CN110511352A - Water blockoff polyurethane injecting paste material and preparation method thereof is reinforced in a kind of filling - Google Patents
Water blockoff polyurethane injecting paste material and preparation method thereof is reinforced in a kind of filling Download PDFInfo
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- CN110511352A CN110511352A CN201910847039.XA CN201910847039A CN110511352A CN 110511352 A CN110511352 A CN 110511352A CN 201910847039 A CN201910847039 A CN 201910847039A CN 110511352 A CN110511352 A CN 110511352A
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- 239000000463 material Substances 0.000 title claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000004814 polyurethane Substances 0.000 title claims abstract description 60
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000011049 filling Methods 0.000 title claims description 27
- 150000002148 esters Chemical class 0.000 claims abstract description 43
- 235000013311 vegetables Nutrition 0.000 claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 40
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 40
- 229920000570 polyether Polymers 0.000 claims abstract description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 25
- -1 polymethylene Polymers 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000012948 isocyanate Substances 0.000 claims abstract description 16
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 16
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920002545 silicone oil Polymers 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 9
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 32
- 239000004014 plasticizer Substances 0.000 claims description 20
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 16
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000010276 construction Methods 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000003245 coal Substances 0.000 abstract description 4
- 238000005553 drilling Methods 0.000 abstract description 4
- 238000007569 slipcasting Methods 0.000 description 11
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 8
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XADCESSVHJOZHK-UHFFFAOYSA-N Meperidine Chemical compound C=1C=CC=CC=1C1(C(=O)OCC)CCN(C)CC1 XADCESSVHJOZHK-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 241001502050 Acis Species 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical class [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- C08G18/28—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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy 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
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 invention discloses a kind of fillings to reinforce water blockoff polyurethane injecting paste material and preparation method thereof, which is characterized in that by obtaining after component A and component the B mixing of volume 1:1；The component A includes the following components by mass fraction: 37~49 parts of polymethylene multi-phenenyl isocyanate, I 5~17 parts of vegetable esters of synthesis；The component B includes the following components by mass fraction: 10~30 parts of polyetherdiol, 5~15 parts of polyether triol, 4~15 parts of polyether tetrols, synthesis II 2~10 parts of vegetable esters, 0.5~1.5 part of silicone oil, 0.2~1 part of composite catalyst.Solvent-free two-pack foamable polyurethane injecting paste material of the invention, have the characteristics that intensity height, good toughness, setting time is short, frothing percentage is high, adhesive property is good, easy construction and safety and environmental protection, the pit-hole especially suitable for engineerings such as subway, coal mine, geological drillings fills up, reinforces and water blockoff.
Description
Technical field
The present invention relates to polyurethane injecting paste materials, reinforce water blockoff polyurethane injecting paste material and its system in particular to a kind of filling
Preparation Method.
Background technique
Traditional water reinforcement injecting paste material is generally divided into two classes, and one kind is inorganic injecting paste material, such as cement class, waterglass
Class etc.；Second class is organic injecting paste material, such as polyurethanes, acrylic amide.Inorganic injecting paste material applies in general to hydrostatic
Environment can not play the role of water reinforcement in the environment that water yield is big, water velocity is fast；There are solidifying bodies for organic injecting paste material
Intensity is low, price is high, and most of organic materials also have certain toxicity, will cause the pollution of underground water.
In recent years, the two-component foaming elastomer for environment-friendly water-based polyurethane injecting paste material occur and not reacting with water is poly-
Urethane injecting paste material.Environment-friendly water-based polyurethane injecting paste material haves the shortcomings that dehydration drying shrinkage or impervious insufficient, and cannot be
It is used under anhydrous condition, in the case where water is less, slip casting effect be cannot be guaranteed, in the higher circumstance of flowing water of water velocity
It is easy to be broken up；The two-component foaming elastomer polyurethane injecting paste material not reacted with water is because cubical expansivity is smaller, generally not
Filling water reinforcement for engineering；Intensity and toughness cannot be considered in terms of, and underground structure often shape occurs because settling or expanding with heat and contract with cold
Become, toughness is too low to be easily led to injecting paste material cracking and multiple leakage occurs, and the durability of impervious leakage-stopping is lower, and it is permanent to be formed
Elastic packing.
