CN115093824B - Water-permeable terrace glue and preparation method and application thereof - Google Patents
Water-permeable terrace glue and preparation method and application thereof Download PDFInfo
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- CN115093824B CN115093824B CN202210695922.3A CN202210695922A CN115093824B CN 115093824 B CN115093824 B CN 115093824B CN 202210695922 A CN202210695922 A CN 202210695922A CN 115093824 B CN115093824 B CN 115093824B
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- 239000003292 glue Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 59
- 239000003085 diluting agent Substances 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 36
- -1 hydroxy acrylic ester Chemical class 0.000 claims abstract description 27
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 25
- 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 abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000004575 stone Substances 0.000 claims abstract description 20
- 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 abstract description 19
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 17
- 239000000919 ceramic Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000004970 Chain extender Substances 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 125000003158 alcohol group Chemical group 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 13
- 238000010276 construction Methods 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000007865 diluting Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 229910052724 xenon Inorganic materials 0.000 description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 7
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011083 cement mortar Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004383 yellowing 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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7607—Compounds of C08G18/7614 and of C08G18/7657
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C7/00—Coherent pavings made in situ
- E01C7/08—Coherent pavings made in situ made of road-metal and binders
- E01C7/30—Coherent pavings made in situ made of road-metal and binders of road-metal and other binders, e.g. synthetic material, i.e. resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Road Paving Structures (AREA)
Abstract
The invention discloses permeable terrace glue and a preparation method and application thereof, and belongs to the field of building materials. Firstly, performing short-chain extension reaction on polyoxypropylene glycol, then adding a diluent, stirring, then adding toluene diisocyanate and diphenylmethane diisocyanate, reacting at the constant temperature of 40-60 ℃ to obtain polyurethane prepolymer, then diluting and dispersing hydroxy acrylic ester, and mixing with the polyurethane prepolymer to react to obtain the permeable floor glue. The permeable terrace glue has the advantages of shorter curing time, stronger bonding capability, better tensile strength and excellent weather resistance, can be widely applied to construction and manufacture of permeable terraces consisting of at least one of ceramic particles, cemented stone and aggregate broken stone, does not generate drying shrinkage on the pavement, has stable layer structure, can be applied to special working areas with larger bearing, high-speed busy road sections, common road sections and pedestrian greenways, and has higher regional adaptability and market economy.
Description
Technical Field
The invention relates to the field of building materials, in particular to permeable terrace glue and a preparation method and application thereof.
Background
The permeable terrace gradually appears in the green road of city, and the rainwater can permeate the characteristics of earth's surface plain soil rapidly through the permeable terrace of many oozes hole, can evacuate a large amount of ponds on roadside top layer fast, and supply groundwater effectively, and the permeable terrace is called ecological terrace that permeates water. At present, the conventionally used permeable terrace is cement mortar, and the permeable terrace needs to be subjected to watering and curing for multiple times, and is easy to dry in the early stage and crack after water loss. Therefore, the materials such as concrete aggregate crushed stone or gum stone, additives, terrace adhesives and the like are usually adopted to be uniformly stirred and paved into the pavement. The aggregate crushed stone has the characteristics of high strength and long weather-proof time under the curing and bonding effects of the adhesive, and can meet the performances of high bearing capacity, high permeability, quick heat dissipation and the like.
The floor adhesive is very important, all floor materials are required to be glued together, and the following conditions are required to be met in order to meet the requirements of the permeable floors: the adhesive has enough strength after being combined with materials such as aggregate broken stone, the tensile strength after film forming is more than or equal to 20Mpa, the surface drying time is less than or equal to 4h, and the adhesive is required to achieve the effects of yellowing resistance, no deformation, strong bonding capability with a base layer, aggregate and gum stones and the like under the external condition of 500h in consideration of long-time exposure to the outside of the permeable terrace and large load bearing weight.
