CN106674481B - A kind of extremely frigid zones concrete works polyurethane foam injecting paste material and method - Google Patents
A kind of extremely frigid zones concrete works polyurethane foam injecting paste material and method Download PDFInfo
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- CN106674481B CN106674481B CN201611011468.6A CN201611011468A CN106674481B CN 106674481 B CN106674481 B CN 106674481B CN 201611011468 A CN201611011468 A CN 201611011468A CN 106674481 B CN106674481 B CN 106674481B
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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
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- 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
- C08G2270/00—Compositions for creating interpenetrating networks
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- 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 invention belongs to macromolecule technical field of fine, disclosed a kind of extremely frigid zones concrete works polyurethane foam injecting paste material and method, the injecting paste material of use is mainly obtained by two component A, B component component hybrid reactions, component A is the polyether polyol of machine Si modification, and B component is organic-silicon-modified isocyanates and poly isocyanate.It is 0.8:1-1.2:1 that the injecting paste material, which is by the mass ratio of component A, two component of B component,.The present invention is modified by organosilicon flexibility, can be improved the reactivity of isocyanates, and obtained polyurathamc has good elasticity, and strong to the cementability of concrete, frothing percentage is moderate, phenomena such as being not easily susceptible to the influence of external environment and produce fracture, fall off.Polymer interpenetration network structure is formed by organosilicon network and polyurethane network, is able to maintain the good intensity of polymer network, so as to play quick water blockoff and permanent durable effect under the adverse circumstances of extremely frigid zones.
Description
Technical field
The invention belongs to macromolecule technical field of fine, it is related to a kind of extremely frigid zones concrete works and is sent out with polyurethane
Steep injecting paste material and method.
Background technique
Concrete is a kind of heterogeneous brittle material containing multiple holes, inside there are a large amount of hole, tensile strength it is low and
Lacking toughness.Once extraneous tension is more than its tensile capacity, crack will be generated, and once there is crack in concrete, not only
Inside concrete can be entered for external etching medium and convenience is provided, accelerate the failure process, influences its durability, and can shadow
Its appearance is rung, the problems such as leakage, freeze-thaw damage, intensity decline are then caused.Wherein slip casting is side the most effective
Method.Slurry injection technique does not destroy original structure on the basis of original concrete structure as far as possible, can again to damage concrete structure into
Row is repaired, and effectively improves concrete anti-seepage reinforcement ability, mechanical property, guarantees structure normal use, extending structure service life,
It is the effective means that anti-Seepage reinforcement and strengthening is carried out to concrete structure.Compared with cement injection, clay slip casting, chemical grouting
Leak stopping is carried out using the liquid chemical grout material of modest viscosity, good to the concrete castability and accessibility of fine crack, curing time is optional
It selects, therefore, chemical grouting becomes common water-proof method for stopping leakage in the engineerings such as building, water conservancy.Polyurethane injecting paste material utilizes different
Cyanate and water react and then the consolidation that foams achievees the purpose that water blockoff and reinforcing, can react in any condition with water and
Solidification, slurries will not be lost because diluting with water；In addition, its induration has variform because forming difference, can be
The plastic body of hardness, is also possible to the rubber bodies of good-extensibility.
However, common polyurethane foam injecting paste material is used at 20 DEG C or so, in extremely frigid zones, construction temperature is often
As low as 10 DEG C hereinafter, and frequent Frozen-thawed cycled need to be subjected to, thus, conventional polyurathamc injecting paste material is not able to satisfy use
It is required that.In addition, grout curing process is sensitive to ambient temperature under psychro-environment, when environment temperature reduces, slurries are easy to appear
Solidify the problems such as slack-off, induration overall performance is caused to decline；Non-volatile content is too low, and the solvent of slurries addition is excessive, leads
Dimension linearity change rate is big after causing induration dry, and volume stability is bad, and durability is poor, material premature failure, percolating water weight
Recurrence life.Conventional polyurethane injecting paste material is difficult to meet above-mentioned application requirement.
