CN116731610B - Preparation method of flexible organosilicon building waterproofing agent - Google Patents
Preparation method of flexible organosilicon building waterproofing agent Download PDFInfo
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- CN116731610B CN116731610B CN202310642939.7A CN202310642939A CN116731610B CN 116731610 B CN116731610 B CN 116731610B CN 202310642939 A CN202310642939 A CN 202310642939A CN 116731610 B CN116731610 B CN 116731610B
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- 238000004078 waterproofing Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000013067 intermediate product Substances 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 23
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 22
- -1 alkoxy silane Chemical compound 0.000 claims abstract description 20
- 229910000077 silane Inorganic materials 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 229920002545 silicone oil Polymers 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical group CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 229920013822 aminosilicone Polymers 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 229920000053 polysorbate 80 Polymers 0.000 claims description 5
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 5
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 4
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000001593 sorbitan monooleate Substances 0.000 claims description 3
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 3
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 19
- 239000000047 product Substances 0.000 abstract description 10
- 239000000839 emulsion Substances 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000035699 permeability Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 230000004224 protection Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XYRAEZLPSATLHH-UHFFFAOYSA-N trisodium methoxy(trioxido)silane Chemical compound [Na+].[Na+].[Na+].CO[Si]([O-])([O-])[O-] XYRAEZLPSATLHH-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- FXSGDOZPBLGOIN-UHFFFAOYSA-N trihydroxy(methoxy)silane Chemical compound CO[Si](O)(O)O FXSGDOZPBLGOIN-UHFFFAOYSA-N 0.000 description 2
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- CAQWNKXTMBFBGI-UHFFFAOYSA-N C.[Na] Chemical group C.[Na] CAQWNKXTMBFBGI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003269 fluorescent indicator Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of preparation of building material waterproofing agents, in particular to a preparation method of a flexible organic silicon building waterproofing agent. The method comprises the steps of performing dealcoholization end-capping reaction on low-viscosity hydroxyl silicone oil by adopting T-type alkoxy silane to obtain an intermediate product A rich in alkoxy, hydrolyzing part of alkoxy of the intermediate product A in a toluene system by controlling reaction conditions to obtain an incompletely hydrolyzed DT resin solution with low polymerization degree, and removing toluene solvent by heating and reduced pressure distillation to obtain the solvent-free DT resin. Adding an emulsifying agent into DT resin, dropwise adding deionized water, and emulsifying to obtain the homogeneous and stable emulsion type building waterproofing agent. The product is environment-friendly, solvent-free and good in stability, has the characteristics of excellent durability, weather resistance, low surface energy and high interface wettability because the main body of the product is the organic silicon resin with low polymerization degree, and is suitable for concrete structures in severe environments.
Description
Technical Field
The invention relates to the technical field of preparation of building material waterproofing agents, in particular to a preparation method of an environment-friendly flexible organosilicon building waterproofing agent with good durability and permeability.
Background
The waterproof principle of the organosilicon building waterproofing agent is different from that of common waterproof materials such as organic paint, asphalt and the like. The organic paint and asphalt can achieve the waterproof effect by blocking the holes of the masonry and concrete structural materials; the organosilicon building waterproofing agent is prepared by chemical reaction with structural materials to form an extremely thin insoluble hydrophobic resin film on the surface of a substrate. Because the organic silicon molecules have the characteristics of hydrophobicity and air permeability, the waterproof agent has water repellency and can keep the normal air permeability of the building. The building treated by the organosilicon building waterproofing agent can keep clean and not stick dust, improve the heat insulation and sound insulation performances of the building, prevent the surface of the building from cracking, and ensure that the building is not easy to be weathered, thereby prolonging the service life of the building. The organosilicon building waterproofing agents can be classified into three types of aqueous solution type, solvent type and emulsion type.
The main component of the aqueous solution type organosilicon building waterproofing agent is methyl sodium silicate solution. When sodium methyl silicate encounters water and carbon dioxide in the air, the sodium methyl silicate is hydrolyzed to generate methyl silicic acid, and the methyl silicic acid is quickly polymerized on the surface of a substrate to form an extremely thin crosslinked polymethyl siloxane film with hydrophobicity. The oligomers remain water-soluble for a period of time and are therefore easily washed away by rain. In addition, sodium methyl silicate has limited use for limestone and marble containing iron salts, which can produce yellow rust spots.
