CN115806721A - Butylbenzene segmented copolymer mixture and preparation method and application thereof - Google Patents
Butylbenzene segmented copolymer mixture and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of synthesis and preparation of high polymer materials, and discloses a butylbenzene segmented polymer mixture and a preparation method and application thereof. The mixture comprises a linear styrene-butadiene block copolymer and a linear styrene-butadiene-styrene block copolymer; the weight ratio of the structural unit A derived from butadiene to the structural unit B derived from styrene in the mixture is 3 to 4; the weight ratio of styrene block to styrene non-block in the mixture is 2.3-3.6; the number average molecular weight is 130,000-170,000, and the molecular weight distribution is 1-1.2. The styrene-butadiene block polymer mixture comprises a linear styrene-butadiene block copolymer with a specific structure and a linear styrene-butadiene-styrene block copolymer with a specific structure, and meanwhile, the mixture has a specific structure, so that the mixture has excellent high and low temperature performance, excellent initial adhesive performance and mechanical property, and can be suitable for self-adhesive waterproof rolls.
Description
Technical Field
The invention relates to the technical field of synthesis and preparation of high polymer materials, in particular to a butylbenzene segmented polymer mixture and a preparation method and application thereof.
Background
With the continuous emergence of new specifications and new standards in the waterproof industry, downstream enterprises have higher and higher requirements on the comprehensive performance of the block styrene-butadiene rubber for the waterproof coiled material. The high-performance waterproof coiled material modified polymer puts forward higher requirements on initial adhesive property, heat resistance, aging resistance, mechanical strength and the like.
For the self-adhesive waterproof coiled material, the styrene-butadiene-styrene block polymer is selected to improve the softening point, ductility, mechanical strength and low-temperature flexibility of the modified asphalt, and the styrene-butadiene-styrene block polymer has no self-adhesion and can show the viscosity under the action of softening oil. The traditional styrene-butadiene-styrene block polymer for the waterproof coiled material has a two-phase separation structure, large cohesive force, poor low-temperature flexibility and brittleness above-5 ℃.
The solution-polymerized styrene-butadiene rubber has better initial adhesive property, but the butadiene and the styrene are completely randomly distributed in a molecular chain, so the strength is relatively poor, and the requirement of the waterproof coiled material on the mechanical strength cannot be met. The linear butylbenzene segmented copolymer has the functions of styrene-butadiene-styrene segmented polymer and solution polymerized butylbenzene, can obtain a waterproof coiled material with more balanced high and low temperature performances, but the peeling strength and penetration index can not meet the requirements of the high-performance self-adhesive waterproof coiled material.
Disclosure of Invention
The invention aims to solve the problem that the mechanical property, the hardness, the initial adhesive property and the extensibility of the styrene-butadiene block polymer for waterproof coiled materials in the prior art cannot be simultaneously met, and provides a styrene-butadiene block polymer mixture, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a styrene-butadiene block polymer mixture characterized in that the mixture comprises a linear styrene-butadiene block copolymer and a linear styrene-butadiene-styrene block copolymer;
the weight ratio of the structural unit A from butadiene to the structural unit B from styrene in the mixture is 3-4; the weight ratio of styrene block to styrene non-block in the mixture is 2.3-3.6; the mixture has a number average molecular weight of 130,000 to 170,000 and a molecular weight distribution of 1 to 1.2.
The second aspect of the present invention provides a method for preparing a styrene-butadiene block polymer mixture, comprising:
(1) In an organic hydrocarbon solvent, in the presence of a structure regulator, carrying out a first anionic solution polymerization reaction on a butadiene monomer and a styrene monomer to obtain a linear butylbenzene segmented copolymer solution;
(2) In an organic hydrocarbon solvent, in the presence of a structure regulator, carrying out a second anionic solution polymerization reaction on a styrene monomer I to obtain a second polymerization reaction product, and contacting the second polymerization reaction product, a butadiene monomer and a styrene monomer II to carry out a third anionic solution polymerization reaction to obtain a linear styrene-butadiene-styrene block copolymer solution;
(3) Mixing the linear styrene-butadiene block copolymer solution obtained in the step (1) with the linear styrene-butadiene-styrene block copolymer solution obtained in the step (2) to obtain a styrene-butadiene block polymer mixture solution;
(4) And coagulating and drying the butylbenzene segmented polymer mixture solution to obtain a butylbenzene segmented polymer mixture.
In a third aspect, the present invention provides a styrene-butadiene block polymer mixture obtained by the above method.
The invention also provides a method for preparing the asphalt modifier by using the styrene-butadiene block polymer mixture.