Existing water reinforcement injecting paste material kind is more on the market at present, but is suitable for underground engineering and exists compared with hollow place
Hole, water yield is big, water velocity is fast and the filling of safety and environmental protection reinforcing water blockoff injecting paste material is less.Based on this, need to develop
A kind of solvent-free two-pack foamable polyurethane injecting paste material not reacted with water, the polyurethane injecting paste material need to have following spy
Point: 1) use scope is extensive, can be used in having water and water-less environment；2) acetone, toluene, two fourths are not used when being synthetically prepared
The toxic solvents such as base tin dilaurate ester, other raw material use non-toxic or low-toxic organic matter as far as possible, reduce production and use
In the process to the pollution of human body, water quality and surrounding enviroment, there is preferable Safety and Environmental Protection；3) setting rate is fast, can be in water flow
Water blockoff use is carried out in the circumstance of flowing water that amount is big, water velocity is fast；4) intensity of solidifying body is high, good toughness, can in engineering compared with
Big pit-hole is filled, and slurries can also reinforce the periphery soil body by diffusion and splitting diffusion；5) it is bonded
Intensity is big, is bonded under circumstance of flowing water with slotted wall strength.
Summary of the invention
The purpose of the present invention is to solve the deficiency of the above background technology, when providing a kind of intensity height, good toughness, solidification
Between it is short, frothing percentage is high, adhesive property is good, the polyurethane injecting paste material of easy construction and safety and environmental protection, make it particularly suited for ground
The pit-hole of the engineerings such as iron, coal mine, geological drilling fills up, reinforces and water blockoff.
The technical solution of the present invention is as follows: water blockoff polyurethane injecting paste material is reinforced in a kind of filling, which is characterized in that by component A
It is obtained with after component B mixing；
The component A includes the following components by mass fraction:
37~49 parts of polymethylene multi-phenenyl isocyanate
I 5~17 parts of vegetable esters of synthesis；
The component B includes the following components by mass fraction:
The composite catalyst is compounded with stannous octoate by 1:1.2-2 mass ratio by triethylenediamine.This programme
Middle polyurethane injecting paste material has reached 53~72s of setting time, 19~25 times of frothing percentage, 48~53MPa of compression strength, has stretched by force
Spend the excellent results of 22.9~26MPa, elongation at break 10.4~12.3%, 6.5~7.5MPa of adhesion strength.
Preferably, the isocyano-content of the polymethylene multi-phenenyl isocyanate is 30.5%~32%, and 25 DEG C viscous
Degree is 150Pas~250Pas.
Preferably, the synthesis vegetable esters I, synthesis vegetable esters II are 8611 plasticizer.
Preferably, by being obtained after the component A of volume 1:1 and component B mixing；
The component A includes the following components by mass fraction:
41~45 parts of polymethylene multi-phenenyl isocyanate
I 11~15 parts of vegetable esters of synthesis；
The component B includes the following components by mass fraction:
The composite catalyst is compounded with stannous octoate by 1:1.5 mass ratio by triethylenediamine.In this programme
Polyurethane injecting paste material has reached 53~58s of setting time, 23~25 times of frothing percentage, 51~53MPa of compression strength, tensile strength
The excellent results of 24.8~26MPa, elongation at break 11.1~12.3%, 7.3~7.5MPa of adhesion strength.
