＝X
1＋X
2＋....X
n，
Tg?Tg
1?Tg
2?????Tg
n
In the formula: X
1, X
2..., X
nBe monomer 1,2 ..., n weight fraction, Tg
1, Tg
2..., Tg
nBe respectively monomer 1,2 ..., n the second-order transition temperature (unit: Kelvin) of homopolymer.The second-order transition temperature of homopolymer for example can be referring to Ullmann ' s Encyclopedia of Industrial Chemistry, VCH, Wein heim, Vol.A21 (1992), 169 pages.
The preparation of the aqueous polymer dispersion DG-DK of anionic stabilization II. to be dried
DG: in polymerization reactor, at first add 600g water, 14g concentration is the ethoxylation Tallow, beef Fatty Alcohol(C12-C14 and C12-C18) (ethoxylation degree: 18 of 20wt%, emulsifying agent) the aqueous solution, 9.8g concentration are the aqueous formic acid, 4.2g sodium bicarbonate (pH buffer reagent) of 10wt% and the mixture of the material 1 of 5wt%, and be heated to 90 ℃, add the material 2 of 10wt% afterwards.After 15 minutes, temperature remains 90 ℃, adds continuously remaining material 1 in 2 hours in this mixture, begins simultaneously with the adding of material 1 but separate the remaining material 2 of adding in 2.5 hours on the space.Then, reaction mixture is continued stirring reaction 2 hours at 90 ℃, be cooled to 60 ℃ then.After adding the solution of 2.8g t-butyl hydroperoxide in 16.2g water, remain in temperature under 60 ℃ the condition, in 1 hour, in polymerization reactor, add the solution of 2.8g formaldehyde sodium sulfoxylate in 15g water continuously, afterwards 60 ℃ of restir 0.5 hour.After 15 minutes, this mixture is cooled to 25 ℃, and to add 56g concentration be that the NaOH aqueous solution of 10wt% neutralizes.After being the screen filtration of 250 μ m with the aperture, the solid content of the aqueous polymer dispersion DG that obtains is 49.3wt%, and the LT value is 5, and the pH of its water base dispersion medium is 8.6.Tg
Fox＝5℃。
Material 1: the water miscible liquid of following component
The 770g n-butyl acrylate,
588g vinylbenzene,
The 42g methacrylic acid,
63g concentration is the (ethoxylation of 20wt% thing ethoxylation Tallow, beef Fatty Alcohol(C12-C14 and C12-C18)
Degree: 18, emulsifying agent) the aqueous solution,
98g concentration is the ethoxylation Tallow, beef fatty alcohol sulphuric acid half ester sodium of 30wt%
The aqueous solution of salt (ethoxylation degree: 30, emulsifying agent),
33.6g concentration is the Natvosol of 5wt%
Brookfield viscosity during 5wt% is 150cps, protective colloid)
The aqueous solution, and
313g water.
Material 2: be dissolved in the 4.2g Sodium persulfate in the 300g water.
DH：
At first in polymerization reactor, add the mixture of following material and be heated to 90 ℃:
450g water,
16.0g concentration is that the ethoxylation of 20wt% is to isooctyl phenol (ethoxylation
Degree: 25, emulsifying agent) the aqueous solution,
1.4g concentration is the sulfate hemiester sodium of the ethoxylation of 35wt% to isooctyl phenol
The aqueous solution of salt (ethoxylation degree: 25, emulsifying agent),
11.2g concentration be 10wt% aqueous formic acid and
4.8g sodium bicarbonate, the pH buffer reagent.
Afterwards, keeping temperature is 90 ℃, and metering adds material 1 continuously in this mixture in 2 hours, begins simultaneously with the adding of material 1 but separate adding material 2 in 2.5 hours on the space.Then with reaction mixture 90 ℃ of restir 120 minutes, be cooled to 60 ℃ afterwards.After adding the 3.2g t-butyl hydroperoxide in the 16.4g water, keeping temperature is 60 ℃, adds the solution of 3.2g formaldehyde sodium sulfoxylate in 15g water in 1 hour, continues to stir 0.5 hour at 60 ℃ then.After 15 minutes, mixture is cooled to 25 ℃.After being the screen filtration of 250 μ m with the aperture, the solid content of the aqueous polymer dispersion DH that obtains is 55.8wt%, and the LT value is 18, and the pH of its water base dispersion medium is 3.5.Tg
Fox＝6℃。
Material 1: the water miscible liquid of following component
The 832g n-butyl acrylate,
720g vinylbenzene,
The 32g Hydroxyethyl acrylate,
The 16g methacrylic acid,
24.0g concentration is that the ethoxylation of 20wt% is to isooctyl phenol (ethoxylation
Degree: 25, emulsifying agent) the aqueous solution.