By the technical scheme, the butylbenzene segmented polymer mixture, the preparation method and the application thereof provided by the invention have the following beneficial effects:
the styrene-butadiene block polymer mixture provided by the invention comprises a linear styrene-butadiene block copolymer with a specific structure and a linear styrene-butadiene-styrene block copolymer with a specific structure, and meanwhile, the mixture has a specific structure, so that the styrene-butadiene block polymer mixture has excellent high and low temperature performance, excellent initial adhesive property and mechanical property, and can be suitable for self-adhesive waterproof coiled materials.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides in a first aspect a styrene-butadiene block polymer mixture characterized in that the mixture comprises a linear styrene-butadiene block copolymer and a linear styrene-butadiene-styrene block copolymer;
the weight ratio of structural unit A from butadiene to structural unit B from styrene in the mixture is 3-4; the weight ratio of block styrene block to non-block styrene in the mixture is 2.3-3.6; the mixture has a number average molecular weight of 130,000 to 170,000 and a molecular weight distribution of 1 to 1.2.
According to the invention, the butylbenzene segmented polymer mixture comprises a linear butylbenzene segmented copolymer with a specific structure and a linear styrene-butadiene-styrene segmented copolymer with a specific structure, and meanwhile, the mixture has the specific structure, so that the butylbenzene segmented polymer mixture has excellent high and low temperature performances, excellent initial adhesive performance and excellent mechanical property, and can be suitable for a self-adhesive waterproof coiled material.
In the present invention, the block styrene is a styrene polymer formed by continuous 5 or more styrene monomers in a molecular chain; the non-block styrene is a styrene polymer formed by 4 or less styrene monomers in a molecular chain.
In the present invention, when the weight ratio of the butadiene-derived structural unit a and the styrene-derived structural unit B in the mixture is controlled to satisfy the above range, the high and low temperature performance of the coil made of the mixture can be balanced. If the content of the structural unit B derived from styrene in the mixture is too low, the physical crosslinking points of the mixture decrease, the hardness decreases, and the high-temperature properties of a coil made of the mixture deteriorate, and the penetration increases; if the content of the structural unit B derived from styrene in the mixture is too high, the hardness of the mixture becomes large and the glass transition temperature rises, resulting in deterioration of low-temperature flexibility of a coil made of the mixture.
In the present invention, when the weight ratio of the block styrene to the non-block styrene in the mixture is controlled to satisfy the above range, the mechanical properties and the elongation of the coil produced from the mixture can be balanced. If the content of non-block styrene in the mixture is too low, the elongation of the coil made from the mixture decreases, resulting in deterioration of the low-temperature flexibility of the coil; if the amount of non-block styrene in the mixture is too high, the mechanical properties are reduced, resulting in unsatisfactory strength of the coil produced from the mixture.
Further, the weight ratio of block styrene to non-block styrene in the mixture is 2.5-3.5.
According to the present invention, the weight ratio of the linear styrene-butadiene block copolymer to the linear styrene-butadiene-styrene block copolymer is 0.4 to 2:1.
in the present invention, when the weight ratio of the linear styrene-butadiene block copolymer to the linear styrene-butadiene-styrene block copolymer in the mixture is controlled to satisfy the above range, the high and low temperature properties of the rubber composition comprising the mixture can be significantly improved. Specifically, the weight of any one of the linear styrene-butadiene block copolymer and the linear styrene-butadiene-styrene block copolymer in the mixture is not less than 30% by weight, preferably not less than 40% by weight.
Further, in the mixture, the weight ratio of the linear styrene-butadiene block copolymer to the linear styrene-butadiene-styrene block copolymer is 0.6 to 1.5.
In the present invention, the content of the 1, 2-structure of butadiene in the mixture is 10 to 16% by weight, and the weight ratio of the 1, 4-structure of butadiene to the 1, 2-structure of butadiene is 5.2 to 9:1, the content of styrene structure is 20-25wt%, and the content of block styrene is 14-20wt%.
In the present invention, when the number average molecular weight and the molecular weight distribution of the mixture are controlled to satisfy the above ranges, the mixture can have good mechanical properties while maintaining good processability
Further, the number average molecular weight of the mixture is 13.5 to 16.5, and the molecular weight distribution is 1.02 to 1.15.
Linear butylbenzene segmented copolymer
According to the present invention, the weight ratio of the structural unit C derived from butadiene to the structural unit D derived from styrene in the linear styrene-butadiene block copolymer is 3 to 4.
