CN114106274B - Waterproof coiled material asphalt modifier and preparation and application thereof - Google Patents
Waterproof coiled material asphalt modifier and preparation and application thereof Download PDFInfo
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- CN114106274B CN114106274B CN202010895398.5A CN202010895398A CN114106274B CN 114106274 B CN114106274 B CN 114106274B CN 202010895398 A CN202010895398 A CN 202010895398A CN 114106274 B CN114106274 B CN 114106274B
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- waterproof coiled
- asphalt
- coiled material
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- 239000000463 material Substances 0.000 title claims abstract description 78
- 239000010426 asphalt Substances 0.000 title claims abstract description 62
- 239000003607 modifier Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 38
- 239000000853 adhesive Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- -1 alkyl lithium Chemical compound 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 238000004078 waterproofing Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010276 construction Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/66—Sealings
- E04B1/665—Sheets or foils impervious to water and water vapor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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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- Electromagnetism (AREA)
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Abstract
The invention belongs to the technical field of waterproof coiled materials, and particularly relates to a waterproof coiled material asphalt modifier, which comprises an S- (B/S) linear polymer; in the S- (B/S) linear polymer, S is a styrene block, and B/S is a butadiene and styrene random copolymerization block; the total styrene content ranges from 10% to 35%; the molecular weight Mn is 10-20 ten thousand; the tensile strength is less than 2.0Mpa. The invention also provides a preparation method and application thereof. The research of the invention finds that the S- (B/S) linear polymer is beneficial to the primary structure characteristic of the S- (B/S) linear polymer, and the combined control of the S content, the molecular weight and the random degree is further matched, so that the application advantage of the S- (B/S) linear polymer in waterproof coiled materials is further improved.
Description
Technical Field
The invention relates to waterproof coiled material asphalt modification, in particular to a polymer taking styrene and butadiene as raw materials for waterproof coiled material asphalt modification and a preparation method thereof.
Background
As is well known to those skilled in the art, styrene thermoplastic elastomers SBC are block copolymers synthesized by anionic polymerization using styrene, butadiene (or isoprene) as the starting material, and the initiator is typically butyl lithium. According to different synthetic routes, a three-step feeding method is adopted: adding styrene into the first step of feeding for polymerization, adding butadiene (or isoprene) into the second step of feeding for polymerization after the polymerization is completed, adding styrene into the third step of feeding for continuous polymerization after the polymerization is completed, and stopping after the polymerization is completed, thus obtaining a linear SBS (SIS) product; the coupling agent coupling method is adopted by two-step feeding: adding styrene for polymerization in the first step, adding butadiene (or isoprene) in the second step after polymerization, and carrying out coupling reaction by using a multi-arm coupling agent (such as silicon tetrachloride and the like) after polymerization, thereby obtaining a star-shaped (divergent) SBS (SIS) product after reaction. The SBC application field is wide, the modified asphalt is one of important application fields, the high-temperature flowing property and the low-temperature brittleness of the asphalt can be effectively improved, the comprehensive performance of the modified asphalt is improved, and the requirements of road construction and waterproof coiled materials are met.
Most of those who engage in the waterproof coiled material industry know that the waterproof coiled material is prepared by uniformly coating polymer modified hot asphalt on a carrier made of polyester non-woven fabric or fabric cloth, and winding and bundling after a layer of film or fine sand is covered on the surface according to the requirement. The quality of the waterproof coiled material mainly depends on the performance of the modified asphalt.
Along with the development of economy, climate change and technological progress, the requirements of the market on the quality of the waterproof coiled material, particularly the high-low temperature performance, are higher and higher, the softening point of the elastomer asphalt modified waterproof coiled material set by the people's republic of China is required to reach 90 ℃ in standard class I, the low-temperature flexibility of the elastomer asphalt modified waterproof coiled material is required to reach-20 ℃, and the softening point of the elastomer asphalt modified waterproof coiled material reaches 105 ℃ in standard class II, and the low-temperature flexibility of the elastomer asphalt modified waterproof coiled material reaches-25 ℃. In recent years, new requirements are put forward on the construction convenience and environmental protection of the waterproof coiled material, and self-adhesive waterproof coiled materials are rapidly developed in the market to adapt to the new requirements. The self-adhesive waterproof coiled material has high requirement on the adhesive force of the coiled material besides high and low temperature performance.
