CN103834159B - Soluble polyurethane chemical grouting material of environment-friendly type and preparation method thereof - Google Patents
Soluble polyurethane chemical grouting material of environment-friendly type and preparation method thereof Download PDFInfo
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- CN103834159B CN103834159B CN201410072943.5A CN201410072943A CN103834159B CN 103834159 B CN103834159 B CN 103834159B CN 201410072943 A CN201410072943 A CN 201410072943A CN 103834159 B CN103834159 B CN 103834159B
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Abstract
A kind of soluble polyurethane chemical grouting material of environment-friendly type, under anaerobic and anhydrous condition, by polyethers, retarder mixes, put in reactor, under stirring, carry out the degassed process of negative pressure dehydration 1.5～3 hours, isocyanates is added after being cooled to 10～42 DEG C, at 78～85 DEG C of temperature, carry out polyreaction 2～3 hours,-NCOwt% the content controlling performed polymer is reaction end between 20～35%, the prepolymer reaction liquid generated cools to 40-50 DEG C, add high boiling point double solvents 10-50 weight portion and foam stabiliser 0.5-3 weight portion, stir, add retarder, surfactant, catalyst, plasticizer, it is uniformly mixed, namely environment-friendly water-soluble polyurethane chemical grouting material is obtained。
Description
Technical field
The invention belongs to the compositions field of polyurethane, be specifically related to soluble polyurethane chemical grouting material of a kind of environment-friendly type and preparation method thereof。
Background technology
Polyurethanes, referred to as polyurethane。English name is polyurethane, referred to as PU。On the main chain of macromolecular structure, the macromolecule polyalcohol containing a lot of carbamate groups (NHCOO) is referred to as polyurethane, and it is formed by organic diisocyanate or polyisocyanates and dihydroxy or polyhydric compound addition polymerization。Polyurethane material is class purposes engineering material widely, and its industrialized production is reacted by organic isocyanate and the multiple compound containing terminal hydroxy group and prepared mostly。The difference of the functional group applied selected in actual production or the difference of processing method, can prepare the polyurethane industrial product that action function difference, manifestation mode are also different。The form of polyurethane synthetic material is varied, there is very soft and very hard foam plastics, corrosion resistant coating, paint, the elastomer that anti-wear performance is good, synthetic leather, coating resin, the elastic fiber of high resilience, the fluid sealant and adhesive etc. that adhesive property is excellent, define one step by step and there is excellent properties and highly important novel artificial synthetic materials series。Development along with polyurethane material product research manufacture and application technology, this high molecular polymer has had changed into the production from daily life to industrial or agricultural, material indispensable from style medical apparatus and instruments to each fields such as aerospace craft manufactures, is widely used in many fields such as room articles for use, garment fabric, medical apparatus and instruments, electronic component, petrochemical industry, automobile making, civil construction, transportation, mine articles for use, aviation, agricultural。
Polyurethane grouting material is divided into water solublity grouting material and oil-soluble grouting material two kinds, and both grouting materials can act as the effect on waterproofing and leakage-stopping, reinforcing engineering basis。Under normal circumstances, after reinforcing with oil-soluble polyurethane material, the mechanical property of the induration formed is better, water resistance good, it is adaptable in the engineering of consolidating crack or water proofing property。After soluble polyurethane material consolidation, the bag water yield of the induration formed is big, and leakage performance is better, it is adaptable to water blockoff, shallow-layer reinforcing engineering etc.。
Soluble polyurethane grouting material is to be synthesized, by isocyanates and water miscible polyether material, the Polymeric Grouting Materials prepared, and is generally the liquid of one pack system。There is quick polyreaction in this grouting material, expands in the volume short time and form induration with the material such as the silt particle soil stone of surrounding after can meeting water。The grouting material of soluble polyurethane mainly has following several advantage: the environment being suitable for low temperature, having a large amount of water to exist；Induration layer is waterproof, has the function of waterproof；Serosity is met water and is produced reaction generation CO2 gas, produces pressure and makes serosity enter among tiny crack, forms secondary pouring, and concrete castability is good；Slurry viscosity is adjustable, and construction equipment is easy, it is easy to clean。