SE506652C2 - Copolymers of styrene and maleic half-ester and their use as additives for cement compositions - Google Patents
Copolymers of styrene and maleic half-ester and their use as additives for cement compositionsInfo
- Publication number
- SE506652C2 SE506652C2 SE9103844A SE9103844A SE506652C2 SE 506652 C2 SE506652 C2 SE 506652C2 SE 9103844 A SE9103844 A SE 9103844A SE 9103844 A SE9103844 A SE 9103844A SE 506652 C2 SE506652 C2 SE 506652C2
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- Sweden
- Prior art keywords
- formula
- ratio
- copolymer
- cement
- copolymers
- Prior art date
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 27
- 239000004568 cement Substances 0.000 title claims description 20
- 239000000203 mixture Substances 0.000 title claims description 19
- 239000000654 additive Substances 0.000 title description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title description 8
- -1 polysiloxane residue Polymers 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 7
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 7
- 150000003839 salts Chemical group 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 229920005604 random copolymer Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims 2
- 239000000178 monomer Substances 0.000 claims 2
- 229910018557 Si O Inorganic materials 0.000 claims 1
- 125000003282 alkyl amino group Chemical group 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 15
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 125000002947 alkylene group Chemical group 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229920001451 polypropylene glycol Polymers 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract 1
- 150000003973 alkyl amines Chemical class 0.000 abstract 1
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 abstract 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920001983 poloxamer Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical group CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 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
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229960003505 mequinol Drugs 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
Abstract
Description
15 20 25 506 652 2 I formel I kan varje alkyl- eller alkylengrupp vara rak eller grenad och varje R är, oberoende, företrädesvis en Czß-alkylengrupp. Mest föredraget är att varje R är lika och är eten. Varje RI är, oberoende, företrädesvis Cla-alkyl, och företrädesvis är alla Rl-grupperna metyl. m är företrädesvis ett tal från 7 till 20, mest föredraget 10-15. In formula I, each alkyl or alkylene group may be straight or branched and each R is, independently, preferably a C 1-6 alkylene group. Most preferably, each R is the same and is ethylene. Each R 1 is, independently, preferably C 1-4 alkyl, and preferably all R 1 groups are methyl. m is preferably a number from 7 to 20, most preferably 10-15.
M är företrädesvis resten av en sampolymer bestående av enheter härledda från etylenoxid och propylenoxid eller resten av en polysiloxan bestående av di- C1_4-alkylsiloxanenheter. Etylenoxid/propylenoxi dsampolymerema kan represen- teras av formeln Ia R2-o-(cH2cH2o>p-,.-H (Ia) CH3 där RZ är väte eller, oberoende, har samma betydelse som Rl ovan, och p, q och r är tal från 0 till 100, med förbehållen att minst en av p, q och r är minst 1 och att q > p+r.M is preferably the remainder of a copolymer consisting of units derived from ethylene oxide and propylene oxide or the remainder of a polysiloxane consisting of di-C 1-4 alkylsiloxane units. The ethylene oxide / propylene oxide copolymers may be represented by the formula Ia R 2 -o- (cH 2 cH 2 O> p -, .- H (Ia) CH 3 where R 2 is hydrogen or, independently, has the same meaning as R 1 above, and p, q and r are numbers from 0 to 100, with the proviso that at least one of p, q and r is at least 1 and that q> p + r.
Föredragna polysiloxaner motsvarar formeln II CH3 si-o -fl (ID CH; q där q har samma betydelse som angivits ovan.Preferred polysiloxanes correspond to the formula II CH3 si-o -fl (ID CH; q where q has the same meaning as given above.
Alternativt är M resten av en polypropylenglykol, som har från 10 till 200 enheter härledda från propylenoxid.Alternatively, M is the remainder of a polypropylene glycol having from 10 to 200 units derived from propylene oxide.
För att få den nödvändiga molekylvikten innehåller sampolymererna enligt uppñnningen minst 12, företrädesvis från 18 till 40 strukturenheter med formeln I, dvs. n är företrädesvis ett tal från 18 till 40. Detta betyder att summan av m+n företrädesvis är ett tal från 25 till 60. Syragrupperna i sampolymererna med strukturenhetema i formeln I kan föreligga i form av fri syra eller i saltform.In order to obtain the necessary molecular weight, the copolymers according to the invention contain at least 12, preferably from 18 to 40 structural units of formula I, i.e. n is preferably a number from 18 to 40. This means that the sum of m + n is preferably a number from 25 to 60. The acid groups in the copolymers with the structural units in formula I may be in the form of free acid or in salt form.
