CN105273230A - Diamino silane waterproof bridging agent for asphalt and cement, and waterproof product and application thereof - Google Patents

Diamino silane waterproof bridging agent for asphalt and cement, and waterproof product and application thereof Download PDF

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Publication number
CN105273230A
CN105273230A CN201410330040.2A CN201410330040A CN105273230A CN 105273230 A CN105273230 A CN 105273230A CN 201410330040 A CN201410330040 A CN 201410330040A CN 105273230 A CN105273230 A CN 105273230A
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waterproof
bridging agent
agent
cement
water
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卢桂才
朱方伍
郭文雄
周为为
赵晓岚
陆善庆
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Abstract

The invention discloses a diamino silane waterproof bridging agent for asphalt and cement. The waterproof bridging agent is N-(beta-aminoethyl)-gamma-aminopropylmethyldimethoxysilane, amino groups at one end of the structural formula of the bridging agent can be connected with carboxy groups in asphalt to form good chemical affinity, the other end of the bridging agent and hydrated calcium silicate or calcium aluminate generated in the cement hydration process are combined to form chemical bonds, the bridging agent and concrete undergo a chemical cross-linking reaction to tightly combine asphalt and cement into one body, related positions have chemical bonds like an erected bridge and have an irreversible bonding effect after curing, and the waterproof bridging agent can be used to prepare waterproof coils, or waterproof coatings, or waterproof ointments or waterproof leak stopping agents, and can infiltrate into cement gel and concrete capillary pores in a peristaltic manner in the cement solidification process in order to realize a tight, firm and irreversible bonding effect.

Description

Two amino silane tar cement waterproof bridging agent and waterproof product thereof and application
Technical field
The present invention relates to a kind of additive of architectural waterproof material, particularly can carry out chemical crosslink reaction with pitch and cement simultaneously, form the chemical bond of good chemical affinity, make it to solidify after play the bridging agent of irreversible cohesive action and waterproof product thereof and application.
Background technology
Common architectural waterproof material is cement and pitch mainly, and pitch is mainly used in the gap plugging on concrete seam or wall limit, or be layered on the leakproof of roof bonding splits, also can make waterproof roll, be laid on the occasion needing antiseepage rainproof.But current pitch is difficult to carry out good leak stopping leakproof, its reason is pitch is very unabiding with the bonding of the cement (concrete) that have cured, mainly pitch is the residue after oil extracts gasoline, kerosene etc., and great majority belong to low-molecular-weight alkanes (chemical formula C nh (2n+2), n is atomicity) and alkanes is water insoluble, but strong with inorganics stiction force, particularly the pitch crossed of non-modified, easily melting during high temperature, embrittlement during low temperature, experiencing the buildings top layer or surface of exposing to the weather, being very easy to aging coming off.Even if carried out modification to pitch, also cannot ensure and concrete adhesion effect.
How to make the surface of waterproof roll can play good adhesive effect, Guangxi Jiyusan Waterproof Decoration Co., Ltd. has carried out years of researches, on October 9th, 2009, the patent of invention of " carrying out the waterproof roll that bonding worked in coordination with by chemically crosslinked and physics mortise and tenon with concrete " is applied for, application number: CN200910114456.X open (bulletin) number: CN101694114A to China Intellectual Property Office, a kind of wet paving of this disclosure of the invention overlays waterproof roll, is modifying asphalt mixture is carried out dip-coating on carcass, control thick sizing, overlay film, the techniques such as rolling are made, and described modifying asphalt mixture is modifying asphalt, softening agent, antioxidant, functional aid and weighting agent, matrix pitch is placed in retort by preparation method, adds tackifier, random polyethylene and styrene-butadiene-styrene block copolymer, be mixed evenly, and heats up, and stirs 1.5-2h, then temperature is dropped to about 180 DEG C, then by filler, softening agent, antioxidant, functional aid is added to retort, stirs 0.5-1h, carries out fully mixed and modified, be then transported to colloidal mill, repeatedly grind material, then pitch good for modification is carried out dip-coating on carcass, control thick sizing, overlay film, rolling, what be just prepared into excellent performance carries out the waterproof roll of chemically crosslinked and physics mortise and tenon collaborative bond (ChemicalBondingandPhysicalCrosslinkingSynergism), abbreviation CPS waterproof roll with concrete.
