CN1780801A - 具有固化促进作用的再分散粉末组合物 - Google Patents
具有固化促进作用的再分散粉末组合物 Download PDFInfo
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- CN1780801A CN1780801A CN200480010189.7A CN200480010189A CN1780801A CN 1780801 A CN1780801 A CN 1780801A CN 200480010189 A CN200480010189 A CN 200480010189A CN 1780801 A CN1780801 A CN 1780801A
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- Prior art keywords
- vinyl
- ester
- polymer powder
- multipolymer
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000843 powder Substances 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims description 31
- 230000001133 acceleration Effects 0.000 title abstract 2
- 230000000694 effects Effects 0.000 title description 14
- -1 acrylic ester Chemical class 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000084 colloidal system Substances 0.000 claims abstract description 14
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229920001519 homopolymer Polymers 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001336 alkenes Chemical class 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 230000007062 hydrolysis Effects 0.000 claims description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 13
- 150000001721 carbon Chemical group 0.000 claims description 13
- 239000004568 cement Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004567 concrete Substances 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011449 brick Substances 0.000 claims description 5
- 159000000007 calcium salts Chemical class 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 claims description 4
- 238000007667 floating Methods 0.000 claims description 4
- 239000010440 gypsum Substances 0.000 claims description 4
- 229910052602 gypsum Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 238000009156 water cure Methods 0.000 claims description 3
- 241000370738 Chlorion Species 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
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- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 239000000178 monomer Substances 0.000 abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 2