Dessa salter kan vara alkali-,jordalka1i-, ferro-, aluminjum-, (alkanol)ammonium- eller (alkyDammoniumsalter. Dessa sampolymerer har företrädesvis formen av alkalimetallsalter, särskilt natriurnsalter.These salts may be alkali, alkaline earth, ferrous, aluminum, (alkanol) ammonium or (alkydammonium) salts. These copolymers are preferably in the form of alkali metal salts, especially sodium salts.
Organiska sampolymerer med strukturenheter enligt formeln I kan framställas med metoder, som är välkända på teknikområdet, exempelvis genom 10 15 20 25 506 652 3 att en slumpsampolymer med följande sammansättning . -cH - cflz- - clzn - ca- C=O C=O \ / x 0 y+z n får reagera med en förening med formeln III Rl-o-(itmm-H an) liksom med föreningar med formeln Ia eller II i de lämpliga mängderna och den bildade sampolymeren eventuellt får reagera med en alkali- eller jordalkalibas, med ferro- eller aluminiumsalter eller med ammoniak, en alkanolamino- eller alkylaminoförening. Beroende på de använda mängderna kan reaktionen av maleinsyraanhydridgrupperna i den ovan visade styren-maleinsyraanhydrid- sampolymeren med föreningar med formeln Ia eller II och III vara i huvudsak fullständig eller också kan det i slutpolymeren finnas kvar ett antal anhydrid- grupper, vilka bildar dikarboxylsyragmpper i vattenlösning. En 100%-ig omvand- ling, som teoretiskt skulle kurma uppnås med ekvimolära mängder av reaktan- tema, kommer givetvis aldrig att uppnås.Organic copolymers having structural units of formula I can be prepared by methods well known in the art, for example by a random copolymer having the following composition. -cH - c fl z- - clzn - ca- C = OC = O \ / x 0 y + zn may react with a compound of formula III R1-o- (itmm-H an) as well as with compounds of formula Ia or II in the the appropriate amounts and the copolymer formed may optionally react with an alkali or alkaline earth metal base, with ferrous or aluminum salts or with ammonia, an alkanolamino or alkylamino compound. Depending on the amounts used, the reaction of the maleic anhydride groups in the styrene-maleic anhydride copolymer shown above with compounds of formula Ia or II and III may be substantially complete or there may be a number of anhydride groups remaining in the final polymer which form dicarboxylic acid groups in aqueous solution. . A 100% conversion, which would theoretically be achieved with equimolar amounts of reactants, will of course never be achieved.
Föredraget är att nästan alla maleinsyraanhydridenheter i styren-malein- syraanhydridsampolymeren omvandlas till halvesterenheter, vilket kan mätas genom bestämning av den erhållna sampolymerens syratal.It is preferred that almost all of the maleic anhydride units in the styrene-maleic anhydride copolymer be converted to half-ester units, which can be measured by determining the acid number of the obtained copolymer.
Sampolymerer av den ovan beskrivna typen fås genom sampolymerisation av styren och maleinsyraanhydrid och är välkända och beskrivs exempelvis i C.E.Copolymers of the type described above are obtained by copolymerization of styrene and maleic anhydride and are well known and are described, for example, in C.E.
Schildknecht, "Vinyl and Related Polymers" John Wiley and Sons, Inc., New York, 1952.Schildknecht, "Vinyl and Related Polymers" John Wiley and Sons, Inc., New York, 1952.
Polyalkylenglykoler med formeln Ia eller III är också välkända föreningar och kan fås genom addition av alkylenoxider, speciellt etylenoxid och propylen- oxid, till alkyl- eller cykloalkylalkoholer eller fenoler, eller genom polyaddition av alkylenoxiderna.Polyalkylene glycols of formula Ia or III are also well known compounds and can be obtained by adding alkylene oxides, especially ethylene oxide and propylene oxide, to alkyl or cycloalkyl alcohols or phenols, or by polyaddition of the alkylene oxides.