Disclosure of Invention
The invention aims to provide an asphalt modifier for a waterproof coiled material, which aims to improve the performance of the waterproof coiled material.
The second object of the invention is to provide a method for preparing the asphalt modifier.
The third object of the invention is to provide the application of the asphalt modifier in asphalt modification of waterproof coiled materials.
The fourth object of the present invention is to provide a modified asphalt for a waterproof roll to which the modifier is added.
The fifth object of the present invention is to provide a waterproof roll comprising the modified asphalt.
A waterproof coiled material asphalt modifier comprises S- (B/S) linear polymer;
in the S- (B/S) linear polymer, S is a styrene block, and B/S is a butadiene and styrene random copolymerization block; the total styrene content ranges from 10% to 35%; the molecular weight Mn is 10-20 ten thousand; the tensile strength is less than 2.0Mpa.
In order to solve the problems of unsatisfactory performance of the waterproof coiled material, particularly unsatisfactory high and low temperature performance, poor cohesion, stripping force, poor wall affinity and the like, the invention discovers that the S- (B/S) linear polymer is used as the asphalt modifier of the waterproof coiled material, which is beneficial to improving the performance of the waterproof coiled material. Further studies have found that controlling the molecular weight of the S- (B/S) linear polymer, the styrene content, and the degree of randomization (tensile strength) of the (B/S) stage helps to further improve the application of the S- (B/S) linear polymer to waterproof rolls.
In the invention, the S- (B/S) linear polymer is a two-stage polymer, wherein the S stage is a polystyrene stage, and the (B/S) stage is a random copolymerization stage of butadiene and styrene. The research of the invention finds that the S- (B/S) linear polymer is beneficial to the primary structure characteristic of the S- (B/S) linear polymer, and the combined control of the S content, the molecular weight and the random degree is further matched, so that the application advantage of the S- (B/S) linear polymer in waterproof coiled materials is further improved.
Preferably, the S- (B/S) linear polymer has a molecular weight Mn in the range of 14 to 16 ten thousand.
Preferably, the S- (B/S) linear polymer has a total styrene (total styrene of S and B/S stages) content in the range of 20 to 25%.
Preferably, in the S- (B/S) linear polymer, the styrene content in the S stage is from 13 to 25%, preferably from 15 to 18%. The residual styrene obtained by subtracting the primary styrene from the total styrene is mixed with butadiene to be used as a raw material for the secondary polymerization reaction.
The research of the invention discovers that the control of the random copolymerization structure characteristic of the B/S is one of the keys for realizing the good effect of the B/S in the waterproof coiled material field.
Preferably, the S- (B/S) linear polymer has a tensile strength of less than 1.2MPa.
In the S- (B/S) linear polymer, the toluene solution viscosity (25 ℃ C., 15%) is 1000-2300mPa.s, preferably 1400-1800mPa.s.
In the invention, the waterproof coiled material asphalt modifier also comprises an auxiliary modifier, and the auxiliary modifier comprises SBS and/or SIS.
In the present invention, the mass ratio of the S- (B/S) linear polymer to the auxiliary modifier is not particularly required.
Preferably, the mass ratio of the S- (B/S) linear polymer to the auxiliary modifier is 3-4:6-7.
The invention also provides a preparation method of the waterproof coiled material asphalt modifier S- (B/S) linear polymer, which comprises the following steps:
step (1):
styrene, a solvent for polymerization, an alkyl lithium initiator and a composite regulator are subjected to first-stage polymerization reaction in advance to obtain S-Li;
step (2):
after the polymerization of the step (1), controlling the temperature of a polymerization system to be 65-80 ℃, and then slowly and continuously inputting a mixed monomer containing styrene and butadiene to carry out second-stage random copolymerization; obtaining S- (B/S) -Li;
after the second random copolymerization is completed, the reaction is stopped, and the S- (B/S) linear polymer is obtained after post-treatment.
According to the invention, the application effect of the obtained S- (B/S) linear polymer in the field of waterproof coiled materials can be unexpectedly improved by the preparation method, particularly the combined control of the polymerization conditions such as the polymerization temperature and the feeding mode in the step (2).
Preferably, in step (2), the temperature of the random copolymerization process is 70-75 ℃.