The permeable terrace using the terrace adhesive can be exposed to air for a long time, is used as a good waterproof strong adhesive, has higher strength time than cement mortar, does not generate drying shrinkage phenomenon, and has stable layer structure. Therefore, developing a curing agent which has better performance, shorter time, can prevent the pavement from water loss and cracking, can be suitable for preparing various permeable terraces and has higher region adaptability is extremely important.
Disclosure of Invention
The invention mainly aims to provide permeable terrace glue and a preparation method and application thereof, and aims to solve the technical problems that in permeable terrace construction, the permeable terrace glue has long time, poor bonding polymerization capability, unsatisfactory tensile strength and weather resistance, and the permeable terrace is easy to crack due to water loss.
In order to achieve the purpose, the invention provides permeable terrace glue, which comprises the following components in parts by weight:
200-300 parts of polyoxypropylene glycol;
10-70 parts of chain extender;
20-50 parts of hydroxy acrylic ester;
toluene Diisocyanate (TDI), 200-400 parts;
50-100 parts of diphenylmethane diisocyanate (MDI);
200-350 parts of diluent.
The viscosity of the permeable terrace glue at 25 ℃ is 100-1000 mpa.s, the finger touch drying time at 25 ℃ is 0-1h, the real drying time at 25 ℃ is 2-3h, the tensile strength is 40-50Mpa, the tensile strength after being soaked in warm water for 72h at 40 ℃ is 35-45Mpa, and the tensile strength after being radiated by 500h xenon lamp is 35-45Mpa.
Optionally, the molecular weight of the polyoxypropylene diol is 2000-3000 and the hydroxyl value is 80-100mg KOH/g.
Optionally, the hydroxyl acrylate has a hydroxyl number of 10 to 30mg KOH/g
Optionally, the chain extender is an alcohol chain extender.
Further alternatively, the alcohol chain extender is at least one of ethylene glycol, propylene glycol and trimethylolpropane.
Optionally, the diluent is at least one of dibutyl ester and ethyl acetate.
In addition, in order to achieve the above purpose, the invention also provides a preparation method of the permeable terrace glue, which comprises the following steps:
S10, mixing the polyoxypropylene glycol and the chain extender according to the weight portion ratio, stirring and dispersing, then heating to 110-120 ℃, and stirring and reacting to obtain a reaction intermediate;
S20, cooling the reaction intermediate to 80-90 ℃, mixing with a part of diluent, stirring uniformly, adding toluene diisocyanate and diphenylmethane diisocyanate, and stirring at the constant temperature of 40-60 ℃ to obtain polyurethane prepolymer;
S30, mixing the hydroxy acrylic ester with the other part of diluent, uniformly dispersing, then mixing with the polyurethane prepolymer of S20, and reacting at the constant temperature of 40-60 ℃ to obtain the permeable terrace glue.
Optionally, in S10, the stirring dispersion speed is 1000-1500rpm.
Optionally, in S10, the stirring reaction time is 3-6h.
Optionally, in S20, the stirring reaction time is 1-3h.
Optionally, in S30, the weight ratio of the hydroxyacrylate to the diluent mixed therewith is 1:0.5-1.
Optionally, in S30, the reaction time is 0.5-1h.
Optionally, in S30, after the hydroxyacrylate is mixed with the other portion of the diluent, the purpose of uniform dispersion is achieved by high-speed stirring, where the rotational speed of the high-speed stirring is 800-1200rpm.
The invention also provides application of the permeable terrace glue, which can be widely applied to manufacturing of permeable terraces consisting of at least one of ceramic particles, gum stones and aggregate broken stones.
And mixing at least one of the ceramic particles, the gum stones and the aggregate broken stones with the permeable terrace glue and other required additives, uniformly stirring, and paving the mixture into a pavement.
The invention has the beneficial effects that:
the invention provides permeable terrace glue, which has the viscosity of 100-1000 mpa.s at 25 ℃, touch finger drying time of 0-1h at 25 ℃, real drying time of 2-3h at 25 ℃, tensile strength of 40-50Mpa, tensile strength of 35-45Mpa after being soaked in warm water at 40 ℃ for 72h, and tensile strength of 35-45Mpa after being radiated by 500h xenon lamp, and has good fluidity, better tensile mildness and excellent weather resistance.
