CN105906778B - A kind of environment protection type high-strength aqueous polyurethane slurry and preparation method thereof - Google Patents
A kind of environment protection type high-strength aqueous polyurethane slurry and preparation method thereof Download PDFInfo
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- CN105906778B CN105906778B CN201610326190.5A CN201610326190A CN105906778B CN 105906778 B CN105906778 B CN 105906778B CN 201610326190 A CN201610326190 A CN 201610326190A CN 105906778 B CN105906778 B CN 105906778B
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- polyether
- polyoxyethylene polyoxypropylene
- ppo
- environment protection
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- 239000002002 slurry Substances 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 39
- 239000004814 polyurethane Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000007613 slurry method Methods 0.000 title description 2
- 229920000570 polyether Polymers 0.000 claims abstract description 121
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 113
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 45
- -1 polyoxypropylene Polymers 0.000 claims abstract description 43
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims abstract description 35
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 26
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 7
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000004615 ingredient Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 14
- 150000003512 tertiary amines Chemical group 0.000 claims description 14
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 11
- 239000012948 isocyanate Substances 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims 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 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical class NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 238000007711 solidification Methods 0.000 abstract description 17
- 230000008023 solidification Effects 0.000 abstract description 17
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000839 emulsion Substances 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 125000001302 tertiary amino group Chemical group 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- 238000012360 testing method Methods 0.000 description 14
- 238000010792 warming Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 230000006835 compression Effects 0.000 description 12
- 238000007906 compression Methods 0.000 description 12
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 description 8
- 238000005070 sampling Methods 0.000 description 6
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HFNUUHLSQPLBQI-UHFFFAOYSA-N acetic acid;calcium Chemical compound [Ca].CC(O)=O HFNUUHLSQPLBQI-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 102100037377 DNA-(apurinic or apyrimidinic site) endonuclease 2 Human genes 0.000 description 1
- 241000721047 Danaus plexippus Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 101000806823 Homo sapiens DNA-(apurinic or apyrimidinic site) endonuclease 2 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000010148 water-pollination 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction 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
- C08G18/08—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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
-
- 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
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- 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
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino 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
- C08G18/28—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
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of environment protection type high-strength aqueous polyurethane slurries and preparation method thereof, belong to adhesive field.The environment protection type high-strength aqueous polyurethane slurry is 100 in mass ratio by the first and second two kinds of components：10~100 compositions：Wherein, first component includes following ingredient：100~30wt% polyoxyethylene polyoxypropylene block polyether-polyurethanes prepolymer, 0~60wt% polyoxypropylene polyether type polyurethane prepolymers and 0~10wt% liquid epoxies；Second component includes following ingredient：30~90wt% aliphatic amine polyoxyethylene polyoxypropylene polyether polyalcohols and 70~10wt% polyoxyethylene polyoxypropylene polyether polyol succinates.The present invention contains hydrophobic phenyl ring, PPO segments and hydrophilic PEO segments, tertiary amine group and tert-amine carboxylate's organic salt, has amphiphilic self-emulsifying, can be with water emulsion dispersion well；Net slurry or aqueous slurry gel solidification speed are adjustable, and induration has higher intensity.
Description
Technical field
The invention belongs to adhesive field, more particularly to a kind of environment protection type high-strength aqueous polyurethane slurry and its preparation method.
Background technology
Polyurethane grouting material is a kind of novel high polymer material, its main component is polyurethane prepolymer, feature
It is permeability is preferable, bond effect is good, water resistance is good etc..The raw material of use and technique difference, composition size performance are used
On the way, the property of solidfied material and the effect of acquirement are different, and the scope of application is very wide, as it can be applied to civil buildings, water conservancy water
Electricity and the fields such as subway tunnel and coal mining.
Currently, having carried out extensive research and application and development in terms of China's polyurethane grouting material, main includes common
Type waterborne polyurethane grouting material, plain edition hydrophobic polyurethane grouting material, dual-component polyurethane reinforcement for rushing danger grouting material, environmental protection
Type polyurethane grouting material and no-solvent type polyurethane grouting material etc., but they some use solvent either plasticizer, hydrophilic
Property solvent or auxiliary agent etc., harmful to environment and human body, intensity is relatively low, and curing rate is difficult to, and application range is limited
System.The high-strength water-based polyurethane grouting material of bi-component environmental-protecting of controllable curing rate with amphipathic self-emulsifying has no
There is document report.
Invention content
The primary purpose of the present invention is that overcoming shortcoming and deficiency existing in the prior art, a kind of environment-friendly type high intensity is provided
Spend aqueous polyurethane slurry.The environment protection type high-strength aqueous polyurethane pulp strength is high, has amphipathic self-emulsifying and solidification speed
It spends adjustable.
