CN106700009B - Polyurethane composition, polyurethane water stop strip and steel-edge water stop strip comprising same - Google Patents
Polyurethane composition, polyurethane water stop strip and steel-edge water stop strip comprising same Download PDFInfo
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- CN106700009B CN106700009B CN201611112918.0A CN201611112918A CN106700009B CN 106700009 B CN106700009 B CN 106700009B CN 201611112918 A CN201611112918 A CN 201611112918A CN 106700009 B CN106700009 B CN 106700009B
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- water stop
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- polyurethane
- polyurethane composition
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 28
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- 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 14
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- 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 10
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- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 8
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- 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 4
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a polyurethane composition, which comprises the following raw materials in parts by weight: 10-40 parts of polyethylene glycol, 50-90 parts of polyether propylene glycol, 10-50 parts of polyether glycerol, 10-25 parts of isocyanate, 5-25 parts of plasticizer, 1-5 parts of modifier and 3-15 parts of nano filler. The invention also provides a preparation method of the polyurethane composition, a polyurethane water stop strip prepared from the polyurethane composition, a steel-edge water stop strip containing the polyurethane water stop strip, and a preparation method of the steel-edge water stop strip. The polyurethane composition can be repeatedly expanded when meeting water, so that the novel water stop can be tightly bonded with concrete, the waterproof performance is excellent, the durability is good, and the problem that the existing tunnel secondary lining water stop cannot radically cure water leakage is solved.
Description
Technical Field
The invention belongs to the field of waterproof materials, and particularly relates to a polyurethane composition capable of repeatedly expanding in water, a polyurethane water stop strip prepared from the composition, and a steel-edge water stop strip comprising the water stop strip. The steel-edged water stop can be widely applied to various tunnel constructions in the construction processes of railways, highways, subways and the like and the waterproofing and seepage prevention of various underground projects.
Background
With the enhancement of comprehensive national force, the construction of railways, highways, subways and municipal engineering in China is greatly accelerated, wherein underground basic engineering such as tunnels, underground engineering and the like is inevitably involved. Construction joints, settlement joints and deformation joints need to be reserved for the reasons that continuous pouring or foundation deformation cannot be carried out, concrete members expand with heat and contract with cold due to temperature change and the like. Waterstops must be installed at these seams to prevent water leakage problems.
The water stop is classified into a rubber water stop, a plastic water stop and a metal water stop according to different materials. The rubber waterstop is made up of natural rubber and synthetic rubber through mixing with assistants and filler, plastifying, pugging and press shaping. The water-stopping material has good elasticity, wear resistance, aging resistance and tear resistance, strong adaptive deformation capability and good waterproof performance. However, in conventional construction, due to the huge vibration force and difficulty in fixing during concrete pouring, the common rubber water stop belt can be displaced, pulled away and twisted to loosen and fall off, so that the leakage phenomenon can be caused under the condition of high water pressure. In order to overcome the defects, the prior art has provided a steel-edge rubber water stop (also called steel-edge water stop) produced by compounding metal and rubber. For example, in the utility model with the publication number CN2299099Y, "a steel-edged rubber water stop" (application date 1997, 4, 21), steel bands are provided on both sides of the rubber band, and mounting holes are provided on the steel bands. The composite water stop utilizes good adhesion between the steel plate and the concrete and between the steel plate and the rubber, so that the water stop is firmly combined with the concrete, new seepage seams cannot be generated between the steel belt and the concrete and between the steel belt and the rubber, and water permeation is effectively prevented. Meanwhile, the steel-edged rubber water stop has good self-adaptability after being installed, overcomes the defect that the rubber water stop needs a multi-party fixing process, and ensures that the construction and installation are more convenient. If the utility model patent of the utility model' slip casting formula meet water inflation steel limit waterstop "(application day 2008 4 month 5 days) of bulletin No. CN201176640Y again discloses one kind and is provided with galvanized steel sheet at the both sides interval of the rubber tape body, is provided with the compound waterstop of meeting water inflation rubber strip at the belt body upstream face. But the expansion effect of the rubber strip is reduced after the rubber strip repeatedly meets water; in addition, the rubber strip has poor low-temperature flexibility, and in cold regions, the rubber strip is easy to damage due to freezing action, cracks are generated, and water leakage is caused.
Along with the increase of underground construction scope and difficulty, higher requirements are put forward to the requirement of waterproof performance of the steel-edged water stop. However, the prior art can not solve the problem of water leakage of the two-lining water stop belt in underground engineering such as tunnels and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a novel polyurethane composition, a water stop strip prepared from the polyurethane composition, and a steel-edge water stop strip comprising the water stop strip. The polyurethane composition can be expanded in water repeatedly, so that the novel water stop can be tightly bonded with concrete, the water resistance is excellent, the durability is good, and the problem that the existing tunnel secondary-lining water stop cannot radically cure water leakage is solved.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a polyurethane composition comprises the following raw materials in parts by weight:
10-40 parts of polyethylene glycol, 50-90 parts of polyether propylene glycol, 10-50 parts of polyether glycerol, 10-25 parts of isocyanate, 5-25 parts of plasticizer, 1-5 parts of modifier and 3-15 parts of nano filler.
Preferably, the polyurethane composition comprises the following raw materials in parts by weight:
20-30 parts of polyethylene glycol, 60-80 parts of polyether propylene glycol, 10-20 parts of polyether glycerol, 15-20 parts of isocyanate, 10-15 parts of plasticizer, 2-3 parts of modifier and 3-5 parts of nano filler.
Preferably, the isocyanate is selected from one or two of toluene diisocyanate and diphenylmethane diisocyanate; more preferably toluene diisocyanate.
Preferably, the plasticizer is selected from one or two of dioctyl phthalate and dibutyl phthalate.
More preferably, the plasticizers are dioctyl phthalate and dibutyl phthalate.
In a preferred embodiment, the plasticizer is 5 to 25 parts by weight, wherein dibutyl phthalate is 1 to 14 parts by weight, and the balance is dioctyl phthalate.
In a more preferred embodiment, the plasticizer comprises 10 to 15 parts by weight of dibutyl phthalate, and the balance is dioctyl phthalate.
Preferably, the modifier is selected from one or two of methyltrimethoxysilane and vinyltrimethoxysilane.
