CN105037680B - A kind of osmosis type modified aqueous polyurethane waterproofing agent - Google Patents
A kind of osmosis type modified aqueous polyurethane waterproofing agent Download PDFInfo
- Publication number
- CN105037680B CN105037680B CN201510349614.5A CN201510349614A CN105037680B CN 105037680 B CN105037680 B CN 105037680B CN 201510349614 A CN201510349614 A CN 201510349614A CN 105037680 B CN105037680 B CN 105037680B
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- CN
- China
- Prior art keywords
- aqueous polyurethane
- waterproofing agent
- polyalcohol
- osmosis type
- type aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 37
- 239000004814 polyurethane Substances 0.000 title claims abstract description 35
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 35
- 238000004078 waterproofing Methods 0.000 title claims abstract description 33
- -1 radical siloxane Chemical class 0.000 claims abstract description 46
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 45
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 28
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 28
- 239000004970 Chain extender Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 150000003077 polyols Chemical class 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000012948 isocyanate Substances 0.000 claims description 11
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- 150000001721 carbon Chemical group 0.000 claims description 10
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
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- DNPNFYJXUGCNNC-UHFFFAOYSA-N 4-hydroxy-2-(hydroxymethyl)butanoic acid Chemical compound OCCC(CO)C(O)=O DNPNFYJXUGCNNC-UHFFFAOYSA-N 0.000 claims description 6
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 4
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 4
- VVORZJSSSMSZJQ-UHFFFAOYSA-N 2-ethyl-4,4-dihydroxybutanoic acid Chemical compound CCC(C(O)=O)CC(O)O VVORZJSSSMSZJQ-UHFFFAOYSA-N 0.000 claims description 4
- AWKFZNCALGANRZ-UHFFFAOYSA-N 4,4-dihydroxy-2-methylbutanoic acid Chemical compound OC(=O)C(C)CC(O)O AWKFZNCALGANRZ-UHFFFAOYSA-N 0.000 claims description 4
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims description 4
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- GNYUQIKGCJOIOO-UHFFFAOYSA-N 3-hydroxy-2-(2-hydroxyethyl)butanoic acid Chemical compound CC(O)C(C(O)=O)CCO GNYUQIKGCJOIOO-UHFFFAOYSA-N 0.000 claims description 3
- QMMBZOSZCYBCDC-UHFFFAOYSA-N NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical class NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC QMMBZOSZCYBCDC-UHFFFAOYSA-N 0.000 claims description 3
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- XWOGAKURPHNKOA-UHFFFAOYSA-N n'-[3-[ethyl(dimethoxy)silyl]propyl]ethane-1,2-diamine Chemical class CC[Si](OC)(OC)CCCNCCN XWOGAKURPHNKOA-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
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- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical class CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 229920001223 polyethylene glycol Polymers 0.000 description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
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- 101000598921 Homo sapiens Orexin Proteins 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to osmosis type aqueous polyurethane waterproofing agent, osmosis type aqueous polyurethane waterproofing agent is prepared by the synthetic composition including polyalcohol, polyisocyanates, internal emulsifying agent, diamino radical siloxane, chain extender and water.The waterproofing agent applies layer concrete（28d）Impermeability pressure ratio it is higher.
Description
Technical field
The present invention relates to osmosis type modified aqueous polyurethane waterproofing agent, in particular it relates to international Patent classificating number
C09J175/00.The invention further relates to the preparation method of osmosis type modified aqueous polyurethane waterproofing agent.
Background technology
In recent years, because some underground structure waterproofing qualities are poor, basement leaking event is caused to happen occasionally.Ground
The leak of lower room not only adversely affects to the living environment of resident living, if underground concrete structure seeps water for a long time, a side
Face can be such that the calcium in concrete is largely lost in；On the other hand the steel bar corrosion in concrete can be made, so as to destroy underground coagulation
The globality of soil structure, and then have impact on the stability and service life of agent structure.Therefore high-rise underground knot is carried out
The waterproof of structure, a comfortable living environment can be not only brought to resident family, and be also century-old to the service life of agent structure
The thing of the matter of fundamental importance.