In the present invention, when the weight ratio of the butadiene-derived structural unit C and the styrene-derived structural unit D in the linear styrene-butadiene block copolymer is controlled to satisfy the above range, it is possible to control the relative contents of the butadiene-derived structural unit a and the styrene-derived structural unit B in the mixture and to achieve a balance of high and low temperature properties of the coil produced from the mixture.
In order to ensure excellent mechanical properties and hardness of the linear styrene-butadiene block copolymer, the content of the styrene block in the linear styrene-butadiene block copolymer is required to be greater than that of the non-styrene block, and in order to ensure excellent ductility of the linear styrene-butadiene block copolymer, the content of the styrene non-block is not required to be less than 20wt% of the total content of the styrene monomer. In the invention, when the weight ratio of the block styrene to the non-block styrene in the linear styrene-butadiene block copolymer is controlled to be 1-3.
Further, the weight ratio of the block styrene to the non-block styrene in the linear styrene-butadiene block copolymer is 1.8-2.6:1.
according to the present invention, the linear styrene-butadiene block copolymer has a number average molecular weight of 130,000 to 170,000 and a molecular weight distribution of 1 to 1.2.
In the invention, when the number average molecular weight and the molecular weight distribution of the linear butylbenzene segmented copolymer are controlled to meet the ranges, the molecular chain of the segmented styrene in the mixture can be ensured to have proper length, and the coiled material prepared from the mixture is further ensured to have the mechanical property and hardness meeting the requirements.
According to the present invention, the weight ratio of the 1, 4-structure of butadiene to the 1, 2-structure of butadiene in the linear styrene-butadiene block copolymer is 5 to 9:1.
in the present invention, when the weight ratio of the 1, 4-structure of butadiene to the 1, 2-structure of butadiene in the linear styrene-butadiene block copolymer is controlled to satisfy the above range, the coil made of the mixture can have good low temperature properties.
Further, the weight ratio of the 1, 4-structure of butadiene to the 1, 2-structure of butadiene in the linear styrene-butadiene block copolymer is 5.5 to 7.5:1.
in the invention, in the linear butylbenzene segmented copolymer, the content of 1, 2-structure of butadiene is 10-16wt%, the content of styrene structure is 20-25wt%, and the content of segmented styrene is 10-19wt%.
Linear styrene-butadiene-styrene block copolymers
According to the present invention, the linear styrene-butadiene-styrene block copolymer is an asymmetric polymer.
In the present invention, the asymmetric polymer means that the third polystyrene segment of the styrene-butadiene-styrene block copolymer contains a small amount of butadiene and styrene copolymer.
According to the present invention, the weight ratio of the structural unit E derived from butadiene to the structural unit F derived from styrene in the linear styrene-butadiene-styrene block copolymer is 3 to 4.
In the present invention, when the weight ratio of the butadiene-derived structural unit E and the styrene-derived structural unit F in the linear styrene-butadiene block copolymer is controlled to satisfy the above range, it is possible to control the relative contents of the butadiene-derived structural unit a and the styrene-derived structural unit B in the mixture and to achieve a balance of high and low temperature properties of the coil produced from the mixture.
According to the invention, the linear styrene-butadiene-styrene block copolymer has a weight ratio of block styrene to non-block styrene of 4 to 6.
In order to ensure excellent mechanical properties of the linear styrene-butadiene-styrene block copolymer, it is required that the styrene block content of the styrene-butadiene-styrene block copolymer is not less than 80wt% of the total styrene monomer content in the linear styrene-butadiene-styrene block copolymer, and that the styrene non-block content of the styrene-butadiene-styrene block copolymer is not less than 15wt% of the total styrene monomer content in the linear styrene-butadiene-styrene block copolymer in order to ensure excellent ductility of the linear styrene-butadiene-styrene block copolymer. In the present invention, the inventors have made the block copolymerization of linear styrene-butadiene-styrene to have excellent mechanical properties, hardness and ductility by controlling the weight ratio of block styrene to non-block styrene in the block copolymerization of linear styrene-butadiene-styrene to be 4 to 6.
Further, the weight ratio of the block styrene to the non-block styrene in the linear styrene-butadiene block copolymer is 4 to 5.5:1.
according to the present invention, the number average molecular weight of the linear styrene-butadiene-styrene block copolymer is 130,000 to 170,000, and the molecular weight distribution is 1 to 1.2.
In the invention, when the number average molecular weight and the molecular weight distribution of the linear styrene-butadiene-styrene block copolymer are controlled to meet the ranges, the molecular chain of the block styrene in the mixture can be ensured to have proper length, and the coiled material prepared from the mixture is further ensured to have the mechanical property and hardness meeting the requirements.