Preferably, in step (2), the monomers are continuously fed at a constant speed for a period of 25 to 50 minutes, preferably 30 to 40 minutes.
In the invention, the polymerization solvent and the auxiliary agent added in the polymerization process can be components known in the industry.
The preferred preparation method of the S- (B/S) linear polymer for modifying the waterproof coiled material asphalt is a polymer synthesized by taking styrene and butadiene as raw materials and butyl lithium as an initiator and adopting an anionic polymerization method. The synthesis method comprises two steps, wherein the first step is to add styrene monomer into a polymerization kettle with a polymerization solvent added in advance, heat the polymerization kettle to a certain temperature, then add initiator butyl lithium to initiate the polymerization of styrene until the styrene is completely polymerized into active polystyrene; and the second step is to add the mixture of butadiene and styrene into the reaction kettle at a certain temperature, continue the second-stage polymerization reaction, stop discharging after the second-stage reaction is completed, and remove the solvent to obtain the styrene-butadiene polymer (S- (B/S) linear polymer) for modifying the asphalt of the waterproof coiled material.
The proper feeding mode is to control the feeding flow and the feeding time by regulating the valve, and the alternating polymerization of the styrene and the butadiene to the maximum limit is forcedly realized by reducing the flow and increasing the feeding time, so that a random or small-block-containing product structure is formed, and the purposes of feeding and simultaneously polymerizing are achieved, and the polymerization reaction is basically completed after the feeding is completed. The feeding time is 25-50min, preferably 30-40min.
The invention also provides application of the waterproof coiled material asphalt modifier, which is used as the asphalt modifier of the waterproof coiled material.
The invention discovers for the first time that the S- (B/S) linear polymer with molecular weight, S content and random degree is used as a modifier of the waterproof coiled material asphalt, and can improve various properties of the waterproof coiled material, such as low-temperature property, adhesive property and affinity with other materials.
The waterproof coiled material can be fire-baked or self-adhesive waterproof coiled material.
The invention also provides waterproof coiled material modified asphalt, which comprises an asphalt base material, plasticizing oil and the waterproof coiled material asphalt modifier.
Preferably, the waterproof coiled material modified asphalt further comprises a filler.
The components such as asphalt base material, plasticizing oil, filler and the like can be components which can be obtained in the field of waterproof coiled materials, and the proportion of the components can be adjusted based on the theory which can be obtained in the technical field of waterproof coiled materials.
The invention also provides a waterproof coiled material, which comprises a carrier and the waterproof coiled material modified asphalt compounded on the carrier.
The beneficial effects are that:
1. the S- (B/S) linear polymer is applied to the waterproof coiled material, and can show good technical effects;
2. controlling the molecular weight, S content and degree of randomization of the S- (B/S) linear polymer can unexpectedly improve its properties in a waterproof roll.
Researches show that the innovative application of the S- (B/S) linear polymer improves the low temperature resistance of waterproof coiled materials including fire-baked and self-adhesive waterproof coiled materials, and generally reduces the low temperature flexibility by about 5 ℃; the cohesive force and the stripping force of the self-adhesive waterproof coiled material are improved, the coiled material is not lifted when stripped, and the stripping layer forms a pyramid until falling off; the affinity of self-adhesive waterproof coiled material and cement wall is improved, the coiled material is attached to the cement wall surface and cannot displace due to self gravity during construction, and the construction of the coiled material is facilitated.
3. Based on the preparation method, the performance of the obtained waterproof coiled material of the S- (B/S) linear polymer can be unexpectedly improved through the control of the preparation conditions.
Detailed Description
For a better understanding of the present invention, the following specific examples are set forth to illustrate, but are not to be construed as in any way limiting the present invention.
In the following cases, except for special statement, the softening point of the modified asphalt is tested according to GB/T4507-2004, the initial adhesion is tested according to GB/T31125-2014, the holding adhesion is tested according to GB/T4851-1998, the 180-degree peel strength is tested according to GB/T2792-2014, and the low-temperature flexibility of the waterproof coiled material is tested according to GB/T328.14-2007.
