CN114644903A - Self-adhesive waterproof roll cementing material and waterproof roll prepared from same - Google Patents
Self-adhesive waterproof roll cementing material and waterproof roll prepared from same Download PDFInfo
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- CN114644903A CN114644903A CN202210370679.8A CN202210370679A CN114644903A CN 114644903 A CN114644903 A CN 114644903A CN 202210370679 A CN202210370679 A CN 202210370679A CN 114644903 A CN114644903 A CN 114644903A
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- palygorskite
- asphalt
- waterproof roll
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- 239000000463 material Substances 0.000 title claims abstract description 71
- 239000000853 adhesive Substances 0.000 title claims abstract description 30
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 60
- 229920001661 Chitosan Polymers 0.000 claims abstract description 39
- 239000010426 asphalt Substances 0.000 claims abstract description 33
- 239000003063 flame retardant Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000010992 reflux Methods 0.000 claims abstract description 12
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 11
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 16
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 3
- 238000004078 waterproofing Methods 0.000 claims description 3
- 229920002799 BoPET Polymers 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 229920001410 Microfiber Polymers 0.000 abstract description 4
- 239000003658 microfiber Substances 0.000 abstract description 4
- 230000003628 erosive effect Effects 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000004753 Schiff bases Chemical group 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction 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
- C09J195/00—Adhesives based on bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/346—Applications of adhesives in processes or use of adhesives in the form of films or foils for building applications e.g. wrap foil
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/26—Presence of textile or fabric
- C09J2400/263—Presence of textile or fabric in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a self-adhesive waterproof roll cementing material and a waterproof roll prepared by the same, belonging to the technical field of building waterproof engineering and comprising the following raw materials: the waterproof material comprises I type waterproof coiled material asphalt, ethylene tar, SBS, organic modified nano palygorskite, ammonium polyphosphate, naphthenic oil and modified chitosan; the modified chitosan is prepared by the following steps: dissolving chitosan in a methanol/acetic acid mixed solution with the volume ratio of 10:1, heating to 50 ℃, preserving heat, adding a flame retardant, heating to reflux, and obtaining the modified chitosan after the reaction is finished. In the technical scheme of the invention, the palygorskite is a natural mineral microfiber, and the palygorskite is added into the asphalt to limit the movement of asphalt molecules, so that the viscosity of the asphalt is further increased, and the stiffness modulus of the asphalt is improved; in addition, the reinforcement network consisting of a large number of microfibers can improve the integrity of the asphalt, reduce the generation of microcracks on the surface of the asphalt, contribute to improving the cohesive work of the asphalt and resist the erosion of water.
Description
Technical Field
The invention belongs to the technical field of building waterproof engineering, and particularly relates to a self-adhesive waterproof roll cementing material and a waterproof roll prepared from the same.
Background
With the development of economy and the progress of times, the requirements on building materials are higher and higher, and the original building materials cannot meet the development requirements of the times. The service life of many buildings is reduced due to water erosion, and the requirements of people on the quality of waterproof materials are more and more emphasized. At present, the elastomer (SBS) modified asphalt waterproof coiled material is still a mainstream product, and particularly when a roof is exposed for use, the excellent high-temperature resistance of the elastomer (SBS) modified asphalt waterproof coiled material is difficult to replace by other materials, however, the elastomer (SBS) modified asphalt waterproof coiled material needs to be subjected to hot melting construction during construction, when a blast burner is baked, open fire has great fire hazard, and the burning of a surface PE film and part of modified asphalt cementing materials in the baking process can also generate dioxin, hydrocarbon substances and the like due to heating decomposition, so that the environment is seriously polluted.
The self-adhesion coiled material is a novel waterproof material which can be constructed at normal temperature and does not need hot melting construction, and is favored by the market at present. The self-adhesive coiled material mainly comprises a waterproof base material and a self-adhesive layer, and is equivalent to the self-adhesive layer which is additionally arranged on the basis of the traditional coiled material. However, the self-adhesive coil still has the problem of poor flame retardant property, so that flame retardant modification is necessary.
Disclosure of Invention
The invention aims to provide a self-adhesive waterproof roll cementing material and a waterproof roll prepared from the same.
The technical problems to be solved by the invention are as follows: the self-adhesive coiled material has poor flame retardant property.