CN200910114456.X discloses that to carry out the functional aid (hereinafter referred to as CPS auxiliary agent) that chemically crosslinked and physics mortise and tenon work in coordination with cohesive action with concrete be poly-methylethoxy base silane or poly-naphthalene formaldehyde sulfonate salt, or both mixtures, in this specification, contriver points out, functionally active auxiliary agent is there is in sizing material due to modifying asphalt mixture, their active group can be formed crosslinked with cement in hydration process, make coiled material and cement slurry or concrete secure bond, this cohesive action is very firm, environment for use factor by coiled material is less, thus it can be bonded on basal plane more enduringly, and form full bonding structure with basal plane, the crosslinking structure that thus two kinds of properties-correcting agent in sizing material are formed with hydrated calcium silicate bonding.Coiled material sizing material layer produces physical adsorption and mortise and tenon effect and is formed with basal plane and bonds in cement solidification process.Cement slurry and water generation hydration reaction, the hydrated product of generation is gathered in the surface formation cohesion film of cement granules.Surface forms plastic gel film formula cement slurry, ensures that it has good mobility, can fill up rough defect on interfacial layer microcosmic, is made the complete wetting formed between coiled material and cement slurry on microcosmic by extruding.After glue-line and cement slurry are fully wetting, make film surface tension force and cement slurry surface tension close, thus make both combine closely, generation physisorption.Meanwhile, the moisture gel film layer that deepens continuously carries out chemical reaction, and thin film layer is inwardly thickened; Being gathered in outside rete to the hydrate of external diffusion by thin film layer makes rete outwards thicken.The speed of infiltrating rete inside due to moisture is greater than the speed of hydrate to external diffusion, and thus produce seepage water pressure, the saturated solution of rete internal water compound outwardly causes rete to break.Breaking of rete makes hydrate contact rapidly and widely with water, reaction is accelerated again, generate the hydrates such as the hydratable silicate gelation system of more amount, calcium hydroxide and aquation calcium sulfate, contact with each other between them and grow into a certain degree, slurry can lose plasticity-completely, set up the reticulated structure be mutually wound around, and constantly produce hydrate in reticulated structure, slurry produces intensity gradually and enters sclerosis formation petrifying water mudstone afterwards.In this process, cement solidification consumes a large amount of water, cause being formed between cement and self-adhesive coiled material in the system of partial closure and produce negative pressure, and the curing exotherm of cement, promote the creep of self-adhesive, make it be deep in concrete kapillary or hole, form physics fourth of the twelve Earthly Branches camphor tree structure, reach reliable bond effect; While self-adhesive glue layer penetrates in concrete kapillary or hole, increase the area that self-adhesive contacts with concrete, promote the fourth of the twelve Earthly Branches camphor tree structure that self-adhesive glue layer and concrete are formed generates more chemical bond, and play " synergistic effect of chemically crosslinked-physics fourth of the twelve Earthly Branches camphor tree ", make basal plane and self-adhesive layer form " interpenetrating(polymer)networks formula " interface structure, thus reach in conjunction with tight, firm, irreversible " skin-type " bond effect technology.Thorough solution modified bituminous pitch coiled material and basal plane cohesive force are large not, and cohesive force is lasting, problem easily affected by environment, achieve the Waterproof structural course that coiled material and basal plane form irreversible, the not impaired integral type that bonds.
In patent CN200910114456.X announcement with after being awarded patent right, Guangxi Jiyusan Waterproof Decoration Co., Ltd. is studied some coupling agents again, finds that some coupling agents (linking agent) also can play chemical crosslink reaction with concrete jointly and cohesive action worked in coordination with by physics mortise and tenon.
Such as: Chinese patent CN201210446551.1, title: reaction bonded type node sealing compound and preparation method thereof, open (bulletin) number: CN102911638A, this reaction bonded type node sealing compound has used linking agent, make to form chemical anastomosis between concrete, improve and concrete cohesive force; The linking agent wherein mentioned is the mixture of the one or more than one in silane coupling agent, titanate coupling agent and aluminate coupling agent; What make that reaction bonded type node sealing compound can be good adheres to more smooth PPR or PVC on the surface, realizes the good sealing of PPR or PVC supplying drainage and concrete surface junction.
Equally, Chinese patent CN201210546765.6, title: polyolefine composite modified asphalt wet paving waterproof roll and production method thereof, a kind of polyolefine composite modified asphalt paving waterproof roll that wets comprises and can jointly play with concrete the modifying asphalt tack coat (2) that cohesive action worked in coordination with by chemical crosslink reaction and physics mortise and tenon, bonding barrier film protective layer (3), with polyolefin thermoplastic elastomer material layer (1), its interlayer structure is as follows: the first layer is polyolefin thermoplastic elastomer material layer (1), middle layer is modifying asphalt tack coat (2), cutting optimal is barrier film protective layer (3), each interlayer is by thermo-compression bonding in production process.Wherein proposing described functional aid is the coupling agent with hydroxyl, hydrogen base or carboxyl, particularly has hydroxyl, hydrogen base or the polysiloxane coupling agent of carboxyl-reactive functional group, poly-naphthalene formaldehyde sulfonate salt or their mixture.
