CN116333577A - Efficient polyurethane grouting waterproof coating and preparation method thereof - Google Patents
Efficient polyurethane grouting waterproof coating and preparation method thereof Download PDFInfo
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- CN116333577A CN116333577A CN202310330331.0A CN202310330331A CN116333577A CN 116333577 A CN116333577 A CN 116333577A CN 202310330331 A CN202310330331 A CN 202310330331A CN 116333577 A CN116333577 A CN 116333577A
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- polyurethane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 59
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 title claims abstract description 14
- 238000000576 coating method Methods 0.000 title claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 58
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 58
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 25
- 239000012948 isocyanate Substances 0.000 claims abstract description 23
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 15
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical group CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- 239000004014 plasticizer Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 5
- 229920005749 polyurethane resin Polymers 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 4
- -1 azelates Chemical class 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical class OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 125000005498 phthalate group Chemical class 0.000 claims description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 abstract description 17
- 230000000903 blocking effect Effects 0.000 abstract description 12
- 238000004132 cross linking Methods 0.000 abstract description 11
- 229920005862 polyol Polymers 0.000 abstract description 2
- 150000003077 polyols Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a high-efficiency polyurethane grouting waterproof coating and a preparation method thereof, wherein the deblocking temperature is used as an entry point, and the advantages of polyurethane hard segments are considered, after polyurethane is grafted with epoxy resin, an end blocking compound which can be deblocked at low temperature is used for blocking isocyanate, so that a unit of isocyanate is utilized for blocking a short chain of polyurethane, the epoxy resin is grafted with a short chain branch, the intermolecular distance of the epoxy resin is increased, meanwhile, a hard segment polyurethane prepolymer formed by connecting low-molecular polyol and isocyanate is short in molecular chain, physical entanglement of epoxy resin chains is not caused, the movement capacity of chain segments is improved, and the polyurethane grafted epoxy resin-hard segment polyurethane is subjected to cross-linking reaction.
Description
Technical Field
The invention relates to the technical field of waterproof materials, in particular to a high-efficiency polyurethane grouting waterproof coating and a preparation method thereof.
Background
Grouting materials are numerous, and at present, common ones are: polyurethane grouting material, epoxy grouting material, acrylic grouting material, water glass grouting material and cement-based grouting material. Generally, the chemical grouting materials have obvious advantages and disadvantages, more epoxy grouting materials, water glass grouting materials and cement-based grouting materials are generally used for structural reinforcement grouting, and polyurethane grouting materials and acrylic grouting materials are generally used for building grouting slurry waterproofing, namely, chemical grouting is performed on local remoistening, crack water seepage and the like of a building, so that a waterproof effect is achieved. The most commonly used modified polyurethane grouting materials are epoxy resin and polyurethane grouting materials at present, and in order to obtain the modified polyurethane grouting materials with lower viscosity and higher consolidation strength, the advantages of combining several polymers are generally selected, for example, the epoxy resin modified polyurethane grouting materials can improve the strength of polyurethane, and a high-permeability polyurethane grafted modified epoxy resin interpenetrating network polymer grouting material and a preparation method thereof are disclosed in Chinese patent document CN 102924692B.
The grouting material adopting the polyurethane/epoxy resin interpenetrating crosslinked network structure combines the advantages of polyurethane and epoxy resin materials, and overcomes the respective limitations. The mechanism of action between polyurethane and epoxy resin is that the segments of polyurethane penetrate into the epoxy resin network irregularly, forming a full or semi-interpenetrating network polymer structure. However, polyurethane/epoxy interpenetrating network polymer grouting materials have the following problems: in the curing process, polyurethane grafting penetrates through epoxy resin molecules, but the intermolecular distance is reduced due to entanglement, the chain segment movement is limited, and the toughening effect is reduced; meanwhile, the collision between epoxy active groups is hindered, the reaction crosslinking is reduced, and the strength is correspondingly reduced.
In order to overcome the problems, chinese patent document CN104277449B discloses a preparation method of polyurethane modified epoxy resin and grouting material based on the resin, wherein isocyanate is firstly adopted to react with hydroxyl on the epoxy resin under a certain condition to obtain polyurethane grafted epoxy resin, and then monohydric alcohol is used for blocking isocyanate on the polyurethane grafted epoxy resin, so that the unit blocking of isocyanate is utilized to graft polyurethane short branched chains on the epoxy resin, the intermolecular force between the epoxy resins is increased, the intermolecular force is reduced, and the movement capability of chain segments is improved; meanwhile, in the curing process, blocked isocyanate can be partially deblocked and participate in curing due to heat release, so that the dual effects of reaction toughening and reaction crosslinking are realized.