The water permeable terrace glue has strong binding capacity and good weather resistance, can be widely applied to construction and preparation of water permeable terraces consisting of at least one of ceramic particles, gum stones and aggregate broken stones, can be applied to special working areas with large bearing capacity, high-speed busy road areas, common road sections and pedestrian greenways, and can lead the layer structure of the water permeable terraces to be stable and not generate drying shrinkage phenomenon.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of permeable terrace glue in embodiments 1 to 5 of the present invention.
FIG. 2 is a diagram of the final product of the invention according to application example 1, using the product obtained in example 1, for the preparation of coloured ceramic granule permeable floors.
FIG. 3 is a diagram of a finished product of the invention according to application example 2 to the preparation of an aggregate crushed stone permeable terrace using the product obtained in example 1.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The description as it relates to "1 st", "2 nd", etc. in the present invention is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "1 st", "2 nd" may include at least one such feature explicitly or implicitly. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The invention provides permeable terrace glue which comprises the following components in parts by weight:
200-300 parts of polyoxypropylene glycol;
10-70 parts of chain extender;
20-50 parts of hydroxy acrylic ester;
toluene Diisocyanate (TDI), 200-400 parts;
50-100 parts of diphenylmethane diisocyanate (MDI);
200-350 parts of diluent.
Specifically, the molecular weight of the polyoxypropylene glycol is 2000-3000, and the hydroxyl value is 80-100mg KOH/g; the hydroxyl value of the hydroxyl acrylic ester is 10-30mg KOH/g.
Specifically, the chain extender is an alcohol chain extender, and in this embodiment, the alcohol chain extender is at least one of ethylene glycol, glycerol, or trimethylolpropane.
Specifically, the diluent is at least one of dibutyl ester and ethyl acetate.
The preparation method of the permeable terrace glue comprises the following steps:
S10, mixing 200-300 parts of polyoxypropylene glycol and 10-70 parts of chain extender according to the weight part ratio, stirring and dispersing, heating to 110-120 ℃, and stirring and reacting to obtain a reaction intermediate.
Specifically, the stirring dispersion speed is 1000-1500rpm, and stirring reaction is carried out for 3-6 hours to obtain a reaction intermediate.
S20, cooling the reaction intermediate to 80-90 ℃, mixing with a part of diluent, stirring uniformly, adding 200-400 parts of toluene diisocyanate and 50-100 parts of diphenylmethane diisocyanate, and stirring at the constant temperature of 40-60 ℃ to obtain the polyurethane prepolymer.
Specifically, the diluent is at least one of dibutyl ester and ethyl acetate.
Specifically, the stirring reaction is continued for 1 to 3 hours.
Before mixing with the diluent, the whole reaction system is cooled to 80-90 ℃, so that the diluent can be prevented from volatilizing too fast due to too high temperature; the toluene diisocyanate and the diphenylmethane diisocyanate are controlled to react at the constant temperature of 40-60 ℃, so that the polyurethane prepolymer is prevented from being cured in advance due to the excessively severe reaction, and the quality of the product is further influenced.
The invention adds diphenylmethane diisocyanate to adjust in the reaction, uses scientific weight proportion, can accelerate and control the film forming speed of the permeable terrace glue, and meanwhile, the obtained permeable terrace glue has better tensile strength, and the tensile strength after being soaked in warm water at 40 ℃ for 72h and irradiated by a 500h xenon lamp can still recover more than 85%, has excellent weather resistance, can be widely applied to various use scenes such as high-temperature humid areas, special operation areas with strict bearing requirements or high-speed busy road sections, and the like, and improves the application range of products.
S30, mixing 20-50 parts of hydroxy acrylic ester with the other part of diluent, uniformly dispersing, then mixing with the polyurethane prepolymer, and reacting at the constant temperature of 40-60 ℃ to obtain the permeable terrace glue.