Solvent-based silicone building waterproofing agents currently exist in two types. The first is a polymethyltriethoxysilane resin solvent type building waterproofing agent; the other is an acrylic ester modified organosilicon building waterproofing agent. The polymethyl triethoxysilane resin is a hydrolytic condensation product of methyl triethoxysilane, is neutral, and needs to be added with alcohols as solvents when in use, and is commonly called No. 3 waterproofing agent in the market. The organic silicon resin network formed by hydrolysis and solidification is of a three-functional Y-shaped structure, cross-linking points are too dense, the film is hard and brittle, and the risk of damage of a waterproof layer is caused by cold and hot alternation or vibration. In addition, because of the existence of a large amount of alcohol solvents, the operation safety risk is increased and the environmental protection pressure is also faced. The acrylic ester modified organosilicon building waterproof agent is a macromolecule with acrylic ester as a main chain and a side chain with siloxy or silicon hydroxyl. Because the molecular main chain is C-C, hydrophobicity and weather resistance inevitably decrease as compared with the Si-O chain of the organosilicon.
Emulsion type building waterproofing agents are also of two types, one is pure silicone resin and the other is acrylic modified silicone resin. The waterproofing agent is prepared by adding silicon resin or acrylic modified silicon resin into an emulsifying agent for external emulsification. Since no or a small amount of organic solvent is used, the solvent is environmentally friendly than the solvent, and thus, extensive researches have been conducted.
The patent application CN103923561A discloses an organosilicon concrete protective agent and a manufacturing method, namely a typical emulsion type building waterproofing agent, which comprises the following main components: alkyl alkoxy silane, hydroxyl-terminated polydimethylsiloxane, an emulsifying agent, an organic solvent and water. The method adopts alkyl alkoxy silane and hydroxyl-terminated polydimethylsiloxane to blend, and the silicon alkoxy can be hydrolyzed and condensed by itself or can be condensed and crosslinked with silicon hydroxyl. A large amount of white oil and solvent oil are adopted as oil phase dispersion media in the formula, so that the drying speed is increased, but environmental protection pressure and construction safety risks are brought. The obtained finished product is a paste without fluidity, can not be sprayed and has poor permeability to concrete microscopic voids.
In addition, as disclosed in Chinese patent No. 113402912B, the silane waterproof material for concrete protection and the preparation method thereof are disclosed, and the waterproof material is prepared by taking the alkane silane, the silane modified fatty alcohol and the amino silane coupling agent as main materials. The concrete itself is used for alkaline catalysis, the trifunctional silane is hydrolyzed, crosslinked and solidified. But the film forming agent silane in the formula is modified by fatty alcohol, and is obtained by grafting polyester glycol or polyether glycol with silane. Wherein the C-O-C bond energy of the polyether glycol is lower, and the ultraviolet resistance and the weather resistance are poorer; polyester diol is not acid-base resistant because of existence of molecular chain ester bonds, and is easy to pulverize after long-time outdoor use. In order to improve the storage stability of the product, some examples also add D40 solvent oil, increasing carbon emissions.
Therefore, it is necessary to provide a novel silane waterproof material which is environment-friendly, solvent-free, high and low temperature resistant, ultraviolet resistant, weather resistant and excellent in permeability, so as to solve the problems.
Disclosure of Invention
The invention aims to overcome the technical problems, and provides a preparation method of a flexible organic silicon building waterproofing agent, which can completely solve the technical problems.
