CN114752310A - SBS modified asphalt waterproof coiled material with self-adhesive layer - Google Patents
SBS modified asphalt waterproof coiled material with self-adhesive layer Download PDFInfo
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- CN114752310A CN114752310A CN202210374506.3A CN202210374506A CN114752310A CN 114752310 A CN114752310 A CN 114752310A CN 202210374506 A CN202210374506 A CN 202210374506A CN 114752310 A CN114752310 A CN 114752310A
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- self
- adhesive layer
- modified asphalt
- sbs modified
- styrene
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- 239000010426 asphalt Substances 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 30
- 239000012790 adhesive layer Substances 0.000 title claims abstract description 29
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims abstract description 78
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003208 petroleum Substances 0.000 claims abstract description 12
- 238000002955 isolation Methods 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 55
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 27
- 230000000844 anti-bacterial effect Effects 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 19
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 18
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 11
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229920003051 synthetic elastomer Polymers 0.000 claims description 5
- 239000005061 synthetic rubber Substances 0.000 claims description 5
- 150000003505 terpenes Chemical class 0.000 claims description 5
- 235000007586 terpenes Nutrition 0.000 claims description 5
- 238000004078 waterproofing Methods 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229920003002 synthetic resin Polymers 0.000 claims description 4
- 239000000057 synthetic resin Substances 0.000 claims description 4
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 4
- 239000005060 rubber Substances 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 2
- 238000000967 suction filtration Methods 0.000 description 9
- 238000004026 adhesive bonding Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000004323 axial length Effects 0.000 description 4
- 239000012856 weighed raw material Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- -1 isothiazolinone compound Chemical class 0.000 description 3
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000005185 salting out Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 241000228197 Aspergillus flavus Species 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 241000079253 Byssochlamys spectabilis Species 0.000 description 1
- 241001515917 Chaetomium globosum Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000221662 Sclerotinia Species 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
- C09J7/243—Ethylene or propylene polymers
-
- 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
- C09J195/00—Adhesives based on bituminous materials, e.g. asphalt, tar, pitch
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a SBS modified asphalt waterproof coiled material with a self-adhesive layer, belonging to the technical field of waterproof materials, wherein the waterproof coiled material comprises a polymer sheet, a self-adhesive layer and an isolation layer, wherein the self-adhesive layer is composed of SBS modified asphalt; the SBS modified asphalt is prepared by the following steps: uniformly mixing petroleum asphalt, modified styrene-butadiene-styrene block copolymer, filler and tackifying resin at the temperature of 150 ℃ and 170 ℃ to obtain SBS modified asphalt; aiming at the condition that the self-adhesive waterproof material in the prior art is mostly rubber blending modified asphalt added with a tackifier and is difficult to form a stable system, maleic anhydride is grafted and modified by styrene-butadiene-styrene block copolymer, so that the modified styrene-butadiene-styrene block copolymer and the asphalt are crosslinked, the integral strength of a self-adhesive layer is improved, the high and low temperature performance and the aging resistance of the self-adhesive layer are improved, the creep property is good, and the self-adhesive waterproof material has better viscosity.
Description
Technical Field
The invention belongs to the technical field of waterproof materials, and particularly relates to an SBS modified asphalt waterproof coiled material with a self-adhesive layer.
Background
The self-adhesive coiled material is a novel waterproof material which can be constructed at normal temperature and does not need hot melting construction, in the preparation of the SBS modified asphalt waterproof coiled material, styrene-butadiene-styrene block copolymer (SBS) is often used for being blended with asphalt to improve the performance of the asphalt, but the thermodynamic incompatibility of rubber and the asphalt cannot be covered by simple mechanical dispersion and wrapping, and a stable system is hardly formed by the styrene-butadiene-styrene block copolymer (SBS) and the asphalt;
but self-adhesion coiled material is a normal atmospheric temperature construction, does not need the novel waterproof material of hot melt construction, receives market favor deeply at present, and its growth rate far exceeds elastomer modified asphalt waterproofing membrane, and ordinary self-adhesion modified asphalt waterproofing membrane's waterproof layer intensity is limited to use for a long time and breed the bacterium easily, life is low moreover, and corrosion resisting property is unsatisfactory.
