CN1083806C - 一种β-萘磺酸甲醛缩合物季铵盐型混凝土外加剂 - Google Patents
一种β-萘磺酸甲醛缩合物季铵盐型混凝土外加剂 Download PDFInfo
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- CN1083806C CN1083806C CN99116049A CN99116049A CN1083806C CN 1083806 C CN1083806 C CN 1083806C CN 99116049 A CN99116049 A CN 99116049A CN 99116049 A CN99116049 A CN 99116049A CN 1083806 C CN1083806 C CN 1083806C
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- RRDQTXGFURAKDI-UHFFFAOYSA-N formaldehyde;naphthalene-2-sulfonic acid Chemical compound O=C.C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 RRDQTXGFURAKDI-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000654 additive Substances 0.000 title claims abstract description 12
- 230000000996 additive effect Effects 0.000 title claims abstract description 12
- 238000009833 condensation Methods 0.000 title claims description 17
- 230000005494 condensation Effects 0.000 title claims description 17
- -1 compound quaternary ammonium salt Chemical class 0.000 title claims description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 58
- 239000007859 condensation product Substances 0.000 abstract description 12
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 abstract description 10
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000003014 reinforcing effect Effects 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- 230000006835 compression Effects 0.000 description 15
- 238000007906 compression Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
- C04B24/226—Sulfonated naphtalene-formaldehyde condensation products
-
- 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
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
本发明涉及一种萘磺酸甲醛缩合物季铵盐型水泥混凝土聚合物添加剂。在水泥混凝土中掺入少量外加剂便可显著改善水泥混凝土的力学性能、工作性能和耐久性能,从而满足不同工程对水泥混凝土的特殊要求。为此,研制性能优异的水泥混凝土外加剂一直是国内外研究的热点。本发明采用离子交换手段制备了六种不同季铵阳离子对应的β-萘磺酸甲醛缩合物盐,它们作为水泥混凝土添加剂,具有显著的分散能力和减水增强早强功能。
Description
本发明涉及一种β-萘磺酸甲醛缩合物季铵盐型混凝土外加剂。
聚合物添加剂在水泥混凝土材料中占有重要地位,只要掺入少量这类添加剂就可显著提高混凝土材料的力学强度、工作性能和耐久性能。因而可以实现机械化施工,满足不同工程对水泥混凝土的特殊要求。国内外常见的水泥混凝土聚合物添加剂主要有如下几类:(1)木质素磺酸盐及其衍生物;(2)萘磺酸甲醛缩合物;(3)多环芳烃磺酸盐甲醛缩合物;(4)聚氧乙烯醚及其衍生物;(5)三聚氰胺磺酸盐甲醛缩合物;(6)丙烯酸及其衍生物的均聚物或共聚物;(7)马来酸盐及其衍生物的均聚物或共聚物。随着国内外经济的发展,现代建筑业对水泥混凝土材料的要求越来越高,因此研制新型高性能水泥混凝土添加剂一直是世界各国在本研究领域的热门课题。