- 229920002554 vinyl polymer Polymers 0.000 abstract description 2
- 125000005157 alkyl carboxy group Chemical group 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229920005601 base polymer Polymers 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
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- 239000003995 emulsifying agent Substances 0.000 description 3
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 229920000945 Amylopectin Polymers 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical class C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 108010073771 Soybean Proteins Proteins 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229940009827 aluminum acetate Drugs 0.000 description 2
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 229940071162 caseinate Drugs 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
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- GOPSAMYJSPYXPL-UHFFFAOYSA-N prop-2-enyl n-(hydroxymethyl)carbamate Chemical compound OCNC(=O)OCC=C GOPSAMYJSPYXPL-UHFFFAOYSA-N 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
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- 238000007711 solidification Methods 0.000 description 2
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- 238000010557 suspension polymerization reaction Methods 0.000 description 2
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- NDGXZYRXRPWLOE-UHFFFAOYSA-N 2-(prop-2-enoylamino)oxyacetic acid Chemical compound OC(=O)CONC(=O)C=C NDGXZYRXRPWLOE-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NJMGRJLQRLFQQX-HYXAFXHYSA-N 2-isopropylmaleic acid Chemical compound CC(C)C(\C(O)=O)=C\C(O)=O NJMGRJLQRLFQQX-HYXAFXHYSA-N 0.000 description 1
- GWRKYBXTKSGXNJ-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxyperoxy)propane Chemical compound CC(C)COOOCC(C)C GWRKYBXTKSGXNJ-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-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