32.9g concentration is the sulfate hemiester sodium of the ethoxylation of 35wt% to isooctyl phenol
The aqueous solution of salt (ethoxylation degree: 25, emulsifying agent),
442g water.
Material 2: be dissolved in the 9.3g Sodium persulfate in the 300g water.
DI: in polymerization reactor, at first add 150g water, 5.6g concentration is the ethoxylation Tallow, beef Fatty Alcohol(C12-C14 and C12-C18) (ethoxylation degree: 18 of 20wt%; emulsifying agent) the aqueous solution, 3.9g concentration are that aqueous formic acid, 1.7g sodium bicarbonate (pH buffer reagent) and the 3.4g concentration of 10wt% is the mixture of the aqueous solution of the polyacrylamide (protective colloid) of 20wt%, and are heated to 90 ℃.Then, temperature remains 90 ℃, adds continuously material 1 in 2 hours in this mixture, begins simultaneously with the adding of material 1 but separate adding material 2 in 2.5 hours on the space.Then, reaction mixture is continued stirring reaction 120 minutes at 90 ℃, be cooled to 60 ℃ then.After adding the solution of 1.1g t-butyl hydroperoxide in 5.5g water, remain in temperature under 60 ℃ the condition, in 1 hour, in polymerization reactor, add the solution of 1.1g formaldehyde sodium sulfoxylate in 5g water, afterwards 60 ℃ of restir 0.5 hour.After 15 minutes, this mixture is cooled to 25 ℃.After being the screen filtration of 250 μ m with the aperture, the solid content of the aqueous polymer dispersion DI that obtains is 55.1wt%, and the LT value is 15, and the pH of its water base dispersion medium is 7.6.Tg
Fox＝5℃。
Material 1: the water miscible liquid 291.2g n-butyl acrylate of following component, 252.0g vinylbenzene, the 16.8g Methacrylamide, 19.6g concentration is the ethoxylation Tallow, beef fatty alcohol sulphuric acid half ester sodium salt (second of 20wt%
Oxygen base degree: 30, emulsifying agent) the aqueous solution, and 156.2g water.
Material 2: be dissolved in the 3.2g Sodium persulfate in the 100g water.
DK: it prepares same DI, but the monomer in the material 1 is made up of 347.2g n-butyl acrylate, 196.0g vinylbenzene and 16.8g Methacrylamide.
After being the screen filtration of 250 μ m with the aperture, the solid content of the aqueous polymer dispersion DK that obtains is 55.7wt%, and the LT value is 47, and the pH of its water base dispersion medium is 5.9.Tg
Fox＝-8℃。
III. the preparation of the aqueous solution PI to PIX of polycation type polyelectrolyte
PI: at first in polymerization reactor, add the mixture of the material 1 of 627g water and 10wt%, be heated to 70 ℃, and add the material 2 of 10wt% and the material 3 of 10wt%.After 5 minutes, temperature remains 70 ℃, begins simultaneously but is separated from each other on the space, adds remaining material 1 in 1 hour in polymerization reactor continuously, adds remaining material 2 in 1.5 hours, adds remaining material 3 in 1.5 hours.Afterwards, reaction mixture was stirred 120 minutes at 70 ℃, be cooled to room temperature, and filter through the filter of 250 μ m.Obtaining solid content is that 19.8wt%, pH are 9.0 clear solution.The K value (in water, is 93 1wt%).
Material 1:196g N-vinyl pyrrolidone and 4g trimethyl ammonium propyl methyl acid amides muriate;
Material 2: be dissolved in the 4g t-butyl hydroperoxide in the 101.7g water;
Material 3: be dissolved in the 3.2g formaldehyde sodium sulfoxylate in the 100g water.
PII: with the preparation of PI, but material 1 is made up of 192g N-vinyl pyrrolidone and 8g trimethyl ammonium propyl methyl acid amides muriate.The solid content of the clear solution that obtains is 19.7wt%, and pH is 9.4.The K value (in water, is 92 1wt%).
