CN107446140A - A kind of low VOC environment-friendly concretes interface treating agent and preparation method thereof - Google Patents
A kind of low VOC environment-friendly concretes interface treating agent and preparation method thereof Download PDFInfo
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- CN107446140A CN107446140A CN201710707213.1A CN201710707213A CN107446140A CN 107446140 A CN107446140 A CN 107446140A CN 201710707213 A CN201710707213 A CN 201710707213A CN 107446140 A CN107446140 A CN 107446140A
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- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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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
- C04B24/24—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
- C08G83/006—After treatment of hyperbranched macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
Abstract
The invention provides a kind of low VOC environment-friendly concretes interface treating agent; cross-linking reaction is carried out by the sepiolite of grafting end-vinyl and carboxyl super branched polyester, vinyl acetate ethylene copolymer emulsion, polyethyleneimine and trimethylolpropane tris (3 aziridinyl propionic ester) to be prepared; with relatively low VOC and excellent viscosity, solve the problems, such as that traditional interface inorganic agent volatile is high, not environmentally.
Description
Technical field
The present invention relates to interfacial agents technical field, more particularly to a kind of low VOC environment-friendly concretes interface treating agent and its system
Preparation Method.
Background technology
Concrete interface treating agent is also known as concrete interface adhesive, interface treating agent etc., abbreviation interfacial agents.Applied to increasing
A kind of finish materials of reinforced concrete surface property, it is a kind of functional form adhesive.Engineering practice proves, uses concrete
Interface treating agent is to prevent a kind of effective technology measure that rendering layer flakes with base course wall, separated, peeling off.Interface treating agent is near
Use and develop comparatively fast over year, for modular product performance, ensure construction quality, China issued concrete interface in 2002
The building material industry standard JC 907-2002 of inorganic agent.Interfacial agents are divided into two kinds of classifications, i.e. dry powder class interfacial agents and liquid by composition
Class interfacial agents.Dry powder class interfacial agents are made up of the additive of the inorganic coagulation materials such as cement, filler, polymer glue powder and correlation
Dry powder class product, need to be mixed and stirred with water or other liquid mixtures during use.Liquid type interfacial agents are containing polymer dispersion liquid
Product, use can be directly brushed in interface during use, can also be proportioned with inorganic coagulation materials and water etc. such as cement makes
With.To be fitted up for architecture indoor, metope is more smooth, and adhesive force is lower, is coated with interface treating agent, and a part of interfacial agents penetrate into basic unit,
Basic unit is embedded in as " anchor ", forms hooking systems, improves adhesive force, another part forms unsmooth, coarse in substrate surface
Gas permeability glued membrane.Plaster or Puttying process membrane basal layer absorbs a part of moisture content and softened, be advantageous to the bonding at interface, reach
To the effect for improving basic unit's interfacial adhesion.Interfacial agents " making hair " can also be used, a part of interfacial agents and cement slurry penetrate into
Basic unit, basic unit is embedded in as " anchor ", the pointed cement mortar burr that another part forms out-of-flatness in metope basic unit, is plastered
When, make coat of plaster, mud burr, wall triplicity together, be integrally formed, the problems such as cracking will not be produced, come off.Such as
Easily come off in slippery walls tiling, can increase substantially contact area using interface treating agent and basic unit adheres to
Power.
Current published interface treating agent is mostly dry powder class interfacial agents, and liquid type interfacial agents are less.Patent CN
A kind of bonding treating agent for concrete inorganic interface is disclosed in 102643059, by portland cement, water reducer, siliceous material, again
Calcium powder, water-loss reducer, redispersible latex powder, thickener modified alta-mud, mineral admixture composition, the repairing for concrete
Bonding, the adhesion process in mass concrete construction Fen Cang storehouses face etc..Patent CN 103755223 discloses one kind by asphalt mixtures modified by epoxy resin
Fat, acrylic acid, calcium formate, quartz sand, the concrete interface treating agent of dicalcium powder composition.Patent CN 104261764 discloses one
Kind of shrinkage type concrete interface treating agent, by economization agent, ethylene-vinyl acetate c emulsion, hydroxypropyl methyl cellulose ether,
Coalescents, defoamer, polycarboxylic acid series high efficiency water reducing agent, Portland cement, silicon ash and water composition, for handling concrete
Interface when interface at structure construction seam between the concrete of first after-pouring or structure repair between new-old concrete.