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0042—Powdery mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0057—Polymers chosen for their physico-chemical characteristics added as redispersable powders
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00146—Sprayable or pumpable mixtures
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Detergent Compositions (AREA)
- Crushing And Grinding (AREA)
- Finishing Walls (AREA)
Abstract
本发明涉及具有固化促进作用的水中可再分散的聚合物粉末组合物，其主要成分为一种或更多种选自以下组中的单体的均聚物或共聚物、一种或更多种保护胶体、任选的抗结块剂，所述组包括：具有1至15个碳原子、非分支或分支型烷基羧酸的乙烯基酯、具有1至15个碳原子的醇的甲基丙烯酸酯及丙烯酸酯、乙烯基芳烃、烯烃、二烯烃及卤乙烯，其特征在于，所述组合物含有一种或更多种选自以下组中的化合物：无机酸或有机酸的碱金属盐及碱土金属盐。
Description
技术领域
本发明涉及具有固化促进作用的水中可再分散的聚合物粉末组合物、其制造方法以及该粉末在水固系统中的用途。
背景技术
以乙烯基酯、氯乙烯、(甲基)丙烯酸酯单体、苯乙烯、丁二烯及乙烯为主要成分的聚合物，主要以其含水分散体或水中可再分散的聚合物粉末的形式适用于广泛的应用场合，例如用作许多不同基底的涂料或粘着剂。使用保护胶体或低分子量表面活性化合物以使该聚合物稳定化。通常使用聚乙烯醇作为保护胶体。
这些产品尤其用作水固性粘合剂中的粘结剂，例如以水泥或石膏为主要成分的砖瓦粘合剂。
混凝土是一种非常通用的材料，其特性可由许多参数加以控制。重要的特性特别是经历时间的可加工性以及混凝土的强度(早期强度及最终强度)。由于组合物进行水合作用，可加工性随时间降低。可添加更多的水或所谓的液化剂或超级增塑剂以消除该影响。但均对混凝土的起始强度及最终强度具有不利影响。为弥补这些缺点，添加所谓的促进剂或早期强度改进剂，而获得更高的起始强度及最终强度。
EP-A 1136507描述了叔醇胺作为本领域技术人员早已熟知的促进剂。不利的是，这些化合物是非常活跃的亲核试剂，因此使大多数所用的以乙酸乙烯酯/乙烯共聚物或苯乙烯/丙烯酸酯共聚物为主要成分、含有塑料的粘结剂中的酯基水解，并且破坏该粘结剂的效果。因此，在EP-A 1136507中，以复杂的方法将醇胺连结在聚合物骨架上。
EP-A 1167317描述了碱金属氢氧化物、碱金属碳酸盐、碱土金属氯化物，尤其是铝盐，作为混凝土的固化促进剂及硬化促进剂。然而不利的是，利用这些化合物促进水泥固化时，机械强度降低。
发明内容
因此，本发明的目的是提供一种用于促进水固性系统固化的试剂，其克服了现有技术的缺点，并使硬化砂浆的强度提高。
本发明涉及具有固化促进作用的水中可再分散的聚合物粉末组合物，其主要成分为一种或更多种选自以下组中的单体的均聚物或共聚物、一种或更多种保护胶体、任选的抗结块剂，该组包括：具有1至15个碳原子、非分支或分支型烷基羧酸的乙烯基酯、具有1至15个碳原子的醇的甲基丙烯酸酯及丙烯酸酯、乙烯基芳烃、烯烃、二烯烃及卤乙烯，其特征在于含有一种或更多种选自以下组中的化合物：无机酸或有机酸的碱金属盐及碱土金属盐。
优选为锂盐、钠盐、钾盐、镁盐及钙盐。优选的无机抗衡离子为碳酸根离子、氯离子、硫酸根离子、硝酸根离子及磷酸根离子。优选的有机抗衡离子为衍生自具有1至4个碳原子的羧酸的羧酸根，如甲酸根离子、乙酸根离子、丙酸根离子及丁酸根离子。更优选为钙盐。最优选为具有1至4个碳原子的羧酸的钙盐，如甲酸钙、乙酸钙。
适合用作基础聚合物的乙烯基酯为具有1至15个碳原子的羧酸的乙烯基酯。优选的乙烯基酯为：乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、乙酸1-甲基乙烯酯、新戊酸乙烯酯及具有9至13个碳原子、α-分支型单羧酸的乙烯基酯，如Veo Va9R或Veo Va10R(壳牌公司的商标名)。更优选为乙酸乙烯酯。
合适的甲基丙烯酸酯或丙烯酸酯为具有1至15个碳原子、非分支或分支型醇的酯，如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯及丙烯酸降冰片基酯。优选为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯及丙烯酸2-乙基己酯。
烯烃及二烯烃的实例为乙烯、丙烯及1，3-丁二烯。合适的乙烯基芳烃为苯乙烯及乙烯基甲苯。合适的卤乙烯为氯乙烯。