But, what disclosed patent documentation described has hydroxyl, the polysiloxane coupling agent of hydrogen base or carboxyl-reactive functional group, poly-naphthalene formaldehyde sulfonate salt or silane coupling agent, in the reaction mechanism of titanate coupling agent and aluminate coupling agent, only propose to carry out chemical crosslink reaction with not solid cement and cohesive action worked in coordination with by physics mortise and tenon, do not recognize the situation can carrying out the chemical bonds of the other end brute force in coupling agent with pitch, so be relatively blindly when selection coupling agent and there is no sense of direction, therefore, the effect of anticipation is not often reached when manufacturing waterproof roll or reaction bonded type node sealing compound, only than common waterproof roll or sealing compound more bonding, aging and the weathering resistance of pitch fails to be significantly improved.
Summary of the invention
The object of this invention is to provide a kind of bridging agent of architectural waterproof material, the aging of pitch and weather resistance can be made to be significantly improved, and chemical crosslink reaction can be carried out with not solid cement simultaneously, form the chemical bond of good chemical affinity, make it solidification after play irreversible cohesive action.
Bridging agent of the present invention, be two amino silane, specifically N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, its molecular formula is: H 2nC 2h 4nHC 3h 6siCH 3(OMe) 2, one end of described silane is combined with the carboxyl of pitch, and the acid group that the other end produces after hydrated cementitious is combined; Erect the waterproof bridge that is prepared water-proof material.
The acid group produced after described hydrated cementitious is silicate, aluminate, sulphur aluminate or iron aluminate.
That is, above-described pair of amino silane tar cement waterproof bridging agent, the amino of structural formula one end of this bridging agent can couple together with the carboxyl of pitch, the reticulated structure that enhancing pitch and auxiliary material are formed, improve the physicals of modifying asphalt, form good chemical affinity, and the other end of silane is in the concrete adding water and cement, produce the chemical bond of aquation, carry out with concrete that chemically crosslinked and physics mortise and tenon are collaborative to bond, pitch and cement are closely coupled as one, there is chemical bond in region of interest, as erected the waterproof bridge that is prepared water-proof material, irreversible cohesive action is played after solidification, waterproof roll can be made, or make waterproof paint, waterproofing unction or water-proof leak preventer, its oil-proofness and flexible resistance are given prominence to, and it is nontoxic, safety and environmental protection, pollution-free, at cement, can wriggle in the process of concrete setting and penetrate in cement gel and concrete pore, reach and combine closely, firmly, irreversible as closely linked as flesh and blood bond effect.Want to take away or peel off waterproof layer, be difficult to accomplish.
Below reaction mechanism:
1, when this N-(β-aminoethyl)-γ-one end of aminopropyltriethoxy dimethoxysilane mixes with the pitch of heating and melting time, following chemical reaction can be there is:
2, for silicate cement, one end of N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane is with as follows with the concrete mechanism of action:
1. water at normal temperature mud generation hydration reaction generates hydrated calcium silicate (C-S-H gel) and Ca (OH) 2, there is Si-OH group in CSH gel, reaction formula: 3CaOSiO 2+ nH 2o=xCaSiO 2yH 2o+ (3-x) Ca (OH) 2;
2. the active group in glue-line meets water hydrolysis:
3. hydrolysis generates Si-OH radical reaction in Si-OH group and CSH gel and generates ehter bond, makes hydrated calcium silicate gel and coiled material surface generate chemical bond (forming ehter bond with CSH) and reacts as follows:
The mechanism that one end and aluminic acid cement, sulphur aluminic acid cement or the iron aluminic acid cement of described N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane react also is the same.
N-of the present invention (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, at the coupling compound with the hydroxyl in cement gel, ehter bond and silicon-dioxide, can not cause the infringement to reinforcing bar.
The application of above-described N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane tar cement waterproof bridging agent, this bridging agent can be combined with uncured pitch and auxiliary material, makes waterproof, waterproof paint, or water-proof leak preventer.
Described 100 weight part waterproof, waterproof paint, or the parts by weight adding waterproof bridging agent in water-proof leak preventer premixed systems are 0.1-15.0.