Architecture indoor fits up multipurpose liquid class interfacial agents, but exists unavoidably in the composition such as wherein used emulsion, auxiliary agent
The small molecular organic compounds of volatile so that the total volatile organic matter of product (volatile organic
Compounds, VOCs) content is higher, it is difficult to meet the ecological requirements of people, more harsh environmentally friendly class standard can not be met,
The main of urgent need solution in the target that VOCs contents are current technological developments, and scientific research in recent years and production is reduced to ask
Topic.Environment Protect in China standard HJ 2541-2016 prescribed products must not the plasticizer containing phthalate, alkyl phenol
The emulsifying agent of polyethenoxy ether class, preservative of isothiazole ketone etc. are, it is specified that general volatile is organic in aqua type architecture adhesion agent
Thing content≤40g/L, the execution of these requirements make the countries such as environmental labelling product and Northern Europe, Canada, the Australia in China
Thus the ecological mark requirement in area to traditional macromolecule emulsion, liquid type interfacial agents, adhesive etc. more closely, propose
Challenge, it is badly in need of new technology to meet the requirement of volatile organic matter content and environmental protection.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of low VOC environment-friendly concretes interface treating agent
And preparation method thereof, there is relatively low VOC content.
Low VOC environment-friendly concretes interface treating agent provided by the invention, by grafting end-vinyl and carboxyl super branched polyester
Sepiolite, vinyl acetate-ethylene copolymerization emulsions, polyethyleneimine and trimethylolpropane-three (3- aziridinyls propionic ester)
Cross-linking reaction is carried out to be prepared.
Sepiolite, vinyl acetate-ethylene copolymerization emulsions, the polyethylene of the grafting end-vinyl and carboxyl super branched polyester
The mass ratio of imines and trimethylolpropane-three (3- aziridinyls propionic ester) is (0.1~1)：(75.65~129.25)：
(0.1~1)：(0.1~1).
The sepiolite of the grafting end-vinyl and carboxyl super branched polyester is preferably prepared in accordance with the following methods：
A) using 3- aminopropyl triethoxysilanes in acid condition, sepiolite is activated；
B) by step A) sepiolite after obtained activation reacted with end-vinyl and carboxyl super branched polyester, obtained
It is grafted the sepiolite of end-vinyl and carboxyl super branched polyester.
The step A) solvent be preferably ethanol.The temperature of the reaction is preferably 40~60 DEG C, and the time of reaction is excellent
Elect 10~15h as.The dosage of the ethanol is 45~55 times of sepiolite quality.
The step A) acid condition, preferably provided by hydrochloric acid, the dosage of the hydrochloric acid is preferably sepiolite
0.5wt%~2wt%, in some embodiments of the invention, the hydrochloric acid dosage is the 1wt% of sepiolite.
The step B) solvent be preferably tetrahydrofuran.The temperature of the reaction is preferably 40~60 DEG C, reaction when
Between be preferably 20~30h.The dosage of the tetrahydrofuran is 45~55 times of sepiolite quality.
The mass ratio of the 3- aminopropyl triethoxysilanes and sepiolite is (4~6):1.
The end-vinyl and the mass ratio of carboxyl super branched polyester and sepiolite are (4~6):1.
The end-vinyl and carboxyl super branched polyester have following structure：
Wherein,
The invention provides the preparation method of low VOC environment-friendly concretes interface treating agent, comprise the following steps：
A) polyvinyl alcohol is dissolved in the water, emulsifying agent, ammonium persulfate and vinyl acetate is then added and carries out for the first time
Polymerisation, obtain vinyl acetate-ethylene copolymerization emulsions；
B) by step A) obtained vinyl acetate-ethylene copolymerization emulsions and grafting end-vinyl and carboxyl super branched polyester
Sepiolite mixes, and carries out second of polymerisation；
C) sodium acid carbonate, polyethyleneimine and trimethylolpropane-three (3- aziridinyls propionic ester) is added to be crosslinked
Reaction, is eventually adding plasticizer and preservative, obtains interface treating agent.
The preparation method of the sepiolite of the grafting end-vinyl and carboxyl super branched polyester is same as above, and will not be repeated here.
The present invention is to the preparation method of the end-vinyl and carboxyl super branched polyester and is not particularly limited, can be according to upper
State structural formula voluntarily to prepare, preferably prepare in accordance with the following methods：
Trimethylolpropane and first dihydromethyl propionic acid carry out first time condensation reaction, after reaction terminates, add the
Two batches of dihydromethyl propionic acids carry out second of condensation reaction, after reaction terminates, add the 3rd batch of dihydromethyl propionic acid and carry out the 3rd
Secondary condensation reaction, then sequentially add succinic anhydride, acrylic acid is reacted.