The technical scheme for solving the technical problems is as follows:
The flexible organosilicon building waterproofing agent comprises the following specific preparation steps:
s1: placing T-type alkoxy silane in a reaction container, wherein the T-type alkoxy silane is one or more of methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane or propyltriethoxysilane; adding 0.1-1.0 g of organic acid as a catalyst, stirring uniformly, raising the temperature to 75-85 ℃, dripping hydroxyl silicone oil with the viscosity of 25-120 mPa.s and the hydroxyl content of 2-9%, dripping for 50-70 min, raising the temperature to 100-105 ℃, preserving heat for reaction, continuously removing generated alcohol in the reaction process, and lowering the temperature to normal temperature until no low boiling point is generated, thus obtaining a pre-end-capped intermediate product A; wherein, the hydroxyl mole ratio of the T-type alkoxy silane to the hydroxyl silicone oil is 3:1, a step of;
the reaction equation is as follows:
S2: diluting the pre-end-capped intermediate product A obtained in the step S1 with toluene 3-30 times of mass, and then dropwise adding deionized water into the system, wherein the molar ratio of the adding amount of the deionized water to the T-type alkoxy silane in the step S1 is 1:2; dripping for 50-70 min, heating to 50-55 ℃, reacting for 1.5-2.5 h at a temperature, partially hydrolyzing alkoxy of an intermediate product A to obtain an intermediate product shown as B, heating to 100-105 ℃, and removing solvent in the system and alcohol generated by thermal condensation reaction under negative pressure to obtain DT resin;
the reaction equation is as follows:
S3: putting the DT resin obtained in the step S2 into an emulsifying machine, and controlling the temperature at 30-40 ℃; adding an emulsifier into the system, wherein the emulsifier is one or more of nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, sorbitan monooleate, polyoxyethylene sorbitan monooleate and isomeric tridecanol ethoxylate, the adding amount of the emulsifier is 3-5% of the mass of DT resin, and stirring for 10-15 min at 30-40 ℃; adding deionized water with the mass 1-2 times of that of DT resin into the system; stirring at 30-40 deg.c for 30-45 min; and adding a pH regulator into the system, stirring for 10-15 min at 30-40 ℃, and regulating the pH to 7.0-8.2 to obtain the premix. Wherein the pH regulator is N, N-dimethylbenzylamine or amino silicone oil with the weight of 0.1-1.0% of solid; injecting the premix into a high-pressure homogenizing emulsifying machine, homogenizing and emulsifying for 2-3 times under the condition of 50-55 MPa, and obtaining the flexible organosilicon building waterproofing agent. The waterproof agent is fine white emulsion, the solid content is about 50%, the viscosity is 5 mN.s, and the surface tension is less than 25mN.m -1.
The beneficial effects of the invention are as follows:
All the organic solvents used in the technical process can be recycled, the organic solvents are not required to be added in the finished product, and only in the curing process after coating construction, the condensation reaction releases a trace amount of methanol or ethanol, thus the waterproof product belongs to a low-VOC waterproof product.
The general waterproof agent can isolate micropores and capillaries (air holes) on the surface of a building and isolate external water and air, thereby playing a role in waterproof. Meanwhile, the waterproof agent also blocks the water in the building material from dispersing, which is the 'waterproof' property of a common waterproof agent, and the surface coating of the building is easy to foam, crack and peel. The polysiloxane molecule of the DT silicone resin has a spiral structure and large free space, so the waterproof agent has good gas permeability. Raindrop diameters are typically 100 μm to 3000 μm, while the size of the water vapor molecules is 0.0004 μm. The water drops cannot penetrate the waterproof layer, but the gaseous water molecules can penetrate. Therefore, the waterproof material has the function of ventilation while preventing liquid water, and is breathable waterproof material.
The invention adopts the technological process of pre-end capping, hydrolysis and emulsification, and the molecular structure of the DT silicone resin of the content is relatively determined. The direct mixing emulsification process of the alkoxy silane and the hydroxyl silicone oil is not adopted, because the process is easy to generate random hydrolysis reaction. Random hydrolysis is easy to cause paste formation in the storage or use process and even cannot be constructed due to the difference of hydrolysis speeds of different silane monomers.
The film forming agent of the waterproof agent is a soft-hard block DT silicone resin structure. The main chain part of the molecule is a soft segment D chain link of polydimethylsiloxane, which can endow the waterproof agent molecular network with certain flexibility and avoid the situation of cracking the waterproof layer caused by overlarge rigidity when the concrete collides, vibrates or expands with heat and contracts with cold.
