CN101024560A - 含有具有非极性壳的微粒子的建筑材料混合物添加剂 - Google Patents
含有具有非极性壳的微粒子的建筑材料混合物添加剂 Download PDFInfo
- Publication number
- CN101024560A CN101024560A CNA2006100817484A CN200610081748A CN101024560A CN 101024560 A CN101024560 A CN 101024560A CN A2006100817484 A CNA2006100817484 A CN A2006100817484A CN 200610081748 A CN200610081748 A CN 200610081748A CN 101024560 A CN101024560 A CN 101024560A
- Authority
- CN
- China
- Prior art keywords
- cavity
- purposes
- polymeric microsphere
- building material
- concrete
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 239000004566 building material Substances 0.000 title claims abstract description 19
- 239000011859 microparticle Substances 0.000 title abstract 2
- 239000000654 additive Substances 0.000 title description 3
- 230000000996 additive effect Effects 0.000 title description 2
- 239000004567 concrete Substances 0.000 claims description 50
- 239000004005 microsphere Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 18
- 239000004568 cement Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 11
- -1 (methyl) n-butyl Chemical group 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000011148 porous material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000010276 construction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007710 freezing Methods 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 108010053481 Antifreeze Proteins Proteins 0.000 description 4
- 230000002528 anti-freeze Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000009746 freeze damage Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000010257 thawing Methods 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 101710095439 Erlin Proteins 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 244000000188 Vaccinium ovalifolium Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012628 flowing agent Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 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 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- APOHFWYEYYKWGG-UHFFFAOYSA-N C(CCCCCCCCCCC)C1=C(C=CC=C1)[Na] Chemical compound C(CCCCCCCCCCC)C1=C(C=CC=C1)[Na] APOHFWYEYYKWGG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
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
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/08—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons
-
- 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