The trimethylolpropane, first dihydromethyl propionic acid, second batch dihydromethyl propionic acid and the 3rd batch of dihydroxy first
The mass ratio of base propionic acid is preferably 1：3：6：12.
Above-mentioned first time condensation reaction, second of condensation reaction, third time condensation reaction preferably urging in p-methyl benzenesulfonic acid
Change effect is lower to be carried out.The dosage of the p-methyl benzenesulfonic acid is preferably the 0.1%~0.5% of dihydromethyl propionic acid gross mass.
Above-mentioned first time condensation reaction, second of condensation reaction, third time condensation reaction are preferably in the condition of decompression stirring
Lower progress.The vacuum of the decompression stirring is preferably 0.1KPa.
The mol ratio of the succinic anhydride and trimethylolpropane is preferably 2:1, the acrylic acid and trimethylolpropane
Mol ratio be preferably 10:1.
The step B) in, the temperature of second of polymerisation is preferably 60~75 DEG C, and the reaction time is preferably 1~2h.
The step C) in, the temperature of cross-linking reaction is preferably 40~50 DEG C, and the reaction time is preferably 1~2h.
The vinyl acetate, polyvinyl alcohol, ammonium persulfate, emulsifying agent, sodium acid carbonate, water, plasticizer, preservative, connect
Sepiolite, polyethyleneimine and (the 3- aziridinyl propionic acid of trimethylolpropane-three of branch end-vinyl and carboxyl super branched polyester
Ester) mass ratio be preferably (10~30)：(3~4)：(0.2~0.3)：(0.2~0.4)：(0.15~0.25)：(60~90)：
(2~4)：(0.1~0.3)：(0.1~1)：(0.1~1)：(0.1~1).
The emulsifying agent is preferably alkoxy polyethylene hydroxy ethanol；The plasticizer is preferably DPG hexichol first
Acid esters；The preservative is preferably DDAC.
Interface treating agent provided by the invention is by vinyl acetate, polyvinyl alcohol, ammonium persulfate, emulsifying agent, bicarbonate
Sodium, water, plasticizer, preservative, sepiolite, polyethyleneimine and the trihydroxy methyl for being grafted end-vinyl and carboxyl super branched polyester
Propane-three (3- aziridinyls propionic ester) passes through the side such as emulsion polymerization, chemistry polymerizing in situ, grafting, crosslinking and physical mixed
Formula is prepared, and the hybrid inorganic-organic VOC formed in it, which eliminates system, can not only effectively reduce VOC content, can also be to boundary
Face agent play a part of thickening, stably, improve adhesive property, system is met environmental requirement.
The interface treating agent of above-mentioned preparation has following structure：
Wherein, HBP finger tips vinyl and carboxyl super branched polyester.M, n and p is respectively construction unit number, m, n, p be equal to
Or the integer more than 1.
The curved line of Si connections refers to Si atoms and is coupled with inorganic matter sepiolite, or the coupling between silane coupler.
Compared with prior art, the invention provides a kind of low VOC environment-friendly concretes interface treating agent, by being grafted end ethene
The sepiolite of base and carboxyl super branched polyester, vinyl acetate-ethylene copolymerization emulsions, polyethyleneimine and trimethylolpropane-three
(3- aziridinyls propionic ester) carries out cross-linking reaction and is prepared, and it is high, no to efficiently solve traditional interface inorganic agent volatile
The problem of environmentally friendly.Specifically, have the advantages that：
(1) sepiolite is a kind of rich magnesium silicate clay mineral of fibrous chain type layer structure, is by two layers of silica four
The octahedra composition of layer of metal cation is pressed from both sides between the body piece of face, the cation, bigger serface, multichannel micropore knot with displacement
Structure, strong adsorptivity.It can pass through the Prolonged absorption polyvinyl acetate degraded production that chemically reacts using with displacement and adsorption function
Raw acidic materials, and distributing for organic molecule impurity is suppressed by the long-acting absorption of physical action.
(2) nonvolatile functional form macromolecular (poly- second with more active function functional groups aminos and '-aziridino is utilized
Alkene imines and trimethylolpropane-three (3- aziridinyls propionic ester)) pass through Michael's addition, open loop addition, amino addition etc.
Chemically react and quick absorption is played to the vinyl monomer, aldehyde type impurities, acid degradation accessory substance of polymerization residual.