However, the alcohol compound is used as a sealing agent, the deblocking temperature is generally higher and generally reaches more than 180 ℃, the blocked isocyanate is deblocked and participates in the curing process with relatively high difficulty, and based on the consideration, the polyurethane grafted epoxy resin grouting material is prepared from the deblocking temperature serving as a cutting point and considering the advantages of polyurethane hard segments.
Disclosure of Invention
Aiming at the problems in the background technology, the invention aims to provide a preparation method of an efficient polyurethane grouting waterproof coating.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of an efficient polyurethane grouting waterproof coating comprises the following steps:
(1) Under the protection of inert gas, heating epoxy resin to 100-110 ℃, cooling to 50-60 ℃, adding diisocyanate and a catalyst, and stirring and reacting for 2-5h at 80-100 ℃ to obtain polyurethane grafted epoxy resin;
(2) Adding 5-10wt% of end-capping compound capable of being deblocked at low temperature into the step, continuously reacting for 1-3h at 80-100 ℃, cooling to 50-60 ℃, adding hard polyurethane prepolymer, continuously stirring and reacting for 1-3h, and then adding epoxy resin curing agent and uniformly mixing to obtain the polyurethane resin;
the end-capping compound capable of being deblocked at low temperature comprises at least one of 2-methylimidazole, 2, 4-dimethylimidazole, 1, 2-dimethylimidazole and methyl ethyl ketoxime.
Further, the mass ratio of the epoxy resin, isocyanate, end-capping compound and hard segment polyurethane prepolymer is 10: (1-5): (0.4-2): (1-5).
Further, the mass ratio of the epoxy resin, isocyanate, end-capping compound and hard segment polyurethane prepolymer is 10: (1-5): (0.5-1.5): (2-3).
Further, the hard segment polyurethane prepolymer is obtained by carrying out addition end capping reaction on low-molecular triol and isocyanate; the isocyanate is at least one selected from diphenylmethane diisocyanate, toluene diisocyanate and isophorone diisocyanate; the low molecular weight triol is at least one selected from trimethylolpropane and glycerol.
Further, the catalyst is selected from one of dibutyl tin dilaurate and triethylamine.
Further, the diisocyanate is selected from one or a mixture of more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and naphthalene diisocyanate.
Further, the epoxy resin curing agent is N, N-dimethylbenzylamine, and the addition amount is 0.5-2 wt% of the epoxy resin.
Further, diluents, organic or inorganic plasticizers are included; the diluent is selected from one or more of ethers, aldehydes, ketones and water, and the plasticizer is selected from one or more of phthalates, glutarates, adipates, azelates, sebacates, phosphates, stearates and laurates.
The second object of the present invention is to provide a high efficiency polyurethane grouting waterproof paint prepared by the above method.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, after the polyurethane is grafted with the epoxy resin, the isocyanate is blocked by using a blocking compound capable of being deblocked at low temperature, so that the unit blocking of isocyanate is utilized, a polyurethane short branched chain is grafted on the epoxy resin, the inter-molecule distance of the epoxy resin is increased, meanwhile, a hard segment polyurethane prepolymer formed by connecting low-molecule polyol and isocyanate is short in molecular chain, physical entanglement of the epoxy resin chain is not caused, and the movement capacity of a chain segment is improved, and the polyurethane grafted epoxy resin-hard segment polyurethane is subjected to a crosslinking reaction.
2. The isocyanate blocking is carried out by adopting the blocking compound capable of being unblocked at low temperature, the unblocking temperature is lower, the unblocking can be carried out under the condition of 70-128 ℃, the exothermic temperature peak value in the curing process of the epoxy resin can be more than 130-160 ℃ (different systems and different additives), therefore, in the curing process, the isocyanate blocked by the blocking compound capable of being unblocked at low temperature can be rapidly unblocked and participate in curing, the rest isocyanate end which is not subjected to grafting reaction with the epoxy resin after the unblocking can react with the hard segment polyurethane prepolymer again to form a crosslinking interpenetrating network, the dual effects of reaction toughening and reaction crosslinking are realized, and the polyurethane-epoxy resin grouting material based on the invention can effectively reduce the physical crosslinking among molecules, and has good strength and toughness.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The raw materials used in the invention are conventional commercial products unless specified; the methods used in the present invention are conventional in the art unless otherwise specified.