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/08—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons
- C04B16/085—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons expanded in situ, i.e. during or after mixing the mortar, concrete or artificial stone ingredients
-
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
-
- 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
- C04B2103/0049—Water-swellable polymers
-
- 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
- C04B2103/0058—Core-shell polymers
-
- 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
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/29—Frost-thaw resistance
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)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及具有非极性壳的聚合物微粒子用于水凝性建筑材料混合物中以改进其抗冻性或抗冻结－融化交替性的用途。
Description
本发明涉及聚合物微粒子用于水凝性建筑材料混合物中以改善其抗冻性或抗冻结-融化交替性的用途。
对于混凝土在融化剂的同时作用下对冻结和冻结-融化交替的抵抗力，它的组织结构的紧密性、一定的基体强度和一定孔组织结构的存在是决定性的。这种水泥结合的混凝土的组织结构被毛细孔(半径：2μm-2mm)或凝胶孔(半径：2-50nm)交织。其中包含的孔隙水取决于孔的直径而在其状态形式方面不同。水在毛细孔中保持其常规性能，而在凝胶孔中按照冷凝水(中孔：50nm)和吸附性结合的表面水(微孔：2nm)进行分类，所述吸附性结合的表面水的冰点可能例如远低于-50℃[M.J.Setzer，Interaction of water with hardened cement paste(水与硬化水泥糊的相互作用)，“Ceramic Transactions”，16(1991)，415-39]。这导致的结果是，甚至在混凝土的深度冷却时，也有一部分孔隙水保持未冻结(亚稳态的水)。但是，在相同的温度下，冰上方的蒸汽压低于水上方的蒸汽压。因为冰和亚稳态的水同时并存存在，所以产生蒸汽压落差，其导致仍然为液体的水向冰扩散并且导致其形成冰，由此发生在较小的孔中的脱水或在较大的孔中的冰积聚。这种由于冷却而引起的水的重新分布在任何有细孔的体系中发生并且决定性地取决于孔分布的类型。
在混凝土中人工引入微细的空气孔也主要产生用于膨胀性的冰和冰水的所谓的卸压空间。在这些孔中，冻结的孔隙水可能膨胀，或抵挡冰和冰水的内部压力和应力，而没有出现微裂纹的形成和因此出现混凝土的冻结损坏。这种空气孔体系的在原理上的作用方式与混凝土的冻结损坏机理相关联地在大量的综述中描述[Schulson，Erland M.(1998)，Ice damage to concrete(冰对混凝土的损坏)，CRREL Special Report98-6；S.Chatterji，Freezing of air-entrained cement-basedmaterials and specific actions of air-ehtraining agents(夹带空气的水泥基材料的冻结和空气夹带剂的特定作用)，“Cement &Concrete Composites”，25(2003)759-65；G.W.Scherer，J.Chen& J.Valenza，Methods for protecting concrete from freeze damage(保护混凝土免受冻结损坏的方法)，US专利6,485,560B1(2002)；M.Pigeon，B.Zuber & J.Marchand，Freeze/thaw resistance(抗冻/融性)，“Advanced Concrete Technology”2(2003)11/1-11/17；B.Erlin & B.Mather，A new process by which cyclic freezing candamage concrete-the Erlin/Mather effect(一种循环冻结可能借以损坏混凝土的新过程-Erlin/Mather效应)，“Cement & ConereteResearch”35(2005)1407-11]。