The sum of parts by weight of the part of the diluent mixed with the reaction intermediate in the step S20 and the other part of the diluent mixed with the hydroxy acrylic ester in the step S30 is 200-350 parts, wherein the weight ratio of the hydroxy acrylic ester to the diluent mixed with the hydroxy acrylic ester is 1:0.5-1
Specifically, after the hydroxy acrylic ester is mixed with the other part of the diluent, stirring is carried out at the rotating speed of 800-1000rpm, so that the effect of uniform dispersion is achieved.
In this example, the hydroxy acrylate is diluted with a diluent and then dispersed at high speed to improve the viscosity of the hydroxy acrylate to react more fully with the polyurethane prepolymer.
The hydroxyl acrylic ester and the alcohol chain extender can also play a role in consuming part of free diisocyanate in the reaction, so that the influence on the process of reacting the isocyanate with the hydroxyl to generate the polyurethane prepolymer is avoided.
Specifically, the reaction time in step S30 is 0.5-1h.
The viscosity of the water permeable terrace glue obtained in the embodiment is 100-1000 mpa.s at 25 ℃, the touch finger drying time at 25 ℃ is 0-1h, the real drying time at 25 ℃ is 2-3h, the tensile strength is 40-50Mpa, the tensile strength after being soaked in warm water at 40 ℃ for 72h is 35-45Mpa, and the tensile strength after being radiated by a 500h xenon lamp is 35-45Mpa.
The water permeable terrace glue obtained by the embodiment can be suitable for preparing a water permeable terrace formed by at least one of ceramic particles, gum stones and aggregate broken stones.
The technical scheme of the present invention will be further described in detail with reference to the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure.
Example 1
The embodiment of the invention provides a preparation method of permeable terrace glue, and referring to fig. 1, fig. 1 is a schematic flow chart of a preparation method of permeable terrace glue according to embodiment 1 of the invention.
In this embodiment, the preparation method of the permeable terrace glue includes the following steps:
S10, mixing 278 parts of polyoxypropylene glycol with the molecular weight of 2000 and the hydroxyl value of 90mg KOH/g and 20 parts of chain extender glycol according to parts by weight, stirring and dispersing at the rotating speed of 1000rpm until the mixture is uniform, then transferring the mixture into a flask, heating the mixture to 110 ℃, and stirring and reacting for 4 hours to obtain a reaction intermediate.
S20, cooling the reaction intermediate of S10 to 80 ℃, adding 247 parts of diluent ethyl acetate, stirring for 0.5h, adding 300 parts of toluene diisocyanate and 75 parts of diphenylmethane diisocyanate, and continuously stirring for reaction for 1h at the constant temperature of 40 ℃ to obtain the polyurethane prepolymer.
S30, mixing 50 parts of hydroxyl acrylic ester with the hydroxyl value of 30mg KOH/g with 50 parts of diluent ethyl acetate, stirring for 10min at the rotating speed of 1000rpm in a high-speed dispersing machine, uniformly dispersing, then mixing with the polyurethane prepolymer, reacting for 1h at the constant temperature of 60 ℃, obtaining the product permeable terrace glue, detecting the viscosity of the permeable terrace glue at the temperature of 20 ℃, and packaging and storing the finished product.
In the embodiment, the obtained permeable terrace glue has good fluidity, shorter curing time, better tensile strength and excellent weather resistance.
Example 2
The embodiment of the invention provides a preparation method of permeable terrace glue, and referring to fig. 1, fig. 1 is a schematic flow chart of a preparation method of permeable terrace glue according to embodiment 2 of the invention.
In this embodiment, the preparation method of the permeable terrace glue includes the following steps:
S10, mixing 250 parts of polyoxypropylene glycol with the molecular weight of 2500 and the hydroxyl value of 100mg KOH/g, 15 parts of glycerol and 50 parts of trimethylolpropane according to parts by weight, stirring and dispersing to be uniform at the rotating speed of 1500rpm, transferring into a flask, heating to 115 ℃, and stirring and reacting for 3 hours to obtain a reaction intermediate.