(3) utilize hyperbranched poly ester terminal quantity abundant and multifarious feature, play macromolecules cross-linking, grafting effect,
Sepiolite is connected to by home position polymerization reaction in polyvinyl acetate strand, be uniformly dispersed, without sedimentation, surpass simultaneously
Remaining end group organically can be connected functional form macromolecular compound by covalent bond in branched polyester, formed it is organic-
The VOC of inorganic hybridization eliminates system, has both played to interface treating agent thickening, anti-settling, the stabilization being evenly distributed, moreover it is possible to have
Effect prevents the VOCs and SVOCs of generation small molecule after depolymerization, and vinylic end group itself also can in hyper-branched polyester in addition
The vinyl monomer remained in phase absorption system after polymerization, play a part of reducing VOCs.
(4) concentration is relatively low when liquids in general type interface treating agent uses, and is needed when directly coating or cement are made mao certain viscous
Degree, and viscosity deficiency after general emulsion dilution, it is necessary to have thickening thickening structure auxiliary, tradition typically uses aldehyde material, such as
Polyvinyl formal is obtained after the poisonous and harmful compound crosslink polyvinyl alcohol such as formaldehyde.And system of the present invention is different from conventional bulk
System, using the VOC absorption systems of hybrid inorganic-organic, in addition to sexual function of volatilizing is reduced, also by being grafted end ethene
The sepiolite of base and carboxyl super branched polyester, polyethyleneimine and trimethylolpropane-three (3- aziridinyls propionic ester) produce
Cross-linked structure, play a part of thickening, anti-settling, improve adhesive property, and then meet the performance of interfacial agents.
(5) in above-mentioned interface treating agent provided by the invention, environment-friend auxiliaries and interface treating agent system compatibility are good, from
Daughter set type be able to be merged mutually, emulsion-stabilizing, not only meet whole synthesis performance and function, additionally it is possible to meet environmental protection standard
Requirement.
Embodiment
In order to further illustrate the present invention, with reference to embodiment to low VOC environment-friendly concretes interface provided by the invention
Inorganic agent and preparation method thereof is described in detail.
Comparative example 1
8kg water is added first in dissolution kettle, 0.3kg polyvinyl alcohol is added into dissolution kettle dissolving under agitation, then will be molten
The polyvinyl alcohol water solution that has solved is sent into polymeric kettle, add 20g emulsifier for mixing it is uniform after, be warming up to 70 DEG C, it is equal to polymeric kettle
Even dropwise addition 20g ammonium persulfates and 1.41kg vinyl acetates, dropwise reaction time are 6 hours, are further continued for reaction 2 hours, are added
After 15g sodium acid carbonates, 50 DEG C are cooled to, after reacting 2 hours, 0.2kg plasticizer and 10g preservatives is added, goes out after being down to room temperature
Material, that is, interface treating agent comparative sample is obtained, the emulsifying agent is alkoxy polyethylene hydroxy ethanol, and the plasticizer is two
Glycol dibenzoate, the preservative are DDAC.
Using GB 18583-2008《Limits of harmful substances in indoor decorating and refurnishing materials adhesive》Gas in standard annex F
Phase chromatography tests total volatile organism content, and the TVOC contents of interface treating agent comparative sample are 47g/L.Using rotary
Viscosimeter is tested to obtain, viscosity 200mPas.
Embodiment 1
(1) preparation of end-vinyl and carboxyl super branched polyester：
33.3 grams of trimethylolpropanes are added in reactor, are warming up to 140 DEG C, point three steps add dihydromethyl propionic acid,
100 grams of dihydromethyl propionic acid is firstly added, 0.7 gram of p-methyl benzenesulfonic acid is added after being well mixed, decompression stirring reaction is to without gas
After bubble produces, 200 grams of dihydromethyl propionic acid is added, stirring reaction to bubble-free is depressurized after being well mixed and is produced, adds 400 grams
Dihydromethyl propionic acid, be well mixed after depressurize stirring reaction to bubble-free produce, add 700 grams of DMFs,
After solid intermediate product dissolving after, add 49.7 grams of succinic anhydrides, 80 DEG C reaction 12 hours after add 178.9 grams of acrylic acid,
Reacted 6 hours at 80 DEG C, be washed with water to product in neutrality after being down to room temperature, be put into vacuum drying oven and dried at 60 DEG C
24 hours, grafting end-vinyl and carboxyl super branched polyester are finally given, wherein, vacuum when depressurizing stirring reaction is
0.1kPa。
(2) it is grafted the preparation of the sepiolite of end-vinyl and carboxyl super branched polyester：
10 grams of sepiolites are scattered in 500 grams of ethanol, add 0.1 gram of hydrochloric acid and 50 grams of 3- aminopropyl-triethoxy silicon
Alkane, 50 DEG C of stirring reactions 12 hours, takes solid powder to be scattered in 500 grams of tetrahydrofurans after filtering, add 50 grams of end ethene
Base and carboxyl super branched polyester, 50 DEG C of stirring reactions 24 hours, take solid powder to be put into vacuum drying oven in 60 after filtering
Dried 24 hours at DEG C, finally give the sepiolite of grafting end-vinyl and carboxyl super branched polyester.