The film forming agent of the waterproof agent of the invention, the T-shaped structural part of the resin network is equivalent to a hard segment and has the function of internal reinforcement. And finally, local crosslinking points are formed by curing, so that the physical strength of the waterproof agent network is improved.
In addition, the invention adopts N, N-dimethylbenzylamine or amino silicone oil as a pH regulator and a curing catalyst. In the emulsification formula process, the acetic acid is neutralized, and the acid and the alkali are balanced. Meanwhile, in the application process, after the coating construction, a trace amount of acetic acid is naturally volatilized at room temperature. The alkoxy group remained on DT resin can be cured at normal temperature under the catalysis of N, N-dimethylbenzylamine or amino silicone oil. The formulation is self-catalyzed and thus does not require alkaline curing by the concrete itself. The construction time is flexible and adjustable, and the coating can be used for secondary coating and supplementary coating. Catalyzing the hydroxyl condensation with the surface of the substrate, improving the binding force of the product and the concrete, and forming the flexible waterproof coating.
The waterproof agent emulsion has low bulk viscosity, and can be diluted by adding water at 25 ℃ for only 5 Pa.s, so that the viscosity can be further reduced. Because the waterproof agent film forming agent is an organosilicon polymer with low surface energy, and is matched with a small amount of surfactant, the surface tension of the emulsion is lower than 25mN.m -1. So the waterproof agent has good permeability to concrete. And the secondary brushing process is carried out, and the penetration depth of the paint to the concrete can reach 40mm through detection of a fluorescent indicator.
Therefore, the waterproof agent prepared by the invention is environment-friendly, solvent-free and good in stability, has the characteristics of excellent durability, weather resistance, low surface energy and high interface wettability because the main body of the waterproof agent is the organic silicon resin with low polymerization degree, and is suitable for concrete structures in severe environments. Meanwhile, the product is provided with a catalyst, and concrete alkaline curing is not needed, so that the product has potential value for other waterproof applications, such as waterproof of fabrics and paper.
The present invention will be described in further detail with reference to the following embodiments.
Detailed Description
Example 1:
S1: 136g of methyltrimethoxysilane (1 mol) and 0.1g of formic acid are placed in a reaction flask, after being stirred uniformly, the temperature is raised to 80 ℃, 70.8g of hydroxyl silicone oil with the viscosity of 25 mPas and the hydroxyl content of 9% is dropwise added for 60min, then the temperature is raised to 100 ℃, the reaction is carried out under the condition of heat preservation, the generated alcohol is continuously removed in the reaction process until no low boiling point is generated, and then the reaction is cooled to normal temperature, thus obtaining an intermediate product A;
S2: diluting the intermediate product A with 900g of toluene, then dropwise adding 9g of deionized water into the system for 60min, heating to 50 ℃, preserving heat for 2h, partially hydrolyzing alkoxy of the intermediate product A, heating to 100 ℃, and removing solvent and alcohol generated by the reaction in the system under negative pressure to obtain DT resin;
S3: 200g of DT resin is put into an emulsifying machine, and the temperature is controlled at 35 ℃; adding 3g of polyoxyethylene sorbitan monooleate and 7g of isomeric tridecanol ethoxylate into the system, and stirring for 10min at 35 ℃; adding 200g of deionized water into the system; stirring at 35deg.C for 30min; adding N, N-dimethylbenzylamine as pH regulator into the system, stirring at 35 deg.C for 10-15 min, and regulating pH to 7.0-8.2 to obtain the invented premixed material. Injecting the premix into a high-pressure homogenizing emulsifying machine, homogenizing and emulsifying for 2 times under the condition of 50MPa to obtain the flexible organosilicon building waterproofing agent.