Disclosure of Invention
In order to solve the technical problems mentioned in the background technology, the invention provides an SBS modified asphalt waterproof coiled material with a self-adhesive layer.
The purpose of the invention can be realized by the following technical scheme:
the utility model provides a take SBS modified asphalt waterproofing membrane of self-adhesive layer, includes the polymer sheet, by self-adhesive layer and the isolation layer that SBS modified asphalt constitutes, the self-adhesive layer complex is on the polymer sheet surface, the isolation layer complex in surperficial self-adhesive layer surface, through flattening, cooling shaping.
The SBS modified asphalt is prepared by the following steps:
weighing the following raw materials in parts by weight: 50-55 parts of petroleum asphalt, 12-14 parts of modified styrene-butadiene-styrene block copolymer, 25-30 parts of filler and 5-10 parts of tackifying resin; and mixing the weighed raw materials at the temperature of 150 ℃ and 170 ℃ to obtain the SBS modified asphalt.
Further, the modified styrene-butadiene-styrene block copolymer was prepared by the following steps:
mixing toluene and styrene-butadiene-styrene block copolymer (SBS), adding acrylic acid, maleic anhydride and a grafting monomer, then adding dibenzoyl peroxide, reacting for 2 hours at the temperature of 40-80 ℃, washing with methanol after the reaction is finished, and drying to constant weight under the vacuum condition of 50 ℃ after the washing is finished to obtain the modified styrene-butadiene-styrene block copolymer. Styrene-butadiene-styrene block copolymer (SBS for short), SBS polarity is lower, with the compatibility of pitch not good, through modifying SBS, improve SBS and compatibility of pitch, through regard acrylic acid, maleic anhydride and graft monomer as reaction monomer, carry on graft modification to SBS, improve compatibility.
Further, the mass ratio of the styrene-butadiene-styrene block copolymer, the acrylic acid, the maleic anhydride, the grafting monomer and the dibenzoyl peroxide is 10: 0.3: 0.5: 0.2: 1.5; the amount ratio of styrene-butadiene-styrene block copolymer to toluene was 10 g: 50 mL.
Further, the graft monomer is prepared by the following steps:
step S11, mixing isothiazolinone and N, N-dimethylformamide, dropwise adding liquid bromine, heating to 60-65 ℃, preserving heat for reaction for 3 hours, adding deionized water after the reaction is finished, and performing suction filtration and recrystallization to obtain a bromine-containing monomer;
step S12, mixing the bromine-containing monomer and N, N-dimethylformamide, adding potassium carbonate and ethanolamine, heating and refluxing for 10-12h, adding deionized water after the reaction is finished, and performing suction filtration and recrystallization to obtain a hydroxyl-containing monomer;
step S13, mixing cyanuric chloride and deionized water, adding a hydroxyl-containing monomer at the temperature of 5 ℃, dropwise adding a sodium carbonate aqueous solution after the hydroxyl-containing monomer is added, stirring for 30min, adding the sodium carbonate aqueous solution to maintain the pH value of the reaction solution to be about 3, and continuously stirring for reaction for 4h to obtain an antibacterial component; the hydroxyl-containing monomer is an isothiazolinone compound, belongs to a safe antibacterial structure, and is subjected to bromination reaction to obtain a bromine-containing monomer, then ethanolamine is reacted to introduce hydroxyl, cyanuric chloride is reacted with the hydroxyl-containing monomer to obtain an antibacterial component, so that subsequent reaction is facilitated;
step S14, adding 2, 4-dihydroxy benzophenone, a sodium carbonate aqueous solution and an antibacterial component into deionized water, stirring and reacting for 4 hours at the temperature of 40 ℃, salting out with saturated salt solution after the reaction is finished, and obtaining a component A through centrifugal suction filtration, washing and drying;
And step S15, mixing the component A, allylamine and toluene at the temperature of 0-5 ℃, adding sodium carbonate aqueous solution to maintain the pH value at about 7, stirring to react for 6 hours, and after the reaction is finished, concentrating the obtained organic phase under reduced pressure to remove the solvent to obtain the grafted monomer.