基于基础聚合物的总重量，任选还可共聚合0.05至50重量％，更优选1至10重量％的辅助单体。辅助单体的实例为：烯键式不饱和单羧酸及二羧酸，优选为丙烯酸、甲基丙烯酸、富马酸及马来酸；烯键式不饱和羧酰胺及腈，优选为丙烯酰胺及丙烯腈；富马酸及马来酸的单酯及二酯，如二乙酯及二异丙酯，马来酸酐；烯键式不饱和磺酸及其盐，优选为乙烯基磺酸、2-丙烯酰胺基-2-甲基丙烷磺酸。其它的实例为预交联的共聚单体，如多重烯键式不饱和共聚单体，如己二酸二乙烯酯、马来酸二烯丙酯、甲基丙烯酸烯丙酯或氰脲酸三烯丙酯；或后交联的共聚单体，如丙烯酰胺基羟基乙酸(AGA)、甲基丙烯酰胺基羟基乙酸甲酯(MAGME)、N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺(NMMA)、N-羟甲基氨基甲酸烯丙酯；烷基醚，如异丁氧基醚或N-羟甲基丙烯酰胺的酯、N-羟甲基甲基丙烯酰胺的酯及N-羟甲基氨基甲酸烯丙酯的酯。环氧基官能的共聚单体也是合适的，如甲基丙烯酸缩水甘油酯及丙烯酸缩水甘油酯。其它的实例为硅官能的共聚单体，如丙烯酰氧基丙基三(烷氧基)硅烷及甲基丙烯酰氧基丙基三(烷氧基)硅烷、乙烯基三烷氧基硅烷及乙烯基甲基二烷氧基硅烷，其中例如可含有甲氧基、乙氧基及乙氧基丙二醇醚基作为烷氧基。还述及具有羟基或CO基的单体，如甲基丙烯酸羟烷基酯及丙烯酸羟烷基酯，如丙烯酸羟乙基酯、丙烯酸羟丙基酯、丙烯酸羟丁基酯、甲基丙烯酸羟乙基酯、甲基丙烯酸羟丙基酯或甲基丙烯酸羟丁基酯，以及诸如双丙酮丙烯酰胺及丙烯酸乙酰基乙酰氧基乙酯或甲基丙烯酸乙酰基乙酰氧基乙酯的化合物。
合适的均聚物及共聚物的实例是：乙酸乙烯酯均聚物、乙酸乙烯酯与乙烯的共聚物、乙酸乙烯酯与乙烯及一种或更多种其它乙烯基酯的共聚物、乙酸乙烯酯与乙烯及丙烯酸酯的共聚物、乙酸乙烯酯与乙烯及氯乙烯的共聚物、苯乙烯/丙烯酸酯共聚物、苯乙烯/1，3-丁二烯共聚物。
优选为乙酸乙烯酯均聚物；
乙酸乙烯酯与1至40重量％乙烯的共聚物；
乙酸乙烯酯与1至40重量％乙烯及1至50重量％一种或更多种选自以下组中的其他共聚单体的共聚物，该组包括：羧酸基中具有1至12个碳原子的乙烯基酯，如丙酸乙烯酯、月桂酸乙烯酯、具有9至13个碳原子的α-分支型羧酸的乙烯基酯，如Veo Va9、Veo Va10及Veo Va11；
乙酸乙烯酯与1至40重量％乙烯及优选1至60重量％具有1至15个碳原子、非分支或分支型醇的丙烯酸酯，尤其是丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚物；及
30至75重量％乙酸乙烯酯、1至30重量％月桂酸乙烯酯或具有9至11个碳原子、α-分支型羧酸的乙烯基酯，以及1至30重量％具有1至15个碳原子、非分支或分支型醇的丙烯酸酯，尤其是丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚物，其还含有1至40重量％的乙烯；
乙酸乙烯酯、1至40重量％乙烯及1至60重量％氯乙烯的共聚物；其中
该聚合物还可含有所述量的所述辅助单体，且重量百分比之和均为100重量％。
优选为(甲基)丙烯酸酯聚合物，如丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚物或甲基丙烯酸甲酯与丙烯酸正丁酯和/或丙烯酸2-乙基己酯的共聚物；
一种或更多种选自以下组中的单体的苯乙烯/丙烯酸酯共聚物，该组包括：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯及丙烯酸2-乙基己酯；
一种或更多种选自以下组中的单体的乙酸乙烯酯/丙烯酸酯共聚物，该组包括：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯及任选的乙烯；
苯乙烯/1，3-丁二烯共聚物；
其中该聚合物还可含有所述量的所述辅助单体，且重量百分比之和均为100重量％。
选择单体及共聚单体的重量份，使得玻璃转化温度Tg为-50℃至+50℃，优选为-30℃至+40℃。该聚合物的玻璃转化温度Tg可利用差示扫描量热法(DSC)由已知的方式测得。Tg也可利用Fox方程预先进行近似计算。依照Fox T.G.，Bull.Am.Physics Soc.1，3，page 123(1956)：
1/Tg＝x1/Tg1+x2/Tg2+…+xn/Tgn，
其中xn代表单体n的质量分数(重量％/100)，而Tgn为单体n的均聚物以开尔文计的玻璃转化温度。均聚物的Tg值记载于“聚合物手册(Polymer Handbook)”，第二版，J.Wiley & Sons，New York(1975)。
根据乳液聚合法或悬浮聚合法制造该均聚物及共聚物，优选为乳液聚合法，聚合作用温度通常为40℃至100℃，优选为60℃至90℃。诸如乙烯、1，3-丁二烯或氯乙烯的气态共聚单体的共聚合作用也可在通常为5至100巴的压力下实施。