According to the present invention, the weight ratio of the 1, 4-structure of butadiene to the 1, 2-structure of butadiene in the linear styrene-butadiene-styrene block copolymer is 5 to 9:1.
in the present invention, when the weight ratio of the 1, 4-structure of butadiene to the 1, 2-structure of butadiene in the linear styrene-butadiene-styrene block copolymer is controlled to satisfy the above range, the coil material prepared from the mixture can have good low-temperature properties.
Further, the weight ratio of the 1, 4-structure of butadiene to the 1, 2-structure of butadiene in the linear styrene-butadiene-styrene block copolymer is 5.5 to 7.5:1.
in the present invention, in the linear styrene-butadiene-styrene block copolymer, the content of 1, 2-structure of butadiene is 10 to 16wt%, the content of styrene structure is 20 to 25wt%, and the content of block styrene is 16 to 21wt%.
The second aspect of the present invention provides a method for preparing a styrene-butadiene block polymer mixture, comprising:
(1) In an organic hydrocarbon solvent, in the presence of a structure regulator, carrying out a first anionic solution polymerization reaction on a butadiene monomer and a styrene monomer to obtain a linear butylbenzene segmented copolymer solution;
(2) In an organic hydrocarbon solvent, in the presence of a structure regulator, carrying out a second anionic solution polymerization reaction on a styrene monomer I to obtain a second polymerization reaction product, and contacting the second polymerization reaction product, a butadiene monomer and a styrene monomer II to carry out a third anionic solution polymerization reaction to obtain a linear styrene-butadiene-styrene block copolymer solution;
(3) Mixing the linear styrene-butadiene block copolymer solution obtained in the step (1) with the linear styrene-butadiene-styrene block copolymer solution obtained in the step (2) to obtain a styrene-butadiene block polymer mixture solution;
(4) And coagulating and drying the butylbenzene segmented polymer mixture solution to obtain a butylbenzene segmented polymer mixture.
According to the invention, a linear butylbenzene segmented copolymer solution and a linear styrene-butadiene-styrene segmented copolymer solution are respectively prepared by anionic solution polymerization and are mixed, and in the state of the copolymer solution, molecular chains of the linear butylbenzene segmented copolymer and molecular chains of the linear styrene-butadiene-styrene segmented copolymer can be mutually interpenetrated and intertwined, so that in a butylbenzene segmented polymer mixture obtained by condensation and drying, the linear butylbenzene segmented copolymer and the linear styrene-butadiene-styrene segmented copolymer are microscopically and uniformly mixed, and finally, a coiled material prepared from the mixture has excellent comprehensive performance.
In the invention, the addition of the structure regulator can realize the regulation and control of the weight ratio of the block styrene to the non-block styrene in the linear styrene-butadiene block copolymer and the linear styrene-butadiene-styrene block copolymer, and finally ensure that the weight ratio of the block styrene to the non-block styrene in the mixture meets the requirements of the invention. The structure regulator is ether (or amine) structure regulator, preferably environment-friendly ether structure regulator, more preferably ether structure regulator with weak regulating ability (such as tetrahydrofuran), and the amount of the structure regulator is 100-200mg/kg relative to the weight of the solvent.
According to the invention, said step (1) comprises the steps of:
(a) In an organic hydrocarbon solvent, in the presence of an organic lithium compound and a structure regulator, carrying out a first anionic solution polymerization reaction on a butadiene monomer and a styrene monomer;
(b) After the butadiene monomer and the styrene monomer are completely converted, carrying out termination reaction on the polymerization reaction product solution obtained in the step (a) in the presence of a terminator;
(c) Adding an antioxidant into the product obtained in the step (b) to obtain the linear butylbenzene segmented copolymer solution.
In the invention, the linear butylbenzene segmented copolymer is prepared according to the method, and the butadiene monomer and the styrene monomer are subjected to anionic solution copolymerization reaction to obtain the linear butylbenzene copolymer containing a butadiene homopolymerization section, a butadiene and styrene copolymerization section and a styrene homopolymerization section.
According to the invention, the initiation temperature of the first anionic solution polymerization reaction is between 45 and 55 ℃.
In the invention, the initiation temperature of the first anionic solution polymerization reaction is controlled to meet the range, so that the highest temperature of the polymerization reaction can be controlled not to exceed 105 ℃ to avoid high-temperature side reaction, and the block styrene and the non-block styrene in the prepared linear butylbenzene block copolymer can meet the requirements of the invention.
According to the invention, the weight ratio of the butadiene monomer to the styrene monomer is from 3 to 4.