Further, the component A includes the following components by mass fraction:
The component A includes the following components by mass fraction:
41 parts of polymethylene multi-phenenyl isocyanate
I 11 parts of vegetable esters of synthesis；
The component B includes the following components by mass fraction:
Material source used in above scheme are as follows:
Polymethylene multi-phenenyl isocyanate is the product PM-200 of Yantai Wanhua chemical groups Co., Ltd, isocyano
Content is 30.5%~32%, and 25 DEG C of viscosity are 150~250mPas；Synthesizing vegetable esters is her limited public affairs of lattice specialization work of Suzhou
Department produces 8611 plasticizer；Polyetherdiol is that oil of SPC produces PPG-400；Polyether triol is Jiangsu Zhongshang Chemical Co., Ltd.'s production
ZSN-330；Polyether tetrols are that Shandong Lanxing Dongda Chemical Co., Ltd produces DD-4110；Silicone oil is Nanjing dolantin generation woundization
Work Co., Ltd produces AK-8805；Triethylenediamine is that BASF AG produces LupragenN201 in composite catalyst；Stannous octoate
For Yunnan Tin Industrial Corp.'s product.
Polyurethane injecting paste material prepared by the present invention is a kind of solvent-free two-component foaming material not reacted with water
Material, is made of following five classes raw material: 1) polymethylene multi-phenenyl isocyanate (PAPI): being the main reaction original of polyurethane products
Material, PAPI are a kind of thick MDI, and usual MDI content is 50% or so, because MDI vapour pressure ratio TDI is much lower, common good logical
Human body is damaged in the case of wind small；2) polyether polyol: being the main reaction material of polyurethane products, compared to polyester polyol,
Polyurethane products water resistance, the resistance to low temperature of polyether polyol synthesis are good, select the hair of relatively small molecular weight polyalcohol synthesis
The compression strength for steeping polyurethane material is relatively large；3) plasticizer: can reduce polyurethane products hardness, promote the plasticity of product
(ductility) improves foam brittleness, and the present invention is using synthesis vegetable esters, asepsis environment-protecting；4) catalyst: can be catalyzed foaming and gel is anti-
Rate is answered, without using the dibutyltindilaurylmercaptide esters of silicon acis being more toxic；5) foam stabiliser: belong to a kind of surfactant, have
Emulsify foam material, stable foam and adjust abscess effect wherein, as organic silicon modified by polyether surfactant (is commonly called as " silicon
Oil ") etc..The above five classes raw material are configured to two component of A, B according to a certain percentage, by two component of A, B with roughly equal volume
After mixing, in a few minutes, generating has higher-strength (48~53MPa of compression strength, 22.9~26MPa of tensile strength), good
The polyurethane product of good adhesive strength (6.5~7.5MPa) and certain toughness (elongation at break 10.4~12.3%).
The present invention also provides the preparation methods that water blockoff polyurethane injecting paste material is reinforced in a kind of above-mentioned filling, which is characterized in that
Step are as follows:
1) polymethylene multi-phenenyl isocyanate, synthesis vegetable esters I are stirred evenly, is sealed as component A；It will gather
Ether glycol, polyether triol, polyether tetrols, synthesis vegetable esters II are dehydrated 2~4h by 100 DEG C~120 DEG C high-temperature vacuums, then cool down
To 50~60 DEG C, after composite catalyst, silicone oil mixing is added, it is sealed as component B；
2) component A, component B are mixed to get filling by volume 1:1 and reinforce water blockoff polyurethane injecting paste material.
The invention has the benefit that
1) solvent-free two-pack foamable polyurethane injecting paste material of the invention has intensity height, good toughness, setting time
It is short, frothing percentage is high, adhesive property is good, easy construction and the characteristics of safety and environmental protection, especially suitable for subway, coal mine, geological drilling
Etc. the pit-holes of engineerings fill up, reinforce and water blockoff.
2) polyurethane injecting paste material of the invention, all raw material are all made of low toxicity or non-toxic organic object, are producing and making
It is much smaller compared with other polyurethane injecting paste materials with the toxic action in the process to human body, water body and surrounding enviroment.The novel poly- ammonia
Ester injecting paste material setting time is short, not soluble in water, big in water flow, and water plugging effect is excellent in the fast circumstance of flowing water of water velocity；
Because its compression strength, adhesion strength are high, frothing percentage is high, to the filling consolidation effect of larger pit-hole also compared with other polyurethane slip casting materials
Expect excellent；During on-site construction, only prepared A, B component it need to will pass through Double-liquid mud-injection pump quickly after mixing in advance, In
Injection needs at slip casting under lower pressure, the effect that water blockoff is reinforced in filling can be rapidly reached, compared to other polyurethane slip castings
It is more safe and efficient for material, and it is convenient to construct, and has good effect in repairing, emergency work.