Polysiloxanerna med formeln II är också välkända föreningar och kan exempelvis fås genom polykondensation av diklordimetylsilan med klortrimetyl- 10 15 20 25 30 5Ü6 652 silan och vatten.The polysiloxanes of formula II are also well known compounds and can be obtained, for example, by polycondensation of dichlorodimethylsilane with chlorotrimethylsilane and water.
De nya sampolymerer med återkommande enheter med formeln I är utmärkta ytaktiva medel och kan användas för att dispergera organiska och oorganiska material. Speciellt kan de användas som tillsatsmedel för cement- blandningar.The new copolymers with recurring units of formula I are excellent surfactants and can be used to disperse organic and inorganic materials. In particular, they can be used as additives for cement mixtures.
Cementblandningar som de organiska sampolymerema enligt uppfinningen kan användas som tillsatsmedel i är olika typer av bruk och betong. Det hydrau- liska bindemedlet kan vara portlandcement, aluminatcement eller blandcement, exempelvis puzzolant cement, slaggcement eller andra typer. Portlandcement år att föredra.Cement mixtures in which the organic copolymers according to the invention can be used as additives are different types of mortar and concrete. The hydraulic binder can be portland cement, aluminate cement or mixed cement, for example pozzolanic cement, slag cement or other types. Portland cement is preferred.
De organiska sampolymererna enligt uppfinningen tillsätts i mängder från 0,01 till 10 vikt-%, företrädesvis från 0,1 till 3 vikt-%, baserat på cementvikten.The organic copolymers of the invention are added in amounts of from 0.01 to 10% by weight, preferably from 0.1 to 3% by weight, based on the cement weight.
I sådana mängder har de organiska sampolymererna enligt uppfinningen förmågan att förbättra fluíditeten på de cementblandningar, som de har tillsatts till, och de är därför utmärkta supersmidighetsfórbättrare. De har också den ytterligare fördelen att deras luftporbildande egenskaper är lägre än desamma för liknande sampolymerer.In such amounts, the organic copolymers of the invention have the ability to improve the liquidity of the cement mixtures to which they have been added, and they are therefore excellent super-flexibility enhancers. They also have the additional advantage that their air pore-forming properties are lower than those of similar copolymers.
I cementblandningama enligt uppfinningen kan vidare ingå andra tillsats- medel, som är konventionella inom cementteknologin, exempelvis accelererande eller retarderande tillsatsmedel, frostskyddsmedel, pigment etc.The cement mixtures according to the invention may further include other additives which are conventional in the cement technology, for example accelerating or retarding additives, antifreeze, pigments, etc.
De följande exemplen, i vilka alla delar, förhållanden och procentsatser är viktbaserade och alla temperaturer är uttryckta i grader C, illustrerar uppfin- ningen.The following examples, in which all parts, ratios and percentages are by weight and all temperatures are expressed in degrees C, illustrate the invention.
Exempel 1 26,13 delar maleinsyraanhydrid smälts vid 60° i en kolv under kväveatmos- får och blandas med 60 delar polyetylenglykol 500. Under omrörning tillsätts 0,01 delar hydrokinonmetyleter och 0,666 delar dodecylmerkaptan och slutligen löses 1,17 delar azodiisobutyronitril så att man får en klar gulaktig lösning (lösning A).Example 1 26.13 parts of maleic anhydride are melted at 60 ° in a flask under a nitrogen atmosphere and mixed with 60 parts of polyethylene glycol 500. While stirring, 0.01 parts of hydroquinone methyl ether and 0.666 parts of dodecyl mercaptan are added and finally 1.17 parts of azodiisobutyronitrile are dissolved to give a clear yellowish solution (solution A).