The conventional synthesis waterproofing agent of tradition mainly has organic silicon waterproofing agent and fluorine material waterproofing agent, but organic silicon is prevented
Aqua mechanical property and adhesion property are poor, and fluorine material waterproofing agent water resistance is preferable, but its price is high, in the market quantity compared with
It is few.
At present, also there is the production and selling of polyurethane water-proof, but it is met water and can reacted, crosslinking generates not soluble in water gather
Zoarium, it is not easy to be diluted with water and washes away, and caused carbon dioxide generates secondary diffusion phenomena in reaction, thus have larger expansion
The advantages that dissipating radius and coagulated volume ratio.But compared with high hydrophobic organosilicon and fluorine material, its water resistance is far from
And and polyurethane water-proof agent common on the market contain a large amount of organic solvents, environment and human body are harmful to.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of osmosis type aqueous polyurethane waterproofing agent, by including more
First alcohol, polyisocyanates, internal emulsifying agent, diamino radical siloxane, the synthetic composition of chain extender and water are prepared, the chain extension
Agent has following structure：
Wherein, R1For the divalent alkyl with 1-5 carbon atom, R2For divalent alkyl or list with 1-2 carbon atom
Key.
The mol ratio 1 of described polyisocyanates and diamino radical siloxane:0.01-0.2.
Described chain extender is selected from 5- (3- aminopropyls) -1H- imidazoles -2- amine, 5- (4- aminobutyls) -1H- imidazoles -2-
One or more in amine, 5- (5- Aminopentyls) -1H- imidazoles -2- amine, 5- (2- amino-ethyls) -1H- imidazoles -2- amine.
Described diamino radical siloxane is selected from N- aminoethyl -3- aminopropyltriethoxy dimethoxysilanes, N- aminoethyl -3- ammonia
Ethyl dimethoxysilane, the one or more in N- aminoethyl -3- aminopropyltriethoxy diethoxy silanes.
Described polyisocyanates is selected from 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, 4,4 ' diphenyl
One kind in methane diisocyanate, IPDI.
Described polyalcohol is selected from hydroxy-terminated polyester, PPG, PEPA, polycarbonate polyol, poly-
One or more in olefinic polyols, polyestercarbonate polyalcohol, polyether carbonate polyol, polyester amide polyol.
Described polyalcohol is carbon-carbon double bonds polyalcohol or carbon-carbon double bonds polyalcohol and not carbon-carbon double bonds polyalcohol
Mixture.
Described internal emulsifying agent is selected from 2,2 dimethylolpropionic acids, 2,2 dihydromethyl propionic acids, 2,2 dihydroxy ethyl butyric acid, and 2,2
Dihydroxy ethyl propionic acid, 2,3 dimethylolpropionic acids, 2,3 dihydromethyl propionic acids, 2,3 dihydroxy ethyl butyric acid, 2,3 dihydroxy ethyl propionic acid
In one or more.
The synthetic composition also includes the compound of the hydroxyl of 2 or more than 2 or with the ammonia of 2 or more than 2
The compound of base.
A kind of preparation method of osmosis type aqueous polyurethane waterproofing agent, comprises the following steps：
（1）Polyalcohol, part polyisocyanates and internal emulsifying agent are uniformly mixed at 7-10 DEG C；
（2）Polyamino siloxanes is slowly added under high velocity agitation, is reacted, and forms the side-chain structure of silicone-containing；
（3）Remaining polyisocyanates is added after reaction completely, 80 DEG C of reactions is warming up to and obtains performed polymer；
（4）Performed polymer is slowly added in the water containing chain extender, triethylamine is then added and neutralizes, obtain water-based poly- ammonia
Ester.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Embodiment
Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of art of the present invention
The identical implication that art personnel are generally understood that.When contradiction be present, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside the claim as entirety.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ",
" 1-3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope be intended to include its end value with
All integers and fraction within the range.