Wherein hydrophobic polyurethane grouting material, adhesion strength is high, and performance is better than waterborne polyurethane grouting material。But needing in formula to add organic solvent, the solvent that hydrophobic polyurethane grouting material of the prior art is conventional has acetone, toluene, dimethylbenzene etc.。Toluene and dimethylbenzene have penetrating odor, toxicity is bigger, workmen and environment there is certain negative effect, flash-point all < 60 DEG C of these three organic solvent simultaneously, belong to flammability hazard chemicals, produced, transport, use each link to bring burning, blast, many unsafe factors such as poisoning。And the natural environment that the mankind are depended on for existence pollutes。
Summary of the invention
It is an object of the invention to avoid above-mentioned weak point of the prior art, and provide a kind of without inflammable, explosive, toxic solvent, the preparation method of the environmentally friendly hydrophobic polyurethane grouting material that the grouting technical specification such as serviceability and adhesion strength is still excellent。
For realizing described purpose, technical scheme provided by the invention is as follows:
The soluble polyurethane chemical grouting material of a kind of environment-friendly type, it is characterised in that preparation process comprises the following steps:
Prepare performed polymer: under anaerobic and anhydrous condition, by polyethers, retarder mixing, put in reactor, under stirring, carry out the degassed process of negative pressure dehydration 1.5～3 hours, add isocyanates after being cooled to 10～42 DEG C, at 78～85 DEG C of temperature, carrying out polyreaction 2～3 hours ,-NCOwt% the content controlling performed polymer is reaction end between 20～35%；Described polyethers is that Hydrophilicrto polyether (EP-4000) mixes with 80/20 ratio with common polyether (N210)；
By step 1) the prepolymer reaction liquid that generates cools to 40-50 DEG C, add high boiling point double solvents 10-50 weight portion and foam stabiliser 0.5-3 weight portion, stir, add retarder, surfactant, catalyst, plasticizer, it is uniformly mixed, namely obtains environment-friendly water-soluble polyurethane chemical grouting material。
Isocyanates is toluene di-isocyanate(TDI), diphenyl methane-4,4 '-diisocyanate or poly methylene poly phenyl poly isocyanate。Soluble polyurethane grouting material generally selects toluene di-isocyanate(TDI) (TDI) as raw material, its flash-point is 127 DEG C, boiling point is 251 DEG C, to take half-dead dosage (LD50) be 4130mg/kg to rat oral, belong to low-toxicity product, close to actual nontoxic scope, react the water-fast urea of generation with water after pre-polymerization, nontoxic, comply fully with environmental requirement。Water solublity serosity does not generally select methyl diphenylene diisocyanate (MDI), because its activity is high, cannot be thoroughly mixed after meeting water, simply solidify in periphery, does not enter internal at all, and when particularly temperature is more than 27 DEG C, performance just becomes apparent from。
Surfactant is the one in water-soluble silicon oil, polyvinyl pyrrolidone, Tween 80 or its any two or more combinations。
Plasticizer is the one in diethyl phthalate, dibutyl phthalate, dioctyl phthalate or its any two or more combinations。
Foam stabiliser is polyalkamer siloxanes。
The content of described plasticizer is the 5-10% of described performed polymer quality；The content of described surfactant is the 1-2% of described performed polymer quality。
The invention have the characteristics that:
1) high-flash: flash-point, more than 100 DEG C, belongs to non-ization danger product liquid, is thus advantageous to the personal safety of transport, environmental conservation and operator。
2) good hydrophilic property: meet first dispersion and emulsion after water and then gel consolidation, it is adaptable to the process of the Anti-seeping technology in crack and retention of excessive fluid under wet condition。
3) hydroexpansivity: induration has water-swellable performance, this is favourable to the loss zone of concrete extension joint。
4) one pack system is easy to operate: product is one-component, does not need complicated preparation serosity, serosity is directly poured into single liquid pump, can be in the milk。
5) response speed is fast: serosity is rapid foamed solidification after meeting water, reaches the purpose of quick sealing。When stifled big flow retention of excessive fluid, it is also possible to use with catalyst mix, further speed up response speed。
6) avirulence: product true border non-toxic type, to human body and environmental friendliness。
Detailed description of the invention
The present invention is described in further detail below。
Embodiment 1