In the present invention, the organolithium compound may be an organolithium compound conventional in the art, such as n-butyllithium. In the present invention, the organic lithium compound is used in an amount of 0.55 to 0.8mmol per 100g of the polymer.
According to the invention, said step (2) comprises the steps of:
(I) In an organic hydrocarbon solvent, in the presence of an organic lithium compound and a structure regulator, carrying out a second anionic solution polymerization reaction on a styrene monomer I to obtain a second polymerization reaction product, and contacting the second polymerization reaction product, a butadiene monomer and a styrene monomer II to carry out a third anionic solution polymerization reaction;
(II) in the presence of a terminating agent, carrying out a terminating reaction on the polymerization reaction product solution obtained in the step (I);
(IV) adding an antioxidant to the polymer solution obtained in step (III).
In the present invention, the styrene monomer I of the linear styrene-butadiene-styrene block polymer prepared according to the above method is subjected to anionic solution polymerization to obtain a styrene homopolymer, and then the butadiene monomer and the styrene monomer II are subjected to anionic copolymerization to obtain a linear styrene-butadiene block polymer containing a styrene homopolymerization section, a butadiene and styrene copolymerization section, and a styrene homopolymerization section.
According to the invention, the initiation temperature of the second anionic polymerization reaction and the third anionic polymerization reaction is each independently 45 to 55 ℃.
In the present invention, by controlling the initiation temperature of the second anionic solution polymerization reaction and the third anionic polymerization reaction to satisfy the above range, not only can the maximum temperature of the polymerization reaction be controlled not to exceed 105 ℃ to avoid the occurrence of high temperature side reactions, but also the block styrene and the non-block styrene in the linear styrene-butadiene-styrene block copolymer prepared can satisfy the requirements of the present invention.
According to the invention, the weight ratio of the styrene monomer I to the styrene monomer II is from 0.65 to 1.
In the present invention, the linear styrene-butadiene-styrene copolymer obtained by controlling the weight ratio of the styrene monomer I to the styrene monomer II to satisfy the above range can have a good mechanical property.
Further, the weight ratio of the styrene monomer I and the styrene monomer II is 0.7 to 0.9.
According to the invention, the ratio of the butadiene monomer to the total weight of the styrene monomer I and the styrene monomer II is from 3 to 4.
In the present invention, the organolithium compound may be an organolithium compound that is conventional in the art, such as n-butyllithium. In the present invention, the amount of the organolithium compound is 0.55 to 0.8mmol/g polymer.
According to the present invention, the antioxidant is used in an amount of 0.3 to 0.6 parts by weight, relative to 100 parts by weight of the total weight of the butadiene monomer and the styrene monomer.
In the invention, in order to enable the butylbenzene segmented polymer mixture to meet the application requirement of the self-adhesive waterproof coiled material, the boiling point of the antioxidant is more than 220 ℃.
According to the invention, the antioxidant is selected from antioxidant 1135 and/or antioxidant 1076, more preferably, the antioxidant is a composite antioxidant of antioxidant 1135 and antioxidant 1076, wherein the weight ratio of the antioxidant 1135 to the antioxidant 1076 is 0.5-2.
In a third aspect, the present invention provides a styrene-butadiene block polymer mixture obtained by the above-mentioned method.
The fourth aspect of the present invention provides an application of the above styrene-butadiene block polymer mixture as an asphalt modifier.
According to the invention, the styrene-butadiene block polymer mixture is used as an asphalt modifier in at least one of self-adhesive modified asphalt waterproof coiled materials, hot-melt modified asphalt waterproof coiled materials and low-temperature-resistant road modified asphalt.
In the invention, the butylbenzene segmented polymer mixture is used as a modifier for preparing the self-adhesive waterproof coiled material. The self-adhesive waterproof coiled material comprises 100 parts of asphalt, 6-12 parts of a styrene-butadiene block polymer mixture, 40-60 parts of rubber oil and 5-15 parts of talcum powder.
The present invention will be described in detail below by way of examples.
The 1, 2-structural unit content, 1, 4-structural unit content, styrene content, block styrene content and non-block styrene content of the butylbenzene block polymer are determined by adopting Bruker AVANCE400 type superconducting nuclear magnetic resonance spectrometer ( 1 H-NMR) test, and (c) a test, 1 the resonance frequency of H nucleus is 300.13MHz, the spectrum width is 2747.253Hz, the pulse width is 5.0 mus, the data point is 16K, the diameter of the sample tube is 5mm, and the solvent is deuterated chloroform CDCl 3 The sample concentration is 15% (W/V), the test temperature is normal temperature, the scanning times are 16 times, and the calibration is carried out by taking the chemical displacement of tetramethylsilane as 0 ppm.