Another object of the present invention is to provide the preparation methods of the aqueous polyurethane slurry.
The purpose of the invention is achieved by the following technical solution：A kind of environment protection type high-strength aqueous polyurethane slurry, by first
Two kinds of components of second are 100 in mass ratio：10~100 compositions：
The first component includes following ingredient by weight percentage：100~30wt% polyoxyethylene polyoxypropylenes
Block polyether-polyurethane prepolymer, 0~60wt% polyoxypropylene polyether type polyurethane prepolymers and 0~10wt% liquid epoxies
Resin.
The polyoxyethylene polyoxypropylene block polyether-polyurethane prepolymer is preferably toluene diisocyanate monomer
TDI, liquefaction xylylene diisocyanate MDI at least contain two terminal hydroxy groups polyoxyethylene polyoxypropylene block polyether (or
Claim block polyether polyol) line style containing active isocyanate key that is obtained for 3~5 hours in 50~90 DEG C of addition reactions or point
Dendritic polyether type polyurethane prepolymer, the polyoxyethylene polyoxypropylene block polyether at least containing two terminal hydroxy groups are preferably
PEO-PPO-PEO, PPO-PEO-PPO three block linear polyether or more block ramiform polyethers of the molecular weight 1000~3000,
Wherein EO accounts for 10~40wt% of EO and PO gross masses；Isocyanate groups (- N=C=O) content in the prepolymer is preferred
For 3~7wt%；
The polyoxyethylene polyoxypropylene block polyether (or block polyether polyol) at least containing two terminal hydroxy groups
Preferably it is prepared as initiator using binary or polyalcohol.
The polyoxypropylene polyether type polyurethane prepolymer is preferably toluene diisocyanate monomer TDI, liquefied mdi and divides
Son amount 300~3000 and at least contain there are two terminal hydroxy group polyoxypropylene polyether polyalcohol in 70~100 DEG C of addition reactions 3~
The polyether polyurethane prepolymer containing active isocyanate key obtained for 5 hours；Isocyanate groups in the prepolymer
(- N=C=O) content is preferably 4~10wt%.
The liquid epoxies is preferably bisphenol A epoxide resin E-51 or E-44.
The second component includes following ingredient by weight percentage：30~90wt% aliphatic amine polyoxyethylene polyoxies
Propylene polyether polyol and 70~10wt% polyoxyethylene polyoxypropylene polyether polyol succinates.
The aliphatic amine polyoxyethylene polyoxypropylene polyether polyalcohol is at least to contain 1 tertiary amine group and at least two
The polyether polyol of terminal hydroxy group；
The aliphatic amine polyoxyethylene polyoxypropylene polyether polyalcohol includes the fat containing only EO chain links and 1 tertiary amine group
Fat amine polyoxyethylene ether dihydric alcohol, preferably octadecylamine polyoxyethylene ether AC-1810, octadecylamine polyoxyethylene ether AC-1830, ten
Diamines polyoxyethylene ether AC-1215；
The aliphatic amine polyoxyethylene polyoxypropylene polyether polyalcohol more preferably with ethylenediamine, N- aminoethyl piperazines,
Diethylenetriamine, triethylene tetramine, tetraethylenepentamine are initiator preparation at least containing 2 tertiary amine groups and at least three end hydroxyl
The aliphatic amine polyoxyethylene polyoxypropylene polyether polyalcohol of base, wherein EO account for 0~40wt%, EO and the PO chain of EO and PO gross masses
Section sum preferably 25~50.
The polyoxyethylene polyoxypropylene polyether polyol succinate is by the polyoxy second at least containing 2 terminal hydroxy groups
The single-ended base monomester succinate and/or multiterminal base succinate that alkene polyoxypropylene polyether polyalcohol is obtained by succinic acid esterification；
The polyoxyethylene polyoxypropylene polyether polyol be preferably molecular weight 4000~400 PEO-PPO, PEO-PPO-PEO,
PPO-PEO-PPO types block polyether, polyoxypropylene polyether polyalcohol；EO accounts for EO in the PPO-PEO-PPO type block polyethers
With 0~40wt% of PO gross masses.
The preparation method of the environment protection type high-strength aqueous polyurethane slurry, includes the following steps：
(1) by 100~30wt% polyoxyethylene polyoxypropylene block polyether-polyurethanes prepolymer, 0~60wt% polyoxies
Propylene polyether polyurethane prepolymer and 0~10wt% liquid epoxies are uniform in mixed at room temperature, obtain first component；
(2) 30~90wt% aliphatic amine polyoxyethylene polyoxypropylene polyether polyalcohols and 70~10wt% polyoxypropylenes are gathered
Ethylene oxide polyether polyol or its succinate are uniform in mixed at room temperature, obtain second component；
(3) it is 100 in mass ratio by the first component of step (1), the second component of step (2)：10~100 is right after mixing
Anhydrous or aqueous base material, aqueous slurry are irrigated or brush, room temperature curing, obtain environment protection type high-strength aqueous polyurethane slurry
Material.