Preparation waterproof, waterproof paint, or the method for water-proof leak preventer be first by asphalt heating to 160-200 DEG C, after reaching molten state, add properties-correcting agent, auxiliary agent and waterproof bridging agent, stirring reaction 0.5-2 hour, finally according to waterproof, waterproof paint, or the performance of water-proof leak preventer, add appropriate filler, obtain waterproof product.
The application of above-described pair of amino silane tar cement waterproof bridging agent, this bridging agent also can be combined with pitch and auxiliary material, makes waterproof roll.The parts by weight adding waterproof bridging agent in described 100 weight part waterproof roll pitches and auxiliary material combination material are 0.1-15.0.
The method preparing waterproof roll be first by asphalt heating to 160-200 DEG C, after reaching molten state, add properties-correcting agent, auxiliary agent and waterproof bridging agent, stirring reaction 0.5-2 hour, finally according to waterproof roll performance, add appropriate filler, be laid on the surface of plastics film, obtain product.
The application of above-described N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane tar cement waterproof bridging agent, this bridging agent is combined with uncured tar cement, can as the water-resistant adhesives being layered on inner wall of building or exterior wall wall brick.
The producer of current production N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane has: Hebei Tai Feng chemical industry limited liability company, Nanjing You Pu Chemical Co., Ltd., Hubei Li Ding Chemical Co., Ltd., the uncommon love (Shanghai) of ladder change into industrial development company limited, Qufu morning twilight Chemical Co., Ltd. etc.
Amino silane bridging agent of the present invention, at the coupling compound with the hydroxyl in cement gel, ehter bond and silicon-dioxide, can not cause the infringement to reinforcing bar.
Embodiment
Below that amino silane of the present invention (N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane) bridging agent is combined with modifying asphalt and auxiliary material, make waterproof roll, or as additive, make the embodiment of waterproof paint, waterproof and water-proof leak preventer:
Embodiment 1; N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane bridging agent waterproof roll; this waterproof roll the first layer is sealed polyethylene plastic layer, middle layer is asphalt tack coat, cutting optimal is barrier film protective layer, and wherein the composition of asphalt tack coat and parts by weight are:
1-1: pitch 30 parts, properties-correcting agent 15 parts; Petrochemical production process produces the third fractional oil 2 parts, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane waterproof bridging agent 0.1 part, 3 parts, weighting agent magnesium oxide, 40 parts, the filler-calcium carbonate powder that come.1-2: pitch 40 parts, properties-correcting agent 18 parts; Petrochemical production process produces the third fractional oil 5 parts, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane waterproof bridging agent 8 parts, 5 parts, weighting agent magnesium oxide, 50 parts, the filler-calcium carbonate powder that come.
1-3: pitch 50 parts, properties-correcting agent 20 parts; Petrochemical production process produces the third fractional oil 10 parts, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane waterproof bridging agent 15 parts, 8 parts, weighting agent magnesium oxide, 60 parts, the filler-calcium carbonate powder that come.
Product process: first by asphalt heating to 160-200 DEG C, after reaching molten state, add properties-correcting agent, auxiliary agent and waterproof bridging agent, stirring reaction 0.5-2 hour, finally according to waterproof roll performance, add appropriate filler, be laid on the surface of plastics film, obtain product.
N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane waterproof roll made is used in the waterproof layer of building roof-covering in certain building site, and paste after 10 days, its stripping strength is 4.3-4.8N/mm.
Embodiment 2, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane bridging agent waterproof
N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane bridging agent waterproof composition and parts by weight are:
2-1: pitch 30 parts; Properties-correcting agent 5 parts; Emulsifying agent 0.2 part; Thickening material 0.5 part; 20 parts, water, bridging agent 0.1 part;
2-2: pitch 50 parts; Properties-correcting agent 10 parts; Emulsifying agent 2 parts; Thickening material 2 parts; 30 parts, water, bridging agent 8 parts;
2-3: pitch 60 parts; Properties-correcting agent 20 parts; Emulsifying agent 3 parts; Thickening material 3 parts; 50 parts, water, bridging agent 15 parts;
The mixture that its medium pitch is petroleum pitch, properties-correcting agent is one or more than one in thermoplastic elastomer asphalt modifier, rubber pitch modifier, emulsifying agent are Cetyltrimethylammonium bromide, bridging agent is N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane; Thickening material is ether of cellulose; The method preparing waterproof be first by asphalt heating to 160-200 DEG C, after reaching molten state, add properties-correcting agent and bridging agent, stirring reaction 0.5-2 hour, adds emulsifying agent, thickening material, auxiliary agent and water, after colloidal mill emulsification, add appropriate filler, obtain product.