S20, cooling the reaction intermediate of S10 to 80 ℃, then adding 180 parts of diluent ethyl acetate, stirring for 0.5h, adding 200 parts of toluene diisocyanate and 50 parts of diphenylmethane diisocyanate, and continuously stirring for reaction for 3h at the constant temperature of 60 ℃ to obtain the polyurethane prepolymer.
S30, mixing 40 parts of hydroxyl acrylic ester with the hydroxyl value of 30mg KOH/g with 20 parts of diluent ethyl acetate, stirring in a high-speed dispersing machine at the rotating speed of 900rpm for 15min, uniformly dispersing, then mixing with the polyurethane prepolymer, reacting for 1h at the constant temperature of 50 ℃, obtaining the product permeable terrace glue, detecting the viscosity of the permeable terrace glue at the temperature of 20 ℃, and packaging and storing the finished product.
The product of this embodiment has the same advantages as those of the product of embodiment 1, and will not be described here again.
Example 3
The embodiment of the invention provides a preparation method of permeable terrace glue, and referring to fig. 1, fig. 1 is a schematic flow chart of a preparation method of permeable terrace glue according to embodiment 3 of the invention.
In this embodiment, the preparation method of the permeable terrace glue includes the following steps:
s10, mixing 250 parts of polyoxypropylene glycol with a molecular weight of 3000 and a hydroxyl value of 80mg KOH/g and 10 parts of ethylene glycol according to parts by weight, stirring and dispersing at a rotation speed of 1300rpm until the mixture is uniform, transferring the mixture into a flask, heating the mixture to 120 ℃, and stirring and reacting for 6 hours to obtain a reaction intermediate.
S20, cooling the reaction intermediate of S10 to 90 ℃, adding 260 parts of dibutyl diluent, stirring for 0.5h, adding 400 parts of toluene diisocyanate and 90 parts of diphenylmethane diisocyanate, and continuously stirring at the constant temperature of 60 ℃ for 2h to obtain the polyurethane prepolymer.
S30, mixing 20 parts of hydroxyl acrylic ester with the hydroxyl value of 30mg KOH/g with 20 parts of diluent dibutyl ester, stirring in a high-speed dispersing machine at the speed of 800rpm for 15min, uniformly dispersing, then mixing with the polyurethane prepolymer, reacting for 0.5h at the constant temperature of 40 ℃, obtaining the product permeable terrace glue, detecting the viscosity of the permeable terrace glue at the temperature of 20 ℃, and packaging and storing the finished product.
The product of this embodiment has the same advantages as those of the product of embodiment 1, and will not be described here again.
Example 4
The embodiment of the invention provides a preparation method of permeable terrace glue, and referring to fig. 1, fig. 1 is a schematic flow chart of a preparation method of permeable terrace glue according to embodiment 4 of the invention.
In this embodiment, the preparation method of the permeable terrace glue includes the following steps:
S10, mixing 300 parts of polyoxypropylene glycol with the molecular weight of 2500 and the hydroxyl value of 100mg KOH/g and 70 parts of glycerol according to parts by weight, stirring and dispersing to be uniform at the rotating speed of 1500rpm, transferring into a flask, heating to 110 ℃, and stirring and reacting for 3 hours to obtain a reaction intermediate.
S20, cooling the reaction intermediate of S10 to 85 ℃, adding 320 parts of diluent ethyl acetate, stirring for 1.5 hours, adding 300 parts of toluene diisocyanate and 100 parts of diphenylmethane diisocyanate, and continuously stirring for 2.5 hours at the constant temperature of 55 ℃ to obtain the polyurethane prepolymer.
S30, mixing 30 parts of hydroxyl acrylic ester with the hydroxyl value of 20mg KOH/g with 30 parts of diluent ethyl acetate, stirring for 10min at the rotating speed of 850rpm in a high-speed dispersing machine, uniformly dispersing, then mixing with the polyurethane prepolymer, reacting for 0.5h at the constant temperature of 50 ℃, obtaining the product permeable terrace glue, detecting the viscosity of the permeable terrace glue at the temperature of 20 ℃, and packaging and storing the finished product.