Preferably, the nano filler is selected from one or more of nano calcium carbonate, kaolin and talcum powder; more preferably nano calcium carbonate.
The polyurethane composition provided by the invention also comprises one or two catalysts selected from stannous octoate and dibutyltin dilaurate as raw materials.
Preferably, the catalyst is stannous octoate and dibutyltin dilaurate.
Preferably, the weight part of the catalyst is 0.01-0.05 part, and more preferably 0.03-0.04 part.
In a preferred embodiment, the catalyst is 0.01 to 0.05 part by weight, wherein stannous octoate is 0.001 to 0.049 part by weight, and the balance is dibutyltin dilaurate.
In a more preferred embodiment, the catalyst comprises 0.03 to 0.04 parts by weight of stannous octoate and 0.005 part by weight of dibutyltin dilaurate in balance.
In a preferred embodiment, the polyurethane composition of the present invention comprises the following components in parts by weight:
10-40 parts of polyethylene glycol, 50-90 parts of polyether propylene glycol, 10-50 parts of polyether glycerol, 10-25 parts of toluene diisocyanate, 5-15 parts of plasticizer, 1-5 parts of methyltrimethoxysilane or vinyl trimethoxysilane, 0.01-0.05 part of catalyst and 3-15 parts of nano calcium carbonate; wherein the plasticizer is 1-14 parts by weight of dibutyl phthalate and the balance of dioctyl phthalate, and the catalyst is 0.001-0.049 parts by weight of stannous octoate and the balance of dibutyltin dilaurate.
In a more preferred embodiment, the polyurethane composition of the present invention comprises the following components in parts by weight:
20-30 parts of polyethylene glycol, 60-80 parts of polyether propylene glycol, 10-15 parts of polyether glycerol, 15-20 parts of toluene diisocyanate, 10-15 parts of plasticizer, 2-3 parts of methyltrimethoxysilane or vinyl trimethoxysilane, 0.03-0.04 part of catalyst and 3-5 parts of nano calcium carbonate; wherein, the plasticizer is 9 weight portions of dibutyl phthalate and the rest of dioctyl phthalate, and the catalyst is 0.005 weight portion of stannous octoate and the rest of dibutyltin dilaurate.
The polyurethane composition is prepared by modifying a prepolymer with a hydrophilic chain segment, which is obtained by the polymerization reaction of a polyether compound with a hydroxyl at the tail end and isocyanate, by a plasticizer, a modifier and the like. When the polyurethane composition disclosed by the invention is contacted with water, on one hand, water molecules are combined with atoms such as N, O with strong electronegativity in polyurethane molecules in a hydrogen bond mode, and simultaneously, an ionic pressure is formed between the water molecules and hydrophilic groups in macromolecules, so that the polyurethane composition continuously absorbs water and expands in volume.
Still another object of the present invention is to provide a method for preparing the above polyurethane composition, comprising the steps of:
preparation of prepolymer
Putting the polyethylene glycol, the polyether propylene glycol and the polyether glycerol in parts by weight into heating equipment, heating to 80-90 ℃, uniformly mixing, adding the isocyanate and the catalyst in parts by weight, and reacting at the constant temperature of 80-90 ℃ for 2-4 hours to obtain a prepolymer with a hydrophilic chain segment;
modification of the prepolymer
Adding the prepolymer obtained in the step I and the plasticizer in parts by weight into a planetary stirrer, and vacuumizing and stirring for 1-2 hours; then adding the filler in parts by weight, and vacuumizing and stirring for 1-2 hours; and finally, adding the modifier in parts by weight, and vacuumizing and stirring for 1-2 hours to obtain the modified polyvinyl chloride.
The preparation method also comprises the step of pressing the prepared polyurethane composition into a sealing device after the step II is finished.
The invention also aims to provide the application of the polyurethane composition in building waterproofing; specifically, the polyurethane composition is used as a water stop strip for preparing a steel-edge water stop strip.
It is therefore a further object of the present invention to provide a polyurethane waterstop strip extruded from the above polyurethane composition.
The invention also aims to provide a steel-edged water stop which comprises a rubber belt body, a galvanized steel plate and the polyurethane water stop; the two galvanized steel plates are symmetrically connected to two sides of the rubber belt body; the number of the polyurethane water stop bars is more than 1, and the polyurethane water stop bars are independently arranged on the upper surface and the lower surface of the galvanized steel plates on the two sides of the rubber belt body.
Preferably, the number of the polyurethane water stop strips is multiple, and the polyurethane water stop strips are respectively and symmetrically arranged on the upper surface and the lower surface of the galvanized steel sheets on the two sides of the rubber belt body.
Preferably, the steel-edged water stop further comprises self-adhesive glue and an isolating membrane; the self-adhesive is arranged on the surface of the polyurethane water stop strip or the surfaces of the galvanized steel plate and the polyurethane water stop strip; the isolating film is arranged outside the self-adhesive.
According to construction conditions and requirements, the self-adhesive glue and the isolating membrane can be arranged in various different modes:
(1) the surface of the polyurethane water stop strip arranged on the surface of one side of the galvanized steel sheet is covered with a layer of self-adhesive, and a layer of isolating membrane is arranged outside the self-adhesive;
(2) the polyurethane water stop strips arranged on the surfaces of the two sides of the galvanized steel sheet are covered with a layer of self-adhesive, and an isolation film is arranged outside the self-adhesive;
(3) the surface of one side of the galvanized steel sheet and the surface of the polyurethane water stop strip arranged on the side surface are covered with a layer of self-adhesive, and the self-adhesive is externally provided with a layer of isolating membrane.
(4) The two side surfaces of the galvanized steel sheet and the surface of the polyurethane water stop strip are covered with a layer of self-adhesive, and a layer of isolating membrane is arranged outside the self-adhesive.
The isolation film layer does not need to be removed and disappears after reacting with the poured concrete.