Example 1
The embodiment provides a high-efficiency polyurethane grouting waterproof coating, which comprises 50g of epoxy resin E51 with an epoxy value of 0.6mol/100g, 20g of diphenylmethane diisocyanate, 5g of 2-methylimidazole, 12g of hard segment polyurethane prepolymer, 1g of dibutyltin dilaurate and 1.5g of N, N-dimethylbenzylamine;
the preparation method comprises the following steps:
1) Preparation of hard segment polyurethane prepolymer:
180mol of trimethylolpropane and 440mol of diphenylmethane diisocyanate are added into a synthesis kettle to react for 2 hours at 45 ℃; then heating to 85 ℃ to continue the reaction for about 2 hours, determining the concentration of isocyanic acid radical by a toluene-di-n-butylamine method in HGT 2409-1992, and stopping heating when the theoretical value of 5.7wt% to 5.8wt% is reached, thus obtaining the hard segment polyurethane prepolymer;
2) Polyurethane-epoxy crosslinked network:
(1) Under the protection of inert gas, heating epoxy resin E51 with the epoxy value of 0.6mol/100g to 110 ℃, cooling to 60 ℃, adding diphenylmethane diisocyanate and dibutyltin dilaurate, and stirring and reacting for 5 hours at 100 ℃ to obtain polyurethane grafted epoxy resin;
(2) Adding a blocking compound which can be deblocked at low temperature, namely 2-methylimidazole, continuously reacting for 3 hours at the temperature of 100 ℃, cooling to 60 ℃, adding a hard segment polyurethane prepolymer, continuously stirring for reacting for 3 hours, and then adding N, N-dimethylbenzylamine, a diluent and a plasticizer, and uniformly mixing to obtain the polyurethane.
Example 2
The embodiment provides a high-efficiency polyurethane grouting waterproof coating, which comprises 50g of epoxy resin E51 with an epoxy value of 0.6mol/100g, 20g of diphenylmethane diisocyanate, 5g of 2, 4-dimethylimidazole, 12g of hard segment polyurethane prepolymer, 1g of dibutyltin dilaurate and 1.5g of N, N-dimethylbenzylamine;
the preparation method comprises the following steps:
1) Preparation of hard segment polyurethane prepolymer:
180mol of trimethylolpropane and 440mol of diphenylmethane diisocyanate are added into a synthesis kettle to react for 2 hours at 45 ℃; then heating to 85 ℃ to continue the reaction for about 2 hours, determining the concentration of isocyanic acid radical by a toluene-di-n-butylamine method in HGT 2409-1992, and stopping heating when the theoretical value of 5.7wt% to 5.8wt% is reached, thus obtaining the hard segment polyurethane prepolymer;
2) Polyurethane-epoxy crosslinked network:
(1) Under the protection of inert gas, heating epoxy resin E51 with the epoxy value of 0.6mol/100g to 110 ℃, cooling to 60 ℃, adding diphenylmethane diisocyanate and dibutyltin dilaurate, and stirring and reacting for 5 hours at 100 ℃ to obtain polyurethane grafted epoxy resin;
(2) Adding a blocking compound which can be deblocked at low temperature, namely 2, 4-dimethyl imidazole, continuously reacting for 3 hours at the temperature of 100 ℃, cooling to 60 ℃, adding a hard segment polyurethane prepolymer, continuously stirring for reacting for 3 hours, and then adding N, N-dimethylbenzylamine, a diluent and a plasticizer, and uniformly mixing to obtain the polyurethane.
Example 3
The embodiment provides a high-efficiency polyurethane grouting waterproof coating, which comprises 50g of epoxy resin E51 with an epoxy value of 0.6mol/100g, 20g of diphenylmethane diisocyanate, 5g of methyl ethyl ketoxime, 12g of hard segment polyurethane prepolymer, 1g of dibutyltin dilaurate and 1.5g of N, N-dimethylbenzylamine;
the preparation method comprises the following steps:
1) Preparation of hard segment polyurethane prepolymer:
180mol of trimethylolpropane and 440mol of diphenylmethane diisocyanate are added into a synthesis kettle to react for 2 hours at 45 ℃; then heating to 85 ℃ to continue the reaction for about 2 hours, determining the concentration of isocyanic acid radical by a toluene-di-n-butylamine method in HGT 2409-1992, and stopping heating when the theoretical value of 5.7wt% to 5.8wt% is reached, thus obtaining the hard segment polyurethane prepolymer;
2) Polyurethane-epoxy crosslinked network:
(1) Under the protection of inert gas, heating the epoxy resin E51 with the epoxy value of 0.6mol/100g to 100 ℃, cooling to 50 ℃, adding diphenylmethane diisocyanate and dibutyltin dilaurate, and stirring and reacting for 4 hours at 80 ℃ to obtain polyurethane grafted epoxy resin;
(2) Adding a capping compound which can be deblocked at low temperature, namely methyl ethyl ketoxime, to the step, continuously reacting for 3 hours at the temperature of 80 ℃, cooling to 50 ℃, adding a hard segment polyurethane prepolymer, continuously stirring and reacting for 2 hours, and then adding N, N-dimethylbenzylamine, a diluent and a plasticizer, and uniformly mixing to obtain the polyurethane.