Specific embodiment
The present invention is described in further detail for specific embodiment below.
In following embodiment, the source of each material and performance parameter are as follows:
Polymethylene multi-phenenyl isocyanate is that Yantai Wanhua chemical groups Co., Ltd produces PM-200, isocyano-content
It is 30.5%~32%, 25 DEG C of viscosity are 150mPas~250mPas；
Synthesizing vegetable esters (synthesis vegetable esters I, synthesis vegetable esters II) is that Suzhou Yi Gete Chemical Co., Ltd. production 8611 increases
Modeling agent, specific gravity 1.12,80 DEG C of fusing point, elongation 275%, thermal stability 70min；
Polyetherdiol is that oil of SPC produces PPG-400, hydroxyl value 279mgKOH/g, acid value 0.04mgKOH/g, moisture content
It is 0.03%, pH value 6.4, viscosity 70mPa ﹒ s/25 DEG C, coloration 45, degree of functionality 2；
Polyether triol is that Jiangsu Zhongshang Chemical Co., Ltd. produces ZSN-330, hydroxyl value 56.5mgKOH/g, acid value
0.03mgKOH/g, moisture content 0.03%, 610mPas/25 DEG C of pH value 6, viscosity, degree of functionality 3；
Polyether tetrols are that Shandong Lanxing Dongda Chemical Co., Ltd produces DD-4110, hydroxyl value 435mgKOH/g, acid
Value is 0.2mgKOH/g, and moisture content 0.2%, pH value 11, viscosity is 3120mPas/25 DEG C, coloration 8, degree of functionality 4；
Silicone oil is that Nanjing Dymatic Shichuang Chemical Co., Ltd. produces AK-8805, density 1.05g/ml, and viscosity is
830mPas/25 DEG C, pH value 6.5, moisture content 0.3%.
Composite catalyst is compounded by triethylenediamine and stannous octoate in 2:3 ratio.Wherein, triethylenediamine
LupragenN201 is produced for BASF AG, 25 DEG C of density are 1.12g/cm3, moisture 0.4%, 60 DEG C of flash-point；Stannous octoate
For Yunnan Tin Industrial Corp.'s production, 25 DEG C of density 1.25g/ml, stannous content 28%, viscosity is 380mPas/20 DEG C.
Each material quality number is as shown in table 1 below in polyurethane injecting paste material in embodiment 1-8.
Each raw material corresponding mass number in 1 embodiment 1-8 of table
Embodiment 1
As shown in table 1, the formula of water blockoff polyurethane injecting paste material is reinforced in the present embodiment filling are as follows: by the component A of volume 1:1
With component B；
Component A includes the polymethylene polyphenyl isocyanates (PAPI, wherein-NCO content is 31%, 25 by mass fraction
DEG C viscosity is 200Pas) 41 parts, 11 parts of synthesis vegetable esters I (8611 plasticizer)；
Component B includes 20 parts of polyetherdiol (PPG-400) by mass fraction, 10 parts of polyether triol (ZSN-330), polyethers
15 parts of tetrol (DD-4110), synthesis 6 parts of vegetable esters II (8611 plasticizer), 1.2 parts of silicone oil (AK-8805), composite catalyst
0.8 part of (by triethylenediamine: stannous octoate mass ratio 1:1.5 is mixed to get).