Preferably, the thickness of the self-adhesive layer is 0.2-0.4 mm, and the raw materials comprise the following components in parts by weight:
2-10 parts of chlorobutyl rubber, 20-30 parts of high molecular weight butyl rubber with the viscosity average molecular weight of 40-50 ten thousand, 30-50 parts of medium molecular weight polyisobutylene with the viscosity average molecular weight of 5-10 ten thousand, 20-40 parts of low molecular weight polyisobutylene with the viscosity average molecular weight of 1000-3000, 0.5-10 parts of vinyl terminated silicone rubber and 1-5 parts of antioxidant;
wherein the vinyl terminated silicone rubber is vinyl terminated silicone rubber, the viscosity average molecular weight is 5-30 ten thousand, and the vinyl mole percentage is more than 1%.
Preferably, the thickness of the self-adhesive layer is 0.2-0.3 mm.
Preferably, the raw materials of the self-adhesive layer comprise the following components in parts by weight:
4-8 parts of chlorobutyl rubber, 20-30 parts of high molecular weight butyl rubber with a viscosity average molecular weight of 40-50 ten thousand, 35-45 parts of medium molecular weight polyisobutylene with a viscosity average molecular weight of 5-10 ten thousand, 25-35 parts of low molecular weight polyisobutylene with a viscosity average molecular weight of 1000-3000, 1-5 parts of vinyl terminated silicone rubber and 1-5 parts of antioxidant;
wherein the vinyl terminated silicone rubber is terminated vinyl silicone rubber, the viscosity average molecular weight is 10-20 ten thousand, and the vinyl mole percentage is more than 1%.
Preferably, the thickness of the isolation film layer is 0.05-0.15 mm, and the raw materials comprise the following components in parts by weight:
40-80 parts of acrylic resin emulsion, 5-15 parts of talcum powder, 1-7 parts of extinction powder, 0.01-3 parts of ultraviolet absorber and 0.5-1.5 parts of antioxidant.
More preferably, the thickness of the isolation film layer is 0.05-0.10 mm.
Further preferably, the raw materials of the isolating layer comprise the following components in parts by weight:
60-80 parts of acrylic resin emulsion, 8-12 parts of talcum powder, 3-6 parts of extinction powder, 0.1-1.5 parts of ultraviolet absorber and 0.5-1.0 part of antioxidant.
The ultraviolet light absorber and antioxidant of the present invention are selected from those commonly used in the art. For example, the ultraviolet absorber may be selected from phenol-substituted benzotriazole-based ultraviolet absorbers such as Exxon Mobil 1018HA, manufactured by Yixing Angel synthetic chemical Co., Ltd., ultraviolet absorbers UV-326/UV-328, UV-9/BP-3, UV-531, etc.; the antioxidant can be one or more selected from pentaerythritol ester, hindered phenol antioxidant or hindered amine antioxidant.
The invention also aims to provide a preparation method of the steel-edged water stop, which comprises the following steps:
II, molding the rubber belt body and the galvanized steel plates on two sides in a one-step mode;
II. fixing polyurethane water stop strip
Extruding and forming the polyurethane composition on the upper and lower surfaces of steel plates at two sides; or the polyurethane composition is extruded and molded, the water stop strip is obtained after curing, and the water stop strip is installed on the galvanized steel plate.
Preferably, the preparation method further comprises the following steps:
v. coating of self-adhesive layer
Preparing raw materials of the self-adhesive layer according to the parts by weight, carrying out hot melting, stirring and mixing to obtain a hot-melt adhesive solution, and then coating the hot-melt adhesive solution on the specific part of the steel-edged water stop obtained in the step II;
coating barrier film layer
Preparing raw materials of the isolating film layer according to parts by weight, adding talcum powder, matting powder, ultraviolet absorbent and anti-agent into the propionic acid resin emulsion in batches, dispersing, grinding and mixing uniformly to obtain an isolating film coating, then coating the isolating film coating on the surface of the self-adhesive layer, and drying to obtain the self-adhesive isolating film.
Preferably, in the step III, the hot melt adhesive solution is obtained through the following steps:
cutting high molecular weight butyl rubber into small blocks, putting the small blocks into an internal mixer, adding chlorobutyl rubber and vinyl terminated rubber into the internal mixer, mixing for 15-30 minutes, cutting the mixture into small blocks after discharging, putting the small blocks into a double-planet mixer, adding medium molecular weight polyisobutylene, low molecular weight polyisobutylene and an antioxidant, starting a stirring paddle and a high-speed dispersing paddle to stir, keeping the vacuum degree of the system at-0.02 MPa, heating the material to 160-180 ℃, stirring and dispersing for 2-5 hours, and then discharging.
The "parts by weight" in the specification of the invention indicates the weight ratio relationship among the components; as practical, 1 part by weight may be 1g, 100g, 1kg, etc.
When the polyurethane composition of the present invention contacts with water, on one hand, water molecules are hydrogen bonded with highly electronegative atoms such as N, O in polyurethane polymer, and simultaneously form ionic pressure and the like with hydrophilic groups in polymer, such that the polyurethane composition continuously absorbs water and expands in volume. Tests prove that the expansion rate of the polyurethane composition can reach 60-300% after the polyurethane composition is soaked in water for 24 hours, and the expansion rate of the polyurethane composition soaked in water for 24 hours is basically kept unchanged after 200 times of cycles of drying for 8 hours and soaking for 24 hours. The polyurethane composition of the present invention is demonstrated to have good repeated expansion upon contact with water. The polyurethane composition is used as a water stop strip to be arranged on steel plates on two sides of a steel-edge water stop belt, the water stop belt is gradually attached to concrete through the water-swelling polyurethane water stop strip under the limiting effect of the two-lining concrete, and when the deformation resistance and the water osmotic pressure reach balance, the water stop belt is stable, so that the effects of long-term water blocking and seepage stopping are achieved.
Preferably, the water-swelling steel-edged water stop is provided with a self-adhesive layer and an isolation film layer. The isolation film layer is a high-molecular anti-sticking coating, can disappear after reacting with cement, does not need to be peeled off additionally, and simplifies construction operation. The self-adhesive layer is butyl rubber self-adhesive and has good adhesive property with a cement hardened body. During construction, after the reaction of the isolation film layer disappears, the self-adhesive layer can block the concrete pores, and the water stop strip can be firmly bonded with the two-lining concrete, so that the long-term waterproof performance of the two-lining concrete is effectively improved, and the problem that the existing tunnel two-lining water stop strip cannot radically cure water leakage is solved.