The prepared hydroxyl-containing monomer reacts with cyanuric chloride to obtain an antibacterial component, then the antibacterial component reacts with 2, 4-dihydroxy benzophenone and allyl amine in sequence, an anti-ultraviolet agent and a carbon-carbon double bond are introduced, the hydroxyl-containing monomer with the antibacterial effect and the 2, 4-dihydroxy benzophenone with the anti-ultraviolet effect are combined, the advantages of both antibacterial and anti-ultraviolet are achieved, and the grafting monomer is grafted onto SBS, so that the mixing effect is improved, and the stability of the action effect is improved.
Further, the isothiazolinone selected in step S11 is one of octyl isothiazolinone and methyl isothiazolinone.
Further, in step S11, the molar ratio of the isothiazolinone to the liquid bromine is 1: 3; the dosage ratio of isothiazolinone to N, N-dimethylformamide is 1 g: 5 mL; in the step S12, the mass ratio of the bromine-containing monomer to the potassium carbonate to the ethanolamine is 5.8-8.8: 4.2: 2.8; the concentration of the sodium carbonate aqueous solution in the step S13 is 1.25 mol/L; the dosage ratio of cyanuric chloride, hydroxyl-containing monomer and sodium carbonate aqueous solution is 1.8 g: 1.7-2.7 g: 5 mL.
Further, the concentration of the aqueous solution of sodium carbonate in step S14 is 1.25mol/L, and the ratio of the amount of the 2, 4-dihydroxybenzophenone to the amount of the antibacterial component to the amount of the aqueous solution of sodium carbonate is 2.1 g: 3.2-4.2 g: 6 mL; the dosage ratio of the component A, the allylamine and the toluene in the step S15 is 5-6 g: 0.6 g: 50 mL.
Furthermore, the tackifying resin is formed by mixing coumarone resin, terpene resin, carbon-nine petroleum resin and the like by mass.
Further, the filler is one of nano calcium carbonate and calcium silicate.
Further, the SBS modified asphalt waterproof coiled material with the self-adhesive layer is prepared by the following steps:
and gluing the polymer sheet and the isolation layer simultaneously by using a double-roll forming machine, wherein the axial length of a forming roll of the double-roll forming machine is 2200mm, and the diameter of the forming roll is 400 mm. Gluing at the temperature of 130-150 ℃, flattening, cooling and forming.
Further, the isolation layer is a PET isolation film.
Further, the polymer sheet is one of synthetic rubber and synthetic resin. The synthetic rubber sheet is made of ethylene propylene diene monomer, butyl rubber, chlorinated polyethylene-rubber blend, chloroprene rubber, regenerated rubber or TPO material; the synthetic resin sheet is made of polyethylene, ethylene-vinyl acetate or polyvinyl chloride.
The invention has the beneficial effects that:
aiming at the condition that the self-adhesive waterproof material in the prior art is mostly rubber blended modified asphalt added with a tackifier and is difficult to form a stable system, the invention carries out graft modification on the styrene-butadiene-styrene block copolymer to ensure that the modified styrene-butadiene-styrene block copolymer and the asphalt are crosslinked, thereby improving the integral strength of a self-adhesive layer, improving the high and low temperature performance and the aging resistance of the self-adhesive layer, having good creep property and better viscosity.
According to the invention, the prepared hydroxyl-containing monomer reacts with cyanuric chloride to obtain an antibacterial component, then the antibacterial component reacts with 2, 4-dihydroxybenzophenone and allyl amine in sequence, an anti-ultraviolet agent and a carbon-carbon double bond are introduced, the hydroxyl-containing monomer with an antibacterial effect and the 2, 4-dihydroxybenzophenone with an anti-ultraviolet effect are combined, the advantages of both antibacterial and anti-ultraviolet are achieved, the grafting monomer is grafted onto the styrene-butadiene-styrene block copolymer, the mixing effect is increased, the stability of the action effect is improved, the antibacterial and mildew-proof effects are improved, the anti-corrosion effect is achieved, and the service life is further prolonged.