Comparative example 1
The comparative example provides a polyurethane-epoxy resin polymer grouting material, which comprises epoxy resin E51 50g, diphenylmethane diisocyanate 20g, N-butanol 5g, hard segment polyurethane prepolymer 12g, dibutyl tin dilaurate 1g and N, N-dimethylbenzylamine 1.5g, wherein the epoxy value of the epoxy resin E is 0.6mol/100 g;
the preparation method is the same as in example 1.
Comparative example 2
The comparative example provides a polyurethane-epoxy resin polymer grouting material, which comprises 50g of epoxy resin E51 with an epoxy value of 0.6mol/100g, 28g of isocyanate-terminated PU-prepolymer and 1.5g of N, N-dimethylbenzylamine;
the preparation method comprises the following steps:
mixing the isocyanate-terminated PU-prepolymer and the hard segment polyurethane prepolymer with epoxy resin, heating to 80 ℃ under stirring, reacting for 5 hours under the protection of nitrogen, adding the diluent 1, 4-butanediol diglycidyl ether, the plasticizer and the curing agent N, N-dimethylbenzylamine, and uniformly mixing to obtain the polyurethane adhesive.
Performance detection
The grouting material samples prepared in the above examples 1 to 3 and comparative examples 1 and 2 were tested for compressive strength, tensile strength, and adhesive strength. The invention has the compression strength according to GB/T1041-1992 standard, the tensile strength according to GB13022-91 standard and the dry and wet bonding strength according to GB/T16777-1997 standard. The test results are shown in Table 1.
Table 1 comparison of results of Performance tests for different samples
| Sample of | Compressive Strength/MPa | Tensile Strength/MPa | Dry bond strength/MPa | Wet bond strength/MPa |
| Example 1 | 107.8 | 60.4 | 7.8 | 6.4 |
| Example 2 | 110.2 | 61.0 | 8.0 | 6.2 |
| Example 3 | 109.7 | 59.8 | 8.1 | 6.3 |
| Comparative example 1 | 98.8 | 45.7 | 6.9 | 5.3 |
| Comparative example 2 | 89.6 | 32.4 | 4.7 | 4.1 |
As can be seen from the data in Table 1, the addition of the compound with low deblocking temperature and the hard segment polyurethane in the sample of the invention has skeleton reinforcing and crosslinking effects, can solve the problem that the polyurethane long chain and the epoxy resin are easy to be biologically entangled, has high deblocking temperature of the alcohol blocking agent, and affects the curing crosslinking effect, and can form an efficient polyurethane-epoxy resin grafting crosslinking through network structure, thereby effectively improving the physicochemical properties of the polymer of the through structure. For example, the polymer has a dry bond strength of greater than 7.5MPa, a wet bond strength of greater than 6MPa, a compressive strength of greater than 105MPa, and a tensile strength of greater than 50MPa.
In the cross-linked product sample using the alcohol end-capping agent in comparative example 1, the dry bonding strength is less than 7MPa, the wet bonding strength is less than 5.5MPa, and the compressive strength is generally less than 100MPa, because the alcohol compound is used as the capping agent, the deblocking temperature is generally higher, usually more than 180 ℃, the blocked isocyanate is relatively difficult to deblock and participate in the curing process, and the subsequent difficult to participate in the cross-linking curing reaction, so that the connection of a cross-linked system is affected.
In contrast, in the sample of the product of the direct grafting reaction of epoxy resin and isocyanate-terminated PU-prepolymer in comparative example 2, the dry bonding strength is less than 5MPa, the wet bonding strength is less than 4.5MPa, the compressive strength is generally less than 90MPa, and the performance is far inferior to that of the product of the invention.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The preparation method of the high-efficiency polyurethane grouting waterproof coating is characterized by comprising the following steps of:
(1) Under the protection of inert gas, heating epoxy resin to 100-110 ℃, cooling to 50-60 ℃, adding diisocyanate and a catalyst, and stirring and reacting for 2-5h at 80-100 ℃ to obtain polyurethane grafted epoxy resin;
(2) Adding 5-10wt% of end-capping compound capable of being deblocked at low temperature into the step, continuously reacting for 1-3h at 80-100 ℃, cooling to 50-60 ℃, adding hard polyurethane prepolymer, continuously stirring and reacting for 1-3h, and then adding epoxy resin curing agent and uniformly mixing to obtain the polyurethane resin;
the end-capping compound capable of being deblocked at low temperature comprises at least one of 2-methylimidazole, 2, 4-dimethylimidazole, 1, 2-dimethylimidazole and methyl ethyl ketoxime.