Embodiment 2
8kg water is added first in dissolution kettle, 0.3kg polyvinyl alcohol is added into dissolution kettle dissolving under agitation, then will be molten
The polyvinyl alcohol water solution that has solved is sent into polymeric kettle, add 20g emulsifier for mixing it is uniform after, be warming up to 70 DEG C, it is equal to polymeric kettle
Even dropwise addition 20g ammonium persulfates and 1.41kg vinyl acetates, dropwise reaction time are 6 hours, add 10g grafting end-vinyls
After the sepiolite of carboxyl super branched polyester, continue reaction 2 hours, after adding 15g sodium acid carbonates, be cooled to 50 DEG C, add 10g
Polyethyleneimine and 10g trimethylolpropanes-three (3- aziridinyls propionic ester), after reacting 2 hours, add 0.2kg plasticizer
With 10g preservatives, discharged after being down to room temperature, that is, obtain interface treating agent, the emulsifying agent is alkoxy polyethylene hydroxy second
Alcohol, the plasticizer are diethylene glycol dibenzoate, and the preservative is DDAC.
Using GB 18583-2008《Limits of harmful substances in indoor decorating and refurnishing materials adhesive》Gas in standard annex F
Phase chromatography tests total volatile organism (TVOC) content, and the TVOC contents of interface treating agent are 30g/L, with comparative example
Sample is compared, and TVOC contents reduce 36.2%, and compatibility is good between each component, and obtaining viscosity after rotated formula viscosimeter test is
2900mPas, not only ensure d spiss but also produced without sedimentation, and meet Environment Protect in China standard HJ 2541-2016《Environment
Famous special product technical requirements adhesive》Requirement.
Embodiment 3
8kg water is added first in dissolution kettle, 0.3kg polyvinyl alcohol is added into dissolution kettle dissolving under agitation, then will be molten
The polyvinyl alcohol water solution that has solved is sent into polymeric kettle, add 20g emulsifier for mixing it is uniform after, be warming up to 70 DEG C, it is equal to polymeric kettle
Even dropwise addition 20g ammonium persulfates and 1.41kg vinyl acetates, dropwise reaction time are 6 hours, add 20g grafting end-vinyls
After the sepiolite of carboxyl super branched polyester, continue reaction 2 hours, after adding 15g sodium acid carbonates, be cooled to 50 DEG C, add 20g
Polyethyleneimine and 20g trimethylolpropanes-three (3- aziridinyls propionic ester), after reacting 2 hours, add 0.2kg plasticizer
With 10g preservatives, discharged after being down to room temperature, that is, obtain interface treating agent, the emulsifying agent is alkoxy polyethylene hydroxy second
Alcohol, the plasticizer are diethylene glycol dibenzoate, and the preservative is DDAC.
Using GB 18583-2008《Limits of harmful substances in indoor decorating and refurnishing materials adhesive》Gas in standard annex F
Phase chromatography tests total volatile organism (TVOC) content, and the TVOC contents of interface treating agent are 26g/L, with comparative example
Sample is compared, and TVOC contents reduce 44.7%, and compatibility is good between each component, and obtaining viscosity after rotated formula viscosimeter test is
8800mPas, not only ensure d spiss but also produced without sedimentation, and meet Environment Protect in China standard HJ 2541-2016《Environment
Famous special product technical requirements adhesive》Requirement.
Embodiment 4
The preparation of concrete interface treating agent：8kg water is added first in dissolution kettle, 0.3kg polyvinyl alcohol is being stirred
Lower addition dissolution kettle dissolving, then the polyvinyl alcohol water solution dissolved is sent into polymeric kettle, it is uniform to add 20g emulsifier for mixing
Afterwards, 70 DEG C are warming up to, 20g ammonium persulfates and 1.41kg vinyl acetates are uniformly added dropwise to polymeric kettle, the dropwise reaction time is 6 small
When, after adding the sepiolite of 40g grafting end-vinyls and carboxyl super branched polyester, continue reaction 2 hours, add 15g carbonic acid
After hydrogen sodium, 50 DEG C are cooled to, adds 40g polyethyleneimines and 40g trimethylolpropanes-three (3- aziridinyls propionic ester), instead
After answering 2 hours, 0.2kg plasticizer and 10g preservatives are added, is discharged after being down to room temperature, that is, obtains interface treating agent, the emulsification
Agent is alkoxy polyethylene hydroxy ethanol, and the plasticizer is diethylene glycol dibenzoate, and the preservative is didecyl two
Ammonio methacrylate.