I en annan kolv utrustad med omrörare, termometer, kylare och två trattar (doseringspumpar) blandas 60 delar polyetylenglykol 500 och 1,3 delar malein- syraanhydrid under omrörning. Kolven spolas med kväve under 5 minuter och hålls under kväve. Den klara, färglösa vätskan upphettas till 100° och när denna temperatur uppnåtts tillsätter man samtidigt lösning A i en takt av 1,45 delar/- 10 15 20 25 30 35 506 652 5 min. och 26,66 delar styren i en takt av 0,45 delar/min. Tillsatsen sker under lh.In another flask equipped with a stirrer, thermometer, cooler and two funnels (dosing pumps), 60 parts of polyethylene glycol 500 and 1.3 parts of maleic anhydride are mixed with stirring. The flask is purged with nitrogen for 5 minutes and kept under nitrogen. The clear, colorless liquid is heated to 100 ° and when this temperature is reached, solution A is added simultaneously at a rate of 1.45 parts / - 10 15 20 25 30 35 506 652 5 min. and 26.66 parts of styrene at a rate of 0.45 parts / min. The addition takes place during lh.
Lösningen rörs sedan om vid 100° under ytterligare lh, 0,12 delar azodiisobutyro- nitril tillsätts och omrörningen fortsätts under ytterligare lh vid samma tempera- tur.The solution is then stirred at 100 ° for an additional 1 h, 0.12 parts of azodiisobutyronitrile are added and stirring is continued for an additional 1 h at the same temperature.
Lösningen upphettas till 140° och 12,83 delar av en polyalkylenglykol, som säljs under varunamnet "Pluronic" PE 6100, tillsätts under loppet av 5 minuter.The solution is heated to 140 ° and 12.83 parts of a polyalkylene glycol, sold under the trade name "Pluronic" PE 6100, are added over the course of 5 minutes.
Temperaturen upprätthålls och blandningen omrörs i ytterligare 2h. Efter kylning till ca 60-70° späds lösningen med 235 delar avjoniserat vatten. Efter kylning till rumstemperatur neutraliseras emulsionen med ca 28,5 delar natrium- hydroxidlösning (30%) och justeras till en halt av 40% fast substans.The temperature is maintained and the mixture is stirred for a further 2 hours. After cooling to about 60-70 °, the solution is diluted with 235 parts of deionized water. After cooling to room temperature, the emulsion is neutralized with about 28.5 parts of sodium hydroxide solution (30%) and adjusted to a content of 40% solids.
Exempel 2-20 Analoga produkter erhålls med förfarandet enligt Exempel 1 med använd- ning av olika mängder polyetylenglykol (uttryckt som molfórhållanden av fri syra till halvester) 1:0,94 1:0,85 1:0,75 110,65 110,55 vid användning av andra hydrofoba polyalkylenglykoler "Pluronic" PE 6100 (BASF) "Pluronic" PE 3100 (BASF) SYNPERONIC PE L-61 (ICI) DOWFAX 20 A 64 (DOW) DOWFAX 20 A 612 (DOW) SYNALOX 50-50 B (DOW) SYNALOX 100-150 D (DOW) SYNALOX 100-D95 (DOW) CC-118 (Nippon Oil & Fats) CD-115 (MBT) vid användning av olika polysiloxaner VP 16 10 (VV acker) SLM 50400/ 6 1 (W acker) SLM 50400/62 (W acker) SLM 50480/ 6 (W acker) och/eller vid användning av olika polyetylenglykoler med molekylvikt = 500 (m= 11) 506 652 10 15 20 25 30 med molekylvikt 350 (m=8) med molekylvíkt 650 (m= 15) Alla synteserna utförs utan tillsats av särskilt lösningsmedel. Polyetylen- glykolen tjänstgör som lösningsmedel vid 100° och förestras med sampolymeren av maleinsyraanhydrid och styren vid 140°.Examples 2-20 Analogous products are obtained by the procedure of Example 1 using different amounts of polyethylene glycol (expressed as molar ratios of free acid to half ester) 1: 0.94 1: 0.85 1: 0.75 110.65 110, 55 using other hydrophobic polyalkylene glycols "Pluronic" PE 6100 (BASF) "Pluronic" PE 3100 (BASF) SYNPERONIC PE L-61 (ICI) DOWFAX 20 A 64 (DOW) DOWFAX 20 A 612 (DOW) SYNALOX 50-50 B (DOW) SYNALOX 100-150 D (DOW) SYNALOX 100-D95 (DOW) CC-118 (Nippon Oil & Fats) CD-115 (MBT) when using different polysiloxanes VP 16 10 (VV acker) SLM 50400/6 1 (W acker) SLM 50400/62 (W acker) SLM 50480/6 (W acker) and / or when using different polyethylene glycols with molecular weight = 500 (m = 11) 506 652 10 15 20 25 with molecular weight 350 (m = 8) with molecular weight 650 (m = 15) All syntheses are performed without the addition of special solvent. The polyethylene glycol acts as a solvent at 100 ° and is esterified with the copolymer of maleic anhydride and styrene at 140 °.