聚合作用是用乳液聚合或悬浮聚合常用的水溶性或单体可溶性引发剂或氧化还原引发剂组合加以引发。水溶性引发剂的实例是：过氧二硫酸的钠盐、钾盐及铵盐，过氧化氢、过氧化叔丁基、过氧化氢叔丁基、过氧二磷酸钾、过氧新戊酸叔丁酯、过氧化氢异丙苯基、过氧化一氢异丙基苯及偶氮双异丁腈。单体可溶性引发剂的实例是：过氧二碳酸联十六烷基酯、过氧二碳酸二环己酯及过氧化二苯甲酰。均以单体的总重量为基准，所述引发剂的使用量通常为0.001至0.02重量％，更优选为0.001至0.01重量％。
使用由所述引发剂与还原剂的组合作为氧化还原引发剂。合适的还原剂是：碱金属及铵的亚硫酸盐及亚硫酸氢盐，如亚硫酸钠；次硫酸的衍生物，如甲醛化次硫酸锌或碱金属的甲醛化次硫酸盐，如羟基甲烷亚磺酸钠，及抗坏血酸。均以单体的总重量为基准，还原剂的量通常为0.001至0.03重量％，优选为0.001至0.015重量％。
聚合作用期间，可使用调节物质以控制分子量。若使用调节剂，以待聚合的单体为基准，调节剂的使用量通常为0.01至5.0重量％，并单独地按计量加入或与反应成分预混合后按计量加入。这些物质的实例是：正十二烷基硫醇、叔十二烷基硫醇、硫醇基丙酸、硫醇基丙酸甲酯、异丙醇及乙醛。
合适的保护胶体为：聚乙烯醇；聚乙烯乙缩醛；聚乙烯吡咯烷酮；水溶性多糖，如淀粉(直链淀粉及支链淀粉)，纤维素及其羧甲基衍生物、甲基衍生物、羟乙基衍生物及羟丙基衍生物；蛋白质，如酪蛋白或酪蛋白酸盐、大豆蛋白、凝胶；磺酸木质素；合成聚合物，如聚(甲基)丙烯酸、(甲基)丙烯酸酯与羧基官能的共聚单体单元的共聚物、聚(甲基)丙烯酰胺、聚乙烯基磺酸及其水溶性共聚物；三聚氰胺甲醛磺酸酯、萘甲醛磺酸酯、苯乙烯/马来酸共聚物及乙烯基醚/马来酸共聚物。
优选水解度为80至100摩尔％的部分水解或完全水解聚乙烯醇，更优选水解度为80至95摩尔％、在浓度为4％的水溶液中的Hppler粘度为1至30毫帕斯卡·秒的部分水解聚乙烯醇(根据Hppler法，在20℃下，DIN 53015)。优选水解度为80至95摩尔％、在浓度为4％的水溶液中的Hppler粘度为1至30毫帕斯卡·秒、经疏水化改性的部分水解聚乙烯醇。其实例为乙酸乙烯酯与疏水性共聚单体的部分水解共聚物，该疏水性共聚单体例如为乙酸异丙烯酯、新戊酸乙烯酯、乙基己酸乙烯酯、具有5个或9至11个碳原子、饱和α-分支型单羧酸的乙烯基酯、马来酸二烷基酯及富马酸二烷基酯，如马来酸二异丙酯及富马酸二异丙酯，氯乙烯、乙烯基烷基醚，如乙烯基丁基醚，烯烃，如乙烯及癸烯。以部分水解聚乙烯醇的总重量为基准，疏水性单元的比例优选为0.1至10重量％。也可使用所述聚乙烯醇的混合物。
最优选水解度为85至94摩尔％、在浓度为4％的水溶液中的Hppler粘度为3至15毫帕斯卡·秒(根据Hppler法，在20℃下，DIN 53015)的聚乙烯醇。所述保护胶体可利用本领域技术人员所熟知的方法制得，并以单体的总重量为基准，在聚合作用中的总添加量通常为1至20重量％。
若在乳化剂存在的情况下实施聚合作用，以单体的量为基准，乳化剂的量为1至5重量％。合适的乳化剂为：阴离子型、阳离子型及非离子型乳化剂，例如阴离子表面活性剂，如链长度为8至18个碳原子的硫酸烷基酯、疏水性基团中具有8至18个碳原子且具有最多40个环氧乙烷单元或环氧丙烷单元的烷基醚硫酸盐或烷基芳基醚硫酸盐、具有8至18个碳原子的磺酸烷基酯或磺酸烷基芳基酯、磺基琥珀酸与一元醇或烷基酚的酯及半酯，或非离子表面活性剂，如具有8至40个环氧乙烷单元的烷基聚二醇醚或烷基芳基聚二醇醚。
聚合作用结束之后，可应用已知的方法，通常通过由氧化还原催化剂引发的后聚合作用，而实施后聚合以去除残留单体。挥发性残留单体还可利用蒸馏作用加以去除，优选在减压下，并任选使诸如空气、氮或水蒸汽的惰性夹带气体流经或流过产品。如此所制含水分散体的固体含量为30至75重量％，优选为50至60重量％。
为制造水中可再分散的聚合物粉末，任选在添加保护胶体作为雾化助剂之后，将该含水分散体加以干燥，例如利用流化床干燥、冻干或喷干。该分散体优选实施喷干。在此情况下，于常用的喷干装置内实施喷干，其中可利用单料喷嘴、双料喷嘴或多料喷嘴或用转盘实施雾化。取决于装置、树脂的Tg及预期的干燥度，出口温度通常选定为45℃至120℃，更优选为60℃至90℃。
以该分散体的聚合物成分为基准，雾化助剂(保护胶体)的总使用量通常为3至30重量％。也就是说，以聚合物成分为基准，干燥过程之前保护胶体的总使用量应为3至30重量％，更优选为5至20重量％。
合适的雾化助剂为：部分水解聚乙烯醇；聚乙烯吡咯烷酮；水溶性多糖，如淀粉(直链淀粉及支链淀粉)，纤维素及其羧甲基衍生物、甲基衍生物、羟乙基衍生物及羟丙基衍生物；蛋白质，如酪蛋白或酪蛋白酸盐、大豆蛋白、凝胶；磺酸木质素；合成聚合物，如聚(甲基)丙烯酸、(甲基)丙烯酸酯与羧基官能共聚单体单元的共聚物、聚(甲基)丙烯酰胺、聚乙烯基磺酸及其水溶性共聚物；三聚氰胺甲醛磺酸酯、萘甲醛磺酸酯、苯乙烯/马来酸共聚物及乙烯基醚/马来酸共聚物。优选不使用除聚乙烯醇以外的其他保护胶体作为雾化助剂，优选作为保护胶体的聚乙烯醇也优选用作雾化助剂。