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
Preparing a grafting monomer:
step S11, mixing methylisothiazolinone and N, N-dimethylformamide, dropwise adding liquid bromine, heating to 60 ℃, keeping the temperature for reaction for 3 hours, adding deionized water after the reaction is finished, and performing suction filtration and recrystallization to obtain a bromine-containing monomer; wherein the molar ratio of the methyl isothiazolinone to the liquid bromine is 1: 3; the dosage ratio of isothiazolinone to N, N-dimethylformamide is 1 g: 5 mL;
step S12, mixing the bromine-containing monomer and N, N-dimethylformamide, adding potassium carbonate and ethanolamine, heating and refluxing for 10 hours, adding deionized water after the reaction is finished, and performing suction filtration and recrystallization to obtain a hydroxyl-containing monomer; wherein the mass ratio of the bromine-containing monomer to the potassium carbonate to the ethanolamine is 5.8: 4.2: 2.8;
step S13, mixing cyanuric chloride and deionized water, adding a hydroxyl-containing monomer at the temperature of 5 ℃, dropwise adding a sodium carbonate aqueous solution after the hydroxyl-containing monomer is added, stirring for 30min, adding the sodium carbonate aqueous solution to maintain the pH value of the reaction solution to be about 3, and continuously stirring for reaction for 4h to obtain an antibacterial component; wherein the concentration of the sodium carbonate aqueous solution is 1.25 mol/L; the dosage ratio of cyanuric chloride, hydroxyl-containing monomer and sodium carbonate aqueous solution is 1.8 g: 1.7 g: 5 mL;
Step S14, adding 2, 4-dihydroxy benzophenone, sodium carbonate aqueous solution and antibacterial components into deionized water, stirring and reacting for 4 hours at 40 ℃, salting out with saturated salt solution after the reaction is finished, and obtaining a component A through centrifugal suction filtration, washing and drying; wherein the concentration of the sodium carbonate aqueous solution is 1.25mol/L, and the dosage ratio of the 2, 4-dihydroxy benzophenone, the antibacterial component and the sodium carbonate aqueous solution is 2.1 g: 3.2 g: 6 mL;
and step S15, mixing the component A, allylamine and toluene at the temperature of 0 ℃, adding a sodium carbonate aqueous solution to maintain the pH value to be about 7, stirring for reaction for 6 hours, and after the reaction is finished, concentrating the obtained organic phase under reduced pressure to remove the solvent to obtain the grafting monomer. Wherein the dosage ratio of the component A, the allyl amine and the toluene is 5 g: 0.6 g: 50mL
Example 2
Preparing a grafting monomer:
step S11, mixing octyl isothiazolinone and N, N-dimethylformamide, dropwise adding liquid bromine, heating to 65 ℃, preserving heat and reacting for 3 hours, adding deionized water after the reaction is finished, and performing suction filtration and recrystallization to obtain a bromine-containing monomer; wherein the molar ratio of the octyl isothiazolinone to the liquid bromine is 1: 3; the dosage ratio of isothiazolinone to N, N-dimethylformamide is 1 g: 5 mL;
Step S12, mixing the bromine-containing monomer and N, N-dimethylformamide, adding potassium carbonate and ethanolamine, heating and refluxing for reaction for 12 hours, adding deionized water after the reaction is finished, and performing suction filtration and recrystallization to obtain a hydroxyl-containing monomer; wherein the mass ratio of the bromine-containing monomer to the potassium carbonate to the ethanolamine is 8.8: 4.2: 2.8;
step S13, mixing cyanuric chloride and deionized water, adding a hydroxyl-containing monomer at the temperature of 5 ℃, dropwise adding a sodium carbonate aqueous solution after the hydroxyl-containing monomer is completely added, stirring for 30min, then adding the sodium carbonate aqueous solution to maintain the pH value of the reaction solution to be about 3, and continuously stirring for reaction for 4h to obtain an antibacterial component; wherein the concentration of the sodium carbonate aqueous solution is 1.25 mol/L; the dosage ratio of cyanuric chloride, hydroxyl-containing monomer and sodium carbonate aqueous solution is 1.8 g: 2.7 g: 5 mL;