Examples 1 to 5
Synthesis of S- (B/S) Linear Polymer
Adding 3000ml of cyclohexane serving as a polymerization solvent, 100PPm of THF serving as an activator and calculated amount of styrene into a small 5L polymerization kettle, heating to about 60 ℃ (+/-2 ℃), adding calculated amount of butyllithium serving as an initiator (designed according to the molecular weight of 15 ten thousand) after breaking impurities by using butyllithium, reacting for 25-30min, controlling the temperature in the kettle to 70-75 ℃ after the first-stage reaction is finished, starting to add calculated amount of styrene and butadiene mixed monomer for carrying out two-stage polymerization reaction, controlling the flow through a valve when the mixed monomer is fed, ensuring the feeding time to be 30-35min, continuously maintaining the reaction for about 5min after the feeding is finished until the temperature in the kettle is not increased and begins to drop, and stopping discharging to obtain the S- (B/S) linear polymer.
The specific feeds are shown in Table 1 below: the total mass of the monomers (styrene+butadiene) in the table was 300g.
TABLE 1
Application example 1
Modified asphalt for common fire-baking waterproof coiled material
The formula comprises the following components:
adding the three-reduction oil into 90# asphalt according to a formula, heating and melting, adding SBS YH-803 and the S- (B/S) linear polymer of examples 1-5, heating to about 180 ℃, stirring for about 30 minutes, shearing a high-shearing emulsifying agent for about 30 minutes at about 4000 revolutions to obtain modified asphalt for the waterproof coiled material, coating the modified asphalt on two sides of a polyester non-woven fabric base tyre according to a certain thickness (about 1 mm), and cooling to obtain the common fire-baked waterproof coiled material.
The performance is shown in Table 2:
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Softening point (DEG C) | 112.7 | 112.9 | 113.0 | 113.3 | 113.5 |
| Low temperature flexibility degree C | -25.5 | -25.1 | -25.0 | -24.8 | -24.7 |
Application example 2
Self-adhesive modified asphalt for waterproof coiled material
The formula comprises the following components:
the modified asphalt prepared under the same conditions and the performance of the coiled material are tested as shown in Table 3:
TABLE 3 Table 3
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Softening point (DEG C) | 105.0 | 105.5 | 105.8 | 105.7 | 106.0 |
| Low temperature flexibility degree C | -30.4 | -30.0 | -29.8 | -29.7 | -29.5 |
| Initial adhesion N | 43 | 45 | 45 | 42 | 40 |
| Holding time min | 89.5 | 90.0 | 90.0 | 90.5 | 90.5 |
| Peel strength N/25mm | 43.4 | 43.0 | 43.3 | 41.7 | 41.5 |
Comparative examples 1 to 3
Adding 3000ml of cyclohexane serving as a polymerization solvent, 100PPm of THF serving as an activator and calculated amount of styrene into a small 5L polymerization kettle, heating to about 50 ℃, adding calculated amount of butyllithium serving as an initiator (designed according to the molecular weight of 15 ten thousand) after breaking impurities by using butyllithium, reacting for 25-30min, controlling the temperature in the kettle to 60-64 ℃ after the first-stage reaction is finished, starting adding calculated amount of butadiene monomer to perform a two-stage polymerization reaction, adding calculated amount of styrene to continue polymerization after the two-stage polymerization reaction is finished (after the two-stage polymerization reaction is finished to the highest temperature and is reduced by 10-15 ℃), and stopping discharging after the reaction is finished (25-35 min), thereby obtaining linear SBS.
The details are shown in Table 4 below: the total mass of the monomers (styrene+butadiene) in the table was 300g.
TABLE 4 Table 4
Comparative application example 1
Modified asphalt for common fire-baking waterproof coiled material
The formula comprises the following components:
adding the three-reduction oil into 90# asphalt according to a formula, heating and melting, adding SBS YH-803 and SBS of comparative examples 1-3, heating to about 180 ℃, stirring for about 30 minutes, shearing a high-shearing emulsifying agent for about 30 minutes at about 4000 revolutions to obtain modified asphalt for the waterproof coiled material, coating the modified asphalt on two sides of a polyester non-woven fabric base tyre according to a certain thickness (about 1 mm), and cooling to obtain the common fire-baked waterproof coiled material.