The present invention is anti-by addition by the polyethers simultaneously containing hydrophilic radical EO chain links and lipophilic group PO chain links in molecule
It should prepare with amphiphilic polyurethane prepolymer as first component, water emulsification easy to implement, the isocyanates in prepolymer
Group is the cured basis of further cross-linking reaction.Aliphatic amine polyoxyethylene polyethenoxy ether in second component not only contains hydrophilic
Property and catalysis isocyanate groups and polyethers in the tertiary amine groups that react of hydroxyl in hydroxyl or water, and in strand simultaneously
Containing multiple hydroxyls, compatibility is stronger, extent of reaction higher, concretion body strength bigger.Meanwhile the polyoxyethylene in second component is poly-
Oxypropylene block polyethers succinate contains the carboxylic acid of slow setting, these carboxylic acids interact with tertiary amine, and to form hydrophily stronger weak
On the one hand sour weak base organic salt can adjust the gel solidification speed of slurries, on the other hand go far towards polyurethane slurries two
The balance of parent's property, rapid emulsion dispersion consolidates simultaneously effectively in the curing reaction of isocyanate groups and hydroxyl when being met with water phase
Body has higher intensity.Tertiary amine also contributes to the curing reaction of epoxy resin simultaneously, helps to improve intensity and adhesive property.
The present invention has the following advantages and effects with respect to the prior art：
(1) present invention is organic containing hydrophobic phenyl ring, PPO segments and hydrophilic PEO segments, tertiary amine group and tert-amine carboxylate
Salt has amphiphilic self-emulsifying, can be with water emulsion dispersion well；
(2) present invention using simultaneously contain catalysis urethane cures and be catalyzed epoxy group ring-opening reaction tertiary amine group and
Multiterminal hydroxyl and the polyethers succinate of deferred action, net slurry or aqueous slurry gel solidification speed are adjustable, induration have compared with
High intensity；
(3) present invention is free of solvent or other poisonous and harmful auxiliary agents, is a kind of environment-friendly type slurry.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
The preparation of 1 waterborne polyurethane prepolymer of embodiment：
(1) propanediol polyoxypropylene polyoxyethylene blocks polyethers L-61 (Jiang Suhai are added in the three-necked flask of 5000mL
Pacify petrochemical industry, HO-PEO-PPO-PEO-H types, average molecular weight 2000) 2000g, toluene di-isocyanate(TDI) TDI is added
435g after stirring evenly, is warming up to 60 DEG C and reacts 5 hours, cooling is spare, is sealed, number is that block polyether polyurethane is pre-
Polymers PU1.Sampling, the content that the isocyanate groups (- N=C=O) of PU1 are determined with di-n-butylamine method are 4.9wt%.
(2) be added in the three-necked flask of 5000mL polyoxyethylene polyoxypropylene block polyether RPE1740 (BASF AG,
HO-PPO-PEO-PPO-H types, average molecular weight 2500) 2500g, toluene di-isocyanate(TDI) TDI 382.8g are added, stirring is equal
After even, it is warming up to 70 DEG C and reacts 4 hours, cooling is spare, is sealed, number is block polyether polyurethane prepolymer PU2.It takes
Sample, the content that the isocyanate groups (- N=C=O) of PU2 are measured with di-n-butylamine method are 3.3wt%.
(3) be added in the three-necked flask of 5000mL polyoxyethylene polyoxypropylene block polyether RPE1720 (BASF AG,
HO-PPO-PEO-PPO-H types, average molecular weight 2000) 2000g, liquefaction xylylene diisocyanate (MDI) (cigarette is added
Tai Wanhua ,-N=C=O content are 28wt%) 660g, it after stirring evenly, is warming up to 80 DEG C and reacts 3 hours, cooling is spare, sealing
It preserves, number is block polyether polyurethane prepolymer PU3.Sampling, the isocyanate groups (- N of PU3 is measured with di-n-butylamine method
=C=O) content be 3.6wt%.
(4) propanediol polyoxypropylene polyoxyethylene blocks polyethers L-43 (Jiang Suhai are added in the three-necked flask of 5000mL
Pacify petrochemical industry, HO-PEO-PPO-PEO-H types, average molecular weight 1850) 1850g, TDI 487.2g are added, stir evenly
Afterwards, it is warming up to 50 DEG C to react 5 hours, cooling is spare, is sealed, number is block polyether polyurethane prepolymer PU4.Sampling,
The content that the isocyanate groups (- N=C=O) of PU4 are measured with di-n-butylamine method is 6.1wt%.