聚合度n=5~13M=CH3N+(C2H5)3,CH3N+(CH2CH2OH)3,CH3N+(n-C4H9)3,
C6H5CH2N+(CH2CH3)3,(CH3)3N+CH2CH2N+(CH3)3,CH3(CH2)15N+(CH3)3,
化学结构式中的M有六种不同型式,因型式不同而有不同的分子量:M为CH3N+(C2H5)3时,分子量为1663~4343;M为CH3N+(CH2CH2OH)3时,分子量为1903~4967;M为CH3N+(n-C4H9)3时,分子量为2083~5435;M为C6H5CH2N+(CH2CH3)3时,分子量为2043~5331;M为(CH3)3N+CH2CH2N+(CH3)3时,分子量为1451~3795;M为CH3(CH2)15N+(CH3)3时,分子量为2503~6537。M的不同型式就形成了六种不同化学结构的β-萘磺酸甲醛缩合物季铵盐混凝土外加剂,它们是以萘磺酸甲醛缩合物钠盐为原料,通过离子交换方法制备的,本发明所提供的混凝土外加剂使用效果见表1:
表1 六种β-萘磺酸甲醛缩合物季铵盐对水泥的性能影响
样品号 | 掺量(%) | 水泥净浆流动度(mm) | 水泥净浆抗压强度(MPa) | ||||
水灰比 | 流动度 | 水灰比 | 3d | 7d | 28d | ||
空白 | 0 | 0.35 | 163 | 0.4 | 16.7 | 31.1 | 45.3 |
A | 0.25 | 0.35 | 206 | 0.32 | 44.4 | 53.6 | 75.5 |
0.75 | 0.35 | 227 | 0.29 | 50.3 | 55.8 | 87.4 | |
B | 0.25 | 0.35 | 194 | 0.32 | 47.8 | 58.4 | 83.3 |
0.75 | 0.35 | 190 | 0.29 | 43.0 | 62.1 | 85.3 | |
C | 0.25 | 0.35 | 220 | 0.32 | 53.8 | 61.3 | 76.9 |
0.75 | 0.35 | 265 | 0.29 | 52.9 | 70.9 | 80.8 | |
D | 0.25 | 0.35 | 188 | 0.32 | 42.1 | 51.4 | 74.8 |
0.75 | 0.35 | 190 | 0.29 | 37.6 | 49.5 | 75.2 | |
E | 0.25 | 0.35 | 206 | 0.32 | 56.7 | 66.6 | 80.0 |
0.75 | 0.35 | 275 | 0.29 | 62.9 | 72.1 | 93.1 | |
F | 0.25 | 0.35 | 223 | 0.32 | 52.2 | 57.5 | 76.6 |
0.75 | 0.35 | 290 | 0.29 | 60.1 | 71.4 | 90.0 |
注1:上表中掺量为添加剂占水泥重量的百分比
注2:A:β-萘磺酸甲醛缩合物CH3N+(C2H5)3盐
B:β-萘磺酸甲醛缩合物CH3N+(n-C4H9)3盐
C:β-萘磺酸甲醛缩合物CH3N+(CH2CH2OH)3盐
D:β-萘磺酸甲醛缩合物C6H5CH2N+(CH2CH3)3盐
E:β-萘磺酸甲醛缩合物(CH3)3N+CH2CH2N+(CH3)3盐
F:β-萘磺酸甲醛缩合物CH3(CH2)15N+(CH3)3盐
水泥净浆流动度按照JGJ56-84中所示的方法测定;水泥净浆固结体抗压强度按照GB119-88所示方法测定。
从表中数据可以看出,本发明提供的六种不同化学结构的季铵阳离子型β-萘磺酸甲醛缩合物作为水泥添加剂能明显提高水泥净浆的流动性能和抗压强度,另外还具有早强功能。
实施例1.
掺入占水泥量0.25%的萘磺酸甲醛缩合物CH3N+(C2H5)3盐,水灰比为0.35的水泥净浆流动度达206mm,水灰比为0.32的水泥净浆28d抗压强度达75.5MPa,与空白水泥净浆28d抗压强度45.3MPa相比,提高了66.7%。
实施例2.
掺入占水泥量0.25%的萘磺酸甲醛缩合物CH3N+(n-C4H9)3盐,水灰比为0.35的水泥净浆流动度达194mm,水灰比为0.32的水泥净浆28d抗压强度达83.3MPa,与空白水泥净浆28d抗压强度45.3MPa相比,提高了83.9%。
实施例3.
掺入占水泥量0.25%的萘磺酸甲醛缩合物CH3N+(CH2CH2OH)3盐,水灰比为0.35的水泥净浆流动度达220mm,水灰比为0.32的水泥净浆28d抗压强度达76.9MPa,与空白水泥净浆28d抗压强度45.3MPa相比,提高了69.8%。
实施例4.
掺入占水泥量0.25%的萘磺酸甲醛缩合物C6H5CH2N+(CH2CH3)3盐,水灰比为0.35的水泥净浆流动度达188mm,水灰比为0.32的水泥净浆28d抗压强度达74.8Mpa,与空白水泥净浆28d抗压强度45.3MPa相比,提高了65.1%。
实施例5.