Summary of the invention
The problem to be solved by the invention is to provide a kind of extremely frigid zones concrete works polyurethane foam injecting paste materials
And method.
For achieving the above object, present invention provide the technical scheme that
A kind of extremely frigid zones polyurethane foam injecting paste material, the injecting paste material are by A, and two component hybrid reaction of B obtains.A,
The mass ratio of two component of B is 0.8:1-1.2:1.
Its component A is organic-silicon-modified polyether polyol.Its preparation process is divided into following two step.
1) preparation of alkoxy end-capped polysiloxanes
Take end hydroxyl silicone oil (viscosity 500mPas) 100g in a round bottom flask, under nitrogen protection heating stirring to 80 DEG C,
Methyltrimethoxysilane 10g is slowly added dropwise with dropping funel, after being added dropwise, after continuing heating stirring 5h, is subtracted using oil pump
Pressure distillation is to there is no bubble generation, and residue is alkoxy end-capped polysiloxanes, reaction equation such as following formula in bottle
It is shown:
2) preparation of organosilicon modified polyether polyalcohol
Take polyether polyol (selected from polyethylene glycol 400-1000, polypropylene glycol 400-1600, polypropylene oxide triol N-
One of 330 or more than one mixture) 100g, the alkoxy end-capped polysiloxanes 10g in 1), nitrogen protection is added
Lower 120 DEG C are stirred to react after 5h and are evaporated under reduced pressure using oil pump to there is no bubbles to generate to get organosilicon modified polyether polyalcohol.
Its B component is the mixture of organic-silicon-modified isocyanates and poly isocyanate, mass ratio 0.5:1-
2:1.
Its organic-silicon-modified isocyanates the preparation method is as follows:
Amido silicon oil (molecular weight 3000) 20g is taken, stirred under nitrogen atmosphere is heated to 100 DEG C, by 40g MDI (4,4`- bis-
Methylenebis phenyl isocyanate) it is slowly added dropwise into reaction system, after being added dropwise, continue heating reaction 3h to get organic
The isocyanates of Si modification.Its reaction equation is as follows:
Its poly isocyanate is commercially available poly MDI.
Due to the adoption of the technical scheme as described above, the present invention has the following advantages:
A kind of extremely frigid zones concrete works of the invention are with polyurethane foam injecting paste material and method advantage: firstly,
By organosilicon modified polyether polyalcohol and isocyanates, the good flexibility of polyether polyol is assigned, reduces the viscous of polyalcohol
Degree, to improve the ability of its molecular motion, improves reactivity.Secondly, organosilicon network imparting polymer is good
Flexibility, so that elasticity is good for polymer network, phenomena such as being not easily susceptible to the influence of external environment and produce fracture, fall off.The
Three, polymer interpenetration network structure is formed by organosilicon network and polyurethane network, so as to keep polymer network good
Good intensity, obtained foams intensity is high, and durability is good.
Specific embodiment
The present invention is further illustrated by following unrestricted embodiment, but it should be understood that the embodiment is only used
With the present invention, rather than to limit the scope of the invention.