"Pluronic" PE 6100 har en molekylvikt av propylenoxidsegmentet om 1750 g/mol och en procenthalt polyetylenoxid av 10%."Pluronic" PE 6100 has a molecular weight of the propylene oxide segment of 1750 g / mol and a percentage of polyethylene oxide of 10%.
"Pluronic" PE 3100 har en molekylvikt av propylenoxidsegmentet om 950 g/mol och en procenthalt polyetylenoxid av 10%."Pluronic" PE 3100 has a molecular weight of the propylene oxide segment of 950 g / mol and a percentage of polyethylene oxide of 10%.
"Synperonic" PE L-61 år en segmentsampolymer av propylenoxid och etylenoxid, som har en molekylvikt av 2090 g/mol."Synperonic" PE L-61 is a block copolymer of propylene oxide and ethylene oxide having a molecular weight of 2090 g / mol.
"Dowfax" 20 A 64 är en segmentsampolymer av propylenoxid och etylen- oxid, som har en molekylvikt av 7209 g/mol."Dowfax" A 64 is a block copolymer of propylene oxide and ethylene oxide having a molecular weight of 7209 g / mol.
"Dowfax" 20 A 612 är en segmentsampolymer av propylenoxid och etylen- oxid, som har en molekylvikt av 1000."Dowfax" A 612 is a block copolymer of propylene oxide and ethylene oxide having a molecular weight of 1000.
"Synalox" 50-50B är en slumpsampolymer av propylenoxid och etylenoxid, som har en molekylvikt av 1200 g/mol."Synalox" 50-50B is a random copolymer of propylene oxide and ethylene oxide, which has a molecular weight of 1200 g / mol.
"Synalox" 100-150 D är en slumpsampolymer av propylenoxid och etylen- oxid, som har en molekylvikt av 2750."Synalox" 100-150 D is a random copolymer of propylene oxide and ethylene oxide, having a molecular weight of 2750.
"Synalox" 100-D95 är en polymer av propylenoxid, som har en molekylvikt av 2000.Synalox 100-D95 is a polymer of propylene oxide having a molecular weight of 2000.
CC-118 är en butyleter av segmentsampolymeren av 27 mol propylenoxid och 4 mol etylenoxid.CC-118 is a butyl ether of the block copolymer of 27 moles of propylene oxide and 4 moles of ethylene oxide.
CD-115 är en segmentsampolymer av propylenoxid och etylenoxíd med metyleter och hydroxiändgrupper. Molekylvikten fór propylenoxidsegmentet är 1900 g/mol och procentandelen polyetylenoxíd är 5%.CD-115 is a block copolymer of propylene oxide and ethylene oxide with methyl ether and hydroxy end groups. The molecular weight for the propylene oxide segment is 1900 g / mol and the percentage of polyethylene oxide is 5%.
VP 1610 är en polydimetylsiloxan med hydroxipropylenândgrupp som har en molekylvikt av 650.VP 1610 is a polydimethylsiloxane having hydroxypropylene end group having a molecular weight of 650.
SLM 50400/61 är sådan en med hydroxipentametylenändgrupp, som har en molekylvikt av 3000.SLM 50400/61 is one having a hydroxypentamethylene end group having a molecular weight of 3000.
SLM 50400/62 är sådan en med hydroxipropylenändgrupp, som har en molekylvikt av 3000.SLM 50400/62 is one having a hydroxypropylene end group having a molecular weight of 3000.
SLM 50480/6 är en polydimetylsiloxan med hydroxipropylenändgrupp, som 10 15 20 25 30 506 552 7 är företrad med 10 etylenoxidgrupper och har en molekylvikt av 1400.SLM 50480/6 is a polydimethylsiloxane having hydroxypropylene end group, which is etherified with 10 ethylene oxide groups and has a molecular weight of 1400.