step S14, adding 2, 4-dihydroxy benzophenone, a sodium carbonate aqueous solution and an antibacterial component into deionized water, stirring and reacting for 4 hours at the temperature of 40 ℃, salting out with saturated salt solution after the reaction is finished, and obtaining a component A through centrifugal suction filtration, washing and drying; wherein the concentration of the sodium carbonate aqueous solution is 1.25mol/L, and the dosage ratio of the 2, 4-dihydroxy benzophenone, the antibacterial component and the sodium carbonate aqueous solution is 2.1 g: 4.2 g: 6 mL;
And step S15, mixing the component A, allylamine and toluene at the temperature of 5 ℃, adding a sodium carbonate aqueous solution to maintain the pH value at about 7, stirring to react for 6 hours, and after the reaction is finished, concentrating the obtained organic phase under reduced pressure to remove the solvent to obtain the grafted monomer. Wherein the dosage ratio of the component A, allyl amine and toluene is 6 g: 0.6 g: 50mL
Example 3
The SBS modified asphalt waterproof coiled material with the self-adhesive layer is prepared by the following steps:
preparing SBS modified asphalt:
mixing toluene and styrene-butadiene-styrene block copolymer, adding acrylic acid, maleic anhydride and the grafting monomer prepared in example 1, then adding dibenzoyl peroxide, reacting for 2 hours at the temperature of 40 ℃, washing with methanol after the reaction is finished, and drying to constant weight at the temperature of 50 ℃ under vacuum condition to obtain the modified styrene-butadiene-styrene block copolymer. Wherein the dosage mass ratio of the styrene-butadiene-styrene block copolymer, the acrylic acid, the maleic anhydride, the grafting monomer and the dibenzoyl peroxide is 10: 0.3: 0.5: 0.2: 1.5; the amount ratio of styrene-butadiene-styrene block copolymer to toluene was 10 g: 50 mL.
Weighing the following raw materials in parts by weight: 50 parts of petroleum asphalt, 12 parts of modified styrene-butadiene-styrene block copolymer, 25 parts of filler and 5 parts of tackifying resin; and mixing the weighed raw materials at 150 ℃ to obtain the SBS modified asphalt.
And gluing the polymer sheet and the PET isolating film simultaneously by using a double-roll forming machine, wherein the axial length of a forming roll of the double-roll forming machine is 2200mm, and the diameter of the forming roll is 400 mm. Gluing at 130 ℃, flattening, cooling and forming.
Wherein the polymer sheet is ethylene propylene diene monomer in synthetic rubber; the tackifying resin is prepared by mixing coumarone resin, terpene resin, carbonine petroleum resin and the like in mass; the filler is nano calcium carbonate.
Example 4
The SBS modified asphalt waterproof coiled material with the self-adhesive layer is prepared by the following steps:
preparing SBS modified asphalt:
mixing toluene and styrene-butadiene-styrene block copolymer, adding acrylic acid, maleic anhydride and the grafting monomer prepared in example 1, then adding dibenzoyl peroxide, reacting for 2 hours at the temperature of 60 ℃, washing with methanol after the reaction is finished, and drying to constant weight under the vacuum condition of 50 ℃ after the washing is finished to obtain the modified styrene-butadiene-styrene block copolymer. Wherein the dosage mass ratio of the styrene-butadiene-styrene block copolymer, the acrylic acid, the maleic anhydride, the grafting monomer and the dibenzoyl peroxide is 10: 0.3: 0.5: 0.2: 1.5; the amount ratio of styrene-butadiene-styrene block copolymer to toluene was 10 g: 50 mL.
Weighing the following raw materials in parts by weight: 50 parts of petroleum asphalt, 13 parts of modified styrene-butadiene-styrene block copolymer, 28 parts of filler and 8 parts of tackifying resin; and mixing the weighed raw materials at 160 ℃ to obtain the SBS modified asphalt.