已反复证实，基于基础聚合物的含量为最高1.5重量％的抑泡剂在雾化作用期间是有利的。通过提高结块稳定性以提高存储稳定性，特别是在具有低玻璃转化温度的粉末的情况下，以聚合物成分的总重量为基准，所得粉末可含有优选最高30重量％的抗结块剂。抗结块剂的实例是：碳酸钙、碳酸镁、滑石、石膏、二氧化硅、高岭土、硅酸盐，其粒径优选为10纳米至10微米。
由固体含量调节待雾化物料的粘度，使所得数值小于500毫帕斯卡·秒(Brookfield粘度，20转及23℃下)，优选小于250毫帕斯卡·秒。待雾化分散体的固体含量大于35％，优选大于40％。
在雾化作用期间可添加其它添加剂以提高的应用技术的性能。在优选的具体实施方案中含有的分散体粉末组合物的其它成分是：颜料、填料、泡沫稳定剂、疏水化剂。
在喷干之前立即添加固化促进成分至相应的聚合物分散体中，并接着实施雾化，以制造该聚合物粉末组合物。任选也可在干燥成为粉末形式之后添加固化促进成分。均以聚合物粉末组合物的总重量为基准，该再分散粉末优选含有1至20重量％，更优选3至15重量％的固化促进成分。
该水中可再分散的聚合物粉末组合物可用于典型的应用领域。例如用于结构化学产品，任选用于具有水固性粘合剂的产品中，如水泥(卜特兰水泥、高铝水泥、火山灰水泥、矿渣水泥、镁氧水泥或磷酸盐水泥)、石膏及水玻璃，用于制造建筑粘着剂，尤其是砖瓦粘着剂及完全绝热粘着剂、粉刷头道浆、抹平剂、地板抹平剂、自找平剂、密封泥浆、接缝砂浆及油漆。优选的应用领域是：用于高层建筑或地下建筑的施工工程的喷射砂浆或混凝土喷浆，以及隧道壁的砌面。
由根据本发明的试剂所制的添加剂有效地促进水泥固化，且不降低成品砂浆的机械强度。此外，对于使用者有利的是：在施工现场用再分散粉末改性砂浆时，对成分需要更少的操作。
具体实施方式
实施例：
分散体：
作为分散体使用由聚乙烯醇稳定化的乙酸乙烯酯与乙烯的共聚物的分散体。根据本领域技术人员所熟知的乳液聚合法制造。使用10重量％水解度为88摩尔％、Hppler粘度为4毫帕斯卡·秒的聚乙烯醇以实施稳定化。该共聚物组合物为92重量％的乙酸乙烯酯及8重量％的乙烯。粉末：
添加相应的促进剂及8重量％水解度为88摩尔％、Hppler粘度为4毫帕斯卡·秒的聚乙烯醇，通过将所述分散体加以喷干而制得粉末。然后利用双料喷嘴将该分散体加以喷洒。使用4巴的预先压缩的空气作为雾化成分，将所形成的小滴用加热至125℃的空气以平行流动的方式加以干燥。所得的干燥粉末中混入10重量％的商购抗结块剂(碳酸镁钙)。
加以干燥。所得的干燥粉末中混入10重量％的商购抗结块剂(碳酸镁钙)。
促进剂：
CaAc＝乙酸钙
CaFo＝甲酸钙
CaNi＝硝酸钙
AmSu＝硫酸铝铵(比较)
AlSu＝硫酸铝(比较)
AlAc＝乙酸铝(比较)
CaPh＝磷酸钙
LiCo＝碳酸锂
NaAc＝乙酸钠
NaFo＝甲酸钠
KAc＝乙酸钾
KFo＝甲酸钾
LiAc＝乙酸锂
测试：
测试所制粉末的粉末特性及其作为混凝土内促进剂的效果。
流动性RF：
流动性仅从外观上由堆积形成的圆锥加以评定。
抗结块性的测定BF：
为测定抗结块性，将分散体粉末装入附有螺纹的铁管内，然后用金属冲头加负荷。加负荷之后于50℃下在干燥箱内储存16小时。冷却至室温之后，将该粉末自管中取出，通过压碎该粉末而定性测定抗结块性。抗结块性以如下方式进行分级：
1至3＝抗结块性非常好
4至6＝抗结块性良好
7至8＝抗结块性合格
9至10＝无抗结块性，粉末压碎后不能流动。
沉淀性能的测定RA：
将再分散体的沉淀性能用作该粉末的可再分散性的度量。由强烈剪切力的作用制得水中浓度为50％的再分散体。
然后测定经稀释的再分散体(固体含量为0.5％)的沉淀性能，为此将100毫升该分散体装入有刻度的管内，并测量沉淀固体的高度。沉淀24小时之后获得以毫米计的数据。数值大于7表示粉末的再分散性不足。
再分散粉末的流动性RF、抗结块性BF及沉淀性能RA的测试结果汇总于1中。
用再分散粉末改性、粘结的砖瓦粘着剂的拉伸粘着强度的测定：
利用下列配方测试砖瓦粘着剂的粘着拉伸强度(聚合物含量为3％)：
石英砂 565份
卜特兰水泥 400份
纤维素 5份
再分散粉末 30份
根据3种储存条件测定粘着拉伸强度：
28T： 干储28天
7T/21N： 7天干储/21天湿储
14T/14TS+70℃/1T： 热储
此项测试的结果汇总于表2中。
表1：
| 实施例 | 添加剂 | 含量[重量％] | RF | BF | RA |
| 1 | 乙酸钙 | 10 | 良好 | 2 | 0.3 |
| 2 | 乙酸钙 | 5 | 良好 | 2.5 | 0.4 |
| 3 | 硝酸钙 | 5 | 良好 | 2.5 | 0.8 |
| 4 | 甲酸钙 | 10 | 良好 | 2.5 | 0.5 |
| 5 | 硝酸钙 | 10 | 良好 | 2.5 | 0.4 |