The product of this embodiment has the same advantages as those of the product of embodiment 1, and will not be described here again.
Example 5
The embodiment of the invention provides a preparation method of permeable terrace glue, and referring to fig. 1, fig. 1 is a schematic flow chart of a preparation method of permeable terrace glue according to embodiment 5 of the invention.
In this embodiment, the preparation method of the permeable terrace glue includes the following steps:
S10, mixing 200 parts of polyoxypropylene glycol with a molecular weight of 3000 and a hydroxyl value of 80mg KOH/g and 50 parts of ethylene glycol according to parts by weight, stirring and dispersing at a rotating speed of 1000rpm until the mixture is uniform, transferring the mixture into a flask, heating the mixture to 110 ℃, and stirring and reacting for 4 hours to obtain a reaction intermediate.
S20, cooling the reaction intermediate of S10 to 90 ℃, then adding 150 parts of diluent ethyl acetate, stirring for 0.5h, adding 350 parts of toluene diisocyanate and 60 parts of diphenylmethane diisocyanate, and continuously stirring for reaction for 1.5h at the constant temperature of 60 ℃ to obtain the polyurethane prepolymer.
S30, mixing 50 parts of hydroxyl acrylic ester with the hydroxyl value of 10mg KOH/g with 50 parts of diluent ethyl acetate, stirring in a high-speed dispersing agent at a rotating speed of 1000rpm for 10min, uniformly dispersing, then mixing with the polyurethane prepolymer, reacting for 1h at the constant temperature of 60 ℃, obtaining the product permeable terrace glue, detecting the viscosity of the permeable terrace glue at the temperature of 20 ℃, and packaging and storing a finished product.
The product of this embodiment has the same advantages as those of the product of embodiment 1, and will not be described here again.
Comparative example 1
Comparative example 1 was prepared in substantially the same manner as in example 1, except that S30 was not used to dilute the hydroxyacrylate with the diluent ethyl acetate.
Comparative examples 2 to 3
Comparative examples 2 to 3 were substantially the same as the preparation method of example 1, except that the reaction intermediate temperatures were adjusted to 100℃and 110℃respectively at S20, and ethyl acetate as a diluent was added thereto to stir uniformly.
Comparative examples 4 to 6
Comparative examples 4 to 6 were substantially the same as the preparation method of example 1, except that after S20 was added to the toluene diisocyanate and diphenylmethane diisocyanate, the temperatures were adjusted to 30℃and 70℃respectively, and a constant temperature stirring reaction was carried out at 80 ℃.
Comparative examples 7 to 9
Comparative examples 7 to 9 were substantially the same as the preparation method of example 1, except that the compositions of the raw materials were different, as detailed in Table 1.
Table 1 comparative examples 7 to 9 raw material composition (parts by weight)
In the table "/" indicates the same as in example 1.
Performance testing
The water permeable floor glues obtained in examples 1 to 5 and comparative examples 1 to 9 were sampled according to a unified standard with a thickness of 1mm, and performance test was performed.
Among them, the tensile strength test was performed in accordance with GB/T10654-2011, the 500h xenon lamp radiation tensile strength was performed in accordance with GB/T16422.2-2014, the film hardness was performed in accordance with GB/T6739-1996, and the test results are shown in tables 2 and 3.
Table 2 properties of the water permeable floor glues obtained in examples 1 to 5
Table 3 Properties of the Water permeable terrace glues obtained in comparative examples 1 to 9
As can be seen from table 2: the terrace glue prepared by the embodiment of the invention has good fluidity and ductility, high tensile strength and shorter curing time, and after being soaked in warm water at 40 ℃ for 72 hours or irradiated by a 500h xenon lamp, the tensile strength is recovered to more than 85%, and the terrace glue has excellent weather resistance and can adapt to different construction environments.
As can be seen from table 3:
in comparative example 1, the hydroxy acrylic ester is diluted without a diluent, the viscosity of a reaction system is high, the hydroxy acrylic ester and polyurethane prepolymer are not fully reacted, and the viscosity of the obtained product at 25 ℃ is slightly high, so that the construction is not facilitated.