In addition, indefinite article " one kind " before key element of the present invention or component and "one" to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
Osmosis type aqueous polyurethane waterproofing agent, by including PPG, polyisocyanates, internal emulsifying agent, diaminourea silicon
The synthetic composition of oxygen alkane, chain extender and water is prepared, and the solid content of the osmosis type aqueous polyurethane waterproofing agent is 30-
50%, the chain extender has following structure：
Wherein, R1For the divalent alkyl with 1-5 carbon atom, R2For divalent alkyl or list with 1-2 carbon atom
Key.
Polyisocyanates
The polyisocyanates that the present invention uses is used by general formula R (NCO)n(R in formula represents that any one is carbon containing and organised
Compound, and n >=2) represent compound.
As this organic polyisocyanates, compound known to any one can be used, wherein representational example
Have：Isosorbide-5-Nitrae-tetramethylene diisocyanate, 1,6- HDIs, the methylene diisocyanate of 1,12- 12, hexamethylene-
1,3- or Isosorbide-5-Nitrae-diisocyanate, 1- isocyanato- -3- isocyanatomethyls -3,5, (alias is different for 5- trimethyl-cyclohexanes
Isophorone diisocyanate, hereinafter referred to as IPDI), double-(4- isocyanatocyclohexyls) methane (being hereinafter referred to as hydrogenated with MDI),
2- or 4- isocyanatocyclohexyls -2 '-isocyanatocyclohexyl methane, 1,3- or Isosorbide-5-Nitrae-bis--(isocyanatomethyl) -
Hexamethylene, double-(4- isocyanato- -3- methylcyclohexyls) methane, 1,3- or Isosorbide-5-Nitrae-α, α, α ', α '-durol dimethyl
Diisocyanate, 2,4- or the isocyanato- toluene of 2,6- bis-, 2,2 '-, 2,4 '-or 4,4 '-two isocyanato- diphenylmethyls
Alkane (abbreviation MDI), 1,5- naphthalene diisocyanates, p- or m- phenylene diisocyanates, xylylene diisocyanate or diphenyl-
4,4 '-diisocyanate etc..
In these materials, from be readily available and be easily controlled with from the aspect of the reaction of aftermentioned hydroxyl, preferably 2,4- first
Phenylene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, 4,4 ' methyl diphenylene diisocyanates, IPDI.
In addition, these diisocyanate can be used alone, can also be applied in combination two or more.
Polyalcohol
Heretofore described polyurethane contains the polyalcohol as monomer component.Polyalcohol is that have more than 2 hydroxyls
Alcohols general designation, the preferred compound with 2~3 hydroxyls.In addition, polyalcohol passes through gel permeation chromatography (GPC) method
The styrene conversion number-average molecular weight of measure is 400~5,000, more preferably 400~4,100, particularly preferably 400~2,
500.If the number-average molecular weight of polyalcohol is in aforementioned range, rigidity (hardness, modulus of elasticity) and toughness can be synthesized
(tensile strength) balances good polyurethane.When the number-average molecular weight of polyalcohol is more than 5,000, obtained polyurethane is easily caused
Rigidity it is low.On the other hand, when the number-average molecular weight of polyalcohol is less than 400, the toughness of polyurethane for being easily caused to obtain is low.
Polyalcohol usually used in polyurethanes technology field can be used, such as hydroxy-terminated polyester can be enumerated, gathered
Ethoxylated polyhydric alcohol, PEPA, polycarbonate polyol, polyolefin polyhydric alcohol, polyestercarbonate polyalcohol, polyether carbonate are more
First alcohol, polyester amide polyol etc..In these materials, from the aspect of hydrolytic resistance is good, preferred, polyethers polyalcohol, polyene
Hydrocarbon polyalcohol, polycarbonate polyol.
PPG, such as polytetramethylene glycol (PTMG), polypropylene glycol (PPG), polyethylene glycol (PEG), polycyclic oxygen
Ethane propane diols (EO-PO), PEO Bisphenol A Ether, PPOX bisphenol-A etc..
The own diester of PEPA, such as polybutene, the own diester of poly- hexamethylene, polycaprolactone polyol.