Tillämpninggexempel A Ett bruk tillblandas enligt DIN 1164, Del 7, med följande beståndsdelar: 1350 g välblandad standardsand, 450 g portlandcement och 180 g kranvatten.Application example A A mortar is mixed in accordance with DIN 1164, Part 7, with the following components: 1350 g of well-mixed standard sand, 450 g of Portland cement and 180 g of tap water.
Kranvattnet innehåller O,3% av föreningen enligt Exempel 1, räknat som torrsub- stans av cementvikten. Bruket blandas under standardbetingelser och omedelbart efter blandningen mäts brukets konsistens enligt DIN 1060, Del 3; DIN 1048, Del 1 eller någon annan standardmetod.The tap water contains 0.3% of the compound according to Example 1, calculated as dry matter by the cement weight. The mill is mixed under standard conditions and immediately after mixing the consistency of the mill is measured according to DIN 1060, Part 3; DIN 1048, Part 1 or any other standard method.
För jämförelse med bruket enligt uppfinningen framställs samma bland- ningar, men utan något tillsatsmedel eller sådana som innehåller en kondensa- tionsprodukt av naftalensulfonat eller melaminsulfonat och formaldehyd med användning av samma dosering (0,3 vikt-% torrsubstans, räknat på cement). Det framgår av försöksresultaten att fluiditetsegenskaperna hos bruket enligt uppfinningen är mycket bättre än dessa egenskaper hos järnfórelsebruket.For comparison with the mortar according to the invention, the same mixtures are prepared, but without any additive or those containing a condensation product of naphthalene sulfonate or melamine sulfonate and formaldehyde using the same dosage (0.3% by weight dry matter, based on cement). It appears from the experimental results that the id uidity properties of the mill according to the invention are much better than these properties of the iron feed mill.
Samma resultat uppnås när man istället för föreningen enligt Exempel 1 använder en förening enligt Exemplen 2-20.The same result is obtained when instead of the compound of Example 1 a compound of Examples 2-20 is used.
Tillämgningexempel B Betongblandningar framställs enligt följande recept: Ballast med meshtal 0-16 mm i området A/B enligt DIN 1045: maskvidd 1 mm 20% maskvind 4 mm 45% maskvidd 8 mm 70% maskvidd 16 mm 100% pulverhalt 8% Portlandcement typ I ASTM C150 (Holderbank, Rekingen, Schweiz) 350 kg/mß betong Blandningsvatten 40% Blandningen utförs i en bandblandare, varvid vattnet tillsätts inom de första 30 sekunderna och blandningen fortsätts under totalt 2 minuter.Application example B Concrete mixtures are prepared according to the following recipe: Ballast with mesh number 0-16 mm in the area A / B according to DIN 1045: mesh width 1 mm 20% mesh wind 4 mm 45% mesh width 8 mm 70% mesh width 16 mm 100% powder content 8% Portland cement type I ASTM C150 (Holderbank, Rekingen, Switzerland) 350 kg / mß concrete Mixing water 40% The mixing is carried out in a belt mixer, whereby the water is added within the first 30 seconds and the mixing is continued for a total of 2 minutes.