PIII: according to embodiment 13 preparations of EP-B 246580.At first in polymerization reactor, add 196g water, 106ml material 1 and 5ml material 2, and be heated to 65 ℃.Temperature remains 65 ℃ then, begins simultaneously, adds remaining material 1 in 5 hours in polymerization reactor continuously, adds remaining material 2 in 7 hours.After reinforced the finishing, continue to stir 1 hour at 65 ℃.Obtain the K value and (, 1wt%) be 71 clear solution at Zhong Shui.
Material 1:
The Methylsulfate of 120g 3-methyl isophthalic acid-vinyl imidazole,
The 280g vinyl pyrrolidone,
250g water, and
0.3g 2 mercapto ethanol transfers to 7.5 with strong aqua with pH value of aqueous solution;
Material 2: be dissolved in the 2.4g 2 in the 75g water, two (2-amidine propane) hydrochlorides of 2 '-azo.
PIV: with the preparation of PIII, but material 1 is made up of following component
120g 3-methyl isophthalic acid-vinyl imidazole muriate,
The 280g vinyl pyrrolidone,
250g water, and
The 1g 2 mercapto ethanol transfers to 7.5 with strong aqua with the pH of the aqueous solution.
Obtain a clear solution.(in water, be 78 1wt%), K value (in the NaCl of the 0.5M aqueous solution) is 40 to the K value.
PV: with the preparation of PIII, but material 1 is made up of following component
200g 3-methyl isophthalic acid-vinyl imidazole muriate,
The 200g vinyl pyrrolidone,
250g water, and
The 1g 2 mercapto ethanol transfers to 7.5 with strong aqua with pH.
Obtain a clear solution.The K value (in water, is 84 1wt%).
PVI: in the polymerization reactor that reflux exchanger is housed, at first add 600g water, and in nitrogen gas stream, under agitation be heated to 65 ℃.After reaching 65 ℃, remain under this temperature, in 4 hours, in polymerization reactor, add continuously material 1, begin simultaneously, added material 2 at 5 hours with the adding of material 1.Afterwards 65 ℃ of restir 2 hours.Obtain a clear solution.(in water, be 91 1wt%), K value (in the NaCl of the 0.5M aqueous solution) is 56 to the K value.
Material 1:
The Methylsulfate of 86g 3-methyl isophthalic acid-vinyl imidazole,
300g N-vinyl pyrrolidone,
400g N-caprolactam, and
500g water.
Material 2: be dissolved in the 3.2g 2 in the 100g water, two (2-amidine propane) dihydrochlorides of 2 '-azo.
PVII: with the preparation of PVI, but material 1 time all is added in the reactor in beginning, and material 2 added in 4 hours continuously.
Obtain a clear solution.(in water, be 85 1wt%), K value (in the NaCl of the 0.5M aqueous solution) is 41 to the K value.
PVIII: with the preparation of PVI, but polymeric reaction temperature is 80 ℃, and material 2 is by the 2.3g in 140g methyl alcohol 2, and 2 '-azo two (2-methylbutyronitrile) is formed.Distillation for removing methanol after polymerization is finished.(in water, be 77 1wt%), K value (in the NaCl of the 0.5M aqueous solution) is 34 to the K value.
PIX: with the preparation of PIII, but material 1 is made up of following component
380g 3-methyl isophthalic acid-vinyl imidazole muriate,
The 20g vinyl pyrrolidone,
250g water, and
The 1g 2 mercapto ethanol transfers to 7.5 with strong aqua with the pH of the aqueous solution.
IV. after adding polyelectrolyte aqueous solution PI-PIX, with aqueous polymer dispersion DA-DK spraying drying and simultaneous test
At first aqueous polymer dispersion DA-DK being diluted to solid content is 40wt%, and it is 25wt% that polyelectrolyte aqueous solution PI-PIX is diluted to solid content.According to the embodiment 1 of EP-A576844, preparation concentration is the aqueous solution of 25wt% poly-(N-vinyl pyrrolidone), uses drying aids as a comparison.Then under vigorous stirring, in the disposable aqueous solution that is added to drying aids of aqueous polymer dispersion, add-on makes that total solid content is 35wt%.
The spraying drying of the water-based mixture that obtains is carried out in the microscale experiment chamber drying machine that the GEA of Germany Wiegand GmbH (Niro Business Unit) produces, adopt the spraying of two nozzle shower nozzles (nozzle diameter is 0.8-2mm) or rotating disk, inlet temperature is 130 ℃, and temperature out is 60 ℃ (speed: about 2kg spraying material/hour).As caking inhibiter, in kiln, be metered into the finely divided silica of 2.5wt% (based on the solid polymer mixture) (maximum median size: 25 μ m) simultaneously with spraying.