The molecular weight and the molecular weight distribution of the butylbenzene segmented polymer are measured by adopting a HLC-8320 type gel permeation chromatograph of Tosoh corporation of Japan, wherein the test conditions comprise: the chromatographic column was TSKgelSuperMultipolypore HZ-N, the standard column was TSKgelSuperMultipolypore HZ, the solvent was chromatographically pure THF, the calibration standard was polystyrene, the sample mass concentration was 1mg/ml, the sample amount was 10.00. Mu.l, the flow rate was 0.35ml/min, and the test temperature was 40.0 ℃.
The softening point of the modified asphalt is measured by adopting an HDLR-IV type asphalt high-temperature softening point tester.
The initial viscosity performance of the modified asphalt is measured by adopting an LT-3000 annular initial viscosity tester.
The peel strength of the modified asphalt was measured by a BLD-200S type electron peel tester.
Experimental apparatus and process: the experiment was carried out in a 5L polymerization reactor, solvent, butadiene and styrene monomers were added from the polymerization line, initiator and structure modifier were added from the top of the polymerization kettle using an injector, after polymerization was completed, treatment was carried out using steam, and the styrene-butadiene block polymer composition was obtained after drying in a masticator.
The pressures mentioned in this experiment are indicated as gauge pressures.
Antioxidants 1135 and 1076 were purchased from enokay reagent;
cyclohexane is purchased from national medicine reagent company, the purity is more than 99.9, a molecular weight sieve is soaked for 15 days, and the water content is less than 5ppm;
styrene, polymer grade, the source is Yanshan petrochemical;
butadiene, polymer grade, from Yanshan petrochemical;
butyl lithium (Li) was purchased from carbofuran reagent, 100ml specification, 1.6 mol.L -1 Cyclohexane solution, diluted to 0.4 mol. L -1 A cyclohexane solution;
tetrahydrofuran (THF) was purchased from carbofuran reagent, 500g standard, chromatographically pure;
SBS4303, supplied by Yanshan division of Beijing, china petrochemical, having a number average molecular weight of 10.8, a molecular weight distribution of 1.64, a 1, 2-structure content of butadiene of 12.8wt%, a weight ratio of 1, 4-structure of butadiene to 1, 2-structure of butadiene of 6.81, a content of structural units derived from styrene of 30.2wt%, a weight ratio of structural units derived from butadiene to structural units derived from styrene of 2.31, a content of block styrene of 29.6wt%, and a weight ratio of block styrene to non-block styrene of 49.3;
SBS4402, supplied by Yanshan division of Beijing, chinese petrochemical, having a number average molecular weight of 10.1, a molecular weight distribution of 1.48, a 1, 2-structure content of butadiene of 13.2wt%, a weight ratio of the 1, 4-structure of butadiene to the 1, 2-structure of butadiene of 6.58, a content of structural units derived from styrene of 40.6wt%, a weight ratio of structural units derived from butadiene to structural units derived from styrene of 1.46, a content of block styrene of 39.5wt%, and a weight ratio of block styrene to non-block styrene of 35.9.
Example 1
This example illustrates a styrene-butadiene block polymer mixture and a method for preparing the same according to the present invention.
Under the protection of nitrogen, adding a cyclohexane solvent, a structure regulator tetrahydrofuran, 1, 3-butadiene and a styrene monomer (the type and the amount are shown in table 1, and the amount listed in the table is metered by pure compounds) into a 5L reactor, controlling the initiation reaction temperature to be within the range of 45-55 ℃, adding a designed amount of n-butyl lithium (the amount is shown in table 1, and the amount listed in the table is metered by pure compounds) into the 5L reactor, and controlling the highest polymerization reaction temperature to be within the range of 90-105 ℃; after completion of the polymerization, the addition of excess water was terminated, and then 0.4% by weight of the total weight of the monomers was added in a weight ratio of 1135 to 1076 of 1:1 to finally obtain a butylbenzene segmented copolymer solution LBS1, and carrying out analysis and test, wherein the results are shown in a table 2.
Under the protection of nitrogen, adding a cyclohexane solvent, a structural regulator tetrahydrofuran and a styrene monomer I (types and using amounts are shown in table 3, and the using amounts are all measured as pure compounds) into a 5L reactor, controlling the initiation reaction temperature to be within the range of 45-55 ℃, adding a designed amount of n-butyl lithium (the using amounts are shown in table 3, and the using amounts are all measured as pure compounds) into the 5L reactor, after the first stage of styrene polymerization is completed, adding mixed butadiene monomer and styrene monomer II into the 5L reactor until the monomers are completely converted, stopping adding excessive water after the polymerization is completed, and then adding 1135 and 1076 with the total weight of 0.4wt% of the monomers, wherein the weight ratio of the added water to the added water is 1:1 to finally obtain styrene-butadiene-styrene block polymer solution SBS1, and carrying out analysis and test, wherein the results are shown in Table 4.