And gluing the polymer sheet and the PET isolating film simultaneously by using a double-roll forming machine, wherein the axial length of a forming roll of the double-roll forming machine is 2200mm, and the diameter of the forming roll is 400 mm. Gluing at 140 deg.C, flattening, cooling and shaping.
Wherein the high polymer sheet is formed by mixing coumarone resin, terpene resin, carbonine petroleum resin and the like serving as ethylene propylene diene monomer tackifying resin in synthetic rubber; the filler is nano calcium carbonate.
Example 5
The SBS modified asphalt waterproof coiled material with the self-adhesive layer is prepared by the following steps:
preparing SBS modified asphalt:
mixing toluene and styrene-butadiene-styrene block copolymer, adding acrylic acid, maleic anhydride and the grafting monomer prepared in example 1, then adding dibenzoyl peroxide, reacting for 2 hours at the temperature of 80 ℃, washing with methanol after the reaction is finished, and drying to constant weight under the vacuum condition of 50 ℃ after the washing is finished to obtain the modified styrene-butadiene-styrene block copolymer. Wherein the dosage mass ratio of the styrene-butadiene-styrene block copolymer, the acrylic acid, the maleic anhydride, the grafting monomer and the dibenzoyl peroxide is 10: 0.3: 0.5: 0.2: 1.5; the amount ratio of styrene-butadiene-styrene block copolymer to toluene was 10 g: 50 mL.
Weighing the following raw materials in parts by weight: 55 parts of petroleum asphalt, 14 parts of modified styrene-butadiene-styrene block copolymer, 30 parts of filler and 10 parts of tackifying resin; and mixing the weighed raw materials at 170 ℃ to obtain the SBS modified asphalt.
And gluing the polymer sheet and the PET isolating film simultaneously by using a double-roll forming machine, wherein the axial length of a forming roll of the double-roll forming machine is 2200mm, and the diameter of the forming roll is 400 mm. Gluing at 150 deg.C, flattening, cooling and shaping.
Wherein the polymer sheet is polyethylene in synthetic resin; the tackifying resin is prepared by mixing coumarone resin, terpene resin, carbonine petroleum resin and the like in mass; the filler is calcium silicate.
Comparative example 1
In comparison with example 4, no grafting monomer was added, and the remaining raw materials and preparation process remained unchanged.
Comparative example 2
Compared with example 4, no maleic anhydride was added, and the rest of the raw materials and the preparation process remained unchanged.
The samples prepared in examples 3 to 5 and comparative examples 1 to 2 were subjected to a mold-proof test; the test mildew species are Aspergillus niger, Aspergillus flavus, Chaetomium globosum, Sclerotinia fragrans and Paecilomyces variotii; the spore concentration is 8 × 10-1.2 × 105cfu/mL spore suspension. Uniformly inoculating the whole sample and the surface of the surrounding culture medium, and covering a dish cover after the sample is dried slightly to be used as a test sample;
The determination of the mildew-proof grade is detailed in Table 1
TABLE 1
| Grade of mould proofing | Phenomenon(s) |
| Level 0 | At an amplification of about 50No obvious mildew growth at double times |
| Level 1 | Mildew can not be seen or hardly seen by the naked eye, but can be obviously seen under a magnifying glass |
| Stage 2 | Mildew is obviously seen by naked eyes, and the coverage area on the surface of the sample is 10-30 percent |
| Grade 3 | The mold growth is obviously seen by naked eyes, and the coverage area on the surface of the sample is 30-60 percent |
| 4 stage | The mold growth is obviously seen by naked eyes, and the coverage area on the surface of the sample is more than 60 percent |
The test results are shown in table 2 below:
TABLE 2
| Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Mildew resistance rating | Level 1 | Level 1 | Level 1 | Grade 3 | Level 1 |
| Contact Angle/° | 152 | 152 | 152 | 150 | 145 |
| Heat resistance/110 deg.C | Without dripping | Without dripping | Without dripping | Without dripping | Drip down |
As can be seen from table 2, the waterproof roll material prepared by the present invention has good waterproof property, and can prevent bacteria from breeding, thereby prolonging the service life.