A kind of extremely frigid zones concrete works polyurethane foam injecting paste material, the injecting paste material are by component A, B component
Hybrid reaction obtains；Component A, B component two constituent mass ratios be 0.8:1-1.2:1；Its step are as follows:
One, component A is organic-silicon-modified polyether polyol, and component A prepares specific steps are as follows:
1) preparation of alkoxy end-capped polysiloxanes takes end hydroxyl silicone oil (viscosity 500mPas) 100g to burn in round bottom
In bottle, heating stirring is to 80 DEG C under nitrogen protection --- 120 DEG C, methyltrimethoxysilane 10g is slowly added dropwise with dropping funel,
After being added dropwise, after continuing heating stirring 5h, it is evaporated under reduced pressure using oil pump to there is no bubbles to generate to get component A；It is residual in bottle
Excess is alkoxy end-capped polysiloxanes, and reaction equation is as follows:
2) preparation of organosilicon modified polyether polyalcohol, takes polyether polyol, is selected from polyethylene glycol 400-1000, and poly- the third two
The alkane in step 1) is added in alcohol 400-1600, one of polypropylene oxide triol N-330 or more than one mixture 100g
The polysiloxanes 10g of oxygroup sealing end, lower 120 DEG C of nitrogen protection are stirred to react after 5h and are evaporated under reduced pressure using oil pump to there is no bubbles
It generates to get organosilicon modified polyether polyalcohol:
Two, B component is the mixture of organic-silicon-modified isocyanates and poly isocyanate, mass ratio 0.5:1-
2:1；
The organic-silicon-modified isocyanates prepares specific steps are as follows: and the molecular weight 3000 for taking amido silicon oil is 20g,
Stirred under nitrogen atmosphere is heated to 100 DEG C, and 40g MDI (4,4`- methyl diphenylene diisocyanate) is slowly added dropwise to reaction
In system, after being added dropwise, continue heating reaction 3h to get organic-silicon-modified isocyanates；Its reaction equation is as follows:
Three, component A and B component are obtained into foaming grouting material according to mass ratio 0.8:1 to 1.2:1 hybrid reaction, it is therein
Poly isocyanate is commercially available poly MDI.
Embodiment 1
400 100g of taking polyethylene glycol, is added alkoxy end-capped polysiloxanes 10g, and the lower 120 DEG C of stirrings of nitrogen protection are anti-
It is evaporated under reduced pressure using oil pump to there is no bubbles to generate to get component A after answering 5h.Poly MDI 50g is taken, the organic of 100g is added
Si modification isocyanates is to get B component.By component A and B component according to mass ratio 0.8:1 as foaming grouting material.
Embodiment 2
1000 100g of taking polyethylene glycol, is added alkoxy end-capped polysiloxanes 10g, and the lower 120 DEG C of stirrings of nitrogen protection are anti-
It is evaporated under reduced pressure using oil pump to there is no bubbles to generate to get component A after answering 5h.Poly MDI 100g is taken, 100g is added has
Machine Si modification isocyanates is to get B component.By component A and B component according to mass ratio 1:1 as foaming grouting material.
Embodiment 3
400 100g of polypropylene glycol is taken, alkoxy end-capped polysiloxanes 10g is added, the lower 120 DEG C of stirrings of nitrogen protection are anti-
It is evaporated under reduced pressure using oil pump to there is no bubbles to generate to get component A after answering 5h.Poly MDI 200g is taken, 100g is added has
Machine Si modification isocyanates is to get B component.By component A and B component according to mass ratio 1.1:1 as foaming grouting material.
Embodiment 4
1600 100g of polypropylene glycol is taken, alkoxy end-capped polysiloxanes 10g is added, the lower 120 DEG C of stirrings of nitrogen protection are anti-
It is evaporated under reduced pressure using oil pump to there is no bubbles to generate to get component A after answering 5h.Poly MDI 50g is taken, the organic of 100g is added
Si modification isocyanates is to get B component.By component A and B component according to mass ratio 1.2:1 as foaming grouting material.
Embodiment 5
Polypropylene oxide N-330 100g is taken, alkoxy end-capped polysiloxanes 10g is added, lower 120 DEG C of nitrogen protection are stirred
It is evaporated under reduced pressure using oil pump to there is no bubbles to generate to get component A after mixing reaction 5h.Poly MDI 50g is taken, is added 100g's
Organic-silicon-modified isocyanates is to get B component.By component A and B component according to mass ratio 1:1 as foaming grouting material.
Embodiment 6
Polypropylene oxide N-330 50g, Macrogol 600 20g, 1000 30g of polypropylene glycol are taken, is added alkoxy end-capped
Polysiloxanes 10g, lower 120 DEG C of nitrogen protection are stirred to react after 5h and are evaporated under reduced pressure using oil pump to there is no bubbles to generate, i.e.,
Obtain component A.Poly MDI 50g is taken, the organic-silicon-modified isocyanates of 100g is added to get B component.Component A and B component are pressed
It is the grouting material that foams according to mass ratio 1:1.