The purpose of the invention can be realized by the following technical scheme:
the self-adhesive waterproof coiled material cementing material comprises the following raw materials in parts by mass: 40-45 parts of I type waterproof coiled material asphalt, 2-5 parts of ethylene tar, 4-10 parts of SBS, 8-15 parts of organic modified nano palygorskite, 6-10 parts of naphthenic oil and 4-7 parts of modified chitosan;
the modified chitosan is prepared by the following steps:
s1, dissolving p-hydroxybenzaldehyde in dry THF, introducing the solution into a three-neck round-bottom glass flask provided with a constant-pressure dropping funnel, a reflux condenser and inert gas, adding triethylamine into the reactor, enabling the solution to become dark yellow, dropwise adding phenylphosphonic dichloride into the reaction container within 30min, refluxing at 70 ℃, continuing to react for 24h under magnetic stirring, finally removing precipitated solid through suction filtration, evaporating the obtained mixture in vacuum and pouring into ice water to obtain white crystalline solid, and drying the white crystalline solid in vacuum at 60 ℃ for 24h to obtain the flame retardant, wherein the dosage ratio of the p-hydroxybenzaldehyde, the THF, the triethylamine and the phenylphosphonic dichloride is 50-52 g: 200-300 mL: 40-45 g: 35-40 g;
the reaction generated in the synthesis process of the flame retardant is as follows:
the process of grafting the chitosan on the flame retardant comprises the following steps:
-CHO in synthetic flame retardants and-NH in chitosan2Reacting to generate-HC (N) -for connection, and grafting the synthesized flame retardant to a chitosan molecular chain;
s2, dissolving chitosan in a methanol/acetic acid mixed solution with a volume ratio of 10:1 in a reactor equipped with a mechanical stirrer and a condenser, heating to 50 ℃ and preserving heat for 2h, adding a flame retardant after preserving heat, continuously heating to 65 ℃ and refluxing for 12h, cooling and filtering after the reaction is finished, washing a filtered solid with ethanol and acetone for 3 times, and drying in vacuum at 70 ℃ for 6h to obtain the modified chitosan, wherein the dosage ratio of the chitosan, the methanol/acetic acid mixed solution and the flame retardant is 16-17g: 280-shaped organic solvent (mL): 15-20 g.
Further, the organic modified nano palygorskite is prepared by the following steps:
a1, mixing HCl solution with palygorskite, stirring vigorously in water bath at 60 ℃, standing, filtering to obtain solid, washing the solid until the washing liquid is neutral, and vacuum drying at 110 ℃ to obtain the final productPre-treating the palygorskite, wherein the dosage ratio of the HCl solution to the palygorskite is 10-20 mL: 3-4g, during which acid activation can dissolve the cementation impurities adhered between the rod-shaped crystals, hydrogen ions in the acid and Na in the crystal channel+And K+And Mg2+And Al3+The replacement is carried out, so that the internal and surface pores of the palygorskite are increased, and the surface area of the palygorskite is increased;
a2, adding pretreated palygorskite into dimethylbenzene, ultrasonically dispersing for 0.5h, adding gamma-aminopropyltriethoxysilane, heating to 80 ℃, stirring for 10h at constant temperature, filtering, washing and vacuum drying at 60 ℃ to obtain the organic modified nano palygorskite, wherein the dosage ratio of the pretreated palygorskite to the gamma-aminopropyltriethoxysilane is 3-5 g:280-320 mL: 3-5mL, and grafting the organic group to the surface of the palygorskite is realized in the process.
Further, the self-adhesive waterproof roll cementing material is prepared by the following steps:
heating the asphalt and the ethylene tar of the I-type waterproof coiled material to 190-class temperature of 200 ℃, adding the naphthenic oil and the fire retardant, uniformly stirring, cooling to 180-class temperature of 190 ℃, adding SBS, heating to 190-class temperature of 200 ℃, stirring for 1.5h, adding the organic modified nano palygorskite and the ammonium polyphosphate, and continuously stirring for 1h to obtain the self-adhesive waterproof coiled material cementing material.