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 it will be appreciated by those skilled in the art that various modifications, additions and substitutions can be made to the embodiments described without departing from the scope of the invention as defined in the appended claims.
Claims (8)
1. The SBS modified asphalt waterproof coiled material with the self-adhesive layer comprises a high polymer sheet, the self-adhesive layer and an isolation layer, wherein the self-adhesive layer is composed of SBS modified asphalt; the SBS modified asphalt is characterized by being prepared through the following steps:
evenly mixing the petroleum asphalt, the modified styrene-butadiene-styrene block copolymer, the filler and the tackifying resin at the temperature of 150 ℃ and 170 ℃ to obtain SBS modified asphalt;
the modified styrene-butadiene-styrene block copolymer is prepared by the following steps:
mixing toluene and a styrene-butadiene-styrene block copolymer, adding acrylic acid, maleic anhydride and a grafting monomer, then adding dibenzoyl peroxide, reacting for 2 hours at the temperature of 40-80 ℃, washing with methanol after the reaction is finished, and drying to constant weight under the vacuum condition of 50 ℃ after the washing is finished to obtain the modified styrene-butadiene-styrene block copolymer.
2. The SBS modified asphalt waterproof coiled material with the self-adhesive layer as claimed in claim 1, wherein raw materials of the SBS modified asphalt comprise, by weight, 50-55 parts of petroleum asphalt, 12-14 parts of modified styrene-butadiene-styrene block copolymer, 25-30 parts of filler and 5-10 parts of tackifying resin.
3. The SBS modified asphalt waterproofing membrane with self-adhesive layer according to claim 1, wherein the grafting monomer is prepared by the following steps:
adding 2, 4-dihydroxy benzophenone, a sodium carbonate aqueous solution and an antibacterial component into deionized water, and then stirring and reacting for 4 hours at the temperature of 40 ℃ to obtain a component A;
and (2) mixing the component A, allyl amine and toluene at the temperature of 0-5 ℃, then adding a sodium carbonate aqueous solution to maintain the pH value, and stirring for reacting for 6 hours to obtain the grafting monomer.
4. The SBS modified asphalt waterproof coiled material with the self-adhesive layer as claimed in claim 1, wherein the tackifying resin is formed by mixing coumarone resin, terpene resin, carbon-nine petroleum resin and the like in mass.
5. The SBS modified asphalt waterproof coiled material with the self-adhesive layer as claimed in claim 1, wherein the filler is one of nano calcium carbonate and calcium silicate.
6. The SBS modified asphalt waterproof coiled material with the self-adhesive layer as claimed in claim 1, wherein the isolation layer is a PET isolation film.
7. The SBS modified asphalt waterproofing membrane with self-adhesive layer according to claim 1, wherein the polymer sheet is one of synthetic rubber and synthetic resin.
8. The SBS modified asphalt waterproof coiled material with the self-adhesive layer according to claim 3, wherein the antibacterial component is prepared through the following steps:
step S11, mixing isothiazolinone and N, N-dimethylformamide, dropwise adding liquid bromine, heating to 60-65 ℃, and reacting for 3 hours under the condition of heat preservation to obtain bromine-containing monomers;
step S12, mixing the bromine-containing monomer and N, N-dimethylformamide, adding potassium carbonate and ethanolamine, and carrying out heating reflux reaction for 10-12h to obtain a hydroxyl-containing monomer;
and step S13, mixing cyanuric chloride and deionized water, adding a hydroxyl-containing monomer at the temperature of 5 ℃, dropwise adding a sodium carbonate aqueous solution after the hydroxyl-containing monomer is added, stirring for 30min, maintaining the pH value of the reaction solution, and continuously stirring for reacting for 4h to obtain the antibacterial component.
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| CN117304373A (en) * | 2023-10-18 | 2023-12-29 | 科顺防水科技股份有限公司 | Modified styrene-butadiene-styrene block copolymer, preparation method thereof, modified asphalt and application thereof |
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