对于混凝土在冻结和融化交替中的改进的稳定性而言的前提条件是，在水泥砖中的任何位置点与最近的人工空气孔之间的间距不超过一定的数值。这个间距也称作间距因子或“Powers间隔因子”[T.C.Powers，The air requirement of frost-resistant concrete(抗冻混凝土的空气要求)，“Proceedings of the Highway Research Board”29(1949)184-202]。实验室测试在此方面已经表明，超过500μm的临界“Power间隔因子”导致在冻结和融化交替中混凝土的损坏。为了在受限的空气孔含量下实现这一点，人工引入的空气孔的直径因此必须小于200-300μm[K.Snyder，K.Natesaiyer & K.Hover，Thestereological and statistical properties of entrained air voidsin concrete：A mathematical basis for air void systemscharacterization(混凝土中夹带的空气空隙的立体空间逻辑学和统计学性能：空气空隙系统表征用的数学基础)，“Materials Science ofConcrete”VI(2001)，129-214]。
人工空气孔体系的形成决定性地取决于骨料的组成和颗粒形态(Formitt)，水泥的类型和数量，混凝土稠度，使用的混合器，混合时间，温度，但是还取决于空气孔形成剂的类型和数量。在考虑相应的生产过程调节的条件下，它们的影响虽然可以得到控制，但是可能发生大量不希望的损害，这最终导致可能超过或达不到混凝土中所希望的空气含量并因而不利地影响混凝土的强度或抗冻性。
这样的人工空气孔可以不直接计量加入，而是通过添加所谓的空气孔形成剂而将通过混合过程带入的空气稳定化[L.Du & K.J.Folliard，Mechanism of air entrainment in concrete(混凝土中空气夹带的机理)，“Cement & Concrete Research”，35(2005)1463-71]。传统的空气孔形成剂大部分是表面活性剂类型的结构并将通过混合过程引入的空气打碎成具有直径为尽可能小于300μm的小空气气泡并在潮湿的混凝土组织结构中将其稳定化。在此区分为两种类型。
一种类型-例如，油酸钠，松香酸的钠盐，或Vinsol(氧化松香)树脂，一种得自松树根的提取物-与在水泥粘胶中的孔溶液中的氢氧化钙反应并作为不溶性的钙盐沉淀出。这种疏水性的盐降低了水的表面张力并在水泥颗粒、空气和水之间的界面处积聚。它们稳定了微小气泡并因此在硬化的混凝土中再次位于这些空气孔的表面处。
另一种类型-例如月桂基硫酸钠(SDS)或十二烷基苯基磺酸钠-相反，与氢氧化钙形成可溶性钙盐，但是其显示一种反常的溶解行为。在一定的临界温度以下，这些表面活性剂显示一种很低的溶解性，在高于该温度的条件下它们具有非常良好的溶解性。通过优选积聚在空气-水界面层处，它们同样降低了表面张力，因而稳定了微小气泡并优选将在硬化混凝土中再次位于这些空气孔的表面处。
在根据现有技术使用空气孔形成剂时，出现大量的问题[L.Du & K.J.Folliard，Mechanism of air entrainment in concrete(混凝土中的空气夹带机理)，“Cement & Concrete Research”35(2005)1463-71。例如，较长的混合时间，不同的混合器转数，在运输混凝土中变化的计量加入过程，可能导致经稳定化的空气(在空气孔中)再次被赶出。
采用延长的运输时间、差的温度调控和不同的泵送设备和输送设备的混凝土输送，以及伴随有变化的后处理、震摇(Ruckel)行为和温度条件的混凝土引入，可能显著改变预先调节的空气孔含量。这在最坏的情况下可能意味着，混凝土不再满足一定的暴露等级所必需的极限值并因而变得不可使用[EN 206-1(2000)，Concrete-Part 1：Secification，performance，production and conformity(混凝土-第1部分：规格、性能、生产和适合度)]。
混凝土中细物质的含量(例如具有不同碱含量的水泥，添加物质，例如飞灰、二氧化硅粉尘或颜色添加剂)同样不利于空气孔的形成。还可能发生与消泡作用的流动剂的相互作用，所述流动剂因而可能赶出空气孔，但是也可能附加地不受控地引入空气孔。
所有这些使得抗冻混凝土的生产困难的影响在如下条件下可以得到避免，即当所必需的空气孔体系不通过上述具有表面活性剂类型结构的空气孔形成剂而产生，而是空气含量通过混合入或固体计量加入聚合物微粒子(微中空球)引起[H.Sommer，A new method of making concreteresistant to frost and de-icing salts(一种使混凝土抗冻的新方法和防冻盐)，“Betonwerk & Fertigteiltechnik”9(1978)476-84]。因为微粒子大部分具有小于100μm的粒度，所以它们在混凝土组织结构中甚至比人工引入的空气孔更细和更均匀地分布。结果是，低的数量就足以达到混凝土充分抗冻结和融化交替。
这样的聚合物微粒子用于改善混凝土的抗冻性和抗冻结-融化交替性的用途根据现有技术是已知的[参见DE2229094A1、US4057526B1、US4082562B1、DE3026719A1]。其中描述的微粒子的特征主要在于，它们具有的空腔小于200μm(直径)并且这种中空核由空气(或气态物质)组成。这同样包括100μm尺度的多孔微粒子，所述微粒子可能具有大量的更小的空腔和/或孔。
在使用中空的微粒子用于在混凝土中人工形成空气孔时，两个因素经证实对于这种技术在市场上的实施是不利的。仅以相对高的剂量才能达到令人满意地提供的混凝土的抗冻结和融化交替性。本发明的目的因此是，提供一种水凝性的建筑材料混合物用的用于改善抗冻性或抗冻结-融化交替性的试剂，其甚至在相对低的剂量下仍发挥其完全的效力。
本发明的目的通过在水凝性的建筑材料混合物中使用具有空腔的聚合物微粒子而实现，其特征在于，微粒子的壳由高于99重量％的具有水溶解性小于10-1mol/l的单体组成。
如果没有另外说明，则在本文中溶解性总是指在水中在20℃下的溶解性。