Som jämförelse framställer man en betongmix, som innehåller en konden- sationsprodukt av naftalensulfonat och förmaldehyd. I båda fallen tillsätts 0,3 506 652 8 vikt-% av tillsatsmedlet, räknat på cement, till blandningsvattnet. Efter bland- ningen bestäms den färska betongens fluiditet antingen enligt ASTM C 143 (sättkon) eller enligt DIN 1048 (skakbord). Betongblandníngar, som innehåller ett tillsatsmedel enligt uppfinningen, uppvisar bättre konsistens och fluiditet än 5 jämförande blandningar utan tillsatsmedel eller med konventionella tillsatsmedel.For comparison, a concrete mix is prepared, which contains a condensation product of naphthalene sulfonate and formaldehyde. In both cases, 0.3 50% by weight of the additive, based on cement, is added to the mixing water. After mixing, the fluidity of the fresh concrete is determined either according to ASTM C 143 (set cone) or according to DIN 1048 (shaking table). Concrete mixtures containing an additive according to the invention show better consistency and luminosity than comparative mixtures without additives or with conventional additives.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4042182 | 1990-12-29 |
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| Publication Number | Publication Date |
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| SE9103844D0 SE9103844D0 (en) | 1991-12-27 |
| SE9103844L SE9103844L (en) | 1992-06-30 |
| SE506652C2 true SE506652C2 (en) | 1998-01-26 |
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| SE9103844A SE506652C2 (en) | 1990-12-29 | 1991-12-27 | Copolymers of styrene and maleic half-ester and their use as additives for cement compositions |
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| Country | Link |
|---|---|
| JP (1) | JP2766807B2 (en) |
| AT (1) | AT405934B (en) |
| CH (1) | CH682237A5 (en) |
| DE (1) | DE4142388C2 (en) |
| FR (1) | FR2671090B1 (en) |
| IT (1) | IT1250077B (en) |
| NO (1) | NO301125B1 (en) |
| SE (1) | SE506652C2 (en) |
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| CH686780A5 (en) * | 1992-07-22 | 1996-06-28 | Sandoz Ag | Fliessfaehige cement mixtures. |
| AT399340B (en) * | 1993-02-01 | 1995-04-25 | Chemie Linz Gmbh | COPOLYMERS BASED ON MALEINIC ACID DERIVATIVES AND VINYL MONOMERS, THEIR PRODUCTION AND USE |
| US5573589A (en) * | 1993-03-10 | 1996-11-12 | Sandoz Ltd. | Cement compositions containing a sulfated polysaccharide and method |
| ES2186683T3 (en) * | 1993-09-08 | 2003-05-16 | Mbt Holding Ag | CEMENTOUS COMPOSITIONS FOR STRATIFIED APPLICATIONS. |
| IT1279390B1 (en) * | 1993-12-21 | 1997-12-10 | Sandoz Ag | ADDITIONAL COPOLYMERS USEFUL AS FLUIDIFYING ADDITIVES FOR CEMENTITIOUS MIXTURES |
| GB9421984D0 (en) * | 1994-11-01 | 1994-12-21 | Sandoz Ltd | Improvements in or relating to organic compounds |
| DE19513126A1 (en) * | 1995-04-07 | 1996-10-10 | Sueddeutsche Kalkstickstoff | Copolymers based on oxyalkylene glycol alkenyl ethers and unsaturated dicarboxylic acid derivatives |
| GB9511700D0 (en) * | 1995-06-09 | 1995-08-02 | Sandoz Ltd | Improvements in or relating to organic compounds |
| US5770656A (en) * | 1995-09-22 | 1998-06-23 | E.I. Du Pont De Nemours And Company | Partial fluoroesters or thioesters of maleic acid polymers and their use as soil and stain resists |
| GB9607570D0 (en) * | 1996-04-12 | 1996-06-12 | Sandoz Ltd | Improvements in or relating to organic compounds |
| AT404730B (en) * | 1997-04-07 | 1999-02-25 | Holderchem Ag | ACRYLIC COPOLYMERS AND POLYMER COMPOSITIONS, AND THEIR USE AS ADDITIVES OR ADDITIVES FOR IMPROVING THE PROPERTIES OF DISPERSIONS AND BUILDING MATERIALS |
| US6310143B1 (en) * | 1998-12-16 | 2001-10-30 | Mbt Holding Ag | Derivatized polycarboxylate dispersants |