| 6 | 甲酸钙 | 5 | 良好 | 2.5 | 0.8 |
| V7 | 硫酸铝铵 | 5 | 良好 | 2 | 3.8 |
| V8 | 硫酸铝 | 10 | 良好 | 5 | 6.5 |
| V9 | 乙酸铝 | 5 | 良好 | 3.5 | 4 |
| 10 | 甲酸钙 | 10 | 良好 | 2.5 | 0.4 |
| 11 | 乙酸钙 | 10 | 良好 | 2 | 0.8 |
| 12 | 甲酸钙 | 10 | 良好 | 2.5 | 1.8 |
| 13 | 乙酸钙 | 10 | 良好 | 2.5 | 0.2 |
| 14 | 磷酸钙 | 5 | 良好 | 2 | 1.3 |
| 15 | 碳酸锂 | 10 | 良好 | 2 | 0.2 |
| 16 | 乙酸钠 | 5 | 良好 | 2 | 0.2 |
| 17 | 乙酸钠 | 10 | 良好 | 2 | 0.2 |
| 18 | 甲酸钠 | 5 | 良好 | 2.5 | 0.3 |
| 19 | 乙酸钾 | 5 | 良好 | 3 | 0.4 |
| 20 | 甲酸钾 | 5 | 良好 | 3 | 0.4 |
| 21 | 甲酸钾 | 10 | 良好 | 3 | 0.2 |
| 22 | 甲酸钠 | 10 | 良好 | 2.5 | 0.1 |
| 23 | 乙酸锂 | 10 | 良好 | 4 | 0.1 |
| V24 | 无 | 0 | 良好 | 4 | 0.5 |
由这些数据可知：用根据本发明的添加剂改性的粉末的特性与根据比较例7至9改性的情况相比没有负面影响。流动性、抗结块性及可再分散性基本上不变。
表2：
| 实施例 | 28T牛顿/平方毫米 | 7T/21N牛顿/平方毫米 | 14T/14TS+70℃/1T牛顿/平方毫米 |
| 1 | 1.98 | 0.63 | 1.42 |
| 2 | 1.89 | 0.62 | 1.46 |
| 3 | 1.82 | 0.64 | 1.7 |
| 4 | 1.95 | 0.77 | 1.57 |
| 5 | 2.01 | 0.63 | 1.58 |
| 6 | 1.96 | 0.62 | 1.47 |
| 7 | 2.13 | 0.64 | 1.46 |
| 8 | 1.77 | 0.81 | 1.57 |
| V9 | 1.84 | 0.66 | 1.51 |
| V10 | 1.84 | 0.84 | 1.64 |
| V11 | 1.91 | 0.83 | 1.6 |
| 12 | 2.11 | 0.83 | 1.51 |
| 13 | 2.04 | 0.78 | 1.44 |
| 14 | 1.53 | 0.72 | 1.39 |
| 15 | 1.79 | 0.78 | 1.40 |
| 16 | 1.66 | 0.87 | 1.49 |
| 17 | 1.83 | 0.80 | 1.40 |
| 18 | 1.97 | 0.83 | 1.39 |
| 19 | 1.66 | 0.68 | 1.37 |
| 20 | 1.65 | 0.72 | 1.47 |
| 21 | 1.7 | 0.71 | 1.42 |
| 22 | 1.95 | 0.83 | 1.76 |
| 23 | 2.04 | 0.64 | 1.50 |
| V24 | 1.63 | 0.57 | 1.36 |
可以明显看出粘着拉伸强度的积极效果，尤其是于湿储之后。
Claims (10)
1、具有固化促进作用的水中可再分散的聚合物粉末组合物，其主要成分为-种或更多种选自以下组中的单体的均聚物或共聚物、一种或更多种保护胶体、任选的抗结块剂，所述组包括：具有1至15个碳原子、非分支或分支型烷基羧酸的乙烯基酯、具有1至15个碳原子的醇的甲基丙烯酸酯及丙烯酸酯、乙烯基芳烃、烯烃、二烯烃及卤乙烯，其特征在于，所述组合物含有一种或更多种选自以下组中的化合物：无机酸或有机酸的碱金属盐及碱土金属盐。
2、根据权利要求1所述的水中可再分散的聚合物粉末组合物，其特征在于含有一种或更多种锂盐、钠盐、钾盐、镁盐及钙盐，它们具有选自以下组中的无机抗衡离子：碳酸根离子、氯离子、硫酸根离子、硝酸根离子及磷酸根离子，或具有选自以下组中的有机抗衡离子：衍生自具有1至4个碳原子的羧酸的羧酸根。
3、根据权利要求1或2所述的水中可再分散的聚合物粉末组合物，其特征在于含有一种或更多种具有1至4个碳原子的羧酸的钙盐。
4、根据权利要求1至3之一所述的水中可再分散的聚合物粉末组合物，其特征在于，所用的均聚物或共聚物是：乙酸乙烯酯均聚物、乙酸乙烯酯与乙烯的共聚物、乙酸乙烯酯与乙烯及一种或更多种其它乙烯基酯的共聚物、乙酸乙烯酯与乙烯及丙烯酸酯的共聚物、乙酸乙烯酯与乙烯及氯乙烯的共聚物、苯乙烯/丙烯酸酯共聚物、苯乙烯/1，3-丁二烯共聚物。