Embodiment 3, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane water-proof leak preventer
N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane water-proof leak preventer, is prepared from by the raw material of following weight part:
3-1: pitch 30 parts; Properties-correcting agent 15 parts, emulsifying agent 0.5 part, waterproof bridging agent 0.5 part, 20 parts, water;
3-2: pitch 40 parts; Properties-correcting agent 18 parts, emulsifying agent 2 parts, waterproof bridging agent 2 parts, 30 parts, water;
3-3: pitch 50 parts; Properties-correcting agent 20 parts, emulsifying agent 3 parts, waterproof bridging agent 3 parts, 50 parts, water;
Its medium pitch is petroleum pitch; Properties-correcting agent is the mixture of one or more than one in thermoplastic elastomer asphalt modifier, rubber pitch modifier; Emulsifying agent is cetyl trimethylammonium bromide, and waterproof bridging agent is N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane.The preparation method of N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane water-proof leak preventer is: pitch, properties-correcting agent and bridging agent are stirred 2h at 150 DEG C, makes it abundant melting mixing, obtain mixture; Start mulser, mixture and emulsion are added to mulser simultaneously and are prepared into emulsion, then add thickening material and appropriate filler, stir, to obtain final product.This water-proof leak preventer is used for the coating of roof cracks, and result shows, water-tight after simulation 60 DEG C of high temperature and 4 DEG C replace lower aging 300 hours, do not seep water, and namely plain asphalt only has crack to produce for 72 hours again, leaks still.
Embodiment 4, compare with the product of Guangxi Jiyusan Waterproof Decoration Co., Ltd.'s patented product of 2009 and CN201210546765.6: CN200910114456.X have employed and to carry out the functional aid that cohesive action worked in coordination with by chemically crosslinked and physics mortise and tenon with concrete, auxiliary agent is poly-methylethoxy base silane or poly-naphthalene formaldehyde sulfonate salt, make waterproof roll, the present invention uses N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane bridging agent; The product of CN201210546765.6 adopts polysiloxane coupling agent; Data are as subordinate list 1:

Claims (6)

1. a two amino silane tar cement waterproof bridging agent, it is characterized in that, it is N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane (H 2nC 2h 4nHC 3h 6siCH 3(OMe) 2), its one end is combined with the carboxyl of pitch, and the acid group that the other end produces after hydrated cementitious is combined, and erects the waterproof bridge that is prepared water-proof material.
2. according to claim 1 pair of amino silane tar cement waterproof bridging agent, it is characterized in that, the acid group produced after described hydrated cementitious is silicate, aluminate, sulphur aluminate or iron aluminate.
3. the application of according to claim 1 pair of amino silane tar cement waterproof bridging agent, it is characterized in that, this bridging agent is combined with uncured pitch and auxiliary material, makes waterproof, waterproof paint, or water-proof leak preventer;
Described 100 weight part waterproof, waterproof paint, or the parts by weight adding waterproof bridging agent in water-proof leak preventer premixed systems are 0.1-15.0.
4. the application of according to claim 4 pair of amino silane tar cement waterproof bridging agent, it is characterized in that, preparation waterproof, waterproof paint, or the method for water-proof leak preventer be first by asphalt heating to 160-200 DEG C, after reaching molten state, add properties-correcting agent, auxiliary agent and waterproof bridging agent, stirring reaction 0.5-2 hour, finally according to waterproof, waterproof paint, or the performance of water-proof leak preventer, add appropriate filler, obtain waterproof product.
5. the application of according to claim 1 pair of amino silane tar cement waterproof bridging agent, it is characterized in that, this bridging agent is combined with pitch and auxiliary material, makes waterproof roll; The parts by weight adding waterproof bridging agent in described 100 weight part waterproof roll pitches and auxiliary material combination material are 0.1-15.0.
6. the application of according to claim 6 pair of amino silane tar cement waterproof bridging agent, it is characterized in that, the method preparing waterproof roll be first by asphalt heating to 160-200 DEG C, after reaching molten state, add properties-correcting agent, auxiliary agent and waterproof bridging agent, stirring reaction 0.5-2 hour, finally according to waterproof roll performance, add appropriate filler, be laid on the surface of plastics film, obtain product.
CN201410330040.2A 2014-07-12 2014-07-12 Diamino silane waterproof bridging agent for asphalt and cement, and waterproof product and application thereof Pending CN105273230A (en)

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Application publication date: 20160127