As is clear from comparative examples 2 to 3, the reaction system temperature before adding the diluent ethyl acetate in the step S20 is too high, the temperature reaches 100 ℃, the temperature reaches 110 ℃, the volatilization of the ethyl acetate is too fast, the requirements of reducing the viscosity of the water permeable terrace glue and increasing the fluidity cannot be met, the actual drying time is long, and the tensile strength and the weather resistance are poor.
As is clear from comparative examples 4 to 6, the reaction temperature in the step S20 has a large influence on the quality of the product, the temperature is low, the reaction is incomplete, the tensile strength of the product after being soaked in warm water at 40 ℃ for 72 hours is only 37Mpa, and the tensile strength is reduced by 23% compared with that of 48 Mpa; after 500h xenon lamp radiation, the tensile strength is only 35Mpa, and compared with the tensile mildness of 48Mpa, the tensile strength is reduced by 27%, and the weather resistance is poor; the reaction temperature is higher, the reaction is severe, the obtained product has the tendency of early solidification, the tensile strength and weather resistance are also not ideal, the environmental adaptability is poor, and the product is not a qualified product.
According to the comparison examples 7-9, the weight proportion of the raw materials of each component has an effect on the quality of the permeable terrace glue of the invention if a chain extender and hydroxy acrylic ester are added, the weather resistance of the product is reduced to a certain extent if the chain extender is not added, the tensile strength and weather resistance of the product are affected if the hydroxy acrylic ester is not added, the hardness is low, the permeable terrace glue is not suitable for special working areas with larger bearing or high-speed busy road areas, the weight proportion of the raw materials is changed, certain performances of the obtained permeable terrace glue are more outstanding, but other performances are correspondingly deteriorated, and the permeable terrace glue is not a qualified product. Namely, the water permeable terrace glue can be obtained only through scientific proportioning.
Application example 1
The permeable terrace glue obtained in the embodiment 1 is applied to permeable terraces taking colored ceramic particles as main raw materials, the colored ceramic particles, the permeable terrace glue in the embodiment 1 and other additives are mixed and uniformly stirred, and the permeable terrace glue is paved into a pavement, as shown in fig. 2, the permeable terrace glue has strong cementing capacity, the pavement does not generate a drying shrinkage phenomenon, and the layer structure is stable.
Application example 2
The permeable terrace glue obtained in the embodiment 1 is applied to the permeable terrace with aggregate broken stone as a main raw material, the aggregate broken stone, the permeable terrace glue of the embodiment 1 and other additives are mixed and uniformly stirred, and the permeable terrace glue is paved into a pavement, as shown in fig. 3, the permeable terrace glue has strong cementing capacity, the pavement does not generate a drying shrinkage phenomenon, and the layer structure is stable.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but rather is intended to cover any equivalents of the structures or equivalent processes disclosed herein or in the alternative, which may be employed directly or indirectly in other related arts.
Claims (10)
1. The permeable terrace glue is characterized by comprising the following components in parts by weight:
200-300 parts of polyoxypropylene glycol;
10-70 parts of chain extender;
20-50 parts of hydroxy acrylic ester;
toluene Diisocyanate (TDI), 200-400 parts;
50-100 parts of diphenylmethane diisocyanate (MDI);
200-350 parts of a diluent;
the preparation method of the permeable terrace glue comprises the following steps:
Mixing the polyoxypropylene glycol and the chain extender according to the weight portion ratio, stirring and dispersing, then heating to 110-120 ℃, and stirring and reacting to obtain a reaction intermediate;
cooling the reaction intermediate to 80-90 ℃, mixing with a part of diluent, stirring uniformly,
Then toluene diisocyanate and diphenylmethane diisocyanate are added, and stirring reaction is carried out at the constant temperature of 40-60 ℃ to obtain polyurethane prepolymer;
And mixing the hydroxy acrylic ester with another part of diluent, uniformly dispersing, then mixing with the polyurethane prepolymer, and reacting at the constant temperature of 40-60 ℃ to obtain the permeable floor glue.