LBS1 and SBS1 were mixed in a weight ratio of 1.
Examples 2 to 7
This example illustrates a styrene-butadiene block polymer mixture and a method for preparing the same according to the present invention.
According to the method of example 1, except that the linear styrene-butadiene copolymer was prepared using the parameters shown in table 1, thereby obtaining linear styrene-butadiene copolymer solutions LBS2-LBS7, respectively, and the analysis test results are shown in table 2; the parameters shown in table 3 were used to prepare linear styrene-butadiene-styrene block polymers, thereby obtaining linear styrene-butadiene-styrene block polymer solutions SBS2-SBS7, respectively, and the analytical test results are shown in table 4; LBS2-LBS7 and SBS2-SBS7 are mixed according to the weight ratio of 1.
Comparative examples 1 to 4
According to the method described in example 1, except that the linear styrene-butadiene copolymer is prepared by using the parameters shown in table 1, so as to obtain linear styrene-butadiene copolymer solutions DLBS1-DLBS4, respectively, and the analysis test results are shown in table 2; linear styrene-butadiene-styrene block polymers were prepared using the parameters shown in table 3 to obtain linear styrene-butadiene-styrene block polymer solutions DSBS1-DSBS4, respectively, and the analytical test results are shown in table 4; DLBS1-DLBS4 and DSBS1-DSBS4 are mixed according to the weight ratio of 1 to 1 respectively, then steam is adopted for condensation, a plastic machine is adopted for drying, the butylbenzene segmented polymer mixture DZSB1-DZSB4 is prepared, and analysis and test are carried out, and the results are shown in Table 5.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
As can be seen from Table 5, the butylbenzene segmented polymer mixture prepared by the invention has low styrene content and high segmented styrene content, so that the mixture has excellent high and low temperature performance, mechanical property and ductility, and can be used as a waterproof coiled material modified polymer.
Example 8
This example illustrates the use of the styrene-butadiene block polymer mixture prepared according to the present invention in a self-adhesive waterproofing roll.
Self-adhesive waterproof coils were prepared using the butylbenzene block polymer mixtures ZSB1-ZSB7 described in examples 1-7, wherein 50 parts of asphalt base, 10 parts of butylbenzene block polymer mixture, 15 parts of rubber oil, and 25 parts of talc, and the coils were prepared according to the test results shown in Table 6.
Comparative example 5
Modified asphalt coils were prepared in the same manner as in example 8, except that DZSB1-DZSB4 were used instead of ZSB1, and the coil test results were obtained as shown in Table 6.
Comparative example 6
Modified asphalt coils were prepared in the same manner as in example 8, except that commercially available SBS numbers 4303, 4402 were used in place of ZSB1, and the coil test results were obtained as shown in Table 6.
TABLE 6
As can be seen from Table 6, the self-adhesive waterproof roll prepared by using the mixture containing the styrene-butadiene block polymer of the invention as a modifier has excellent low-temperature performance, peel strength and adhesive property.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A styrene-butadiene block polymer mixture, characterized in that the mixture comprises a linear styrene-butadiene block copolymer and a linear styrene-butadiene-styrene block copolymer;
the weight ratio of the structural unit A from butadiene to the structural unit B from styrene in the mixture is 3-4; the weight ratio of styrene block to styrene non-block in the mixture is 2.3-3.6; the mixture has a number average molecular weight of 130,000 to 170,000 and a molecular weight distribution of 1 to 1.2.
2. The styrene-butadiene block polymer mixture of claim 1, wherein the weight ratio of the linear styrene-butadiene block copolymer to the linear styrene-butadiene-styrene block copolymer is 0.4-2:1.
3. the styrene-butadiene block polymer mixture according to claim 1 or 2, wherein the weight ratio of the structural unit C derived from butadiene and the structural unit D derived from styrene in the linear styrene-butadiene block copolymer is 3 to 4;
preferably, the weight ratio of the block styrene to the non-block styrene in the linear styrene-butadiene block copolymer is 1-3;
preferably, the number average molecular weight of the linear styrene-butadiene block copolymer is 130,000 to 170,000;
preferably, the weight ratio of the 1, 4-butadiene structure to the 1, 2-butadiene structure in the linear styrene-butadiene block copolymer is 5 to 9:1.