通过主要使用水溶性非常差的单体，得到具有非常非极性的表面的微粒子。已经令人惊奇地发现，通过使用这样的微粒子，可以在提高抗冻性或抗冻结/融化交替性方面达到极其良好的效力。这种作用比使用具有极性表面的粒子时明显更好。
作为解释，对于这种预料不到的效果-不希望该理论限制本发明的范围-推测，这样的具有非极性表面的微粒子具有对建筑材料混合物的较差结合。结果是，在微粒子和建筑材料基体之间的界面处可能发生毛细孔的形成，所述毛细孔有助于提高抗冻性或抗冻结/融化交替性。
壳根据本发明由高于99重量％的具有水溶解性小于10-1mol/l的单体组成。优选壳由高于99.5重量％的这样的单体组成。特别优选壳唯一地由这样的单体组成。
由于本发明的非极性壳的作用明显与非极性表面相关，所以当在微粒子的多壳结构的情况下，最外部的壳满足如下条件下时是足够的：高于99重量％是由具有水溶解性小于10-1mol/l的单体组成。也在这种情况下，具有99.5％的这些单体的单体组成是优选的，并且在最外部的壳中唯一地使用这些单体是特别优选的。
优选，壳，非必要地外壳，由苯乙烯组成。在本发明的另一个优选的实施方案中，壳，非必要地外壳，由苯乙烯和/或(甲基)丙烯酸正己酯和/或(甲基)丙烯酸正丁酯和/或(甲基)丙烯酸异丁酯和/或(甲基)丙烯酸丙酯和/或甲基丙烯酸乙酯和/或(甲基)丙烯酸乙基己酯。
表达方式“(甲基)丙烯酸酯”在此既表示甲基丙烯酸酯，例如甲基丙烯酸甲酯、甲基丙烯酸乙酯等，又表示丙烯酸酯，例如丙烯酸甲酯、丙烯酸乙酯等，以及上述两者的混合物。
本发明的微粒子可以优选通过乳液聚合反应制备并优选具有平均粒度为100-5000nm；特别优选平均粒度为200-2000nm。最优选平均粒度为250-1000nm。平均粒度的测定例如通过依据透射电子显微镜照片对统计学上显著量的粒子进行计数而进行。
通过乳液聚合反应制备时，微粒子以水分散体的形式得到。相应地，微粒子添加到建筑材料混合物中的过程优选同样以这种形式进行。
在制备时和在分散体中，微粒子的空腔被水填充。粒子通过如下方式发挥其在建筑材料混合物中用于提高抗冻性和抗冻结-融化交替性的作用：水在建筑材料混合物的硬化时和硬化后-至少部分地-失去，由此相应地存在气体填充或空气填充的中空球。
根据优选的实施方案，所用的微粒子由聚合物颗粒组成，所述聚合物颗粒具有一个核(A)和至少一个壳(B)，其中核/壳聚合物颗粒借助碱而溶胀。
粒子的核(A)含有一种或多种烯属不饱和羧酸(衍生物)单体，该单体可以实现核的溶胀；这些单体优选选自丙烯酸、甲基丙烯酸、马来酸、马来酸酐、富马酸、衣康酸和巴豆酸和它们的混合物。丙烯酸和甲基丙烯酸是特别优选的。
(非必要为最外部的)壳B含有按本发明所述的单体。如果微粒子作为多壳形式或作为梯度胶乳形式构成，则对于在核和最外部的壳之间使用的单体不适用任何特别的限制。
通过乳液聚合反应制备这种聚合物微粒子的过程，以及它们借助于碱，例如碱金属或碱土金属氢氧化物(Alkali-oder Alkalihydroxide)以及氨或胺进行的溶胀，同样描述于欧洲专利文献EP22633B1、EP73529B1以及EP188325B1中。
所用微粒子的聚合物含量依赖于直径和水含量可以为2-98重量％(聚合物重量，基于水填充的粒子的总重量)。优选，聚合物含量为2-60重量％，特别优选聚合物含量为2-40重量％。
在本发明范围内毫无困难地可能的是，将由水填充的微粒子直接作为固体形式添加到建筑材料混合物中。为此，将微粒子-如上文所述-凝结并且通过常用的方法(例如过滤、离心、沉降和滗析)而从水分散体中分离并然后将粒子干燥。
由水填充的微粒子以优选的数量为0.01-5体积％，特别是0.1-0.5体积％加入建筑材料混合物中。建筑材料混合物，例如以混凝土或灰浆形式，可以在此包含常规水凝性的粘结剂，例如水泥、石灰、石膏或无水石膏。
通过使用水填充的微粒子的主要优点在于，仅将极其少的空气夹带入混凝土中。结果是，可以实现混凝土的明显改进的抗压强度。这些比采用传统的空气孔形成得到的混凝土的抗压强度高出约25-50％。因而可以达到这样的强度等级，其在其它情况下只能通过显著更低的水/水泥值(W/Z值)而调节。但是，低的W/Z值在某些情况下又明显限制了混凝土的加工性。此外，更高的抗压强度可能导致，对于强度形成所必需的在混凝土中的水泥含量可以降低，由此每立方米混凝土的价格显著降低。
Claims (14)
1.具有空腔的聚合物微粒子用于水凝性建筑材料混合物中的用途，其特征在于，微粒子的壳由高于99重量％的具有水溶解性小于10-1mol/l的单体构成。
2.权利要求1的具有空腔的聚合物微粒子用于水凝性建筑材料混合物中的用途，其特征在于，微粒子的壳唯一地由具有水溶解性小于10-1mol/l的单体构成。
3.权利要求1的具有空腔的聚合物微粒子的用途，其特征在于，外壳含有苯乙烯。
4.权利要求1的具有空腔的聚合物微粒子的用途，其特征在于，外壳含有苯乙烯和/或(甲基)丙烯酸正己酯和/或(甲基)丙烯酸正丁酯和/或(甲基)丙烯酸异丁酯和/或(甲基)丙烯酸丙酯和/或甲基丙烯酸乙酯和/或(甲基)丙烯酸乙基己酯。
5.权利要求1的具有空腔的聚合物微粒子的用途，其特征在于，微粒子由如下的聚合物颗粒组成，该聚合物颗粒含有借助含水碱而溶胀的含有一种或多种不饱和羧酸(衍生物)单体的聚合物核(A)，以及主要由非离子型烯属不饱和单体组成的聚合物外壳(B)。
6.权利要求5的具有空腔的聚合物微粒子的用途，其特征在于，不饱和的羧酸(衍生物)单体选自丙烯酸、甲基丙烯酸、马来酸、马来酸酐、富马酸、衣康酸和巴豆酸。
7.权利要求1的具有空腔的聚合物微粒子的用途，其特征在于，微粒子具有2-98重量％的聚合物含量。
8.权利要求1的具有空腔的聚合物微粒子的用途，其特征在于，微粒子具有的平均粒度为100-5000nm。