Drawings
The present invention will be described in detail with reference to the accompanying drawings.
Fig. 1 is a schematic structural view of a steel-edged water stop according to embodiment 15.
Fig. 2 is a schematic view of a steel-edged waterstop structure according to embodiment 16.
Fig. 3 is a schematic structural view of the steel-edged water stop of embodiment 17.
Fig. 4 is a schematic structural view of the steel-edged water stop of embodiment 18.
Fig. 5 is a schematic structural view of the steel-edged water stop of embodiment 19.
Detailed Description
The invention is illustrated below with reference to specific examples. It will be understood by those skilled in the art that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way.
The experimental procedures in the following examples are conventional unless otherwise specified. The raw materials and reagents used in the following examples are all commercially available products unless otherwise specified. The main raw materials and the brands thereof and the information of manufacturers:
polyether propylene glycol (Tdiol-2000), polyether propylene glycol (TDB-4000) and polyether glycerol
(TEP-240): tianjin petrochemical three plants;
polyethylene glycol (TT-1200): tianjin Tiantai fine chemicals, Inc.;
toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI): bayer or Basff products;
dibutyl phthalate (DBP), dioctyl phthalate (DOP), dibutyltin dilaurate (DY-12): beijing chemical second plant;
vinyltrimethoxysilane (A-151) and methyltrimethoxysilane (D-20): jiangsu Danyang high-green chemical plant;
high molecular weight butyl rubber (viscosity average molecular weight 40-50 ten thousand), Yanshan petrochemical butyl rubber IIR-1751 or IIR-1953;
medium molecular weight polyisobutylene (viscosity average molecular weight 5-10 ten thousand): jihua group fine chemicals, Inc.;
low molecular weight polyisobutylene (viscosity average molecular weight 1000-3000): weifang coastal petrochemical Co., Ltd, BH-1300 or BH-2300;
chlorobutyl rubber: CIIR 1066 or CIIR 1068, EXXON chlorinated butyl rubber, usa;
vinyl-terminated silicone rubber: jinzhen jinbosheng science and technology limited, Dongguan Huijinmei organosilicon materials limited, Jiangxi Xinhuo organosilicon factory or Zhejiang Runzao organosilicon new materials limited;
acrylic resin emulsion: acrylic emulsion of Zhejiang Xinlihua Koikesen brand;
ultraviolet absorber (MPE): exxon mobil 1018 HA;
antioxidant: yixing Angel synthetic chemical Co., Ltd is antioxidant 1010.
Examples 1 to 7Polyurethane composition
The composition of the raw materials of the polyurethane compositions of the above examples is shown in table 1, wherein 1 part by weight is 1 kg.
The polyurethane composition is prepared by the following steps:
I. preparation of prepolymer
Putting the polyethylene glycol, the polyether propylene glycol and the polyether glycerol in parts by weight into heating equipment, heating to 80-90 ℃, uniformly mixing, adding the isocyanate and the catalyst in parts by weight, and reacting at the constant temperature of 80-90 ℃ for 2-4 hours to obtain a prepolymer with a hydrophilic chain segment;
modification of the prepolymer
Adding the prepolymer obtained in the step I and the plasticizer in parts by weight into a planetary stirrer, and vacuumizing and stirring for 1-2 hours; then adding the filler in parts by weight, vacuumizing and stirring for 1-2 hours; and finally, adding the modifier in parts by weight, vacuumizing and stirring for 1-2 hours, and pressing the reaction product into a sealing device to obtain the modified polyurethane.
TABLE 1 polyurethane composition raw materials (unit: parts by weight) of examples 1 to 7
Examples 8 to 14Polyurethane waterstop strip
And (3) respectively extruding the polyurethane compositions prepared in the embodiments 1 to 7 into strips to obtain the polyurethane water stop strips of the embodiments 8 to 14.
Comparative examples 1 to 7Strip-shaped polyurethane
The composition of the raw materials of the strip polyurethane is shown in table 2 (wherein, 1 part by weight is 1kg), and the strip polyurethane is prepared by the following steps:
I. preparation of prepolymer
Putting the polyethylene glycol, the polyether propylene glycol and the polyether glycerol in parts by weight into heating equipment, heating to 80-90 ℃, uniformly mixing, adding the isocyanate and the catalyst in parts by weight, and reacting at the constant temperature of 80-90 ℃ for 2-4 hours to obtain a prepolymer with a hydrophilic chain segment;
modification of the prepolymer and Forming of the polyurethane
Adding the prepolymer obtained in the step I and the plasticizer in parts by weight into a planetary stirrer, and vacuumizing and stirring for 1-2 hours; then adding the filler in parts by weight, and vacuumizing and stirring for 1-2 hours; and finally, adding the modifier in parts by weight, vacuumizing and stirring for 1-2 hours, and extruding the reaction product into strips to obtain the modified polycarbonate.
TABLE 2 polyurethane composition raw materials for comparative examples 1 to 7 (unit: parts by weight)
Test example 1Performance measurement of polyurethane water stop strips of examples 8 to 14 and strip-shaped polyurethane of comparative examples 1 to 7
Under the same conditions, the single water swelling rate (single water swelling rate and rehydration swelling rate), the tensile strength, and the 100% modulus of elongation were measured for the polyurethane water-stop strip of the above example and the strip-shaped polyurethane of the comparative example, respectively.
The water absorption expansion rate test method comprises the following steps: reference is made to the immersion method in GB/T1033.1 (determination of Density of non-foamed plastics) part 1 of the immersion method, hydrometer method and titration method. The single water absorption expansion rate is the water absorption expansion rate of the tested sample after being soaked in water for 24 hours; the rehydration expansion rate is the water absorption expansion rate of the sample after 200 times of drying (8h) -soaking (24h) cycles and soaking for 24 hours. The water absorption expansion rate is calculated by the following formula:
the calculation formula of the sample volume is derived, and V is m 1 -m 2
V-volume of sample
m 1 Mass of the sample in air
m 2 Quality of the sample in Water
The water swelling ratio A ═ V of the sample 1 -V 0 )/V 0
Wherein A-Water swelling Rate (%) of the sample
V 0 Initial volume of sample
V 1 Volume of sample after Water absorption
Tensile strength test method: referring to GB/T16777-2009 test method for waterproof building coatings, the sample is an I-shaped dumbbell type sample, and the stretching speed of a tensile machine is 500 mm/min.