Polycarbonate polyol, the reaction life of the polyester-diols such as polycaprolactone polyol and alkylene carbonates can be enumerated
Into thing, make reaction product of reactant mixture and organic dicarboxylic acid obtained by ethylene carbonate and polyol reaction etc..
Furthermore it is also possible to use 1,3-PD, BDO, 1,6- hexylene glycols, diethylene glycol, polyethylene glycol, poly-
The glycol such as propane diols, polytetramethylene glycol and phosgene, diallyl carbonate, the reaction product of ring type carbonic ester.
As said polyolefins polyalcohol, the present inventor is surprised to find that to select carbon-carbon double bonds more by experiment
First alcohol, when especially carbon-carbon double bonds polyalcohol is not used cooperatively with other, as hydroxy terminated polybutadiene, castor oil system are polynary
Alcohol, partly-hydrolysed ethylene vinyl acetate copolymer, the aqueous polyurethane waterproofing agent for polymerizeing to obtain have more preferable impermeabilisation
Performance.There is the polyalcohol of carbon-carbon double bond by using intramolecular, carbon-carbon double bond can be imported on polyurethane skeleton, using tool
The polyalcohol for having double bond can obtain the more preferable waterproofing agent of anti-permeability performance, and possible mechanism is that the inorganic constituents in cement promotes
Simultaneously chemical bonding in capillary hole wall, greatly suppresses the migration of hydrone for the oxidation of double bond.Preferably, using polyethylene glycol with
When the mixture of castor oil polyhydric alcohol is as polyalcohol, the anti-permeability performance of waterproofing agent is more preferable.
Internal emulsifying agent
Described internal emulsifying agent refers to 2 hydroxyls or amino and with carboxyl or sulfonic material, selectable
Including 2,2 dimethylolpropionic acids, 2,2 dihydromethyl propionic acids, 2,2 dihydroxy ethyl butyric acid, 2,2 dihydroxy ethyl propionic acid, 2,3 dihydroxy first
Base butyric acid, 2,3 dihydromethyl propionic acids, 2,3 dihydroxy ethyl butyric acid, 2,3 dihydroxy ethyl propionic acid.Described polyisocyanates and interior breast
The mol ratio 1 of agent:0.001-0.1.
Diamino radical siloxane
Diaminourea siloxane structure such as following formula：
In above formula,
R1 is C-C segments and/or C-O segments；
In R2, R3, R4, one of them is siloxanes, other two independent expression hydrogen atom, alkyl or aralkyl.
Selectable diamino radical siloxane is N- aminoethyl -3- aminopropyltriethoxy dimethoxysilanes, N- aminoethyl -3- ammonia
Ethyl dimethoxysilane, N- aminoethyl -3- aminopropyltriethoxy diethoxy silanes.
The mol ratio 1 of described polyisocyanates and diamino radical siloxane:0.01-0.2.
Chain extenderThe chain extender has following structure：
Wherein, R1For the divalent alkyl with 1-5 carbon atom, R2For divalent alkyl or list with 1-2 carbon atom
Key.
As a kind of preferable technical scheme, the mol ratio 1 of described polyisocyanates and chain extender:0.01-0.1.
After cement solidification, substantial amounts of the nanometer even hole of micron level be present, this some holes interconnects so that cement is prevented
It is water-based can not be high, as after micropore, aqueous polyurethane gradually dries out, and uses above-mentioned chain extender, energy for aqueous polyurethane filling
Enough obtain more preferable anti-permeability performance.
Found by the experiment of the present inventor, it is preferably impervious that chain extender selects R2 to have for the chain extender of singly-bound
Permeability energy, possible mechanism are the activity reductions of hydrogen on imidazoles, and chain extender can select 5- (3- aminopropyls) -1H- imidazoles -2-
Amine, 5- (4- aminobutyls) -1H- imidazoles -2- amine, 5- (5- Aminopentyls) -1H- imidazoles -2- amine, 5- (2- amino-ethyls) -1H-
One or more in imidazoles -2- amine.