Claims (1)
1. a kind of extremely frigid zones concrete works polyurethane foam injecting paste material, it is characterised in that: the injecting paste material is by A group
Divide, B component hybrid reaction obtains；Component A, B component two constituent mass ratios be 0.8:1-1.2:1；Its step are as follows:
One, component A is organic-silicon-modified polyether polyol, and component A prepares specific steps are as follows:
1) preparation of alkoxy end-capped polysiloxanes takes the end hydroxyl silicone oil 100g of viscosity 500mPas in a round bottom flask,
Heating stirring is to 80 DEG C under nitrogen protection --- and 120 DEG C, methyltrimethoxysilane 10g is slowly added dropwise with dropping funel, is added dropwise
After, after continuing heating stirring 5h, it is evaporated under reduced pressure using oil pump to there is no bubbles to generate to get component A；Residue in bottle
As alkoxy end-capped polysiloxanes, reaction equation are as follows:
2) preparation of organosilicon modified polyether polyalcohol, takes polyether polyol, is selected from polyethylene glycol 400-1000, polypropylene glycol
The alcoxyl in step 1) is added in 400-1600, one of polypropylene oxide triol N-330 or more than one mixture 100g
The polysiloxanes 10g of base sealing end, lower 120 DEG C of nitrogen protection are stirred to react after 5h and are evaporated under reduced pressure using oil pump to there is no bubbles to produce
Life is to get organosilicon modified polyether polyalcohol；
Two, B component is the mixture of organic-silicon-modified isocyanates and poly isocyanate, mass ratio 0.5:1-2:1；
The organic-silicon-modified isocyanates prepares specific steps are as follows: the molecular weight 3000 for taking amido silicon oil is 20g, nitrogen
It is heated with stirring to 100 DEG C under protection, 40g MDI (4,4`- methyl diphenylene diisocyanate) is slowly added dropwise to reaction system
In, after being added dropwise, continue heating reaction 3h to get organic-silicon-modified isocyanates；Its reaction equation is as follows:
Three, component A and B component are obtained into foaming grouting material, poly therein according to mass ratio 0.8:1 to 1.2:1 hybrid reaction
Isocyanates is commercially available poly MDI.
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| CN108503789B (en) * | 2018-03-02 | 2020-11-10 | 黎明化工研究设计院有限责任公司 | Open-cell polyurethane high-resilience foam composition and foam preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103075A (en) * | 1985-04-22 | 1987-01-28 | 煤炭工业部煤炭科学研究院北京开采研究所 | Reinforcing, water blockoff polyurethane material |
| CN1318589A (en) * | 2001-05-28 | 2001-10-24 | 中国科学院广州化学研究所 | Modified furfural-acetone epoxy as reinforcing, concreting and grouting material and its preparation |
| CN1470544A (en) * | 2003-06-24 | 2004-01-28 | 中国科学院广州化学研究所 | Method for preparing amino silicone oil modified polyurethane |
| CN104974332A (en) * | 2015-07-03 | 2015-10-14 | 中国铁道科学研究院铁道建筑研究所 | Foaming-free fast-curing high-strength leak-stopping waterproof polyurethane grouting material |
-
2016
- 2016-11-17 CN CN201611011468.6A patent/CN106674481B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103075A (en) * | 1985-04-22 | 1987-01-28 | 煤炭工业部煤炭科学研究院北京开采研究所 | Reinforcing, water blockoff polyurethane material |
| CN1318589A (en) * | 2001-05-28 | 2001-10-24 | 中国科学院广州化学研究所 | Modified furfural-acetone epoxy as reinforcing, concreting and grouting material and its preparation |
| CN1470544A (en) * | 2003-06-24 | 2004-01-28 | 中国科学院广州化学研究所 | Method for preparing amino silicone oil modified polyurethane |
| CN104974332A (en) * | 2015-07-03 | 2015-10-14 | 中国铁道科学研究院铁道建筑研究所 | Foaming-free fast-curing high-strength leak-stopping waterproof polyurethane grouting material |
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