A waterproof roll comprises an upper protective film, an upper cementing material layer, a tire base layer, a lower cementing material layer and a lower protective film which are sequentially compounded from top to bottom, wherein the upper cementing material layer and the lower cementing material layer use a self-adhesive waterproof roll cementing material as a raw material.
Further, the upper protective film and the lower protective film are both PET films.
Further, the base layer is polyester non-woven fabric.
The invention has the beneficial effects that:
(1) in the technical scheme of the invention, the chitosan is modified, and the fire retardant is reacted with-NH on the chitosan through a-CHO functional group2Nucleophilic addition reaction is carried out, so that the flame retardant is grafted to the chitosan chain, and the generated-HC-N-is of a Schiff base structure, thereby improving the water resistanceThermal stability of the coil; wherein the flame retardant mechanism of the flame retardant is as follows: when the waterproof roll encounters open fire, the phosphorus-containing part in the modified chitosan and ammonium polyphosphate are decomposed to form phosphoric acid, pyrophosphoric acid or polyphosphoric acid substances, and the acids can promote the chitosan to generate carbonaceous substances through dehydration reaction, so that an integrated carbon layer can be generated, further combustion of the waterproof roll is hindered, and the flame retardant effect is achieved; the fire resistance of the waterproof coiled material is improved by blending the modified chitosan with raw materials such as I-type waterproof coiled material asphalt, SBS and the like.
(2) In the technical scheme of the invention, after the silane coupling agent is used for surface grafting modification of the palygorskite, the compatibility of the palygorskite and the asphalt is increased, a large number of pore channel structures exist in the palygorskite, and meanwhile, the surface of the palygorskite has strong surface charges so that the palygorskite is mutually repelled and dispersed, so that the palygorskite has large specific surface area; because of the chemical characteristics of the crystal of the palygorskite, 4 kinds of electronegative adsorption centers exist on the surface of the palygorskite, and the palygorskite can adsorb a large number of light components in asphalt and is connected with polar macromolecular chains in the asphaltene, so that the viscosity of the asphalt is increased, the temperature sensitivity is reduced, the thermal volatilization of volatile components is reduced, the high-temperature stability and the ageing resistance of the palygorskite are improved, and the thermal stability and the ageing resistance of the waterproof coiled material are endowed.
(3) In the technical scheme of the invention, the palygorskite is a natural mineral microfiber, and a staggered three-dimensional space network structure formed after asphalt is added plays a role in limiting the movement of asphalt molecules, so that the viscosity of the asphalt is further increased, and the stiffness modulus of the asphalt is improved; in addition, the reinforcement network consisting of a large number of microfibers can improve the integrity of the asphalt, reduce the generation of microcracks on the surface of the asphalt, contribute to improving the cohesive work of the asphalt and resist the erosion of water to the waterproof coiled material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The organic modified nano palygorskite is prepared by the following steps:
a1, mixing 10mL of HCl solution with the concentration of 0.1mol/L with 3g of palygorskite, violently stirring in a water bath at 60 ℃, standing, performing suction filtration to obtain a solid, washing the solid to be neutral, and performing vacuum drying at 110 ℃ to obtain pretreated palygorskite;
a2, adding 3g of pretreated palygorskite into 280mL of dimethylbenzene, ultrasonically dispersing for 0.5h, adding 3mL of gamma-aminopropyltriethoxysilane, heating to 80 ℃, stirring for 10h at a constant temperature, filtering, washing and vacuum drying at 60 ℃ to obtain the organic modified nano palygorskite.
Example 2
The organic modified nano palygorskite is prepared by the following steps:
a1, mixing 15mL of HCl solution with the concentration of 0.1mol/L with 3.5g of palygorskite, violently stirring in a water bath at 60 ℃, standing, performing suction filtration to obtain a solid, washing the solid to be neutral, and performing vacuum drying at 110 ℃ to obtain pretreated palygorskite;
a2, adding 4g of pretreated palygorskite into 300mL of dimethylbenzene, ultrasonically dispersing for 0.5h, adding 4mL of gamma-aminopropyltriethoxysilane, heating to 80 ℃, stirring for 10h at a constant temperature, filtering, washing and vacuum drying at 60 ℃ to obtain the organic modified nano palygorskite.