Following method is used to estimate the redispersible of the polymer powder that obtains:
In vial, add 90g water, and add the 10g polymer powder at 25 ℃.Use German Janke﹠amp; Kundel, IKA-Labortechnik, the Ultra-Turrax1 that Staufen produces stirs this mixture 1 minute under the rotating speed of 9500rpm, and pours in the graduated cylinder.Graduated cylinder is sealed with plastics stopper, left standstill 72 hours at 25 ℃ then.Then, this redispersion body is acutely shaken, and sieve with the screen cloth of 72 μ m.The screen cloth that will contain filter cake in 80 ℃ loft drier dry 12 hours, the dried condensation product of weighing, and calculate its weight percentage with respect to initial used polymer powder (10g).The results are shown in table 2.Give the add-on (with dry weight basis, with respect to the weight percentage of dispersed polymeres) of drying aids in the table 2.
Table 2
Spray-dired mixture
*) numeral nozzle diameter (mm) behind the shower nozzle.
| Dispersion | The spraying drying auxiliary agent | Spray method | Condensation product | |
| DA | ?PIII | 15% weight | Shower nozzle 1.5 | 1.2% weight |
| DA | ?PVIII | 15% weight | Shower nozzle 1.5 | 0.8% weight |
| DA | ?PVII | 15% weight | Shower nozzle 1.5 | 1.0% weight |
| DA | ?PVI | 15% weight | Shower nozzle 1.5 | 2.2% weight |
| DA | ?PIV | 5% weight | Shower nozzle 0.8 | 0.6% weight |
| DA | ?PIV | 10% weight | Shower nozzle 0.8 | 0.4% weight |
| DA | ?PIV | 15% weight | Shower nozzle 1.5 | 0.5% weight |
| DA | ?PV | 15% weight | Shower nozzle 1.3 | 0.3% weight |
| DA | ?PIX | 15% weight | Shower nozzle 1.3 | 0.7% weight |
| DB | ?PIV | 15% weight | Shower nozzle 1.3 | 0.8% weight |
| DC | ?PIV | 15% weight | Shower nozzle 1.3 | 0.8% weight |
| DD | ?PIV | 15% weight | Shower nozzle 0.8 | 0.4% weight |
| DD | ?PI | 10% weight | Rotating disk | 1.0% weight |
| DD | ?PII | 10% weight | Rotating disk | 0.9% weight |
| DE | ?PIV | 15% weight | Shower nozzle 0.8 | 0.5% weight |
| DF | ?PIV | 15% weight | Shower nozzle 0.8 | 0.2% weight |
| DG | ?PIV | 15% weight | Shower nozzle 0.8 | 0.9% weight |
| DG | ?PI | 10% weight | Rotating disk | 1.0% weight |
| DG | ?PII | 10% weight | Rotating disk | 1.1% weight |
| DH | ?PIV | 15% weight | Shower nozzle 0.8 | 2.0% weight |
| DI | ?PIV | 15% weight | Shower nozzle 2.0 | 0.2% weight |
| DK | ?PIV | 15% weight | Shower nozzle 1.5 | 0.5% weight |
| DA | ?VP | 15% weight | Shower nozzle 1.5 | 4.0% weight |
Claims (32)
1. the aqueous polymer dispersion that is added with drying aids by drying prepares the method for polymer powder, the polymer particles that this dispersion is scattered in the aqueous medium has the plus or minus surface charge, wherein, in aqueous polymer dispersion to be dried, add a kind of polyelectrolyte as drying aids, the mode that this polyelectrolyte can be dissociated into polyion and counter ion is dissolved in the water base dispersion medium, and the electric charge of polyion is opposite with the surface charge polarity of dispersive polymer particles.
2. the process of claim 1 wherein that the dispersive polymer particles has positive surface charge.
3. the process of claim 1 wherein that the dispersive polymer particles has negative surface charge.
4. each method among the claim 1-3, wherein, the number-average molecular weight of described polyelectrolyte is 1000 to 3 * 10
6
5. each method among the claim 1-4, wherein, the polyion of used polyelectrolyte is an organic polymer.