Tensile strength calculation formula: p ═ F/(B X D)
In the formula, P-specimen Strength (MPa)
F-maximum tensile force (N) of specimen
B-Width of the sample (mm)
D-thickness of sample (mm)
Modulus at definite elongation: this is the strength at which the tensile elongation of the specimen is 100%.
And (3) measuring results: see Table 3
TABLE 3 measurement results of Properties
And (4) conclusion:
the single water absorption expansion rate of the polyurethane water stop strip which can be used for the steel-edge water stop belt is required to be 60-300%, preferably 90-160%, and most preferably about 130%; the rehydration expansion rate must be 60% -260%, preferably 90% -160%, and most preferably about 130%; and the smaller the difference between the single water absorption expansion rate and the rehydration expansion rate, the better. As can be seen from the data shown in table 3:
1) examples 8 to 14 (corresponding to the polyurethane compositions of examples 1 to 7, respectively) all can be used as a water stop for a steel-edged water stop, and have good and stable repeated water-swelling properties. However, example 8 is the most preferred embodiment of the invention, followed by examples 9 and 10, again examples 11 and 12, and again examples 13 and 14.
2) The raw material components and the preparation method of the comparative examples 1 to 7 are the same as those of the polyurethane composition of the invention, but because the use amounts of the components are different, particularly the use amounts of the polyether compounds (polyethylene glycol, polyether propylene glycol and polyether glycerol) are respectively or not in the limited range of the invention, the single water absorption expansion rate and the rehydration expansion rate of the prepared polyurethane composition can not meet the requirements, and the prepared polyurethane composition can not be used as a water stop strip of a steel-edge water stop.
Example 15Steel-edged water stop
Fig. 1 shows that the steel-edged water stop of this embodiment includes a rubber belt body 1, galvanized steel sheets 3, and polyurethane water stop strips 4, the galvanized steel sheets 3 are two and are symmetrically connected to both sides of the rubber belt body 1, the polyurethane water stop strips 4 are a plurality of and are respectively and symmetrically disposed on the upper and lower surfaces of the galvanized steel sheets 3 on both sides of the rubber belt body 1. The middle part of the rubber belt body 1 is provided with a hollow through hole 2.
The steel-edged water stop is prepared by the following method:
I. the rubber belt body and the steel plates at two sides are molded by one-time casting;
II. fixing polyurethane water stop strip
Extruding and forming the polyurethane composition prepared in example 1 on the upper and lower surfaces of a galvanized steel sheet on both sides; or the polyurethane water stop strip prepared in the example 8 is fixed on the upper surface and the lower surface of the galvanized steel plates on two sides through wedge-shaped rubber bolts.
Example 16Steel-edged water stop
Fig. 2 shows the steel-edged water stop of this embodiment, including the rubber belt body 1, galvanized steel sheet 3, polyurethane sealing strip 4, self-adhesive 5, galvanized steel sheet 3 is two to symmetric connection is in 1 both sides of rubber belt body, polyurethane sealing strip 4 is a plurality of, and sets up in the upper and lower surface of 1 both sides galvanized steel sheet 3 of rubber belt body respectively symmetrically. The middle part of the rubber belt body 1 is provided with a hollow through hole 2. And a layer of self-adhesive glue 5 is covered on the surface of the polyurethane water stop strip 4 on one side surface of the galvanized steel plate 3, and a layer of isolating membrane is arranged outside the self-adhesive glue.
The composition of the raw materials of the self-adhesive layer and the barrier film layer is shown in table 4, wherein 1 part by weight is 1 kg.
The steel edge water stop is prepared by the following method:
I. the rubber belt body and the steel plates at two sides are molded at one time;
II. fixing polyurethane water stop strip
Extruding and forming the polyurethane composition prepared in example 3 on the upper and lower surfaces of a galvanized steel sheet on both sides; or the polyurethane waterstop prepared in the embodiment 10 is fixed on the upper and lower surfaces of the galvanized steel plates on two sides through wedge-shaped rubber bolts;
coating self-adhesive layer
Cutting high molecular weight butyl rubber into small pieces, putting the small pieces into an internal mixer, adding chlorobutyl rubber and vinyl terminated rubber into the internal mixer, mixing for 15-30 minutes, cutting the mixture into small pieces after discharging, putting the small pieces into a double-planetary mixer, adding medium molecular weight polyisobutylene, low molecular weight polyisobutylene and an antioxidant, starting a stirring paddle and a high-speed dispersing paddle to stir, keeping the vacuum degree of a system at-0.02 MPa, heating the material to 160-180 ℃, stirring and dispersing for 2-5 hours, then discharging, and coating the discharged material on the surface of the polyurethane waterstop on one side of the galvanized steel plate of the steel edge waterstop obtained in the step II;
coating isolation film layer
Preparing raw materials of the isolation film layer according to parts by weight, adding talcum powder, matting powder, ultraviolet absorbent and anti-agent into the propionic acid resin emulsion in batches, dispersing, grinding and mixing uniformly to obtain an isolation film coating, then coating the isolation film coating on the surface of the self-adhesive layer of the steel-edged water stop obtained in the step III, and drying to obtain the isolation film coating.
Example 17Steel-edged water stop
Fig. 3 shows the steel-edged water stop of this embodiment, including rubber belt body 1, galvanized steel sheet 3, polyurethane sealing strip 4, self-adhesive 5, galvanized steel sheet 3 is two to symmetric connection is in rubber belt body 1 both sides, polyurethane sealing strip 4 is a plurality of, and the symmetry sets up respectively in the upper and lower surface of rubber belt body 1 both sides galvanized steel sheet 3. The middle part of the rubber belt body 1 is provided with a hollow through hole 2. And a layer of self-adhesive glue 5 is covered on the surfaces of all the polyurethane water stop strips 4 on the two side surfaces of the galvanized steel sheet, and a layer of isolating membrane is arranged outside the self-adhesive glue.
The raw material composition of the self-adhesive layer and the barrier film layer was the same as that of example 16.