(5) with reference to " synthesis of the block polymer demulsifiers such as Dong monarch and demulsification rule Chemical Engineers, 2005, (9):
64-66 " prepares glycerine ramiform block polyether：
Initiator glycerine (glycerine) and catalyst potassium hydroxide are added in 0.5 liter of autoclave, N is used2Fully blow
Pipeline and kettle are swept, stir and is warming up to 90 DEG C, vacuumizes and continues to heat up, until stopping in (about 0.5 hour) vacuumizes at 120 DEG C,
Ethylene oxide is added dropwise, is reacted at 125 ± 5 DEG C ,≤0.3MPa, until initiator and molar ratio reach 1：15,
Obtain hydrophilic head.In autoclave, 120 DEG C are warming up to by same operation step, propylene oxide is added dropwise after vacuumizing in stopping,
It is reacted at 135 ± 5 DEG C ,≤0.4MPa, adds propylene oxide until initiator and propylene oxide molar ratio reach 1：30, after
It is reacted again at 135 ± 5 DEG C 0.5 hour, it is cooling, it then uses in the glacial acetic acid of equivalent and potassium hydroxide, obtains putting down on strand
Equal EO and PO numbers are polyethers shown in following formula, which is 2492：[H-(OP)10(OE)5]OCH2-CH[O(EO)5
(PO)10-H]-CH2O[(EO)5(PO)10-H]
Polyethers 2492g is added in the three-necked flask of 5000mL, TDI 678.6g are added at room temperature, stir evenly
Afterwards, it is warming up to 90 DEG C to react 3 hours, cooling is spare, is sealed, number is block polyether polyurethane prepolymer PU5.Sampling,
The content that isocyanate groups (- N=C=O) are measured with di-n-butylamine method is 6.0wt%.
(6) polyoxypropylene polyether polyalcohol N-210 is added in the three-necked flask of 5000mL, and (Shandong east is big, HO-PPO-H
Type, average molecular weight 1000) 1000g and N303 (Shandong east is big, average molecular weight 3000, three terminal hydroxy groups) 30g, it is added
Toluene di-isocyanate(TDI) TDI 520.6g after stirring evenly, are warming up to 70 DEG C and react 5 hours, and cooling is spare, is sealed, and compiles
Number be polyoxypropylene polyether prepolymer PU6.Sampling, the isocyanate groups (- N=C=O) of PU6 are measured with di-n-butylamine method
Content is 9.4wt%.
(7) polyoxypropylene polyether polyalcohol N-220 is added in the three-necked flask of 5000mL, and (Shandong east is big, HO-PPO-H
Type, average molecular weight 2000) (Shandong east is big, HO- (PPO-H) by 2000g and N-3302Type, average molecular weight 3000)
200g is added liquefaction xylylene diisocyanate (MDI) (- N=C=O contents are 28wt%) 858g, after stirring evenly, rises
Temperature to 100 DEG C react 3 hours, cooling it is spare, be sealed, number is polyoxypropylene polyether prepolymer PU7.Sampling, just with two
The content that butylamine method measures the isocyanate groups (- N=C=O) of PU7 is 4.6wt%.
The preparation of 2 aliphatic amine polyoxyethylene polyoxypropylene polyether polyalcohol of embodiment：
With reference to " synthesis, structure and the demulsification performance research oilfield chemistries of the multi-block polyethers such as Zhang Jiehui, 1997,14
(4):It is prepared by 324-328 "：
(1) initiator tetraethylenepentamine and catalyst acetic acid calcium, potassium hydroxide are added in 0.5 liter of autoclave, are used
N2Abundant scavenging pipeline and kettle stir and are warming up to 90 DEG C, vacuumize and continue to heat up, until 120 DEG C of whens stop for (about 0.5 hour)
It vacuumizes, propylene oxide is added dropwise, is reacted at 135 ± 5 DEG C ,≤0.4MPa, until initiator and propylene oxide molar ratio reach
To 1：49, it is cooling, it then uses in the glacial acetic acid of equivalent and potassium hydroxide, the reactive hydrogen obtained on each N is average by under respectively
Tetraethylenepentamine polyethenoxy ether TEPAPPO1, the TEPAPPO1 average molecular weight of the substitutions of PPO shown in formula is 3031, contains 5
Tertiary amine and 7 terminal hydroxy groups：[H-(OP)7]2N-[CH2CH2N[(PO)7-H]]3-CH2CH2N[(PO)7-H]2。
(2) initiator ethylenediamine and catalyst acetic acid calcium, potassium hydroxide are added in 0.5 liter of autoclave, use N2It fills