9.权利要求8的具有空腔的聚合物微粒子的用途，其特征在于，微粒子具有的平均粒度为200-2000nm。
10.权利要求9的具有空腔的聚合物微粒子的用途，其特征在于，微粒子具有的平均粒度为250-1000nm。
11.权利要求1的具有空腔的聚合物微粒子的用途，其特征在于，微粒子的用量为0.01-5体积％，基于建筑材料混合物。
12.权利要求11的具有空腔的聚合物微粒子的用途，其特征在于，微粒子的用量为0.1-0.5体积％，基于建筑材料混合物。
13.权利要求1的具有空腔的聚合物微粒子的用途，其特征在于，建筑材料混合物由粘结剂组成，该粘结剂选自水泥、石灰、石膏和无水石膏。
14.权利要求1的具有空腔的聚合物微粒子的用途，其特征在于，所述建筑材料混合物是指混凝土或灰浆。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006008967.7 | 2006-02-23 | ||
| DE102006008967A DE102006008967A1 (de) | 2006-02-23 | 2006-02-23 | Additive Baustoffmischungen mit Mikropartikeln mit unpolaren Schalen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101024560A true CN101024560A (zh) | 2007-08-29 |
Family
ID=38319875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006100817484A Pending CN101024560A (zh) | 2006-02-23 | 2006-05-10 | 含有具有非极性壳的微粒子的建筑材料混合物添加剂 |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20070193478A1 (zh) |
| EP (1) | EP1986972A2 (zh) |
| JP (1) | JP2009527445A (zh) |
| KR (1) | KR20080110996A (zh) |
| CN (1) | CN101024560A (zh) |
| BR (1) | BRPI0708240A2 (zh) |
| CA (1) | CA2643455A1 (zh) |
| DE (1) | DE102006008967A1 (zh) |
| RU (1) | RU2008137542A (zh) |
| WO (1) | WO2007096231A2 (zh) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2002247681A1 (en) * | 2001-02-07 | 2002-09-12 | Rohm Gmbh And Co. Kg | Hot sealing compound for aluminum foils applied to polypropylene and polystyrene |
| DE10350786A1 (de) * | 2003-10-29 | 2005-06-02 | Röhm GmbH & Co. KG | Mischungen zur Herstellung von Reaktivschmelzklebstoffen sowie daraus erhältliche Reaktivschmelzklebstoffe |
| DE102004035937A1 (de) * | 2004-07-23 | 2006-02-16 | Röhm GmbH & Co. KG | Plastisole mit verringerter Wasseraufnahme |
| DE102005042389A1 (de) * | 2005-06-17 | 2006-12-28 | Röhm Gmbh | Heißversiegelungsmasse für Aluminium- und Polyethylenterephthalatfolien gegen Polypropylen-Polyvinylchlorid- und Polystyrolbehälter |
| DE102005045458A1 (de) * | 2005-09-22 | 2007-03-29 | Röhm Gmbh | Verfahren zur Herstellung von ABA-Triblockcopolymeren auf (Meth)acrylatbasis |
| DE102005046681A1 (de) * | 2005-09-29 | 2007-04-05 | Construction Research & Technology Gmbh | Verwendung von polymeren Mikropartikeln in Baustoffmischungen |
| DE102005052130A1 (de) * | 2005-10-28 | 2007-05-03 | Röhm Gmbh | Spritzbare Akustikmassen |
| US8915997B2 (en) | 2013-05-16 | 2014-12-23 | Navs, Llc | Durable concrete and method for producing the same |