The environmentally friendly polyurethane grouting material of the present invention is prepared according to the following step
Prepare performed polymer: under anaerobic and anhydrous condition, by polyethers, retarder mixing, put in reactor, under stirring, carry out the degassed process of negative pressure dehydration 1.5～3 hours, add toluene di-isocyanate(TDI) after being cooled to 10～42 DEG C, at 78～85 DEG C of temperature, carrying out polyreaction 2～3 hours ,-NCOwt% the content controlling performed polymer is reaction end between 20～35%；Described polyethers is that Hydrophilicrto polyether (EP-4000) mixes with 80/20 ratio with common polyether (N210)；
By step 1) the prepolymer reaction liquid that generates cools to 40-50 DEG C, add high boiling point double solvents 10-50 weight portion and foam stabiliser polyalkamer siloxanes 0.5-3 weight portion, stir, add Benzenecarbonyl chloride., Tween 80, catalyst, diethyl phthalate, it is uniformly mixed, namely obtains environment-friendly water-soluble polyurethane chemical grouting material。
Obtained environmentally friendly hydrophobic polyurethane grouting material, quality index is as follows: solid content wt95%；Add hardening time after 5% water hardening time/25 DEG C of 350s；25 DEG C of 240mPa s of viscosity；Frothing percentage 2500%；Comprcssive strength 15MPa。
Embodiment 2
A kind of soluble polyurethane chemical grouting material of environment-friendly type, preparation process comprises the following steps:
Prepare performed polymer: under anaerobic and anhydrous condition, by polyethers, retarder mixing, put in reactor, under stirring, carry out the degassed process of negative pressure dehydration 1.5 hours, add isocyanates after being cooled to 10 DEG C, at 78 DEG C of temperature, carrying out polyreaction 2 hours ,-NCOwt% the content controlling performed polymer is reaction end between 20%；Described polyethers is that Hydrophilicrto polyether (EP-4000) mixes with 80/20 ratio with common polyether (N210)；
By step 1) the prepolymer reaction liquid that generates cools to 40 DEG C, add high boiling point double solvents 10 weight portion and foam stabiliser 0.5 weight portion, stir, add retarder, surfactant, catalyst, plasticizer, it is uniformly mixed, namely obtains environment-friendly water-soluble polyurethane chemical grouting material。
Isocyanates is toluene di-isocyanate(TDI), diphenyl methane-4,4 '-diisocyanate or poly methylene poly phenyl poly isocyanate。Soluble polyurethane grouting material generally selects toluene di-isocyanate(TDI) (TDI) as raw material, its flash-point is 127 DEG C, boiling point is 251 DEG C, to take half-dead dosage (LD50) be 4130mg/kg to rat oral, belong to low-toxicity product, close to actual nontoxic scope, react the water-fast urea of generation with water after pre-polymerization, nontoxic, comply fully with environmental requirement。Water solublity serosity does not generally select methyl diphenylene diisocyanate (MDI), because its activity is high, cannot be thoroughly mixed after meeting water, simply solidify in periphery, does not enter internal at all, and when particularly temperature is more than 27 DEG C, performance just becomes apparent from。
Surfactant is the one in water-soluble silicon oil, polyvinyl pyrrolidone, Tween 80 or its any two or more combinations。
Plasticizer is the one in diethyl phthalate, dibutyl phthalate, dioctyl phthalate or its any two or more combinations。
Foam stabiliser is polyalkamer siloxanes。
The content of described plasticizer is the 5% of described performed polymer quality；The content of described surfactant is the 1% of described performed polymer quality。
Embodiment 3
The soluble polyurethane chemical grouting material of a kind of environment-friendly type, it is characterised in that preparation process comprises the following steps:
Prepare performed polymer: under anaerobic and anhydrous condition, by polyethers, retarder mixing, put in reactor, under stirring, carry out the degassed process of negative pressure dehydration 3 hours, add isocyanates after being cooled to 42 DEG C, at 85 DEG C of temperature, carrying out polyreaction 3 hours ,-NCOwt% the content controlling performed polymer is reaction end between 35%；Described polyethers is that Hydrophilicrto polyether (EP-4000) mixes with 80/20 ratio with common polyether (N210)；
By step 1) the prepolymer reaction liquid that generates cools to 50 DEG C, add high boiling point double solvents 50 weight portion and foam stabiliser 3 weight portion, stir, add retarder, surfactant, catalyst, plasticizer, it is uniformly mixed, namely obtains environment-friendly water-soluble polyurethane chemical grouting material。