Example 3
The organic modified nano palygorskite is prepared by the following steps:
a1, mixing 20mL of HCl solution with the concentration of 0.1mol/L with 4g of palygorskite, violently stirring in a water bath at 60 ℃, standing, performing suction filtration to obtain a solid, washing the solid to be neutral, and performing vacuum drying at 110 ℃ to obtain pretreated palygorskite;
a2, adding 5g of pretreated palygorskite into 320mL of dimethylbenzene, ultrasonically dispersing for 0.5h, adding 5mL of gamma-aminopropyltriethoxysilane, heating to 80 ℃, stirring for 10h at a constant temperature, filtering, washing and vacuum drying at 60 ℃ to obtain the organic modified nano palygorskite.
Example 4
The modified chitosan is prepared by the following steps:
dissolving 50g of p-hydroxybenzaldehyde in 200mL of dry THF, adding 40g of triethylamine, stirring and mixing uniformly, adding 35g of phenylphosphonic dichloride, refluxing at 70 ℃, stirring and reacting for 24 hours, removing precipitated solids by suction filtration after the reaction is finished, evaporating the filtrate in vacuum, and pouring the filtrate into ice water to obtain white crystalline solids, and drying the white crystalline solids to obtain the flame retardant;
dissolving 16g of chitosan in 280mL of methanol/acetic acid mixed solution with the volume ratio of 10:1, heating to 50 ℃, preserving heat for 2h, adding 15g of flame retardant, then heating to 65 ℃, carrying out reflux reaction for 12h, and after the reaction is finished, carrying out cooling filtration, washing and vacuum drying at 70 ℃ to obtain the modified chitosan.
Example 5
The modified chitosan is prepared by the following steps:
dissolving 51g of p-hydroxybenzaldehyde in 250mL of dry THF, adding 42g of triethylamine, stirring and mixing uniformly, adding 37g of phenylphosphonic dichloride, refluxing at 70 ℃, stirring and reacting for 24 hours, removing precipitated solids by suction filtration after the reaction is finished, evaporating the filtrate in vacuum, and pouring the filtrate into ice water to obtain white crystalline solids, and drying the white crystalline solids to obtain the flame retardant;
dissolving 16.5g of chitosan in 300mL of methanol/acetic acid mixed solution with the volume ratio of 10:1, heating to 50 ℃, preserving heat for 2h, adding 17g of flame retardant, then heating to 65 ℃, carrying out reflux reaction for 12h, and after the reaction is finished, carrying out cooling filtration, washing and vacuum drying at 70 ℃ to obtain the modified chitosan.
Example 6
The modified chitosan is prepared by the following steps:
dissolving 52g of p-hydroxybenzaldehyde in 300mL of dry THF, adding 45g of triethylamine, stirring and mixing uniformly, adding 40g of phenylphosphonic dichloride, refluxing at 70 ℃, stirring and reacting for 24 hours, removing precipitated solids by suction filtration after the reaction is finished, evaporating the filtrate in vacuum, and pouring the filtrate into ice water to obtain white crystalline solids, and drying the white crystalline solids to obtain the flame retardant;
dissolving 17g of chitosan in 320mL of methanol/acetic acid mixed solution with the volume ratio of 10:1, heating to 50 ℃, preserving heat for 2h, adding 20g of flame retardant, then heating to 65 ℃, carrying out reflux reaction for 12h, and after the reaction is finished, carrying out cooling filtration, washing and vacuum drying at 70 ℃ to obtain the modified chitosan.
Example 7
The self-adhesive waterproof roll cementing material comprises the following raw materials in parts by mass: 40 parts of I type waterproof coiled material asphalt, 2 parts of ethylene tar, 4 parts of SBS, 8 parts of organic modified nano palygorskite prepared in example 1, 1 part of ammonium polyphosphate, 6 parts of naphthenic oil and 4 parts of modified chitosan prepared in example 4;
the preparation method of the self-adhesive waterproof roll cementing material comprises the following steps:
heating the asphalt and the ethylene tar of the I-type waterproof coiled material to 190 ℃, adding the naphthenic oil and the flame retardant, uniformly stirring, cooling to 180 ℃, adding SBS, heating to 190 ℃, stirring for 1.5h, adding the organic modified nano palygorskite and the ammonium polyphosphate, and continuously stirring for 1h to obtain the self-adhesive waterproof coiled material cementing material.