2. The preparation method of the efficient polyurethane grouting waterproof coating according to claim 1, wherein the mass ratio of the epoxy resin, isocyanate, end-capping compound and hard segment polyurethane prepolymer is 10: (1-5): (0.4-2): (1-5).
3. The preparation method of the efficient polyurethane grouting waterproof coating according to claim 2, wherein the mass ratio of the epoxy resin, isocyanate, end-capping compound and hard segment polyurethane prepolymer is 10: (1-5): (0.5-1.5): (2-3).
4. The preparation method of the high-efficiency polyurethane grouting waterproof coating according to claim 1, wherein the hard segment polyurethane prepolymer is obtained by performing addition end capping reaction on low-molecular triol and isocyanate;
the isocyanate is at least one selected from diphenylmethane diisocyanate, toluene diisocyanate and isophorone diisocyanate;
the low molecular weight triol is at least one selected from trimethylolpropane and glycerol.
5. The method for preparing the efficient polyurethane grouting waterproof paint according to claim 1, wherein the catalyst is selected from one of dibutyl tin dilaurate and triethylamine.
6. The method for preparing the efficient polyurethane grouting waterproof paint according to claim 1, wherein the diisocyanate is selected from one or a mixture of more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and naphthalene diisocyanate.
7. The preparation method of the efficient polyurethane grouting waterproof coating according to claim 1, wherein the epoxy resin curing agent is N, N-dimethylbenzylamine, and the addition amount is 0.5-2 wt% of the epoxy resin.
8. The method for preparing the high-efficiency polyurethane grouting waterproof paint according to claim 1, which is characterized by further comprising a diluent and a plasticizer; the diluent is selected from one or more of ethers, aldehydes, ketones and water, and the plasticizer is selected from one or more of phthalates, glutarates, adipates, azelates, sebacates, phosphates, stearates and laurates.
9. A high-efficiency polyurethane grouting waterproof paint prepared by the method according to any one of claims 1 to 8.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0317116A (en) * | 1989-06-14 | 1991-01-25 | Nippon Polyurethane Ind Co Ltd | Blocking agent for isocyanate, compound bearing blocked isocyanate groups, and cold curable composition, coating composition, and adhesive composition containing the same |
| KR20100071505A (en) * | 2008-12-19 | 2010-06-29 | 진도화성주식회사 | Manufacturing method of polyurethane-epoxy hybrid resins |
| CN102924692A (en) * | 2012-09-07 | 2013-02-13 | 湖南工业大学 | High-permeability polyurethane graft-modified epoxy resin interpenetrating-network polymer grouting material and preparation method thereof |
| CN104277449A (en) * | 2014-09-26 | 2015-01-14 | 北京铁科首钢轨道技术股份有限公司 | Preparation method of polyurethane modified epoxy resin and grouting material based on resin |
| CN111484598A (en) * | 2020-04-14 | 2020-08-04 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | High-strength single-component tunnel lining structure protective coating |
-
2023
- 2023-03-30 CN CN202310330331.0A patent/CN116333577A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0317116A (en) * | 1989-06-14 | 1991-01-25 | Nippon Polyurethane Ind Co Ltd | Blocking agent for isocyanate, compound bearing blocked isocyanate groups, and cold curable composition, coating composition, and adhesive composition containing the same |
| KR20100071505A (en) * | 2008-12-19 | 2010-06-29 | 진도화성주식회사 | Manufacturing method of polyurethane-epoxy hybrid resins |
| CN102924692A (en) * | 2012-09-07 | 2013-02-13 | 湖南工业大学 | High-permeability polyurethane graft-modified epoxy resin interpenetrating-network polymer grouting material and preparation method thereof |
| CN104277449A (en) * | 2014-09-26 | 2015-01-14 | 北京铁科首钢轨道技术股份有限公司 | Preparation method of polyurethane modified epoxy resin and grouting material based on resin |
| CN111484598A (en) * | 2020-04-14 | 2020-08-04 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | High-strength single-component tunnel lining structure protective coating |
Non-Patent Citations (1)
| Title |
|---|
| 李阿峰: "低温解封封闭异氰酸酯固化剂的合成及应用研究", 中国优秀硕士学位论文全文数据库工程科技I辑, no. 2013, pages 018 - 163 * |
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