The above-described steel-edged waterstop was produced by substantially the same method as in example 16, except that: and step III, coating a self-adhesive layer, and coating the adhesive solution on the surfaces of all the polyurethane water stop strips of the steel-edge water stop band obtained in the step II.
Example 18Steel-edged water stop
Fig. 4 shows the steel-edged water stop of this embodiment, including the rubber belt body 1, galvanized steel sheet 3, polyurethane sealing strip 4, self-adhesive 5, galvanized steel sheet 3 is two to symmetric connection is in 1 both sides of rubber belt body, polyurethane sealing strip 4 is a plurality of, and sets up in the upper and lower surface of 1 both sides galvanized steel sheet 3 of rubber belt body respectively symmetrically. The middle part of the rubber belt body 1 is provided with a hollow through hole 2. The surface of one side of the galvanized steel sheet 3 and the surface of the polyurethane water stop strip 4 are covered with a layer of self-adhesive glue 5, and a layer of isolating membrane is arranged outside the self-adhesive glue.
The composition of the raw materials of the self-adhesive layer and the barrier film layer is shown in table 4, wherein 1 part by weight is 1 kg.
The steel-edged water stop is prepared by the following method:
I. the rubber belt body and the steel plates at two sides are molded at one time;
II. fixing polyurethane water stop strip
Extruding and forming the polyurethane composition prepared in the example 4 on the upper and lower surfaces of the galvanized steel sheets on two sides; or the polyurethane water stop strip prepared in the example 11 is fixed on the upper and lower surfaces of the galvanized steel plates on both sides through wedge-shaped rubber bolts;
coating self-adhesive layer
Cutting high molecular weight butyl rubber into small blocks, putting the small blocks into an internal mixer, adding chlorobutyl rubber and vinyl terminated rubber into the internal mixer, mixing for 15-30 minutes, cutting the mixture into small blocks after discharging, putting the small blocks into a double-planetary mixer, adding medium molecular weight polyisobutylene, low molecular weight polyisobutylene and an antioxidant, starting a stirring paddle and a high-speed dispersing paddle to stir, keeping the vacuum degree of the system at-0.02 MPa, heating the material to 160-180 ℃, stirring and dispersing for 2-5 hours, then discharging, and coating the discharged material on one side surface of the steel-edge waterstop belt obtained in the step II except for a rubber belt body;
coating isolation film layer
Preparing raw materials of the isolation film layer according to parts by weight, adding talcum powder, matting powder, ultraviolet absorbent and anti-agent into the propionic acid resin emulsion in batches, dispersing, grinding and mixing uniformly to obtain an isolation film coating, then coating the isolation film coating on the surface of the self-adhesive layer of the steel-edged water stop obtained in the step III, and drying to obtain the isolation film coating.
Example 19Steel-edged water stop
Fig. 5 shows the steel-edged water stop of this embodiment, which includes a rubber belt body 1, two galvanized steel sheets 3 and a plurality of polyurethane water stop strips 4, wherein the two galvanized steel sheets 3 are symmetrically connected to two sides of the rubber belt body 1, and the plurality of polyurethane water stop strips 4 are symmetrically disposed on the upper and lower surfaces of the galvanized steel sheets 3 on two sides of the rubber belt body 1. The middle part of the rubber belt body 1 is provided with a hollow through hole 2. The surfaces of two sides of the galvanized steel sheet 3 and the surface of the polyurethane water stop strip 4 are covered with a layer of self-adhesive glue 5, and a layer of isolating membrane is arranged outside the self-adhesive glue.
The composition of the raw materials of the self-adhesive layer and the barrier film layer is shown in table 4, wherein 1 part by weight is 1 kg.
The above-mentioned steel-edged waterstop was produced by substantially the same method as in example 16 except that: the polyurethane water stop strip is prepared in embodiment 14, and the self-adhesive layer and the isolation film layer are respectively coated on the upper surface and the lower surface of the galvanized steel sheet 3 and the surface of the polyurethane water stop strip 4.
Test example 1Steel-edged Water stop Performance measurement of examples 15, 16, 18 and 19
1. And (3) measuring the seepage-proofing performance of the steel-edged water stop:
simulating on-site tunnel concrete pouring, fixing the steel-edge water stop, embedding the thin tube between the steel-edge water stop and backing concrete, simulating to pour concrete on two sides, pressurizing and adding water in a pipeline embedded between the steel-edge water stop and the back concrete after the concrete is hardened, introducing water into the embedded hose and pressurizing, recording the pressure when water seepage begins, wherein the larger the pressure is, the better the seepage-proofing effect is. The results are shown in Table 4.
2. And (3) measuring the bonding property of the steel-edge water stop and the concrete:
pouring concrete on one side of the steel-edge water stop, after the concrete is hardened to 28 days, drilling a core at the corresponding part of the galvanized steel plate with the polyurethane water stop (for the steel-edge water stop in example 15, drilling a core at any part of the galvanized steel plate for sampling), testing the bonding strength (expressed by adhesive force) of the water stop and the concrete, and testing according to the method of GB/T5210-2006 adhesion test by a color paint and varnish pulling method, wherein the water stop can break from the part with weak adhesive force. The bond strength calculation formula is as follows:
σ＝F/A，
wherein F is the destructive power in newtons (N),
a is the area of the sample in square millimeters (mm) 2 )。
The greater the peel force, the better the adhesion. The results are shown in Table 4.
And (4) conclusion:
the steel-edged water stop has excellent water seepage resistance and good cohesiveness with concrete; and the steel-edge water stop belt provided with the self-adhesive layer and the isolation film layer has more outstanding performance.
Table 4 raw material ratios and measurement results of properties of self-adhesive layers and separators in examples 15 to 17
a : the mol percent of vinyl is less than 1 percent;
b : the viscosity average molecular weight is in parentheses;
c : the mole percent of vinyl is more than 1 percent.
Claims (30)
1. A polyurethane composition comprises the following raw materials in parts by weight:
10-40 parts of polyethylene glycol, 50-90 parts of polypropylene glycol, 10-50 parts of polyglycerol, 10-25 parts of isocyanate, 5-25 parts of plasticizer, 1-5 parts of modifier, 3-15 parts of nano filler and 0.01-0.05 part of catalyst;
wherein the isocyanate is selected from one or two of toluene diisocyanate and diphenylmethane diisocyanate;
the plasticizer is selected from one or two of dioctyl phthalate and dibutyl phthalate;
the modifier is selected from one or two of methyltrimethoxysilane and vinyl trimethoxysilane;
the nano filler is selected from one or more of nano calcium carbonate, kaolin and talcum powder;
the catalyst is selected from one or two of stannous octoate and dibutyltin dilaurate.