Embodiment 2
As shown in table 1, the formula of water blockoff polyurethane injecting paste material is reinforced in the present embodiment filling are as follows: by the component A of volume 1:1
With component B；
Component A includes the polymethylene polyphenyl isocyanates (PAPI, wherein-NCO content is 32%, 25 by mass fraction
DEG C viscosity is 150Pas) 45 parts, 15 parts of synthesis vegetable esters I (8611 plasticizer)；
Component B includes 25 parts of polyetherdiol (PPG-400) by mass fraction, 12 parts of polyether triol (ZSN-330), polyethers
12 parts of tetrol (DD-4110), synthesis 8 parts of vegetable esters II (8611 plasticizer), 1.4 parts of silicone oil (AK-8805), composite catalyst
1 part of (by triethylenediamine: stannous octoate mass ratio 1:1.5 is mixed to get).
Embodiment 3
As shown in table 1, the formula of water blockoff polyurethane injecting paste material is reinforced in the present embodiment filling are as follows: by the component A of volume 1:1
With component B；
Component A include by mass fraction polymethylene polyphenyl isocyanates (PAPI, wherein-NCO content be 30.5%,
25 DEG C of viscosity are 42 parts of 250Pas), 12 parts of synthesis vegetable esters I (8611 plasticizer)；
Component B includes 21 parts of polyetherdiol (PPG-400) by mass fraction, 11 parts of polyether triol (ZSN-330), polyethers
13 parts of tetrol (DD-4110), synthesis 7 parts of vegetable esters II (8611 plasticizer), 1.3 parts of silicone oil (AK-8805), composite catalyst
0.9 part of (by triethylenediamine: stannous octoate mass ratio 1:1.5 is mixed to get).
Embodiment 4
As shown in table 1, the formula of water blockoff polyurethane injecting paste material is reinforced in the present embodiment filling are as follows: by the component A of volume 1:1
With component B；
Component A include by mass fraction polymethylene polyphenyl isocyanates (PAPI, wherein-NCO content be 31.5%,
25 DEG C of viscosity are 44 parts of 180Pas), 13 parts of synthesis vegetable esters I (8611 plasticizer)；
Component B includes by 24 parts of the polyetherdiol (PPG-400) of mass fraction, 11.5 parts of polyether triol (ZSN-330), gathers
14 parts of ether tetrol (DD-4110), synthesis 7.5 parts of vegetable esters II (8611 plasticizer), 1.4 parts of silicone oil (AK-8805), composite catalyzing
0.85 part of agent (by triethylenediamine: stannous octoate mass ratio 1:1.5 is mixed to get).
Embodiment 5
As shown in table 1, the formula of water blockoff polyurethane injecting paste material is reinforced in the present embodiment filling are as follows: by the component A of volume 1:1
With component B；
Component A include by mass fraction polymethylene polyphenyl isocyanates (PAPI, wherein-NCO content be 31.5%,
25 DEG C of viscosity are 37 parts of 220Pas), 5 parts of synthesis vegetable esters I (8611 plasticizer)；
Component B includes 10 parts of polyetherdiol (PPG-400) by mass fraction, 5 parts of polyether triol (ZSN-330), polyethers
4 parts of tetrol (DD-4110), synthesis 2 parts of vegetable esters II (8611 plasticizer), 0.5 part of silicone oil (AK-8805), composite catalyst (by
Triethylenediamine: stannous octoate mass ratio 1:1.2 is mixed to get) 0.2 part.
Embodiment 6
As shown in table 1, the formula of water blockoff polyurethane injecting paste material is reinforced in the present embodiment filling are as follows: by the component A of volume 1:1
With component B；
Component A includes the polymethylene polyphenyl isocyanates (PAPI, wherein-NCO content is 31%, 25 by mass fraction
DEG C viscosity is 150Pas) 40 parts, 8 parts of synthesis vegetable esters I (8611 plasticizer)；
Component B includes 15 parts of polyetherdiol (PPG-400) by mass fraction, 8 parts of polyether triol (ZSN-330), polyethers
7 parts of tetrol (DD-4110), synthesis 4 parts of vegetable esters II (8611 plasticizer), 0.8 part of silicone oil (AK-8805), composite catalyst (by
Triethylenediamine: stannous octoate mass ratio 1:2.0 is mixed to get) 0.5 part.