6. each method among the claim 1-5, wherein, used polyelectrolyte solubleness in water under 25 ℃ and 1atm is 〉=1g/100g water.
7. each method among the claim 1-6, wherein, used polyelectrolyte can be obtained by the monomer radical polymerization with at least one ethylenically unsaturated group, and described monomer comprises at least a monomer that can carry out the group of ionic dissociation in aqueous medium that has.
8. the method for claim 7, wherein, as the described at least a monomer that can carry out the dissociative group in aqueous medium that has, used polyelectrolyte contains the polymerized unit of compound shown in the formula (I):
A in the formula
N Be Cl
-, Br
-, I
-, SO
4 2-, CO
3 2, CH
3-OSO
3 -Or CH
3-CH
2-OSO
3,
R
1-R
5Be C independently of each other
1-C
20Alkyl, phenmethyl or H, and
N is 1 or 2.
9. the method for claim 7, wherein, as the described at least a monomer that can carry out the dissociative group in aqueous medium that has, used polyelectrolyte contains the polymerized unit of compound shown in the formula (II):
In the formula
X is NH or O,
R
4Be H or C
1-C
20Alkylidene group,
R
5Be C
1-C
20Alkylidene group,
R
1, R
2And R
3Be C independently of each other
1-C
20Alkyl,
B
N Be Cl
-, Br, I
-, SO
4 2-, CO
3 2-, CH
3-OSO
3 -Or CH
3-CH
2-OSO
3 -, and
N is 1 or 2.
10. the method for claim 7, wherein, as the described at least a monomer that can carry out the dissociative group in aqueous medium that has, used polyelectrolyte contains the polymerized unit of compound shown in the formula (III):
R in the formula
1-R
6Be H or C independently of each other
1-C
20Alkyl, but one of them is-CH=CH
2,
C
N Be Cl
-, Br
-, I
-, SO
4 2-, CO
3 2-, CH
3-OSO
3 -Or CH
3-CH
2-OSO
3 -, and
N is 1 or 2.
11. the method for claim 7, wherein, as the described at least a monomer that can carry out the dissociative group in aqueous medium that has, used polyelectrolyte contains the polymerized unit of compound shown in the formula (IV):
In the formula
D
N Be Cl
-, Br
-, I
-, SO
4 2-, CO
3 2-, CH
3-OSO
3 -Or CH
3-CH
2-OSO
3 -, and
N is 1 or 2.
12. the method for claim 7, wherein, as the described at least a monomer that can carry out the dissociative group in aqueous medium that has, used polyelectrolyte contains C
3-C
6α, the polymerized unit of β-monoethylenically unsaturated carboxylic acid salt.
13. the method for claim 7, wherein, as the described at least a monomer that can carry out the dissociative group in aqueous medium that has, used polyelectrolyte contains the polymerized unit of vinyl sulfonic acid or its a kind of salt.
14. the method for claim 7, wherein, as the described at least a monomer that can carry out the dissociative group in aqueous medium that has, used polyelectrolyte contains the polymerized unit of compound shown in the formula V:
In the formula
R
1And R
2C respectively does for oneself
1-C
10Alkylidene group,
X is O or NH, and
E
Be alkalimetal ion, NH
4 +Or (alkaline-earth metal ions)
1/2
15. the method for claim 7, wherein, as the described at least a monomer that can carry out the dissociative group in aqueous medium that has, used polyelectrolyte contains the polymerized unit of compound shown in the formula (VI):
In the formula
R
1, R
2And R
3C respectively does for oneself
1-C
3Alkyl,
R
4Be C
1-C
5Alkylidene group,
X is O or NH, and
F
Be alkalimetal ion, NH
4 +Or (alkaline-earth metal ions)
1/2
16. the method for claim 7, wherein, as the described at least a monomer that in aqueous medium, can carry out the dissociative group that has, used polyelectrolyte contain formula (VII) or (VIII) shown in the polymerized unit of compound:
R in the formula
1Be C
1-C
5Alkyl, and G
Be alkalimetal ion, NH
4 +Or (alkaline-earth metal ions)
1/2
17. each method among the claim 7-16, wherein, described polyelectrolyte contains at least a polymerized unit with ethylenically unsaturated monomer of the group that can carry out ionic dissociation in aqueous medium of 5-100wt%.
18. each method among the claim 7-16, wherein, described polyelectrolyte contains at least a polymerized unit with ethylenically unsaturated monomer of the group that can carry out ionic dissociation in aqueous medium of 20-100wt%.