Example 8
The self-adhesive waterproof coiled material cementing material comprises the following raw materials in parts by mass: 42 parts of I type waterproof coiled material asphalt, 4 parts of ethylene tar, 7 parts of SBS, 12 parts of organic modified nano palygorskite prepared in example 2, 1.5 parts of ammonium polyphosphate, 8 parts of naphthenic oil and 6 parts of modified chitosan prepared in example 5;
the preparation method of the self-adhesive waterproof roll cementing material comprises the following steps:
heating the asphalt and the ethylene tar of the I-type waterproof coiled material to 195 ℃, then adding the naphthenic oil and the flame retardant, uniformly stirring, cooling to 185 ℃, then adding the SBS, heating to 195 ℃, stirring for 1.5h, then adding the organic modified nano palygorskite and the ammonium polyphosphate, and continuously stirring for 1h to obtain the self-adhesive waterproof coiled material cementing material.
Example 9
The self-adhesive waterproof coiled material cementing material comprises the following raw materials in parts by mass: 45 parts of I type waterproof coiled material asphalt, 5 parts of ethylene tar, 10 parts of SBS, 15 parts of organic modified nano palygorskite prepared in example 3, 2 parts of ammonium polyphosphate, 10 parts of naphthenic oil and 6 parts of modified chitosan prepared in example 6;
the preparation method of the self-adhesive waterproof roll cementing material comprises the following steps:
heating the asphalt and the ethylene tar of the I-type waterproof coiled material to 200 ℃, then adding the naphthenic oil and the flame retardant, uniformly stirring, cooling to 190 ℃, then adding the SBS, heating to 200 ℃, stirring for 1.5h, then adding the organic modified nano palygorskite and the ammonium polyphosphate, and continuously stirring for 1h to obtain the self-adhesive waterproof coiled material cementing material.
Comparative example 1
The comparative example is different from example 7 in that the organically modified nano-palygorskite prepared in example 1 is replaced by palygorskite, and the rest steps and raw materials are the same.
Comparative example 2
This comparative example is different from example 8 in that the modified chitosan prepared in example 4 was replaced with chitosan, and the remaining steps and raw materials were the same.
Comparative example 3
The present comparative example is different from example 9 in that the organically modified nano palygorskite prepared in example 3 was replaced with palygorskite, the modified chitosan prepared in example 6 was replaced with chitosan, and the rest of the steps and raw materials were the same.
Now, the performance of the waterproof rolls prepared by the self-adhesive waterproof roll cementing materials prepared in examples 7 to 9 and comparative examples 1 to 3 was tested according to the test standard GB23441-2009, and the test results are shown in table 1 below:
TABLE 1
As can be seen from table 1 above, the waterproofing membrane prepared by the self-adhesive waterproofing membrane cement prepared by the example of the present invention has better flame retardancy, water resistance and adhesiveness than the comparative example.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. The self-adhesive waterproof roll cementing material is characterized in that: the composite material comprises the following raw materials in parts by mass: 40-45 parts of I type waterproof coiled material asphalt, 2-5 parts of ethylene tar, 4-10 parts of SBS, 8-15 parts of organic modified nano palygorskite, 1-2 parts of ammonium polyphosphate, 6-10 parts of naphthenic oil and 4-7 parts of modified chitosan;
the modified chitosan is prepared by the following steps:
s1, dissolving p-hydroxybenzaldehyde in dry THF, adding triethylamine, stirring and mixing uniformly, adding phenylphosphonic dichloride, refluxing at 70 ℃, stirring and reacting for 24 hours, removing precipitated solids through suction filtration after the reaction is finished, evaporating the filtrate in vacuum, and pouring the filtrate into ice water to obtain white crystalline solids, and drying the white crystalline solids to obtain the flame retardant;
s2, dissolving chitosan in a methanol/acetic acid mixed solution with the volume ratio of 10:1, heating to 50 ℃, preserving heat for 2 hours, adding a flame retardant, heating to 65 ℃, carrying out reflux reaction for 12 hours, and after the reaction is finished, cooling, filtering, washing and drying to obtain the modified chitosan.