Embodiment 7
As shown in table 1, the formula of water blockoff polyurethane injecting paste material is reinforced in the present embodiment filling are as follows: by the component A of volume 1:1
With component B；
Component A includes the polymethylene polyphenyl isocyanates (PAPI, wherein-NCO content is 32%, 25 by mass fraction
DEG C viscosity is 250Pas) 47 parts, 16 parts of synthesis vegetable esters I (8611 plasticizer)；
Component B includes 25 parts of polyetherdiol (PPG-400) by mass fraction, 13 parts of polyether triol (ZSN-330), polyethers
10 parts of tetrol (DD-4110), synthesis 5 parts of vegetable esters II (8611 plasticizer), 1 part of silicone oil (AK-8805), composite catalyst (by
Triethylenediamine: stannous octoate mass ratio 1:1.8 is mixed to get) 0.6 part.
Embodiment 8
As shown in table 1, the formula of water blockoff polyurethane injecting paste material is reinforced in the present embodiment filling are as follows: by the component A of volume 1:1
With component B；
Component A include by mass fraction polymethylene polyphenyl isocyanates (PAPI, wherein-NCO content be 30.5%,
Viscosity is 180Pas) 49 parts, 17 parts of synthesis vegetable esters I (8611 plasticizer)；
Component B includes 30 parts of polyetherdiol (PPG-400) by mass fraction, 15 parts of polyether triol (ZSN-330), polyethers
11 parts of tetrol (DD-4110), synthesis 10 parts of vegetable esters II (8611 plasticizer), 1.5 parts of silicone oil (AK-8805), composite catalyst
0.7 part of (by triethylenediamine: stannous octoate mass ratio 1:1.4 is mixed to get).
Injecting paste material preparation and construction method in above-described embodiment 1-8 are as follows:
1) by each component raw material quality match, weigh respectively corrresponding quality part polymethylene multi-phenenyl isocyanate,
Polyetherdiol, polyether triol, polyether tetrols, synthesis vegetable esters I, synthesis vegetable esters II, composite catalyst (triethylenediamine,
Stannous octoate), silicone oil.
2) polymethylene multi-phenenyl isocyanate weighed by quality proportioning, synthesis vegetable esters I are stirred evenly, sealing is protected
It deposits as component A；Polyetherdiol, polyether triol, polyether tetrols, synthesis vegetable esters II are passed through into 100 DEG C~120 DEG C high-temperature vacuums
It is dehydrated 2~4h, then is cooled to 50~60 DEG C (preferably through being cooled to 50 DEG C again after 120 DEG C of vacuum dehydration 2h), compound urge is added
After agent, silicone oil are mixed, it is sealed as component B；
3) position of injected hole, the embedded spacing of injected hole, the size of injected hole and buried depth are first determined when site operation, so
The injected hole for the embedded PVC material that drills afterwards；
4) component A, component B are weighed respectively by the volume ratio of 1:1, is then mixed in the mixer of Double-liquid mud-injection pump equal
It is even, slip casting is started by injected hole using the low pressure of 0.5~1.0MPa；
5) when observing that closing on injected hole has the generation of fragmentary polyurethane, stop slip casting, next injected hole is infused
Slurry, all injected hole slip castings are completed, and slip casting effect, timely after-teeming slurry are observed；
6) when carrying out slip casting filling water blockoff to larger hole, according to hole size, various sizes of Nylon Bag is selected, by Buddhist nun
Imperial bag is placed in injected hole, and sack and slip casting aperture tied silk or cord bind the securely then slip casting into Nylon Bag, to poly- ammonia
Hole can be blocked after ester foaming solidification and carries out water blockoff, to reduce the consumption of polyurethane injecting paste material, reduction is constructed into
This.