Using GB 18583-2008《Limits of harmful substances in indoor decorating and refurnishing materials adhesive》Gas in standard annex F
Phase chromatography tests total volatile organism (TVOC) content, and the TVOC contents of interface treating agent are 21g/L, with comparative example
Sample is compared, and TVOC contents reduce 55.3%, and compatibility is good between each component, and obtaining viscosity after rotated formula viscosimeter test is
16700mPas, not only ensure d spiss but also produced without sedimentation, and meet Environment Protect in China standard HJ 2541-2016《Ring
Border famous special product technical requirements adhesive》Requirement.
Embodiment 5
8kg water is added first in dissolution kettle, 0.3kg polyvinyl alcohol is added into dissolution kettle dissolving under agitation, then will be molten
The polyvinyl alcohol water solution that has solved is sent into polymeric kettle, add 20g emulsifier for mixing it is uniform after, be warming up to 70 DEG C, it is equal to polymeric kettle
Even dropwise addition 20g ammonium persulfates and 1.41kg vinyl acetates, dropwise reaction time are 6 hours, add 80g grafting end-vinyls
After the sepiolite of carboxyl super branched polyester, continue reaction 2 hours, after adding 15g sodium acid carbonates, be cooled to 50 DEG C, add 80g
Polyethyleneimine and 80g trimethylolpropanes-three (3- aziridinyls propionic ester), after reacting 2 hours, add 0.2kg plasticizer
With 10g preservatives, discharged after being down to room temperature, that is, obtain interface treating agent, the emulsifying agent is alkoxy polyethylene hydroxy second
Alcohol, the plasticizer are diethylene glycol dibenzoate, and the preservative is DDAC.
Using GB 18583-2008《Limits of harmful substances in indoor decorating and refurnishing materials adhesive》Gas in standard annex F
Phase chromatography tests total volatile organism (TVOC) content, and the TVOC contents of interface treating agent are 16g/L, with comparative example
Sample is compared, and TVOC contents reduce 66%, and compatibility is good between each component, and obtaining viscosity after rotated formula viscosimeter test is
21100mPas, not only ensure d spiss but also produced without sedimentation, and meet Environment Protect in China standard HJ 2541-2016《Ring
Border famous special product technical requirements adhesive》Requirement.
Embodiment 6
8kg water is added first in dissolution kettle, 0.3kg polyvinyl alcohol is added into dissolution kettle dissolving under agitation, then will be molten
The polyvinyl alcohol water solution that has solved is sent into polymeric kettle, add 20g emulsifier for mixing it is uniform after, be warming up to 70 DEG C, it is equal to polymeric kettle
Even dropwise addition 20g ammonium persulfates and 1.41kg vinyl acetates, dropwise reaction time are 6 hours, add 100g grafting end ethene
After the sepiolite of base and carboxyl super branched polyester, continue reaction 2 hours, after adding 15g sodium acid carbonates, be cooled to 50 DEG C, add
100g polyethyleneimines and 100g trimethylolpropanes-three (3- aziridinyls propionic ester), after reacting 2 hours, add 0.2kg and increase
Agent and 10g preservatives are moulded, is discharged after being down to room temperature, that is, obtains interface treating agent, the emulsifying agent is alkoxy polyethylene hydrogen-oxygen
Base ethanol, the plasticizer are diethylene glycol dibenzoate, and the preservative is DDAC.
Using GB 18583-2008《Limits of harmful substances in indoor decorating and refurnishing materials adhesive》Gas in standard annex F
Phase chromatography tests total volatile organism (TVOC) content, and the TVOC contents of interface treating agent are 11g/L, with comparative example
Sample is compared, and TVOC contents reduce 76.6%, and compatibility is good between each component, and obtaining viscosity after rotated formula viscosimeter test is
29000mPas, not only ensure d spiss but also produced without sedimentation, and meet Environment Protect in China standard HJ 2541-2016《Ring
Border famous special product technical requirements adhesive》Requirement.