| KR20160087194A (ko) | 2015-01-13 | 2016-07-21 | 정재삼 | 마스크 팩 |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7505525A (nl) * | 1975-05-12 | 1976-11-16 | Akzo Nv | Werkwijze voor de bereiding van een vorstbesten- dig beton. |
| CA1180474A (en) * | 1979-06-26 | 1985-01-02 | Alexander Kowalski | Sequential heteropolymer dispersion and a particulate material obtainable therefrom useful in coating compositions as a thickening and/or opacifying agent |
| US4594363A (en) * | 1985-01-11 | 1986-06-10 | Rohm And Haas Company | Production of core-sheath polymer particles containing voids, resulting product and use |
| EP0725092A3 (de) * | 1995-02-06 | 1997-08-27 | Chemie Linz Gmbh | Redispergierbare, pulverförmige Kern-Mantel-Polymere, deren Herstellung und Verwendung |
| US6498209B1 (en) * | 1998-03-31 | 2002-12-24 | Roehm Gmbh & Co. Kg | Poly(meth)acrylate plastisols |
| DE19826412C2 (de) * | 1998-06-16 | 2002-10-10 | Roehm Gmbh | Geruchsvermindertes, kalthärtendes (Meth)acrylat-Reaktionsharz für Bodenbeschichtungen, dieses Reaktionsharz aufweisende Bodenbeschichtungen sowie Verfahren zur Herstellung solcher Bodenbeschichtungen |
| DE19833062A1 (de) * | 1998-07-22 | 2000-02-03 | Elotex Ag Sempach Station | Redispergierbares Pulver und dessen wäßrige Dispersion, Verfahren zur Herstellung sowie Verwendung |
| DE19928352A1 (de) * | 1999-06-21 | 2000-12-28 | Roehm Gmbh | Verbesserte Poly(meth)acrylatptastisole und Verfahren zu ihrer Herstellung |
| DE10227898A1 (de) * | 2002-06-21 | 2004-01-15 | Röhm GmbH & Co. KG | Verfahren zur Herstellung sprühgetrockneter Poly(meth)acrylatpolymere, ihre Verwendung als Polymerkomponente für Plastisole und damit hergestellte Plastisole |
| DE10350786A1 (de) * | 2003-10-29 | 2005-06-02 | Röhm GmbH & Co. KG | Mischungen zur Herstellung von Reaktivschmelzklebstoffen sowie daraus erhältliche Reaktivschmelzklebstoffe |
| WO2005123618A2 (en) * | 2004-06-15 | 2005-12-29 | Construction Research & Technology Gmbh | Providing freezing and thawing resistance to cementitious compositions |
| DE102004035937A1 (de) * | 2004-07-23 | 2006-02-16 | Röhm GmbH & Co. KG | Plastisole mit verringerter Wasseraufnahme |
| DE102005042389A1 (de) * | 2005-06-17 | 2006-12-28 | Röhm Gmbh | Heißversiegelungsmasse für Aluminium- und Polyethylenterephthalatfolien gegen Polypropylen-Polyvinylchlorid- und Polystyrolbehälter |
| DE102005046681A1 (de) * | 2005-09-29 | 2007-04-05 | Construction Research & Technology Gmbh | Verwendung von polymeren Mikropartikeln in Baustoffmischungen |