19. each method among the claim 7-16, wherein, described polyelectrolyte contains at least a polymerized unit with ethylenically unsaturated monomer of the group that can carry out ionic dissociation in aqueous medium of 40-100wt%.
20. each method among the claim 1-19 wherein, is dispersed in polymkeric substance in the described aqueous polymer dispersion by acid of 70-100wt% acrylic or methacrylic and C
1-C
12The ester of alkanol or vinylbenzene radical polymerization form.
21. each method among the claim 1-19, wherein, the polymkeric substance that is dispersed in the described aqueous polymer dispersion is formed by 70-100wt% vinylbenzene or divinyl radical polymerization.
22. each method among the claim 1-19, wherein, the polymkeric substance that is dispersed in the described aqueous polymer dispersion is formed by 40-100wt% vinylchlorid or vinylidene chloride radical polymerization.
23. each method among the claim 1-19, wherein, the polymkeric substance that is dispersed in the described aqueous polymer dispersion is formed by 40-100wt% vinyl-acetic ester, propionate or ethylene free radical polymerization.
24. each method among the claim 1-23, wherein, the second-order transition temperature that is dispersed in the polymkeric substance in the described aqueous polymer dispersion is≤50 ℃.
25. each method among the claim 1-23, wherein, the second-order transition temperature that is dispersed in the polymkeric substance in the described aqueous polymer dispersion is≤25 ℃.
26. each method among the claim 1-25, wherein, the described dry spray-drying process that adopts.
27. the method for claim 26, wherein, the temperature in of hot blast is 100-200 ℃, and the temperature out of hot blast is 30-90 ℃.
28. the polymer powder that can obtain by each method among the claim 1-27.
29. contain the polymer powder of spherical polymer particulate and polyelectrolyte, described polymer particles has the plus or minus surface charge, and the electric charge that the polyion of described polyelectrolyte has is opposite with the surface charge polarity of described spherical polymer particulate.
30. the polymer powder of claim 28 or 29 after adding entry as the purposes of the additive of binding agent, lacquer, finishing agent, tackiness agent, coating and the synthetic resins of water cure material.
31. as the purposes of auxiliary agent, the dispersed polymeres particulate of this dispersion has the plus or minus surface charge to polyelectrolyte in drying of aqueous polymer dispersions, and the electric charge of the polyion of this polyelectrolyte is opposite with the surface charge polarity of dispersed polymeres particulate.
32. aqueous polymer dispersion is used to prepare the purposes of polymer powders redispersible after adding polyelectrolyte, the dispersed polymeres particulate of this dispersion has the plus or minus surface charge, and the electric charge of the polyion of this polyelectrolyte is opposite with the surface charge polarity of dispersed polymeres particulate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96122881 CN1153181A (en) | 1995-10-28 | 1996-10-28 | Preparation of polymer powders which are redispersible in aqueous medium |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19540305.3 | 1995-10-28 | ||
| CN 96122881 CN1153181A (en) | 1995-10-28 | 1996-10-28 | Preparation of polymer powders which are redispersible in aqueous medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1153181A true CN1153181A (en) | 1997-07-02 |
Family
ID=5127474
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96122881 Pending CN1153181A (en) | 1995-10-28 | 1996-10-28 | Preparation of polymer powders which are redispersible in aqueous medium |
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| Country | Link |
|---|---|
| CN (1) | CN1153181A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151493A (en) * | 2014-08-04 | 2014-11-19 | 成都理工大学 | Emulsion collapse agent and preparation method thereof |
| CN104609478A (en) * | 2014-11-05 | 2015-05-13 | 河南师范大学 | Polymeric ferric sulfate co-desiccant and application thereof |
-
1996
- 1996-10-28 CN CN 96122881 patent/CN1153181A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151493A (en) * | 2014-08-04 | 2014-11-19 | 成都理工大学 | Emulsion collapse agent and preparation method thereof |
| CN104151493B (en) * | 2014-08-04 | 2016-08-24 | 成都理工大学 | A kind of emulsion anti-sloughing agent and preparation method thereof |
| CN104609478A (en) * | 2014-11-05 | 2015-05-13 | 河南师范大学 | Polymeric ferric sulfate co-desiccant and application thereof |
| CN104609478B (en) * | 2014-11-05 | 2016-05-11 | 河南师范大学 | A kind of bodied ferric sulfate helps drier and application thereof |
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