Isocyanates is toluene di-isocyanate(TDI), diphenyl methane-4,4 '-diisocyanate or poly methylene poly phenyl poly isocyanate。Soluble polyurethane grouting material generally selects toluene di-isocyanate(TDI) (TDI) as raw material, its flash-point is 127 DEG C, boiling point is 251 DEG C, to take half-dead dosage (LD50) be 4130mg/kg to rat oral, belong to low-toxicity product, close to actual nontoxic scope, react the water-fast urea of generation with water after pre-polymerization, nontoxic, comply fully with environmental requirement。Water solublity serosity does not generally select methyl diphenylene diisocyanate (MDI), because its activity is high, cannot be thoroughly mixed after meeting water, simply solidify in periphery, does not enter internal at all, and when particularly temperature is more than 27 DEG C, performance just becomes apparent from。
Surfactant is the one in water-soluble silicon oil, polyvinyl pyrrolidone, Tween 80 or its any two or more combinations。
Plasticizer is the one in diethyl phthalate, dibutyl phthalate, dioctyl phthalate or its any two or more combinations。
Foam stabiliser is polyalkamer siloxanes。
The content of described plasticizer is the 10% of described performed polymer quality；The content of described surfactant is the 2% of described performed polymer quality。
Claims (8)
1. the soluble polyurethane chemical grouting material of an environment-friendly type, it is characterised in that preparation process comprises the following steps:
1) performed polymer is prepared: under anaerobic and anhydrous condition, by polyethers, retarder mixing, put in reactor, under stirring, carry out the degassed process of negative pressure dehydration 1.5～3 hours, add isocyanates after being cooled to 10～42 DEG C, at 78～85 DEG C of temperature, carrying out polyreaction 2～3 hours ,-NCOwt% the content controlling performed polymer is reaction end between 20～35%；Described polyethers is that Hydrophilicrto polyether EP-4000 and common polyether N210 mixes with 80/20 ratio；
2) prepolymer reaction liquid step 1 generated cools to 40-50 DEG C, add high boiling point double solvents 10-50 weight portion and foam stabiliser 0.5-3 weight portion, stir, add retarder, surfactant, catalyst, plasticizer, it is uniformly mixed, namely obtains environment-friendly water-soluble polyurethane chemical grouting material。
2. the soluble polyurethane chemical grouting material of environment-friendly type according to claim 1, it is characterised in that: isocyanates is toluene di-isocyanate(TDI), diphenyl methane-4,4 '-diisocyanate or poly methylene poly phenyl poly isocyanate。
3. the soluble polyurethane chemical grouting material of environment-friendly type according to claim 1 and 2, it is characterised in that: isocyanates selects toluene di-isocyanate(TDI)。
4. the soluble polyurethane chemical grouting material of environment-friendly type according to claim 1 and 2, it is characterised in that: retarder is phosphoric acid or Benzenecarbonyl chloride.。
5. the soluble polyurethane chemical grouting material of environment-friendly type according to claim 1, it is characterised in that: surfactant is the one in water-soluble silicon oil, polyvinyl pyrrolidone, Tween 80 or its any two or more combinations。
6. the soluble polyurethane chemical grouting material of environment-friendly type according to claim 1, it is characterised in that: plasticizer is the one in diethyl phthalate, dibutyl phthalate, dioctyl phthalate or its any two or more combinations。
7. the soluble polyurethane chemical grouting material of environment-friendly type according to claim 4, it is characterised in that: foam stabiliser is polyalkamer siloxanes。
8. the soluble polyurethane chemical grouting material of environment-friendly type according to claim 1, it is characterised in that: the content of described plasticizer is the 5-10% of described performed polymer quality；The content of described surfactant is the 1-2% of described performed polymer quality。
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| CN104194320A (en) * | 2014-09-11 | 2014-12-10 | 北京东方雨虹防水技术股份有限公司 | Polyurethane grouting material and preparation method thereof |
| CN105567188B (en) * | 2014-10-10 | 2018-04-03 | 中国石油天然气股份有限公司 | Auxiliary agent for improving the solidifying class sealing agent leak stopping performance of cyanogen and preparation method thereof, cyanogen coagulates class sealing agent |
| CN106800769B (en) * | 2017-01-24 | 2020-02-18 | 中电建十一局工程有限公司 | Preparation method of water-coated water-swellable polyurethane grouting material |
| CN109233259B (en) * | 2018-08-03 | 2021-02-26 | 河南能源化工集团研究总院有限公司 | Organic-inorganic composite reinforcing material and preparation method thereof |
| CN109679052B (en) * | 2019-01-04 | 2021-07-20 | 郑州大学 | Double-slurry quick-setting high polymer repair material for underground pipeline and preparation method thereof |
| CN110041494A (en) * | 2019-05-14 | 2019-07-23 | 山东科技大学 | A kind of environmental protection flame retardant high bonding modified polyurethane injecting paste material |
| CN112480656A (en) * | 2020-12-28 | 2021-03-12 | 无锡琛华复合材料有限公司 | Environment-friendly polyurethane glass fiber composite material and preparation method thereof |
| CN115925360A (en) * | 2022-12-08 | 2023-04-07 | 四川童燊防水工程有限公司 | Chemical grouting material for urban subway construction and method thereof |
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