Certainly, the present invention it is also an option that the compound with 2 or the hydroxyl of more than 2, with 2 or more than 2
The compound of amino be used cooperatively with foregoing chain extender.
Compound with 2 or the hydroxyl of more than 2 for example there are for example, ethylene glycol, diethylene glycol, triethylene glycol, third
Glycol, DPG, tripropylene glycol, 1,3-PD, 1,2- butanediols, 1,3-BDO, BDO, 2,3- fourths two
Alcohol, 3- methyl isophthalic acids, 5- pentanediols, neopentyl glycol, 2- methyl isophthalic acids, ammediol, 2- methyl-2-propyls -1,3-PD, 2- fourths
Base -2- ethyls -1,3-PD, 1,5-PD, 1,6- hexylene glycols, 2- methyl -2,4- pentanediol, 2,2,4- trimethyl -1,
3- pentanediols, 2- ethyls -1,3- hexylene glycol, 2,5- dimethyl -2,5- hexylene glycol, 2- butyl -2- hexyls -1,3-PD, 1,
The alicyclic ring of the aliphatic diol of 8- ethohexadiols, 2- methyl isophthalic acids, 8- ethohexadiols, 1,9- nonanediols etc., double hydroxymethyl hexamethylenes etc.
Glycol with aromatic rings of race's glycol, benzene dimethanol, double hydroxyl-oxethyl benzene etc. etc..
Compound with 2 or the amino of more than 2 for example there are for example, 2,4- or 2,6- toluenediamine, xyxylene
Diamines, 4, the aromatic diamine, ethylenediamine, 1,2- propane diamine, 1,6- hexamethylene diamines, 2,2- diformazans of 4 '-diphenylmethanediamiand etc.
Base -1,3- propane diamine, 2- methyl isophthalic acids, 5- pentanediamines, 1,3- 1,5-DAPs, 2,2,4- or 2,4,4- trimethylhexane diamines, 2-
Aliphatic diamine, the 1- ammonia of butyl -2- ethyls -1,5- pentanediamine, 1,8- octamethylenediamines, 1,9- nonamethylene diamines, 1,10- decamethylene diamines etc.
Base -3- amino methyls -3,5,5- trimethyl-cyclohexanes (IPDA), 4,4 '-double-hexyl methane diamines (hydrogenation MDA), different sub- third
Alicyclic diamine of butylcyclohexyl -4, the double aminomethyl cyclohexanes of 4 '-diamines, Isosorbide-5-Nitrae-diaminocyclohexane, 1,3- etc. etc..These
Chain extender can be used alone, can also 2 kinds or more than 2 be used in combination.Wherein, preferred ethylenediamine, propane diamine, 1,3- in the present invention
1,5-DAP, 2- methyl isophthalic acids, 5- pentanediamines, wherein, more preferably ethylenediamine, propane diamine.
A kind of preparation method of osmosis type aqueous polyurethane waterproofing agent, comprises the following steps：
（1）PPG, part polyisocyanates and internal emulsifying agent are uniformly mixed at 7-10 DEG C；
（2）Polyamino siloxanes is slowly added under high velocity agitation, is reacted, and forms the side-chain structure of silicone-containing；
（3）Remaining polyisocyanates is added after reaction completely, 80 DEG C of reactions is warming up to and obtains performed polymer；
（4）Performed polymer is slowly added in the water containing chain extender, triethylamine is then added and neutralizes, obtain water-based poly- ammonia
Ester.
Preferably, step（1）Reaction time be 0.5-3 hours；Step（2）Reaction time be 2-6 hours；
Due to amino and isocyanates reactivity ratio's hydroxyl and isocyanates it is strong, so the present invention is using compared with low temperature
Under the conditions of degree, suppress the reaction of hydroxyl and isocyanates, in order to polysiloxane-grafted into polyisocyanates containing amino,
Obtain the performed polymer containing polysiloxane, containing multiple isocyanate groups.