Embodiment 7
9kg water is added first in dissolution kettle, 0.4kg polyvinyl alcohol is added into dissolution kettle dissolving under agitation, then will be molten
The polyvinyl alcohol water solution that has solved is sent into polymeric kettle, add 20g emulsifier for mixing it is uniform after, be warming up to 70 DEG C, it is equal to polymeric kettle
Even dropwise addition 30g ammonium persulfates and 1.2kg vinyl acetates, dropwise reaction time are 5 hours, add 50g grafting end-vinyls
After the sepiolite of carboxyl super branched polyester, continue reaction 1 hour, after adding 15g sodium acid carbonates, be cooled to 50 DEG C, add 50g
Polyethyleneimine and 50g trimethylolpropanes-three (3- aziridinyls propionic ester), after reacting 1 hour, add 0.3kg plasticizer
With 15g preservatives, discharged after being down to room temperature, that is, obtain interface treating agent, the emulsifying agent is alkoxy polyethylene hydroxy second
Alcohol, the plasticizer are diethylene glycol dibenzoate, and the preservative is DDAC.
Using GB 18583-2008《Limits of harmful substances in indoor decorating and refurnishing materials adhesive》Gas in standard annex F
Phase chromatography tests total volatile organism (TVOC) content, and the TVOC contents of interface treating agent are 19g/L, with comparative example
Sample is compared, and TVOC contents reduce 59.6%, and compatibility is good between each component, and obtaining viscosity after rotated formula viscosimeter test is
19000mPas, not only ensure d spiss but also produced without sedimentation, and meet Environment Protect in China standard HJ 2541-2016《Ring
Border famous special product technical requirements adhesive》Requirement.
Embodiment 8
7kg water is added first in dissolution kettle, 0.4kg polyvinyl alcohol is added into dissolution kettle dissolving under agitation, then will be molten
The polyvinyl alcohol water solution that has solved is sent into polymeric kettle, add 20g emulsifier for mixing it is uniform after, be warming up to 70 DEG C, it is equal to polymeric kettle
Even dropwise addition 20g ammonium persulfates and 1.5kg vinyl acetates, dropwise reaction time are 4 hours, add 55g grafting end-vinyls
After the sepiolite of carboxyl super branched polyester, continue reaction 2 hours, after adding 15g sodium acid carbonates, be cooled to 50 DEG C, add 50g
Polyethyleneimine and 50g trimethylolpropanes-three (3- aziridinyls propionic ester), after reacting 1 hour, add 0.4kg plasticizer
With 20g preservatives, discharged after being down to room temperature, that is, obtain interface treating agent, the emulsifying agent is alkoxy polyethylene hydroxy second
Alcohol, the plasticizer are diethylene glycol dibenzoate, and the preservative is DDAC.
Using GB 18583-2008《Limits of harmful substances in indoor decorating and refurnishing materials adhesive》Gas in standard annex F
Phase chromatography tests total volatile organism (TVOC) content, and the TVOC contents of interface treating agent are 18g/L, with comparative example
Sample is compared, and TVOC contents reduce 61.7%, and compatibility is good between each component, and obtaining viscosity after rotated formula viscosimeter test is
19400mPas, not only ensure d spiss but also produced without sedimentation, and meet Environment Protect in China standard HJ 2541-2016《Ring
Border famous special product technical requirements adhesive》Requirement.
Embodiment 9
6.5kg water is added first in dissolution kettle, 0.35kg polyvinyl alcohol is added into dissolution kettle dissolving under agitation, then will
The polyvinyl alcohol water solution dissolved is sent into polymeric kettle, after addition 30g emulsifier for mixing is uniform, 70 DEG C is warming up to, to polymeric kettle
20g ammonium persulfates and 1.4kg vinyl acetates is uniformly added dropwise, the dropwise reaction time is 3 hours, adds 55g grafting end ethene
After the sepiolite of base and carboxyl super branched polyester, continue reaction 1 hour, after adding 15g sodium acid carbonates, be cooled to 50 DEG C, add
60g polyethyleneimines and 40g trimethylolpropanes-three (3- aziridinyls propionic ester), after reacting 2 hours, add 0.2kg plasticising
Agent and 30g preservatives, discharge after being down to room temperature, that is, obtain interface treating agent, and the emulsifying agent is alkoxy polyethylene hydroxy
Ethanol, the plasticizer are diethylene glycol dibenzoate, and the preservative is DDAC.
Using GB 18583-2008《Limits of harmful substances in indoor decorating and refurnishing materials adhesive》Gas in standard annex F
Phase chromatography tests total volatile organism (TVOC) content, and the TVOC contents of interface treating agent are 16g/L, with comparative example
Sample is compared, and TVOC contents reduce 66%, and compatibility is good between each component, and obtaining viscosity after rotated formula viscosimeter test is
19900mPas, not only ensure d spiss but also produced without sedimentation, and meet Environment Protect in China standard HJ 2541-2016《Ring
Border famous special product technical requirements adhesive》Requirement.