2. The polyurethane composition according to claim 1, wherein the polyurethane composition comprises the following raw materials in parts by weight:
20-30 parts of polyethylene glycol, 60-80 parts of polyether propylene glycol, 10-20 parts of polyether glycerol, 15-20 parts of isocyanate, 10-15 parts of plasticizer, 2-3 parts of modifier, 3-5 parts of nano filler and 0.03-0.04 part of catalyst.
3. A polyurethane composition according to claim 1 or 2, characterised in that the isocyanate is toluene diisocyanate.
4. A polyurethane composition according to claim 1 or 2, characterized in that the plasticizers are dioctyl phthalate and dibutyl phthalate.
5. The polyurethane composition according to claim 4, wherein the plasticizer is 5 to 25 parts by weight, and the dibutyl phthalate is 1 to 14 parts by weight, and the balance is dioctyl phthalate.
6. The polyurethane composition of claim 5, wherein the plasticizer comprises about 10 to about 15 parts by weight of dibutyl phthalate, and the balance is dioctyl phthalate.
7. A polyurethane composition according to claim 1 or 2, characterized in that the nanofiller is nanocalcium carbonate.
8. A polyurethane composition according to claim 1 or 2 characterised in that the catalyst is stannous octoate and dibutyltin dilaurate.
9. The polyurethane composition of claim 8, wherein the catalyst is present in an amount of 0.01 to 0.05 parts by weight, and wherein the stannous octoate is present in an amount of 0.001 to 0.049 parts by weight, and the balance is dibutyltin dilaurate.
10. The polyurethane composition of claim 9, wherein the catalyst is present in an amount of 0.03 to 0.04 parts by weight, and wherein the stannous octoate is present in an amount of 0.005 parts by weight, and the balance is dibutyltin dilaurate.
11. The polyurethane composition according to claim 1, wherein the raw materials of the polyurethane composition comprise the following components in parts by weight:
10-40 parts of polyethylene glycol, 50-90 parts of polypropylene glycol, 10-50 parts of polyglycerol, 10-25 parts of toluene diisocyanate, 5-15 parts of plasticizer, 1-5 parts of methyltrimethoxysilane or vinyltrimethoxysilane, 0.01-0.05 part of catalyst and 3-15 parts of nano calcium carbonate; wherein the plasticizer is 1-14 parts by weight of dibutyl phthalate and the balance of dioctyl phthalate, and the catalyst is 0.001-0.049 parts by weight of stannous octoate and the balance of dibutyltin dilaurate.
12. The polyurethane composition according to claim 11, wherein the raw materials of the polyurethane composition comprise the following components in parts by weight:
20-30 parts of polyethylene glycol, 60-80 parts of polypropylene glycol, 10-15 parts of polyglycerol, 15-20 parts of toluene diisocyanate, 10-15 parts of plasticizer, 2-3 parts of methyltrimethoxysilane or vinyl trimethoxysilane, 0.03-0.04 part of catalyst and 3-5 parts of nano calcium carbonate; wherein, the plasticizer is 9 weight portions of dibutyl phthalate and the rest is dioctyl phthalate, and the catalyst is 0.005 weight portion of stannous octoate and the rest is dibutyltin dilaurate.
13. A process for preparing a polyurethane composition as claimed in any one of claims 1 to 12 comprising the steps of:
I. preparation of prepolymer
Putting the polyethylene glycol, the polypropylene glycol and the polyglycerol in parts by weight into heating equipment, heating to 80-90 ℃, uniformly mixing, adding the isocyanate and the catalyst in parts by weight, and reacting at the constant temperature of 80-90 ℃ for 2-4 hours to obtain a prepolymer with a hydrophilic chain segment;
modification of the prepolymer
Adding the prepolymer obtained in the step I and the plasticizer in parts by weight into a planetary stirrer, and vacuumizing and stirring for 1-2 hours; then adding the filler in parts by weight, vacuumizing and stirring for 1-2 hours; and finally, adding the modifier in parts by weight, and vacuumizing and stirring for 1-2 hours to obtain the modified polyvinyl chloride.
14. The method of manufacturing according to claim 13, further comprising: after step II is completed, the prepared polyurethane composition is pressed into a sealing device.
15. Use of the polyurethane composition according to any one of claims 1 to 12 or the polyurethane composition prepared by the preparation method according to claim 13 or 14 for waterproofing buildings.
16. The use of claim 15, wherein the polyurethane composition is used as a water stop strip for the preparation of a steel-edged water stop.
17. A polyurethane waterstop strip, which is extruded from the polyurethane composition according to any one of claims 1 to 12 or the polyurethane composition obtained by the production method according to claim 13 or 14.
18. A steel-edged water stop comprising a rubber belt body, a galvanized steel sheet, and the polyurethane water stop of claim 17; the two galvanized steel plates are symmetrically connected to two sides of the rubber belt body; the number of the polyurethane water stop strips is more than 1, and the polyurethane water stop strips are independently arranged on the upper surface and the lower surface of the galvanized steel sheets on the two sides of the rubber belt body.
19. The steel-edged water stop according to claim 18, wherein the plurality of polyurethane water stop strips are symmetrically arranged on the upper and lower surfaces of the galvanized steel sheets on both sides of the rubber band body.
20. The steel-edged water stop as defined in claim 18 or 19, further comprising a self-adhesive glue and a separator; the self-adhesive is arranged on the surface of the polyurethane water stop strip or the surfaces of the galvanized steel plate and the polyurethane water stop strip; the isolating film is arranged outside the self-adhesive.
21. The steel-edged water stop of claim 20 wherein the barrier membrane layer disappears after reaction with the poured concrete without removal.