5、根据权利要求1至4之一所述的水中可再分散的聚合物粉末组合物，其特征在于，所用的保护胶体包括：水解度为80至100摩尔％、在浓度为4％的水溶液中的Hppler粘度为1至30毫帕斯卡·秒(根据Hppler法，在20℃下，DIN 53015)、任选经疏水化改性的部分水解或完全水解聚乙烯醇。
6、根据权利要求1至5之一所述的水中可再分散的聚合物粉末组合物，其特征在于，以粉末组合物的总重量为基准，固化促进成分的含量为1至20重量％。
7、用于制造根据权利要求1至6之一所述的水中可再分散的聚合物粉末组合物的方法，其特征在于，在进行喷雾干燥之前立即添加固化促进成分或在干燥成为粉末形式之后添加。
8、根据权利要求1至6之一所述的水中可再分散的聚合物粉末组合物在结构化学产品中的用途，其是用于具有水固性粘合剂的产品中，如水泥、石膏及水玻璃。
9、根据权利要求1至6之一所述的水中可再分散的聚合物粉末组合物的用途，其是用于制造建筑粘着剂、砖瓦粘着剂及完全绝热粘着剂、粉刷头道浆、抹平剂、地板抹平剂、自找平剂、密封泥浆、接缝砂浆及油漆。
10、根据权利要求1至6之一所述的水中可再分散的聚合物粉末组合物的用途，其是用于高层建筑或地下建筑的施工工程的喷射砂浆或混凝土喷浆，以及隧道壁的砌面。
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- 2004-03-04 JP JP2006504540A patent/JP2006523594A/ja active Pending
- 2004-03-04 CN CNB2004800101897A patent/CN100432027C/zh not_active Expired - Lifetime
- 2004-03-04 RU RU2005135563/04A patent/RU2314274C2/ru not_active IP Right Cessation
- 2004-03-04 WO PCT/EP2004/002210 patent/WO2004092094A1/de active IP Right Grant
- 2004-03-04 DE DE502004001110T patent/DE502004001110D1/de not_active Expired - Lifetime
- 2004-03-04 ES ES04717101T patent/ES2268639T5/es not_active Expired - Lifetime
- 2004-03-04 US US10/553,310 patent/US7744694B2/en active Active
- 2004-03-04 EP EP04717101.2A patent/EP1615861B2/de not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115516047A (zh) * | 2020-05-05 | 2022-12-23 | 瓦克化学股份公司 | 粉末涂料组合物 |
| CN115515912A (zh) * | 2020-05-28 | 2022-12-23 | 瓦克化学股份公司 | 制备用于建筑材料干式配制品的水可再分散聚合物粉末的方法 |
| CN115515912B (zh) * | 2020-05-28 | 2023-09-15 | 瓦克化学股份公司 | 制备用于建筑材料干式配制品的水可再分散聚合物粉末的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070037925A1 (en) | 2007-02-15 |
| EP1615861A1 (de) | 2006-01-18 |
| EP1615861B2 (de) | 2013-06-12 |
| DE502004001110D1 (de) | 2006-09-14 |
| DE10317882A1 (de) | 2004-11-11 |
| RU2005135563A (ru) | 2007-05-27 |
| ATE334948T1 (de) | 2006-08-15 |
| US7744694B2 (en) | 2010-06-29 |
| ES2268639T5 (es) | 2013-10-16 |
| ES2268639T3 (es) | 2007-03-16 |
| WO2004092094A8 (de) | 2005-12-22 |
| CN100432027C (zh) | 2008-11-12 |
| WO2004092094A1 (de) | 2004-10-28 |
| JP2006523594A (ja) | 2006-10-19 |
| RU2314274C2 (ru) | 2008-01-10 |
| EP1615861B1 (de) | 2006-08-02 |
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