The performance is shown in Table 5:
TABLE 5
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Softening point of | 113.8 | 114.3 | 114.7 |
| Flexibility at low temperature | -21.5 | -21.3 | -20.7 |
Comparative application example 2
Self-adhesive modified asphalt for waterproof coiled material
The formula comprises the following components:
the test results of the properties of the modified asphalt and the coiled materials prepared under the same conditions are shown in Table 6:
TABLE 6
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Softening point (DEG C) | 106.5 | 107.0 | 107.5 |
| Low temperature flexibility degree C | -22.4 | -21.7 | -20.9 |
| Initial adhesion N | 19.6 | 18.5 | 18.0 |
| Holding time min | 15.5 | 16.2 | 17.0 |
| Peel strength N/25mm | 26.7 | 26.0 | 25.6 |
In conclusion, the addition of the polymer can effectively improve the performance of the asphalt waterproof coiled material.
Claims (12)
1. The waterproof coiled material asphalt modifier is characterized by comprising S- (B/S) linear polymer;
in the S- (B/S) linear polymer, S is a styrene block, and B/S is a butadiene and styrene random copolymerization block; the total styrene content ranges from 20 to 25%; the molecular weight Mn is 14-16 ten thousand; tensile strength is less than 2.0Mpa;
the styrene content in the styrene block is 15-18%.
2. The asphalt modifier for waterproof coiled materials according to claim 1, wherein the tensile strength of the S- (B/S) linear polymer is less than 1.2Mpa.
3. The waterproofing membrane asphalt modifier of any one of claims 1 to 2 further comprising an auxiliary modifier, wherein the auxiliary modifier comprises SBS and/or SIS.
4. The waterproof coiled material asphalt modifier according to claim 3, wherein the mass ratio of the S- (B/S) linear polymer to the auxiliary modifier is 3-4:6-7.
5. A method for preparing the waterproof coiled material asphalt modifier S- (B/S) linear polymer according to any one of claims 1 to 4, which is characterized by comprising the following steps:
step (1):
styrene, a solvent for polymerization, an alkyl lithium initiator and a composite regulator are subjected to first-stage polymerization reaction in advance to obtain S-Li;
step (2):
after the polymerization of the step (1), controlling the temperature of a polymerization system to be 65-80 ℃, and then slowly and continuously inputting a mixed monomer containing styrene and butadiene to carry out second-stage random copolymerization; obtaining S- (B/S) -Li;
after the second random copolymerization is completed, the reaction is stopped, and the S- (B/S) linear polymer is obtained after post-treatment.
6. The process according to claim 5, wherein in step (2), the temperature of the random copolymerization is 70 to 75 ℃.
7. The process according to claim 5, wherein in step (2), the monomer mixture is continuously fed at a constant speed for 25 to 50 minutes.
8. Use of the asphalt modifier for a waterproof roll according to any one of claims 1 to 4 as a modifier for asphalt for a waterproof roll.
9. The use of the asphalt modifier for a waterproof roll according to claim 8, wherein the waterproof roll is a fire-baked or self-adhesive waterproof roll.
10. A waterproof coiled material modified asphalt, which is characterized by comprising an asphalt base material, plasticizing oil and the waterproof coiled material asphalt modifier of any one of claims 1 to 4.
11. The waterproof roll modified asphalt of claim 10, further comprising a filler.
12. A waterproof roll, characterized by comprising a carrier and the waterproof roll modified asphalt of claim 10 or 11 compounded on the carrier.
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| CN102887980A (en) * | 2011-07-20 | 2013-01-23 | 中国石油化工集团公司 | Styrene-butadiene copolymer as well as preparation method and application thereof |
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| CN107722647A (en) * | 2016-08-12 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of thermoplastic elastomer modified pitch of SBC and its application in self-adhesive waterproof web |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9080050B2 (en) * | 2011-03-02 | 2015-07-14 | Basf Se | Use of vinylaromatic-diene copolymers in lactam compositions |
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| US6031053A (en) * | 1994-06-17 | 2000-02-29 | Basf Aktiengesellschaft | Thermoplastic elastomer |
| CN102887980A (en) * | 2011-07-20 | 2013-01-23 | 中国石油化工集团公司 | Styrene-butadiene copolymer as well as preparation method and application thereof |
| CN106699999A (en) * | 2015-08-05 | 2017-05-24 | 中国石油化工股份有限公司 | Linear SBS and preparation method thereof, oil-extended rubber and modified asphalt |
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