Point scavenging pipeline and kettle stir and are warming up to 90 DEG C, vacuumize and continue to heat up, until 120 DEG C of whens stop within (about 0.5 hour) taking out it is true
Sky is added dropwise propylene oxide, is reacted at 135 ± 5 DEG C ,≤0.4MPa, until initiator and propylene oxide molar ratio reach 1：
20, obtain oleophylic head.In autoclave, 120 DEG C are warming up to by same operation step, epoxy second is added dropwise after vacuumizing in stopping
Alkane is reacted at 125 ± 5 DEG C ,≤0.3MPa, adds ethylene oxide until initiator and molar ratio reach 1：6
It is reacted again at 125 ± 5 DEG C 0.5 hour afterwards, it is cooling, it then uses in the glacial acetic acid of equivalent and potassium hydroxide, obtains on each N
The reactive hydrogen ethylenediamine polyoxyethylene polyoxypropylene ether that the average PPO-PEO diblocks shown in following formula replace respectively
EDAPPOPEO2, EDAPPOPEO2 average molecular weight are 1484, contain 2 tertiary amines and 4 terminal hydroxy groups：[H-(OE)1.5(OP)5]2N-CH2CH2N[(PO)5(EO)1.5-H]2。
(3) initiator diethylenetriamine and catalyst acetic acid calcium, potassium hydroxide are added in 0.5 liter of autoclave, are used
N2Abundant scavenging pipeline and kettle stir and are warming up to 90 DEG C, vacuumize and continue to heat up, until 120 DEG C of whens stop for (about 0.5 hour)
It vacuumizes, ethylene oxide is added dropwise, is reacted at 125 ± 5 DEG C ,≤0.3MPa, until initiator and molar ratio reach
To 1：10, obtain hydrophilic head.In autoclave, 120 DEG C are warming up to by same operation step, ring is added dropwise after vacuumizing in stopping
Ethylene Oxide is reacted at 135 ± 5 DEG C ,≤0.4MPa, adds propylene oxide until initiator and propylene oxide molar ratio reach
1：40, after reacted again at 135 ± 5 DEG C 0.5 hour, it is cooling, then use in the glacial acetic acid of equivalent and potassium hydroxide, obtain each
The reactive hydrogen diethylenetriamine polyoxyethylene poly-oxygen propylene aether that the average PEO-PPO diblocks shown in following formula replace respectively on N
DETAPEOPPO3, DETAPEOPPO3 average molecular weight are 2863, contain 3 tertiary amines and 5 terminal hydroxy groups：[H-(OP)8(OE)2]2N-CH2CH2N[(EO)2(PO)8-H]CH2CH2N[(EO)2(PO)8-H]2。
The preparation of 3 polyoxyethylene polyoxypropylene block polyether succinate of embodiment：
With reference to " the surface-active of the such as Wu Jinchuan fatty alcohols ethylene oxide/oxypropylene segmentation polyethers mono succinate sodium sulfonate
Petrochemical industry, 1997,26 (9):620~622 " prepare：
(1) block polyether L-62 (Jiangsu Hai'an petrochemicals, mean molecule are added in the three-necked flask of 5000mL
It is 20wt% that amount, which is 2500, EO contents) 2500g, the maleic anhydride of 2mol is added, the esterification 4h at 100 DEG C is cooling
It must be shown below containing there are two the disuccinic acid monoesters MAPE1 of end carboxyl, it is spare：HOOCCH=CHCOO (EO)n(PO)m
(EO)nOCCH=CHCOOH.
(2) block polyether L-62 (Jiangsu Hai'an petrochemicals, mean molecule are added in the three-necked flask of 5000mL
It is 20wt% that amount, which is 2500, EO contents) 2500g, the maleic anhydride of 1.5mol is added, esterification 4h, cold at 100 DEG C
But it obtains as shown in above formula containing there are two the monomester succinate of the disuccinic acid monoesters of end carboxyl and 1 end carboxyl shown in following formula
Mixture M APE2, it is spare：HOOCCH=CHCOO (EO)n(PO)m(EO)nH。
(3) it is added according to glycerine block polyether [H- (OP) made from 2 method of embodiment in the three-necked flask of 5000mL10
(OE)5]OCH2-CH[O(EO)5(PO)10-H]-CH2O[(EO)5(PO)10- H] (molecular weight 2492) 2492g, the suitable of 3mol is added
Anhydride maleique is warming up to 120 DEG C at 100 DEG C and continues esterification 4h after esterification 2h, cooling be shown below contains
There are three three monomester succinate MAPE3 of end carboxyl：[HOOCCH=CHCO- (OP)10(OE)5]OCH2-CH[O(EO)5(PO)10-
OCCH=CHCOOH]-CH2O[(EO)5(PO)10- OCCH=CHCOOH].