4. the styrene-butadiene block polymer mixture according to any one of claims 1 to 3, wherein the linear styrene-butadiene-styrene block copolymer is an asymmetric polymer;
preferably, the weight ratio of the structural unit E derived from butadiene to the structural unit F derived from styrene in the linear styrene-butadiene-styrene block copolymer is 3 to 4;
preferably, the linear styrene-butadiene-styrene block copolymer has a weight ratio of block styrene to non-block styrene of 4 to 6;
preferably, the number average molecular weight of the linear styrene-butadiene-styrene block copolymer is 130,000 to 170,000;
preferably, the weight ratio of the 1, 4-butadiene structure to the 1, 2-butadiene structure in the linear styrene-butadiene-styrene block copolymer is 5 to 9:1.
5. a method for preparing a styrene-butadiene block polymer mixture, which is characterized by comprising the following steps:
(1) In an organic hydrocarbon solvent, in the presence of a structure regulator, carrying out a first anionic solution polymerization reaction on a butadiene monomer and a styrene monomer to obtain a linear butylbenzene segmented copolymer solution;
(2) In an organic hydrocarbon solvent, in the presence of a structure regulator, carrying out a second anionic solution polymerization reaction on a styrene monomer I to obtain a second polymerization reaction product, and contacting the second polymerization reaction product, a butadiene monomer and a styrene monomer II to carry out a third anionic solution polymerization reaction to obtain a linear styrene-butadiene-styrene block copolymer solution;
(3) Mixing the linear styrene-butadiene block copolymer solution obtained in the step (1) with the linear styrene-butadiene-styrene block copolymer solution obtained in the step (2) to obtain a styrene-butadiene block polymer mixture solution;
(4) And coagulating and drying the butylbenzene segmented polymer mixture solution to obtain a butylbenzene segmented polymer mixture.
6. The method for preparing a butylbenzene block polymer mixture according to claim 5, wherein said step (1) comprises the steps of:
(a) In an organic hydrocarbon solvent, in the presence of an organic lithium compound and a structure regulator, carrying out a first anionic solution polymerization reaction on a butadiene monomer and a styrene monomer;
(b) After the butadiene monomer and the styrene monomer are completely converted, carrying out termination reaction on the polymerization reaction product solution obtained in the step (a) in the presence of a terminator;
(c) Adding an antioxidant into the product obtained in the step (b) to obtain the linear butylbenzene segmented copolymer solution.
7. The method of claim 6, wherein the first anionic solution polymerization reaction is initiated at a temperature of 45-55 ℃;
preferably, the weight ratio of the butadiene monomer to the styrene monomer is 3 to 4.
8. The production method according to any one of claims 5 to 7, wherein the step (2) includes the steps of:
(I) In an organic hydrocarbon solvent, in the presence of an organic lithium compound and a structure regulator, carrying out a second anionic solution polymerization reaction on a styrene monomer I to obtain a second polymerization reaction product, and contacting the second polymerization reaction product, a butadiene monomer and a styrene monomer II to carry out a third anionic solution polymerization reaction;
(II) in the presence of a terminating agent, carrying out a terminating reaction on the polymerization reaction product solution obtained in the step (I);
(IV) adding an antioxidant to the polymer solution obtained in the step (III).
9. The method of claim 8, wherein the initiation temperature of the second anionic polymerization reaction and the third anionic polymerization reaction are each independently 45-55 ℃;
preferably, the weight ratio of the styrene monomer I to the styrene monomer II is from 0.65 to 1;
preferably, the ratio of the butadiene monomer to the total weight of the styrene monomer I and the styrene monomer II is from 3 to 4.
10. The preparation method according to any one of claims 6 to 9, wherein the antioxidant is used in an amount of 0.3 to 0.6 parts by weight, relative to 100 parts by weight of the total weight of the butadiene monomer and the styrene monomer;
preferably, the antioxidant is selected from antioxidant 1135 and/or antioxidant 1076, more preferably, the antioxidant is a composite antioxidant of antioxidant 1135 and antioxidant 1076, wherein the weight ratio of the antioxidant 1135 to the antioxidant 1076 is 0.5-2.
11. A styrene-butadiene block polymer mixture obtained by the production method according to any one of claims 6 to 10.
12. Use of a styrene-butadiene block polymer mixture according to claims 1-4 and 11 as an asphalt modifier.
13. The use of claim 12, wherein the styrene-butadiene block polymer mixture is used as an asphalt modifier in at least one of self-adhesive modified asphalt waterproofing rolls, hot-melt modified asphalt waterproofing rolls and low-temperature-resistant road-modified asphalt.
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