Embodiment 1, a kind of osmosis type aqueous polyurethane waterproofing agent, by including polyalcohol, polyisocyanates, internal emulsification
Agent, diamino radical siloxane, the synthetic composition of chain extender and water are prepared, and the chain extender has following structure：
Wherein, R1For the divalent alkyl with 1-5 carbon atom, R2For divalent alkyl or list with 1-2 carbon atom
Key.
Embodiment 2, identical with embodiment 1, difference is the mol ratio 1 of polyisocyanates and diamino radical siloxane:
0.01-0.2。
Embodiment 3, identical with embodiment 1, described chain extender is selected from 5- (3- aminopropyls) -1H- imidazoles -2-
Amine, 5- (4- aminobutyls) -1H- imidazoles -2- amine, 5- (5- Aminopentyls) -1H- imidazoles -2- amine, 5- (2- amino-ethyls) -1H-
One or more in imidazoles -2- amine.
Embodiment 4, identical with embodiment 1, described diamino radical siloxane is selected from N- aminoethyl -3- aminopropyltriethoxies
Dimethoxysilane, N- aminoethyl -3- aminopropyl ethyldimethoxysilanes, N- aminoethyl -3- aminopropyltriethoxy diethoxies
One or more in silane.
Embodiment 5, identical with embodiment 1, described polyisocyanates is selected from 2,4- toluene di-isocyanate(TDI)s, 2,6-
Toluene di-isocyanate(TDI), 4, one kind in 4 ' methyl diphenylene diisocyanates, IPDI.
Embodiment 6, identical with embodiment 1, described polyalcohol is selected from hydroxy-terminated polyester, PPG, gathered
Ester polyol, polycarbonate polyol, polyolefin polyhydric alcohol, polyestercarbonate polyalcohol, polyether carbonate polyol, polyester acyl
One or more in amine polyol.
Embodiment 7, identical with embodiment 1, described polyalcohol is carbon-carbon double bonds polyalcohol or carbon-carbon double bonds
The mixture of polyalcohol and not carbon-carbon double bonds polyalcohol.
Embodiment 8, identical with embodiment 1, described internal emulsifying agent is selected from 2,2 dimethylolpropionic acids, 2,2 dihydroxy first
Base propionic acid, 2,2 dihydroxy ethyl butyric acid, 2,2 dihydroxy ethyl propionic acid, 2,3 dimethylolpropionic acids, 2,3 dihydromethyl propionic acids, 2,3 two
Ethoxy butyric acid, the one or more in 2,3 dihydroxy ethyl propionic acid.
Embodiment 9, identical with embodiment 1, the synthetic composition also includes the change of the hydroxyl of 2 or more than 2
Compound or the compound with the amino of 2 or more than 2.
A kind of embodiment 10, preparation method of osmosis type aqueous polyurethane waterproofing agent, comprises the following steps：
（1）Polyalcohol, part polyisocyanates and internal emulsifying agent are uniformly mixed at 7-10 DEG C；
（2）Polyamino siloxanes is slowly added under high velocity agitation, is reacted, and forms the side-chain structure of silicone-containing；
（3）Remaining polyisocyanates is added after reaction completely, 80 DEG C of reactions is warming up to and obtains performed polymer；
（4）Performed polymer is slowly added in the water containing chain extender, triethylamine is then added and neutralizes, obtain water-based poly- ammonia
Ester.
Hereinafter, the present invention is explained in more detail by embodiment, it should be appreciated that these embodiments are only
It is illustrating and nonrestrictive.If without other explanations, raw materials used is all commercially available.
The present invention is described in detail referring to several examples.
Raw material sources：
A1 polyoxypropyleneglycols：Number-average molecular weight 2000 or so, the production of Nanjing Nanjing petrochemical plant；
A2 PPOX triols：Number-average molecular weight 1500 or so, the production of Nanjing Nanjing petrochemical plant；
A3 castor oil polyhydric alcohols U.S. Fan Telusi, number-average molecular weight 2000 or so.
A4 hydroxy terminated polybutadienes Japan Cao reaches NISSO PB, number-average molecular weight 2000 or so.