Embodiment 4
A kind of environment protection type high-strength aqueous polyurethane slurry, is prepared by following steps：
(1) take block polyether polyurethane prepolymer PU1 made from 100g embodiments 1 as first component at room temperature, 9g is implemented
Block polyether succinate MAPE3 mixing made from fatty amine polyethenoxy ether TEPAPPO1 made from example 2 and 1g embodiments 3 is equal
It is even to be used as second component, then the first and second components are uniformly mixed rapidly, carry out reverse mould rapidly, when testing the surface solidification of net slurry respectively
Between, 1 day compression strength and tensile strength.
(2) equally, take block polyether polyurethane prepolymer PU1 made from 100g embodiments 1 as first component, 9g at room temperature
Block polyether succinate MAPE3 made from fatty amine polyethenoxy ether TEPAPPO1 made from embodiment 2 and 1g embodiments 3 is mixed
It closes and is uniformly used as second component, then first and second liang of components and 55g water are uniformly mixed rapidly, carry out reverse mould rapidly, test respectively contains
The compression strength of the surface solidification time of water slurry, 1 day.
Embodiment 5
A kind of environment protection type high-strength aqueous polyurethane slurry, is prepared by following steps：
(1) block polyether polyurethane prepolymer PU2,60g polyoxypropylene polyether types made from 30g embodiments 1 are taken at room temperature
Polyurethane prepolymer PU6 and 10g epoxy resin E-44, which is uniformly mixed, is used as first component, fatty amine block made from 60g embodiments 2
Made from polyethers EDAPPOPEO2,10g octadecylamine polyoxyethylene ether AC-1810 (Jiangsu Hai'an petrochemical industry) and 30g embodiments 3
Block polyether succinate MAPE1, which is uniformly mixed, is used as second component, is then rapidly uniformly mixed the first and second components, is fallen rapidly
Mould tests the compression strength of surface solidification time, 1 day and tensile strength of net slurry respectively.
(2) equally, take block polyether polyurethane prepolymer PU2,60g polyoxypropylene made from 30g embodiments 1 poly- at room temperature
Ether-based polyurethane prepolymer PU6 and 10g epoxy resin E-44, which is uniformly mixed, is used as first component, fatty amine made from 60g embodiments 2
Block polyether EDAPPOPEO2,10g octadecylamine polyoxyethylene ether AC-1810 (Jiangsu Hai'an petrochemical industry) and 30g embodiments 3 are made
The block polyether succinate MAPE1 obtained, which is uniformly mixed, is used as second component, then rapidly mixes first and second liang of components and 100g water
Uniformly, reverse mould is carried out rapidly, tests the compression strength of surface solidification time, 1 day of aqueous slurry respectively.
Embodiment 6
A kind of environment protection type high-strength aqueous polyurethane slurry, is prepared by following steps：
(1) block polyether polyurethane prepolymer PU2 made from 40g embodiments 1 and 60g polyoxypropylene polyether types are taken at room temperature
Polyurethane prepolymer PU6, which is uniformly mixed, is used as first component, fatty amine block polyether EDAPPOPEO2 made from 30g embodiments 2 and
Block polyether succinate MAPE1 made from 70g embodiments 3, which is uniformly mixed, is used as second component, then rapidly mixes the first and second components
It closes uniformly, carries out reverse mould rapidly, test the compression strength of surface solidification time, 1 day and tensile strength of net slurry respectively.
(2) equally, block polyether polyurethane prepolymer PU2 made from 40g embodiments 1 and 60g polyoxypropylenes are taken at room temperature
Polyether polyurethane prepolymer PU6, which is uniformly mixed, is used as first component, fatty amine block polyether made from 30g embodiments 2
Block polyether succinate MAPE1 made from EDAPPOPEO2 and 70g embodiments 3, which is uniformly mixed, is used as second component, then rapidly
First and second liang of components and 100g water are uniformly mixed, carry out reverse mould rapidly, test the surface solidification time, 1 day of aqueous slurry respectively
Compression strength.
Embodiment 7
A kind of environment protection type high-strength aqueous polyurethane slurry, is prepared by following steps：
(1) block polyether polyurethane prepolymer PU3,45g polyoxypropylene polyether types made from 50g embodiments 1 are taken at room temperature
Polyurethane prepolymer PU6 and 5g epoxy resin E-44, which is uniformly mixed, is used as first component, fatty amine block made from 25g embodiments 2
Block polyether succinate MAPE2 made from polyethers DETAPEOPPO3 and 25g embodiment 3, which is uniformly mixed, is used as second component, then
The first and second components are uniformly mixed rapidly, carry out reverse mould rapidly, respectively test net slurry the compression strength of surface solidification time, 1 day and
Tensile strength.