The interface treating agent prepared from above-described embodiment and comparative example, the present invention, has relatively low VOC, has simultaneously
There is excellent viscosity.
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (9)
1. a kind of low VOC environment-friendly concretes interface treating agent, it is characterised in that by grafting end-vinyl and carboxyl super branched polyester
Sepiolite, vinyl acetate-ethylene copolymerization emulsions, polyethyleneimine and trimethylolpropane-three (3- aziridinyls propionic ester)
Cross-linking reaction is carried out to be prepared.
2. low VOC environment-friendly concretes interface treating agent according to claim 1, it is characterised in that the grafting end ethene
The sepiolite of base and carboxyl super branched polyester is prepared in accordance with the following methods：
A) using 3- aminopropyl triethoxysilanes in acid condition, sepiolite is activated；
B) by step A) sepiolite after obtained activation reacted with end-vinyl and carboxyl super branched polyester, is grafted
The sepiolite of end-vinyl and carboxyl super branched polyester.
3. according to the low VOC environment-friendly concretes interface treating agent described in claim 2, it is characterised in that the end-vinyl and
Carboxyl super branched polyester has following structure：
Wherein,
4. a kind of preparation method of low VOC environment-friendly concretes interface treating agent, it is characterised in that comprise the following steps：
A) polyvinyl alcohol is dissolved in the water, emulsifying agent, ammonium persulfate and vinyl acetate is then added and carries out first time polymerization
Reaction, obtains vinyl acetate-ethylene copolymerization emulsions；
B) by step A) obtained vinyl acetate-ethylene copolymerization emulsions and grafting end-vinyl and the Hai Pao of carboxyl super branched polyester
Stone mixes, and carries out second of polymerisation；
C sodium acid carbonate, polyethyleneimine and trimethylolpropane-three (3- aziridinyls propionic ester)) are added and carries out cross-linking reaction,
Plasticizer and preservative are eventually adding, obtains interface treating agent.
5. preparation method according to claim 4, it is characterised in that the vinyl acetate, polyvinyl alcohol, persulfuric acid
Ammonium, emulsifying agent, sodium acid carbonate, water, plasticizer, preservative, sepiolite, the poly- second for being grafted end-vinyl and carboxyl super branched polyester
The mass ratio of alkene imines and trimethylolpropane-three (3- aziridinyls propionic ester) is (10~30)：(3~4)：(0.2~
0.3)：(0.2~0.4)：(0.15~0.25)：(60~90)：(2~4)：(0.1~0.3)：(0.1~1)：(0.1~1)：
(0.1~1).
6. preparation method according to claim 4, it is characterised in that the grafting end-vinyl and carboxyl super branched polyester
Sepiolite prepare in accordance with the following methods：
A) using 3- aminopropyl triethoxysilanes in acid condition, sepiolite is activated；
B) by step A) sepiolite after obtained activation reacted with end-vinyl and carboxyl super branched polyester, is grafted
The sepiolite of end-vinyl and carboxyl super branched polyester.
7. preparation method according to claim 6, it is characterised in that the end-vinyl and carboxyl super branched polyester according to
It is prepared by following methods：
Trimethylolpropane carries out first time condensation reaction with first dihydromethyl propionic acid, after reaction terminates, adds second batch
Dihydromethyl propionic acid carries out second of condensation reaction, after reaction terminates, adds the 3rd batch of dihydromethyl propionic acid and carries out third time contracting
Reaction is closed, then sequentially adds succinic anhydride, acrylic acid is reacted.
8. preparation method according to claim 7, it is characterised in that the trimethylolpropane, first dihydroxymethyl
The mass ratio of propionic acid, second batch dihydromethyl propionic acid and the 3rd batch of dihydromethyl propionic acid is 1：3：6：12.
9. preparation method according to claim 4, it is characterised in that the emulsifying agent is alkoxy polyethylene hydroxy second
Alcohol；The plasticizer is dipropylene glycol dibenzoate；The preservative is DDAC.
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| CN112573870A (en) * | 2019-09-29 | 2021-03-30 | 华新水泥股份有限公司 | Self-leveling terrace material and preparation method thereof |
| CN116903285A (en) * | 2023-07-10 | 2023-10-20 | 青岛众祥高分子材料有限公司 | Modified sepiolite and preparation method thereof |
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