Example 2:
S1: 89g of methyltriethoxysilane (0.5 mol), 82g of propyltrimethoxysilane (0.5 mol) and 0.15g of glacial acetic acid are placed in a reaction flask, after being stirred uniformly, the temperature is raised to 75 ℃, 283.2g of hydroxyl silicone oil with the viscosity of 120 mPa.s and the hydroxyl content of 2% is dropwise added for 50min, then the temperature is raised to 105 ℃, the reaction is kept at the temperature, the generated alcohol is continuously removed in the reaction process until no low boiling point is generated, and the reaction is cooled to the normal temperature, so that an intermediate product A is obtained;
S2: diluting the intermediate product A with 1700g of toluene, then dropwise adding 9g of deionized water into the system for 50min, heating to 55 ℃, preserving heat for reaction for 1.5h, partially hydrolyzing alkoxy of the intermediate product A, heating to 105 ℃, and removing solvent and alcohol generated by the reaction in the system under negative pressure to obtain DT resin;
S3: putting 300g of DT resin into an emulsifying machine, and controlling the temperature at 30 ℃; adding 7.5g of fatty alcohol polyoxyethylene ether and 7.5g of isomeric tridecanol ethoxylate into the system, and stirring for 15min at 30 ℃; adding 300g of deionized water into the system; stirring at 30deg.C for 45min; adding water-soluble amino silicone oil with an amine value of 0.2 as a pH regulator into the system, stirring for 10-15 min at 30 ℃, and regulating the pH to 7.0-8.2 to obtain the premix. Injecting the premix into a high-pressure homogenizing emulsifying machine, homogenizing and emulsifying for 3 times under the condition of 50MPa to obtain the flexible organosilicon building waterproofing agent.
Example 3:
S1: 103.18g of propyltriethoxysilane (0.5 mol), 82g of propyltrimethoxysilane (0.5 mol) and 0.12g of glacial acetic acid are placed in a reaction flask, after being stirred uniformly, the temperature is raised to 85 ℃, 113.3g of hydroxyl silicone oil with the viscosity of 50 mPa.s and the hydroxyl content of 5% is dropwise added for 70min, then the temperature is raised to 102 ℃, the reaction is kept at the temperature, the generated alcohol is continuously removed in the reaction process until no low boiling point is generated, and the temperature is reduced to normal temperature, so that an intermediate product A is obtained;
S2: diluting the intermediate product A with 4000g of toluene, then dropwise adding 9g of deionized water into the system for 70min, heating to 52 ℃, preserving heat for 2.5h, partially hydrolyzing alkoxy of the intermediate product A, heating to 102 ℃, and removing solvent and alcohol generated by the reaction in the system under negative pressure to obtain DT resin;
S3: 200g of DT resin is put into an emulsifying machine, and the temperature is controlled at 40 ℃; then adding 5g of sorbitan monooleate and 3g of polyoxyethylene nonylphenol ether into the system, and stirring for 12min at 40 ℃; adding 250g of deionized water into the system; stirring at 40deg.C for 35min; adding N, N-dimethylbenzylamine as pH regulator into the system, stirring at 40 deg.C for 10-15 min, and regulating pH to 7.0-8.2 to obtain the invented premixed material. Injecting the premix into a high-pressure homogenizing emulsifying machine, homogenizing and emulsifying for 3 times under the condition of 50MPa to obtain the flexible organosilicon building waterproofing agent.
Example 4:
s1: 164g of propyltrimethoxysilane (1 mol) and 1.0g of glacial acetic acid are placed in a reaction flask, after being stirred uniformly, the temperature is raised to 80 ℃, 141.6g of hydroxyl silicone oil with the viscosity of 60 mPas and the hydroxyl content of 3% are added dropwise for 60min, then the temperature is raised to 100 ℃, the reaction is carried out under the condition of heat preservation, the generated alcohol is continuously removed in the reaction process until no low boiling point is generated, and then the reaction is cooled to the normal temperature, so that an intermediate product A is obtained;
S2: diluting the intermediate product A with 1000g of toluene, then dropwise adding 9g of deionized water into the system for 65min, heating to 53 ℃, preserving heat for reaction for 2h, partially hydrolyzing alkoxy of the intermediate product A, heating to 100 ℃, and removing solvent and alcohol generated by reaction in the system under negative pressure to obtain DT resin;
S3: 200g of DT resin is put into an emulsifying machine, and the temperature is controlled at 35 ℃; then adding 6g of polyoxyethylene sorbitan monooleate into the system, and stirring for 10min at 35 ℃; adding 400g of deionized water into the system; stirring at 35deg.C for 30min; adding water-soluble amino silicone oil with an amine value of 0.2 as a pH regulator into the system, stirring for 10-15 min at 35 ℃, and regulating the pH to 7.0-8.2 to obtain the premix. Injecting the premix into a high-pressure homogenizing emulsifying machine, homogenizing and emulsifying for 3 times under the condition of 55MPa to obtain the flexible organosilicon building waterproofing agent.