(2) equally, take block polyether polyurethane prepolymer PU3,45g polyoxypropylene made from 50g embodiments 1 poly- at room temperature
Ether-based polyurethane prepolymer PU6 and 5g epoxy resin E-44, which is uniformly mixed, is used as first component, fatty amine made from 25g embodiments 2
Block polyether succinate MAPE2 made from block polyether DETAPEOPPO3 and 25g embodiment 3, which is uniformly mixed, is used as second component,
Then first and second liang of components and 75g water are uniformly mixed rapidly, carry out reverse mould rapidly, when testing the surface solidification of aqueous slurry respectively
Between, 1 day compression strength.
Embodiment 8
A kind of environment protection type high-strength aqueous polyurethane slurry, is prepared by following steps：
(1) block polyether polyurethane prepolymer PU4 made from 50g embodiments 1 and 50g polyoxypropylene polyether types are taken at room temperature
Polyurethane prepolymer PU7, which is uniformly mixed, is used as first component, fatty amine block polyether DETAPEOPPO3 made from 25g embodiments 2 and
Block polyether succinate MAPE2 made from 25g embodiments 3, which is uniformly mixed, is used as second component, then rapidly mixes the first and second components
It closes uniformly, carries out reverse mould rapidly, test the compression strength of surface solidification time, 1 day and tensile strength of net slurry respectively.
(2) equally, block polyether polyurethane prepolymer PU4 made from 50g embodiments 1 and 50g polyoxypropylenes are taken at room temperature
Polyether polyurethane prepolymer PU7, which is uniformly mixed, is used as first component, fatty amine block polyether made from 25g embodiments 2
Block polyether succinate MAPE2 made from DETAPEOPPO3 and 25g embodiments 3, which is uniformly mixed, is used as second component, then rapidly
First and second liang of components and 75g water are uniformly mixed, carry out reverse mould rapidly, the surface solidification time, 1 day for testing aqueous slurry respectively are anti-
Compressive Strength.
Embodiment 9
A kind of environment protection type high-strength aqueous polyurethane slurry, is prepared by following steps：
(1) take block polyether polyurethane prepolymer PU5 made from 100g embodiments 1 as first component at room temperature, 8g is implemented
Lauryl amine polyoxyethylene ether AC-1215 (Jiangsu Hai'an oil of fatty amine polyethenoxy ether TEPAPPO1,1g made from example 2
Work) and 9g embodiments 3 made from block polyether succinate MAPE3 be uniformly mixed be used as second component, then rapidly by first and second groups
Divide and be uniformly mixed, carry out reverse mould rapidly, tests the compression strength of surface solidification time, 1 day and tensile strength of net slurry respectively.
(2) equally, take block polyether polyurethane prepolymer PU5 made from 100g embodiments 1 as first component, 8g at room temperature
Lauryl amine polyoxyethylene ether AC-1215 (Jiangsu Hai'an stones of fatty amine polyethenoxy ether TEPAPPO1,1g made from embodiment 2
Oiling work) and 9g embodiments 3 made from block polyether succinate MAPE3 be uniformly mixed be used as second component, then rapidly by first
Two component of second and 59g water are uniformly mixed, and carry out reverse mould rapidly, test the pressure resistance of surface solidification time, 1 day of aqueous slurry respectively
Degree.
The test result of 1 embodiment 4~9 of table
By in the test result table 1 of embodiment 4~9 it is found that after the aqueous polyurethane slurries that prepare of the present invention are mixing cured
With faster curing rate, net slurry induration has very high compression strength and tensile strength, and slurry has hydrophilic parent
Oil is amphipathic, on the one hand accelerates with solidification in water mixed process, another aspect water content is 33% (the first and second mixed serums and water
Mass ratio be 2：1) consolidated uniform when, still there is higher compression strength.In general, tertiary amine catalytic cures polyurethane
Gel time when (when not aqueous) uniform speed quickly, second component are not added with succinate is within 1 minute, reality of the invention
It applies and then reaches in example 200 seconds or more, have the characteristics that curing gel time lengthening and adjustable.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (6)
1. a kind of environment protection type high-strength aqueous polyurethane grouting material, which is characterized in that be in mass ratio by the first and second two kinds of components
100：10 ~ 100 compositions：
The first component is by ingredient as follows by weight percentage：100 ~ 30wt% polyoxyethylene polyoxypropylene block polyethers
Type polyurethane prepolymer, 0 ~ 60wt% polyoxypropylene polyether type polyurethane prepolymers and 0 ~ 10wt% liquid epoxies composition；
The second component is by ingredient as follows by weight percentage：30 ~ 90wt% aliphatic amine polyoxyethylene polyoxypropylene polyethers
Polyalcohol and 70 ~ 10wt% polyoxyethylene polyoxypropylene polyether polyol succinates composition；
The polyoxyethylene polyoxypropylene polyether polyol succinate is to be gathered by the polyoxyethylene at least containing 2 terminal hydroxy groups
The single-ended base monomester succinate and/or multiterminal base succinate that oxypropylene polyether polyol is obtained by succinic acid esterification；It is described
Polyoxyethylene polyoxypropylene polyether polyol be molecular weight 4000 ~ 400 PEO-PPO, PEO-PPO-PEO, PPO-PEO-PPO
Type block polyether；EO accounts for 0 ~ 40wt% of EO and PO gross masses in the PPO-PEO-PPO type block polyethers；
Isocyanate content in the polyoxyethylene polyoxypropylene block polyether-polyurethane prepolymer is 3 ~ 7wt%；Institute
It is 4 ~ 10wt% to state the isocyanate content in polyoxypropylene polyether type polyurethane prepolymer；
The aliphatic amine polyoxyethylene polyoxypropylene polyether polyalcohol is at least to contain 1 tertiary amine group and at least two end hydroxyl
The polyether polyol of base.