-
2006
- 2006-02-23 DE DE102006008967A patent/DE102006008967A1/de not_active Withdrawn
- 2006-03-24 US US11/387,803 patent/US20070193478A1/en not_active Abandoned
- 2006-05-10 CN CNA2006100817484A patent/CN101024560A/zh active Pending
-
2007
- 2007-01-30 EP EP07704247A patent/EP1986972A2/de not_active Withdrawn
- 2007-01-30 BR BRPI0708240-1A patent/BRPI0708240A2/pt not_active Application Discontinuation
- 2007-01-30 CA CA002643455A patent/CA2643455A1/en not_active Abandoned
- 2007-01-30 WO PCT/EP2007/050895 patent/WO2007096231A2/de not_active Ceased
- 2007-01-30 JP JP2008555730A patent/JP2009527445A/ja not_active Withdrawn
- 2007-01-30 KR KR1020087020694A patent/KR20080110996A/ko not_active Withdrawn
- 2007-01-30 RU RU2008137542/03A patent/RU2008137542A/ru not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| US20070193478A1 (en) | 2007-08-23 |
| DE102006008967A1 (de) | 2007-08-30 |
| BRPI0708240A2 (pt) | 2011-05-24 |
| RU2008137542A (ru) | 2010-03-27 |
| WO2007096231A2 (de) | 2007-08-30 |
| KR20080110996A (ko) | 2008-12-22 |
| JP2009527445A (ja) | 2009-07-30 |
| EP1986972A2 (de) | 2008-11-05 |
| CA2643455A1 (en) | 2007-08-30 |
| WO2007096231A3 (de) | 2008-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101028970B (zh) | 含有在建筑材料混合物中溶胀的微粒子的建筑材料混合物添加剂 | |
| CN101024558A (zh) | 含有不同尺寸的微粒子的建筑材料混合物添加剂 | |
| CN101024562A (zh) | 含有壳为多孔性和/或亲水性的微粒子的建筑材料混合物添加剂 | |
| CN101024557B (zh) | 含有喷雾干燥的微粒子的建筑材料混合物添加剂 | |
| CA2642800A1 (en) | Additive building material mixtures comprising non-ionic emulsifiers | |
| CA2642996A1 (en) | Additive building material mixtures comprising microparticles with extremely thin shells | |
| KR20080110996A (ko) | 비극성 쉘을 갖는 미립자를 포함하는 부가적인 건축 자재 혼합물 | |
| CA2642900A1 (en) | Additive building material mixtures comprising sterically or electrostatically repelling monomers in the shells of the microparticles | |
| CN101024564A (zh) | 含有离子型乳化剂的建筑材料混合物添加剂 | |
| US20070204543A1 (en) | Additive building material mixtures containing ionically swollen microparticles | |
| MX2008009251A (en) | Additive building material mixtures comprising microparticles with apolar shells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20090403 Address after: Darmstadt Applicant after: Win ROM limited liability company Co-applicant after: Res & Technology GmbH Const Address before: Darmstadt Applicant before: Evonik Roehm GmbH |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20070829 |