掺入占水泥量0.25%的萘磺酸甲醛缩合物(CH3)3N+CH2CH2N+(CH3)3盐,水灰比为0.35的水泥净浆流动度达206mm,水灰比为0.32的水泥净浆28d抗压强度达80.0MPa,与空白水泥净浆28d抗压强度45.3MPa相比,提高了76.6%。
实施例6.
掺入占水泥量0.25%的萘磺酸甲醛缩合物CH3(CH2)15N+(CH3)3盐,水灰比为0.35的水泥净浆流动度达223mm,水灰比为0.32的水泥净浆28d抗压强度达76.6MPa,与空白水泥净浆28d抗压强度45.3MPa相比,提高了69.1%。
Claims (2)
1.一种β-萘磺酸甲醛缩合物季铵盐型混凝土外加剂,以β-萘磺酸甲醛缩合物钠盐为原料,通过离子交换方法制备,其特征在于它们的组成包括如下的阳离子:CH3N+(C2H5)3,CH3N+(CH2CH2OH)3,CH3N+(n-C4H9)3,C6H5CH2N(CH2CH3)3,(CH3)3N+CH2CH2N+(CH3)3,CH3(CH2)15N+(CH3)3,其化学结构式为:
聚合度n=5~13式中M分别为CH3N+(CH2CH2OH)3,C6H5CH2N+(CH2CH3)3,(CH3)3N+CH2CH2N+(CH3)3,CH3(CH2)15N+(CH3)3,CH3N+(C2H5)3。CH3N+(n-C4H9)3,
2.根据权利要求书1中所述的外加剂,其特征在于结构式中M有六种型式,因型式不同而有不同的分子量:
M为CH3N+(C2H5)3时,分子量为1663~4343
M为CH3N+(CH2CH2OH)3时,分子量为1903~4967
M为CH3N+(n-C4H9)3时,分子量为2083~5435;
M为C6H5CH2N+(CH2CH3)3时,分子量为2043~5331;
M为(CH3)3N+CH2CH2N+(CH3)3时,分子量为1451~2795;
M为CH3(CH2)15N+(CH3)3时,分子量为2503~6527。
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CN99116049A CN1083806C (zh) | 1999-02-04 | 1999-02-04 | 一种β-萘磺酸甲醛缩合物季铵盐型混凝土外加剂 |
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CN1093098C (zh) * | 2000-03-22 | 2002-10-23 | 中国科学院广州化学研究所 | 用三聚氰胺磺酸盐甲醛缩合物对水泥混凝土改性的方法 |
CN103787600B (zh) * | 2013-12-24 | 2015-10-14 | 辽宁工程技术大学 | 一种地基注入用水泥组合物 |
CN105645822B (zh) * | 2015-12-29 | 2017-11-03 | 吉林省融川特种材料设备有限公司 | 钢筋混凝土高效复合抗腐蚀防水剂 |
CN108641076B (zh) * | 2018-06-15 | 2020-06-12 | 广西建津科技有限公司 | 一种高分子水泥混凝土添加剂及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US4373956A (en) * | 1981-09-14 | 1983-02-15 | Martin Marietta Corporation | Additive for hydraulic cement mixes |
CN1030574A (zh) * | 1987-06-25 | 1989-01-25 | 清华大学 | 烷芳磺酸萘磺酸醛缩合物高效减水剂 |
CN1107817A (zh) * | 1994-12-14 | 1995-09-06 | 华南理工大学 | 三合剂配制高抗渗、抗蚀混凝土的方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4373956A (en) * | 1981-09-14 | 1983-02-15 | Martin Marietta Corporation | Additive for hydraulic cement mixes |
CN1030574A (zh) * | 1987-06-25 | 1989-01-25 | 清华大学 | 烷芳磺酸萘磺酸醛缩合物高效减水剂 |
CN1107817A (zh) * | 1994-12-14 | 1995-09-06 | 华南理工大学 | 三合剂配制高抗渗、抗蚀混凝土的方法 |
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