Example 5:
S1: 178g of methyltriethoxysilane (1 mol) and 0.83g of glacial acetic acid are placed in a reaction flask, after being stirred uniformly, the temperature is raised to 80 ℃, 94.4g of hydroxyl silicone oil with the viscosity of 70 mPas and the hydroxyl content of 6% is dropwise added for 60min, then the temperature is raised to 100 ℃, the reaction is carried out under the condition of heat preservation, the generated alcohol is continuously removed in the reaction process until no low boiling point is generated, and then the reaction is cooled to normal temperature, so as to obtain an intermediate product A;
S2: diluting the intermediate product A with 2000g of toluene, then dropwise adding 9g of deionized water into the system for 55min, heating to 55 ℃, preserving heat for reaction for 1.5h, partially hydrolyzing alkoxy of the intermediate product A, heating to 105 ℃, and removing solvent and alcohol generated by the reaction in the system under negative pressure to obtain DT resin;
S3: 200g of DT resin is put into an emulsifying machine, and the temperature is controlled at 35 ℃; adding 4g of polyoxyethylene sorbitan monooleate, 4g of fatty alcohol polyoxyethylene ether and 2g of nonylphenol polyoxyethylene ether into the system, and stirring for 10min at 35 ℃; adding 250g of deionized water into the system; stirring at 35deg.C for 30min; adding N, N-dimethylbenzylamine as pH regulator into the system, stirring at 35 deg.C for 10-15 min, and regulating pH to 7.0-8.2 to obtain the invented premixed material. Injecting the premix into a high-pressure homogenizing emulsifying machine, homogenizing and emulsifying for 3 times under the condition of 52MPa to obtain the flexible organosilicon building waterproofing agent.
And (3) detection:
the flexible silicone building waterproofing agents obtained in examples 1 to 5 were respectively coated on the concrete prefabricated member,
① Water absorption test was performed according to the DL/T5126-2021 standard;
② Performing contact angle test;
③ After aging in a salt fog box for 336 hours, the contact angle test is carried out;
a commercial brand of common building waterproofing agent is taken as a comparative example 1, a blank is taken as a comparative example 2, and the test results are shown in the following table 1:
TABLE 1
As can be seen from the above Table 1, the water absorption average value of the flexible organosilicon building waterproofing agent obtained by the invention is far smaller than that of the data of comparative examples 1 and 2, and the waterproofing agent of examples 1 to 5 is coated on the concrete prefabricated member for the second time, so that the waterproof performance of the concrete prefabricated member can be obviously improved. The average water absorption data of example 2 is slightly higher than those of examples 1, 3, 4 and 5 because the viscosity of the hydroxyl silicone oil used in the formulation is slightly higher, and the bulk viscosity of the emulsion is high, resulting in slightly smaller penetration thickness.
As can be seen from the contact angle average value data, the water drops in examples 1 to 5 have large contact angles, the hydrophobicity of the waterproofing agent is obviously better than that of the waterproofing agents in comparative examples 1 and 2, and the waterproofing effect of the waterproofing agent prepared by the invention is further excellent. The concrete surface treated by the waterproof agent is just like a layer of hydrophobic coat. The rainwater is dropped on the water-cooling device, the waterproof effect like lotus leaves is shown.
Comparing the average contact angle data with the average contact angle data after 336 hours in the salt fog box, the waterproofing agents of examples 1-5 have obviously better attenuation of hydrophobic effect than comparative example 1, further illustrating that the waterproofing agent prepared by the invention has excellent durability and weather resistance. And after the salt fog ageing, the water drop contact angle retention values of the examples 2,3 and 4 are large, and the attenuation of the hydrophobic effect is better than that of the examples 1 and 5. Because propyl trimethoxy silane or propyl triethoxy silane is partially or totally adopted in the formula, the steric hindrance of the propyl is larger than that of the methyl. The obtained coating has high flexibility and adhesive force and is not easy to fall off from the surface of concrete.