B1 TDI：Chemical pure, Shanghai 5-linked chemical plant；
B2 MDI：Chemical pure, Shanghai 5-linked chemical plant；
C1 methylol aminomethyl butyric acid：Chemistry is pure, Shanghai one chemical reagent work of purple；
D1 aminoethylaminopropyl dimethyl silicone polymers：Number-average molecular weight 3400；Jiangxi spark chemical plant；
E1 1,6- hexylene glycol：Chemical pure, Shanghai 5-linked chemical plant；
E2 1,3- 1,5-DAP chemistry are pure, Shanghai 5-linked chemical plant；
E3 5- (4- aminobutyls) -1H- imidazoles -2- methylamine chemistry is pure, Shanghai 5-linked chemical plant；
E4 5- (4- aminobutyls) -1H- imidazoles -2- aminations are pure, Shanghai 5-linked chemical plant；
E5 5- (3- aminopropyls) -1H- imidazoles -2- aminations are pure, Shanghai 5-linked chemical plant.
Evaluation method：
According to GB18445-2012 cementitious capillary waterproofing materials, band coating concrete is tested（28d）It is impervious
Pressure（MPa）And band coating concrete（28d）Impermeability pressure ratio（%）, the impermeability pressure of benchmark mortar or concrete（28d）
For 0.3.
Embodiment 1-6.
Embodiment 7-12.
| Component/parts by weight | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| A1 | 79 | 79 | 79 | 79 | 79 | 79 |
| A3 | 80 | 80 | 80 | 80 | 80 | 80 |
| B1 | 118.5 | 118.5 | 118.5 | 118.5 | 118.5 | 118.5 |
| C1 | 3 | 3 | 3 | 3 | 3 | 3 |
| D1 | 4 | 4 | 4 | 4 | 4 | 4 |
| E1 | 2 | |||||
| E2 | 1 | 1 | ||||
| E3 | 3 | 2 | ||||
| E4 | 3 | 2 | ||||
| E5 | 3 | |||||
| Triethylamine | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
| Water | 320 | 320 | 320 | 320 | 320 | 320 |
| Pressure ratio % | 241 | 264 | 285 | 280 | 291 | 299 |
Preparation technology：
（1）PPG, part polyisocyanates and internal emulsifying agent are uniformly mixed under 7-10 degrees Celsius；
（2）Polyamino siloxanes is slowly added under high velocity agitation, is reacted, and forms the side-chain structure of silicone-containing；
（3）Remaining polyisocyanates is added after reaction completely, 80 DEG C of reactions is warming up to and obtains performed polymer；
（4）Performed polymer is slowly added in the water containing chain extender, triethylamine is then added and neutralizes, obtain water-based poly- ammonia
Ester.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.It is every
The equivalent changes and modifications done according to present invention, it is encompassed by the scope of the claims of the present invention.
Claims (10)
- A kind of 1. osmosis type aqueous polyurethane waterproofing agent, by including polyalcohol, polyisocyanates, internal emulsifying agent, diaminourea silica The synthetic composition of alkane, chain extender and water is prepared, and the chain extender has following structure：Wherein, R1For the divalent alkyl with 1-5 carbon atom, R2For divalent alkyl or singly-bound with 1-2 carbon atom.
- 2. osmosis type aqueous polyurethane waterproofing agent according to claim 1, it is characterised in that described polyisocyanates with The mol ratio 1 of diamino radical siloxane:0.01-0.2.
- 3. osmosis type aqueous polyurethane waterproofing agent according to claim 1, it is characterised in that described chain extender is selected from 5- (3- aminopropyls) -1H- imidazoles -2- amine, 5- (4- aminobutyls) -1H- imidazoles -2- amine, 5- (5- Aminopentyls) -1H- imidazoles - One or more in 2- amine, 5- (2- amino-ethyls) -1H- imidazoles -2- amine.
- 4. osmosis type aqueous polyurethane waterproofing agent according to claim 1, it is characterised in that described diamino radical siloxane Selected from N- aminoethyl -3- aminopropyltriethoxy dimethoxysilanes, N- aminoethyl -3- aminopropyl ethyldimethoxysilanes, N- ammonia One or more in ethyl -3- aminopropyltriethoxy diethoxy silanes.