2. environment protection type high-strength aqueous polyurethane grouting material according to claim 1, which is characterized in that the polyoxy
Ethylene oxypropylene block polyether polyurethane prepolymer be toluene diisocyanate monomer TDI, liquefied mdi at least contain two end
The polyoxyethylene polyoxypropylene block polyether of hydroxyl contains active isocyanate in what 50 ~ 90 DEG C of addition reactions obtained for 3 ~ 5 hours
The line style of key or branched polyether polyurethane prepolymer, the polyoxyethylene polyoxypropylene at least containing two terminal hydroxy groups are embedding
Section polyethers is PEO-PPO-PEO, PPO-PEO-PPO three block linear polyether or more block branch of the molecular weight 1000 ~ 3000
Type polyethers, wherein EO account for 10 ~ 40wt% of EO and PO gross masses.
3. environment protection type high-strength aqueous polyurethane grouting material according to claim 1, which is characterized in that the polyoxy
Propylene polyether polyurethane prepolymer is toluene diisocyanate monomer TDI, liquefied mdi and molecular weight 300 ~ 3000 and at least contains
The polyoxypropylene polyether polyalcohol of two terminal hydroxy groups contains active isocyanate in what 70 ~ 100 DEG C of addition reactions obtained for 3 ~ 5 hours
The polyether polyurethane prepolymer of key.
4. environment protection type high-strength aqueous polyurethane grouting material according to claim 1, which is characterized in that the liquid
Epoxy resin is bisphenol A epoxide resin E-51 or E-44.
5. environment protection type high-strength aqueous polyurethane grouting material according to claim 1, which is characterized in that the fat
Amine polyoxyethylene polyoxypropylene polyether polyol is with ethylenediamine, N- aminoethyl piperazines, diethylenetriamine, triethylene tetramine, four
Five amine of ethylene is the aliphatic amine polyoxyethylene polyoxy third at least containing 2 tertiary amine groups and at least three terminal hydroxy group prepared by initiator
It is 25 ~ 50 that alkene polyether polyol, wherein EO, which account for EO and 0 ~ 40wt%, EO and PO the chain link sum of PO gross masses,.
6. the preparation method of environment protection type high-strength aqueous polyurethane grouting material described in claim 1, includes the following steps：
（1）By 100 ~ 30wt% polyoxyethylene polyoxypropylene block polyether-polyurethanes prepolymer, 0 ~ 60wt% polyoxypropylene polyethers
Type polyurethane prepolymer and 0 ~ 10wt% liquid epoxies are uniform in mixed at room temperature, obtain first component；
（2）30 ~ 90wt% aliphatic amine polyoxyethylene polyoxypropylene polyether polyalcohols and 70 ~ 10wt% polyoxyethylene polyoxypropylenes is poly-
Ethoxylated polyhydric alcohol succinate is uniform in mixed at room temperature, obtains second component；
（3）By step（1）First component, step（2）Second component in mass ratio be 100：10 ~ 100 after mixing to anhydrous
Or aqueous base material, aqueous slurry are irrigated or brush, room temperature curing, obtain environment protection type high-strength aqueous polyurethane injection material
Material.
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| CN105906778A (en) | 2016-08-31 |
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Denomination of invention: Environment-friendly high-intensity waterborne polyurethane slurry and preparation method thereof Effective date of registration: 20191121 Granted publication date: 20181002 Pledgee: China Co truction Bank Corp Guangzhou Tianhe subbranch Pledgor: Guangzhou Chemical Grouting Engineering Co., Ltd., Chinese Academy of Sciences Registration number: Y2019440000208 |
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Date of cancellation: 20210910 Granted publication date: 20181002 Pledgee: China Co. truction Bank Corp Guangzhou Tianhe subbranch Pledgor: GUANGZHOU CHEMICAL GROUTING Co.,Ltd. CAS Registration number: Y2019440000208 |