22. The steel-edged waterstop according to claim 20, wherein the thickness of the self-adhesive layer is 0.2-0.4 mm, and the raw materials comprise the following components in parts by weight:
2-10 parts of chlorobutyl rubber, 20-30 parts of high molecular weight butyl rubber with the viscosity average molecular weight of 40-50 ten thousand, 30-50 parts of medium molecular weight polyisobutylene with the viscosity average molecular weight of 5-10 ten thousand, 20-40 parts of low molecular weight polyisobutylene with the viscosity average molecular weight of 1000-3000, 0.5-10 parts of vinyl terminated silicone rubber and 1-5 parts of antioxidant; the vinyl-terminated silicone rubber is vinyl-terminated silicone rubber, the viscosity average molecular weight is 5-30 ten thousand, and the vinyl mole percentage is more than 1%.
23. The steel-edged water stop as claimed in claim 22, wherein the thickness of the self-adhesive layer is 0.2 to 0.3 mm.
24. The steel-edged water stop as claimed in claim 22, wherein the raw material of the self-adhesive layer comprises the following components in parts by weight:
4-8 parts of chlorobutyl rubber, 20-30 parts of high molecular weight butyl rubber with the viscosity average molecular weight of 40-50 ten thousand, 35-45 parts of medium molecular weight polyisobutylene with the viscosity average molecular weight of 5-10 ten thousand, 25-35 parts of low molecular weight polyisobutylene with the viscosity average molecular weight of 1000-3000, 1-5 parts of vinyl terminated silicone rubber and 1-5 parts of antioxidant; the vinyl-terminated silicone rubber is vinyl-terminated silicone rubber, the viscosity average molecular weight is 10-20 ten thousand, and the vinyl mole percentage is more than 1%.
25. The steel-edged water stop as claimed in claim 20, wherein the thickness of the barrier film layer is 0.05 to 0.15 mm; the raw materials comprise the following components in parts by weight:
40-80 parts of acrylic resin emulsion, 5-15 parts of talcum powder, 1-7 parts of extinction powder, 0.01-3 parts of ultraviolet absorber and 0.5-1.5 parts of antioxidant.
26. The steel-edged water stop as claimed in claim 25, wherein the thickness of the separation film layer is 0.05 to 0.10 mm.
27. The steel-edged water stop as claimed in claim 25, wherein the raw materials of the separation layer comprise the following components in parts by weight:
60-80 parts of acrylic resin emulsion, 8-12 parts of talcum powder, 3-6 parts of extinction powder, 0.1-1.5 parts of ultraviolet absorber and 0.5-1.0 part of antioxidant.
28. A method of making a steel-edged water stop as claimed in any one of claims 18 to 27, comprising the steps of:
I. molding the rubber belt body and the galvanized steel plates on two sides in a one-step mode;
II. fixing polyurethane water stop strip
Extruding and forming the polyurethane composition on the upper and lower surfaces of two steel plates; or the polyurethane composition is extruded and molded firstly, the water stop strip is obtained after curing, and then the water stop strip is arranged on the galvanized steel plate.
29. The method of claim 28, further comprising the steps of:
coating self-adhesive layer
Preparing raw materials of the self-adhesive layer according to parts by weight, carrying out hot melting, stirring and mixing to obtain a hot-melt adhesive solution, and then coating the hot-melt adhesive solution on the surface of the steel-edge water stop strip obtained in the step II except the rubber strip body, or coating the hot-melt adhesive on the surface of the water stop strip of the steel-edge water stop strip obtained in the step II;
coating isolation film layer
Preparing raw materials of the isolating film layer according to parts by weight, adding talcum powder, matting powder, ultraviolet absorbent and antioxidant into acrylic resin emulsion in batches, dispersing, grinding and mixing uniformly to obtain an isolating film coating, then coating the isolating film coating on the surface of the self-adhesive layer, and drying to obtain the self-adhesive isolating film.
30. A preparation method according to claim 29, wherein in the step III, the hot melt adhesive solution is obtained by the following steps:
cutting high molecular weight butyl rubber into small blocks, putting the small blocks into an internal mixer, adding chlorobutyl rubber and vinyl terminated rubber into the internal mixer, mixing for 15-30 minutes, cutting the mixture into small blocks after discharging, putting the small blocks into a double-planetary mixer, adding medium molecular weight polyisobutylene, low molecular weight polyisobutylene and an antioxidant, starting a stirring paddle and a high-speed dispersion paddle to stir, keeping the vacuum degree of a system at-0.02 MPa, heating the material to 160-180 ℃, stirring and dispersing for 2-5 hours, and then discharging.
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| CN107699081B (en) * | 2017-10-25 | 2020-05-22 | 中国铁道科学研究院金属及化学研究所 | Self-adhesive water stop and preparation method thereof |
| CN108167000A (en) * | 2018-01-30 | 2018-06-15 | 中铁二十二局集团第工程有限公司 | Lateral enhanced rubber waterstop |
| CN109056837A (en) * | 2018-09-18 | 2018-12-21 | 广东能辉新材料科技有限公司 | Exempt to take off type self-adhering rubber waterstop and preparation method thereof |
| CN109627410A (en) * | 2018-12-21 | 2019-04-16 | 山东诺威聚氨酯股份有限公司 | High-adhesion puffed rice sole polyurethane binder and preparation method thereof |
| CN110982032A (en) * | 2019-12-09 | 2020-04-10 | 上海东大化学有限公司 | Antibacterial water-swellable resin and preparation method and application thereof |
| CN112048171B (en) * | 2020-09-02 | 2022-05-24 | 中国铁道科学研究院集团有限公司金属及化学研究所 | Polyurethane composition capable of repeatedly swelling in water and application thereof in waterstop |
| CN113980456A (en) * | 2021-11-15 | 2022-01-28 | 南京臻致新材料科技有限公司 | Waterproof tape of polyurethane composition component |
| CN115592990B (en) * | 2022-10-12 | 2023-11-28 | 上安实业江苏有限公司 | Processing technology of steel plate rubber water stop |
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| CN101899262A (en) * | 2010-08-16 | 2010-12-01 | 上海应用技术学院 | Polyurethane-urea waterproof coating and preparation method thereof |
| CN102676039A (en) * | 2012-05-29 | 2012-09-19 | 苏州中材非金属矿工业设计研究院有限公司 | Moisturecured one-component polyurethane paint and preparation method thereof |
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