| JP4394765B2 (en) | 1999-02-15 | 2010-01-06 | Ｂａｓｆポゾリス株式会社 | Cement additive |
| US6528593B1 (en) | 1999-09-10 | 2003-03-04 | The Dow Chemical Company | Preparing copolymers of carboxylic acid, aromatic vinyl compound and hydrophobic polyalkylene oxide |
| FR2815342B1 (en) | 2000-10-13 | 2003-08-01 | Francais Ciments | CEMENTITIOUS COMPOSITION, ITS USE FOR THE PRODUCTION OF A SELF-LEVELING LIQUID SCREW AND A SCREEN THUS OBTAINED |
| DE102006062441A1 (en) | 2006-12-27 | 2008-07-03 | Byk-Chemie Gmbh | Comb polymer is useful as a wetting agent and dispersant comprises styrene units and derivatized maleic anhydride units with phosphate or quaternary ammonium functions |
| KR100990861B1 (en) | 2008-02-26 | 2010-11-01 | 주식회사 제닉 | pH-SENSITIVE POLYETHYLENE OXIDE CO-POLYMER AND SYNTHETIC METHODE THEREOF |
| WO2017189309A1 (en) * | 2016-04-26 | 2017-11-02 | Dow Global Technologies Llc | Clay insensitive concrete superplasticizer |
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| BE604593A (en) * | 1960-06-02 | 1900-01-01 | ||
| BE621179A (en) * | 1961-08-08 | |||
| US3392155A (en) * | 1961-08-08 | 1968-07-09 | Sinclair Research Inc | Low molecular weight maleic compound copolymers partially esterified with monohydric polyether alcohols |
| DE1745555B1 (en) * | 1967-05-10 | 1972-05-25 | Wacker Chemie Gmbh | PROCESS FOR THE PREPARATION OF Aqueous POLYMERISATE DISPERSIONS |
| US3563930A (en) * | 1968-04-01 | 1971-02-16 | Atlantic Richfield Co | Cement composition |
| US3544344A (en) * | 1968-04-18 | 1970-12-01 | Sinclair Research Inc | Set retarded plaster composition |
| US4655838A (en) * | 1984-09-27 | 1987-04-07 | Idemitsu Petrochemical Co., Ltd. | Cement additive composition |
| US4654050A (en) * | 1985-01-18 | 1987-03-31 | The Lubrizol Corporation | Esters of carboxy-containing interpolymers |
| DE3514878A1 (en) * | 1985-04-25 | 1986-11-06 | Henkel KGaA, 4000 Düsseldorf | Oil-soluble esters of copolymers of maleic anhydride |
| DE3619363A1 (en) * | 1986-06-09 | 1987-12-10 | Brockhues Chem Werke Ag | METHOD FOR COLORING CONCRETE |
| DE3728786A1 (en) * | 1987-08-28 | 1989-03-09 | Sandoz Ag | Polymeric compounds, their preparation and use |
| DE3800091A1 (en) * | 1987-08-28 | 1989-07-13 | Sandoz Ag | COPOLYMERS, THEIR PRODUCTION AND USE |
| JP2882648B2 (en) * | 1989-08-17 | 1999-04-12 | 株式会社クラレ | Manufacturing method of thermoplastic water-soluble resin |
| JP2747521B2 (en) * | 1990-08-23 | 1998-05-06 | 株式会社ネオス | Additive for coal-water slurry |
-
1991
- 1991-12-18 CH CH3759/91A patent/CH682237A5/en not_active IP Right Cessation
- 1991-12-19 AT AT0251591A patent/AT405934B/en not_active IP Right Cessation
- 1991-12-20 IT ITRM910967A patent/IT1250077B/en active IP Right Grant
- 1991-12-20 DE DE4142388A patent/DE4142388C2/en not_active Expired - Fee Related
- 1991-12-27 NO NO915105A patent/NO301125B1/en unknown
- 1991-12-27 FR FR9116262A patent/FR2671090B1/en not_active Expired - Fee Related
- 1991-12-27 SE SE9103844A patent/SE506652C2/en not_active IP Right Cessation
- 1991-12-27 JP JP3346186A patent/JP2766807B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| NO915105L (en) | 1992-06-30 |
| DE4142388C2 (en) | 1999-12-09 |
| CH682237A5 (en) | 1993-08-13 |
| JPH06211940A (en) | 1994-08-02 |
| DE4142388A1 (en) | 1992-07-02 |
| SE9103844D0 (en) | 1991-12-27 |
| NO915105D0 (en) | 1991-12-27 |
| AT405934B (en) | 1999-12-27 |
| JP2766807B2 (en) | 1998-06-18 |
| IT1250077B (en) | 1995-03-30 |
| SE9103844L (en) | 1992-06-30 |
| FR2671090B1 (en) | 1993-05-07 |
| ITRM910967A0 (en) | 1991-12-20 |
| NO301125B1 (en) | 1997-09-15 |
| FR2671090A1 (en) | 1992-07-03 |
| ATA251591A (en) | 1999-05-15 |
| ITRM910967A1 (en) | 1993-06-20 |
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