2. The permeable floor glue according to claim 1, wherein the polyoxypropylene diol has a molecular weight of 2000-3000 and a hydroxyl value of 80-100mg KOH/g; the hydroxyl value of the hydroxyl acrylic ester is 10-30mg KOH/g.
3. The permeable floor glue of claim 1, wherein the chain extender is an alcohol chain extender.
4. A water permeable floor glue according to claim 3, wherein the alcohol chain extender is at least one of ethylene glycol, propylene glycol and trimethylolpropane.
5. The permeable floor glue of claim 1, wherein the diluent is at least one of dibutyl ester and ethyl acetate.
6. The method for preparing the permeable terrace glue as claimed in any one of claims 1 to 5, comprising the steps of:
Mixing the polyoxypropylene glycol and the chain extender according to the weight portion ratio, stirring and dispersing, then heating to 110-120 ℃, and stirring and reacting to obtain a reaction intermediate;
cooling the reaction intermediate to 80-90 ℃, mixing with a part of diluent, stirring uniformly,
Then toluene diisocyanate and diphenylmethane diisocyanate are added, and stirring reaction is carried out at the constant temperature of 40-60 ℃ to obtain polyurethane prepolymer;
And mixing the hydroxy acrylic ester with another part of diluent, uniformly dispersing, then mixing with the polyurethane prepolymer, and reacting at the constant temperature of 40-60 ℃ to obtain the permeable floor glue.
7. The method for preparing the permeable terrace glue according to claim 6, wherein in the step of mixing the polyoxypropylene glycol and the chain extender according to the weight portion ratio, stirring and dispersing, then heating to 110-120 ℃, and stirring and reacting to obtain the reaction intermediate, the rotation speed of stirring and dispersing is 1000-1500rpm, and the stirring and reacting time is 3-6h.
8. The method for preparing permeable terrace glue according to claim 6, wherein in the step of cooling the reaction intermediate to 80-90 ℃, mixing with a part of diluent, stirring uniformly, adding toluene diisocyanate and diphenylmethane diisocyanate, and stirring at a constant temperature of 40-60 ℃ for reaction to obtain polyurethane prepolymer, the stirring reaction time is 1-3h.
9. The method for preparing the permeable terrace glue according to claim 6, wherein the weight ratio of the hydroxy acrylic ester to the diluent mixed with the hydroxy acrylic ester is 1:0.5-1.
10. The use of the permeable terrace glue according to any one of claims 1 to 5 for preparing permeable terraces, characterized in that the permeable terraces are prepared from any one or more of ceramic particles, gum stones and aggregate crushed stones.
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| KR101746777B1 (en) * | 2016-07-25 | 2017-06-27 | 이은숙 | Strong heat shield granite blocks and a method of manufacturing a water permeable |
| CN108102558A (en) * | 2018-03-06 | 2018-06-01 | 叶陈瑶 | A kind of high intensity is wet, light dual cure polyurethane binder and preparation method thereof and application method |
| CN109370409A (en) * | 2018-10-25 | 2019-02-22 | 江门市长河化工实业集团有限公司 | A kind of aqueous polyurethane floor material and preparation method thereof |
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| CN104004490A (en) * | 2014-06-05 | 2014-08-27 | 刘海宁 | Preparation method of compound high molecular adhesive for water permeable brick or water permeable pavement |
| KR101746777B1 (en) * | 2016-07-25 | 2017-06-27 | 이은숙 | Strong heat shield granite blocks and a method of manufacturing a water permeable |
| CN108102558A (en) * | 2018-03-06 | 2018-06-01 | 叶陈瑶 | A kind of high intensity is wet, light dual cure polyurethane binder and preparation method thereof and application method |
| CN109370409A (en) * | 2018-10-25 | 2019-02-22 | 江门市长河化工实业集团有限公司 | A kind of aqueous polyurethane floor material and preparation method thereof |
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