Therefore, the waterproof agent prepared by the invention is environment-friendly, solvent-free and good in stability, has the characteristics of excellent durability, weather resistance, low surface energy and high interface wettability because the main body of the waterproof agent is the organic silicon resin with low polymerization degree, and is suitable for concrete structures in severe environments.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, but any simple modification or equivalent variation of the above embodiment according to the technology of the present invention falls within the scope of the present invention.
Claims (8)
1. The preparation method of the flexible organic silicon building waterproofing agent is characterized by comprising the following steps of:
S1: placing T-type alkoxy silane in a reaction vessel, adding organic acid as a catalyst, stirring uniformly, raising the temperature to 75-85 ℃, dropwise adding hydroxyl silicone oil for 50-70 min, then raising the temperature to 100-105 ℃, preserving heat for reaction, continuously removing generated alcohol in the reaction process, and cooling to normal temperature until no low boiling point is generated, thus obtaining an intermediate product A;
the T-type alkoxy silane is one or more of methyltrimethoxy silane, methyltriethoxy silane, propyltrimethoxy silane and propyltriethoxy silane;
the viscosity of the hydroxyl silicone oil is 25-120 mPa.s, and the hydroxyl content is 2-9%;
the molar ratio of the hydroxyl groups of the T-type alkoxy silane to the hydroxyl silicone oil is 3:1, a step of;
s2: diluting the intermediate product A obtained in the step S1 by toluene, then dropwise adding deionized water into the system for 50-70 min, heating to 50-55 ℃, carrying out heat preservation reaction for 1.5-2.5 h, partially hydrolyzing the alkoxy of the intermediate product A to obtain an intermediate product shown in B, heating to 100-105 ℃, and removing the solvent in the system and alcohol generated by the reaction under negative pressure to obtain DT resin;
S3: putting the DT resin obtained in the step S2 into an emulsifying machine, and controlling the temperature at 30-40 ℃; adding an emulsifying agent into the system, and stirring for 10-15 min at 30-40 ℃; adding deionized water into the system, and stirring for 30-45 min at 30-40 ℃; adding a pH regulator into the system, stirring for 10-15 min at 30-40 ℃, and regulating the pH to 7.0-8.2 to obtain a premix, wherein the pH regulator is N, N-dimethylbenzylamine or amino silicone oil; injecting the premix into a high-pressure homogenizing emulsifying machine, homogenizing and emulsifying for 2-3 times under the condition of 50-55 MPa to obtain the flexible organosilicon building waterproofing agent;
Wherein the reaction equations of the S1 and S2 steps are as follows:
2. The method for preparing a flexible silicone building waterproofing agent according to claim 1, wherein the organic acid in step S1 is volatilizable formic acid or acetic acid.
3. The method for preparing a flexible silicone building waterproofing agent according to claim 1, wherein the organic acid is added in an amount of 0.1 to 1.0g in step S1.
4. The method for preparing a flexible organosilicon building waterproofing agent according to claim 1, wherein the addition amount of toluene in the step S2 is 3 to 30 times the mass of the intermediate product a.
5. The method for preparing a flexible organosilicon building waterproofing agent according to claim 1, wherein the molar ratio of deionized water in step S2 to T-type alkoxysilane in step S1 is 1:2.
6. The method for preparing the flexible organosilicon building waterproofing agent according to claim 1, wherein the emulsifier in the step S3 is one or more of nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, sorbitan monooleate, polyoxyethylene sorbitan monooleate and isomeric tridecanol ethoxylate.
7. The method for preparing a flexible organosilicon building waterproofing agent according to claim 1, wherein the addition amount of the emulsifier in the step S3 is 3-5% of the mass of the DT resin.
8. The method for preparing a flexible organosilicon building waterproofing agent according to claim 1, wherein the deionized water addition amount in the step S3 is 1-2 times of the mass of the DT resin.
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