2. The self-adhesive waterproof roll cementing material of claim 1, which is characterized in that: in step S1, the dosage ratio of p-hydroxybenzaldehyde, THF, triethylamine and phenylphosphonyl dichloride is 50-52 g: 200-300 mL: 40-45 g: 35-40 g;
in step S2, the dosage ratio of chitosan, methanol/acetic acid mixed solution and flame retardant is 16-17g:280-320 mL: 15-20 g.
3. The self-adhesive waterproof roll cementing material of claim 1, which is characterized in that: the organic modified nano palygorskite is prepared by the following steps:
a1, mixing HCl solution with the concentration of 0.1mol/L with palygorskite, stirring in water bath at 60 ℃, standing, performing suction filtration to obtain solid, washing the solid to be neutral, and performing vacuum drying at 110 ℃ to obtain pretreated palygorskite;
a2, adding the pretreated palygorskite into dimethylbenzene, ultrasonically dispersing for 0.5h, adding gamma-aminopropyl triethoxysilane, heating to 80 ℃, stirring for 10h at a constant temperature, filtering, washing and vacuum drying at 60 ℃ to obtain the organic modified nano palygorskite.
4. The self-adhesive waterproof roll cementing material of claim 3, which is characterized in that: in the step A1, the dosage ratio of the HCl solution to the palygorskite is 10-20 mL: 3-4 g;
in the step A2, the dosage ratio of the palygorskite to the xylene to the gamma-aminopropyltriethoxysilane is 3-5 g:280-320 mL: 3-5 mL.
5. The self-adhesive waterproof roll cementing material of claim 1, which is prepared by the following steps:
heating the asphalt and the ethylene tar of the I-type waterproof coiled material to 190-plus-200 ℃, then adding the naphthenic oil and the modified chitosan, uniformly stirring, cooling to 180-plus-190 ℃, then adding the SBS, heating to 190-plus-200 ℃, stirring for 1.5h, then adding the organic modified nano palygorskite and the ammonium polyphosphate, and continuously stirring for 1h to obtain the self-adhesive waterproof coiled material cementing material.
6. A waterproof roll material is characterized in that: the self-adhesive waterproof roll cementing material of any one of claims 1 to 5 is taken as a raw material and comprises an upper protective film, an upper cementing material layer, a tire base layer, a lower cementing material layer and a lower protective film which are sequentially compounded from top to bottom.
7. The waterproof roll according to claim 6, wherein the upper protective film and the lower protective film are both PET films.
8. The waterproofing membrane according to claim 6 wherein the base layer is a polyester nonwoven fabric.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118085591A (en) * | 2024-02-28 | 2024-05-28 | 江苏增光新材料科技股份有限公司 | High-viscosity high-elastic modulus modified asphalt |
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| CN1730563A (en) * | 2005-08-23 | 2006-02-08 | 西北师范大学 | Paligorskite composition modified asphalt and its manufacturing method |
| CN105669905A (en) * | 2016-01-25 | 2016-06-15 | 东南大学 | Preparation method of intumescent flame retardant synergist adopting saccharide derivatives |
| CN110760289A (en) * | 2018-07-25 | 2020-02-07 | 中国石油化工股份有限公司 | Flame-retardant self-adhesive waterproof roll cementing material, preparation method thereof and waterproof roll prepared from same |
| CN111662332A (en) * | 2020-06-02 | 2020-09-15 | 桂林理工大学 | Organophosphorus flame retardant with active amino groups and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730563A (en) * | 2005-08-23 | 2006-02-08 | 西北师范大学 | Paligorskite composition modified asphalt and its manufacturing method |
| CN105669905A (en) * | 2016-01-25 | 2016-06-15 | 东南大学 | Preparation method of intumescent flame retardant synergist adopting saccharide derivatives |
| CN110760289A (en) * | 2018-07-25 | 2020-02-07 | 中国石油化工股份有限公司 | Flame-retardant self-adhesive waterproof roll cementing material, preparation method thereof and waterproof roll prepared from same |
| CN111662332A (en) * | 2020-06-02 | 2020-09-15 | 桂林理工大学 | Organophosphorus flame retardant with active amino groups and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118085591A (en) * | 2024-02-28 | 2024-05-28 | 江苏增光新材料科技股份有限公司 | High-viscosity high-elastic modulus modified asphalt |
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