Performance detection
The epoxy modified polyurethane water blockoff strengthening grouting material DMPU- produced with commercially available Shaanxi dolantin waterproof material Co., Ltd
D-GJ-530 (modified version) is comparative example 1；HW soluble polyurethane (water-soluble) with the exploitation of East China surveying and designing institute is comparison
Example 2, the castor oil type polyurethane slurry material (the molten type of oil) developed with Guangzhou Inst of Chemistry, Chinese Academy of Sciences are implemented for comparative example 3
The Specifeca tion speeification of polyurethane injecting paste material made from example 1-8 is as shown in table 2:
Polyurethane injecting paste material main performance obtained by 2 embodiment of table
From table 2 it can be seen that the polyurethane injecting paste material performance indicator of Examples 1 to 8 is all satisfied " polyurethane injection material
Material " requirement of OPU product in (JC/T 2041-2010).The polyurethane injecting paste material of embodiment 1-8 has reached setting time 53
~72s, 19~25 times of frothing percentage, 48~53MPa of compression strength, 22.9~26MPa of tensile strength, elongation at break 10.4~
12.3%, the excellent results of 6.5~7.5MPa of adhesion strength, it is with higher when keeping good compression strength, tensile strength
Elongation at break preferably takes into account intensity and toughness.
Therefore, the polyurethane in the present invention for the filling of the engineerings pit-holes such as subway, coal mine, geological drilling, reinforcing and water blockoff
Injecting paste material also has good toughness while having high intensity, has good feasibility and application, because of its solidification
Time is short, and frothing percentage is high, react with water, thus solve general polyurethane material be not suitable for water flow greatly, water velocity
The shortcomings that fast circumstance of flowing water, compared to other polyurethane materials, more safety and environmental protection in the production and use process.
Claims (6)
1. water blockoff polyurethane injecting paste material is reinforced in a kind of filling, which is characterized in that after component A and component the B mixing of volume 1:1
It obtains；
The component A includes the following components by mass fraction:
37~49 parts of polymethylene multi-phenenyl isocyanate
I 5~17 parts of vegetable esters of synthesis；
The component B includes the following components by mass fraction:
The composite catalyst is compounded with stannous octoate by 1:1.2-2 mass ratio by triethylenediamine.
2. water blockoff polyurethane injecting paste material is reinforced in filling as described in claim 1, which is characterized in that the more benzene of polymethylene
The isocyano-content of based isocyanate is 30.5%~32%, and 25 DEG C of viscosity are 150mPas~250mPas.
3. water blockoff polyurethane injecting paste material is reinforced in filling as described in claim 1, which is characterized in that the synthesis vegetable esters I,
Synthesizing vegetable esters II is 8611 plasticizer.
4. water blockoff polyurethane injecting paste material is reinforced in filling as described in claim 1, which is characterized in that by the component A of volume 1:1
It is obtained with after component B mixing；
The component A includes the following components by mass fraction:
41~45 parts of polymethylene multi-phenenyl isocyanate
I 11~15 parts of vegetable esters of synthesis；
The component B includes the following components by mass fraction:
The composite catalyst is compounded with stannous octoate by 1:1.5 mass ratio by triethylenediamine.
5. water blockoff polyurethane injecting paste material is reinforced in filling as claimed in claim 4, which is characterized in that the component A includes pressing
The following components of mass fraction:
41 parts of polymethylene multi-phenenyl isocyanate
I 11 parts of vegetable esters of synthesis；
The component B includes the following components by mass fraction:
6. the preparation method that water blockoff polyurethane injecting paste material is reinforced in a kind of filling as described in claim 1, which is characterized in that step
Suddenly are as follows:
1) polymethylene multi-phenenyl isocyanate, synthesis vegetable esters I are stirred evenly, is sealed as component A；By polyethers two
Alcohol, polyether triol, polyether tetrols, synthesis vegetable esters II are dehydrated 2~4h by 100 DEG C~120 DEG C high-temperature vacuums, then are cooled to 50
It~60 DEG C, after composite catalyst, silicone oil mixing is added, is sealed as component B；
2) component A, component B are mixed to get filling by volume 1:1 and reinforce water blockoff polyurethane injecting paste material.
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Cited By (2)
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