- 5. osmosis type aqueous polyurethane waterproofing agent according to claim 1, it is characterised in that described polyisocyanates choosing From 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, 4,4 '-methyl diphenylene diisocyanate, isophorone two One kind in isocyanates.
- 6. osmosis type aqueous polyurethane waterproofing agent according to claim 1, it is characterised in that described polyalcohol is selected from hydroxyl Base end capped polyesters, PPG, PEPA, polycarbonate polyol, polyolefin polyhydric alcohol, polyestercarbonate are polynary One or more in alcohol, polyether carbonate polyol, polyester amide polyol.
- 7. osmosis type aqueous polyurethane waterproofing agent according to claim 1, it is characterised in that described polyalcohol be containing Carbon-to-carbon double bond polyalcohol or carbon-carbon double key polyalcohol and the mixture without carbon-to-carbon double bond polyalcohol.
- 8. osmosis type aqueous polyurethane waterproofing agent according to claim 1, it is characterised in that described internal emulsifying agent is selected from 2,2- dimethylolpropionic acids, 2,2- dihydromethyl propionic acids, 2,2- dihydroxy ethyl butyric acid, 2,2- dihydroxy ethyl propionic acid, 2,3- dihydroxies Methylbutanoic acid, 2,3- dihydromethyl propionic acids, 2,3- dihydroxy ethyl butyric acid, the one or more in 2,3- dihydroxy ethyl propionic acid.
- 9. osmosis type aqueous polyurethane waterproofing agent according to claim 1, it is characterised in that the synthetic composition also wraps Include the compound of the hydroxyl of 2 or more than 2 or the compound with the amino of 2 or more than 2.
- 10. a kind of preparation method of the osmosis type aqueous polyurethane waterproofing agent prepared described in claim 1, comprises the following steps：(1) polyalcohol, part polyisocyanates and internal emulsifying agent are uniformly mixed at 7-10 DEG C；(2) diamino radical siloxane is slowly added under high velocity agitation, is reacted, and forms the side-chain structure of silicone-containing；(3) remaining polyisocyanates is added after reaction completely, is warming up to 80 DEG C of reactions and obtains performed polymer；(4) performed polymer is slowly added in the water containing chain extender, then adds triethylamine and neutralize, obtain aqueous polyurethane.
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| CN105237037A (en) * | 2015-11-24 | 2016-01-13 | 烟台顺隆化工科技有限公司 | Water-proofing agent for natural stone building |
| CN111527118A (en) * | 2017-12-28 | 2020-08-11 | 科思创德国股份有限公司 | Aqueous dispersion |
| CN110016321B (en) * | 2019-03-12 | 2020-10-30 | 长沙理工大学 | Waterproof bonding layer material for bridge deck pavement and preparation method thereof |
| CN112127156B (en) * | 2020-09-25 | 2021-04-20 | 珠海华大浩宏新材料有限公司 | Environment-friendly fluorine-containing waterproof agent and preparation method thereof |
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| CN103739811A (en) * | 2013-12-18 | 2014-04-23 | 上海东和胶粘剂有限公司 | Waterborne polyurethane and preparation method thereof |
| CN103756608A (en) * | 2013-12-18 | 2014-04-30 | 上海东和胶粘剂有限公司 | High-frequency hot pressing adhesive |
| CN103820019A (en) * | 2014-03-07 | 2014-05-28 | 广州北峻工业材料有限公司 | Water-based polyurethane-containing stripping coating and preparation method thereof |
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| CN103739811A (en) * | 2013-12-18 | 2014-04-23 | 上海东和胶粘剂有限公司 | Waterborne polyurethane and preparation method thereof |
| CN103756608A (en) * | 2013-12-18 | 2014-04-30 | 上海东和胶粘剂有限公司 | High-frequency hot pressing adhesive |
| CN103820019A (en) * | 2014-03-07 | 2014-05-28 | 广州北峻工业材料有限公司 | Water-based polyurethane-containing stripping coating and preparation method thereof |
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