WO2014008799A1 - 含玻璃化温度高于100°c嵌段的嵌段共聚物及制备方法 - Google Patents

含玻璃化温度高于100°c嵌段的嵌段共聚物及制备方法 Download PDF

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WO2014008799A1
WO2014008799A1 PCT/CN2013/077116 CN2013077116W WO2014008799A1 WO 2014008799 A1 WO2014008799 A1 WO 2014008799A1 CN 2013077116 W CN2013077116 W CN 2013077116W WO 2014008799 A1 WO2014008799 A1 WO 2014008799A1
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membl
parts
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许少宏
高翔
罗英武
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents

Definitions

  • This invention relates to a block copolymer material, and more particularly to a method for preparing a block copolymer latex having a glass transition temperature higher than 100 °c by a reversible addition fragmentation chain transfer emulsion polymerization.
  • thermoplastic elastomer As a kind of polymer material which has rubber elasticity at room temperature and plastic processing at high temperature, the thermoplastic elastomer has a rapid market demand, and the demand for styrene block copolymer is the largest. According to reports, the market demand for styrenic block copolymers in 2013 is expected to reach 2 million tons / year, close to half of the global thermoplastic elastomer market demand. However, the heat resistance temperature of the styrenic block copolymer is limited by the glass transition temperature (100 ° C) of the polystyrene segment.
  • a styrenic block copolymer having a higher glass transition temperature (Tg) hard segment is synthesized, which is expected to be used as a high heat resistance thermoplastic elastomer in a wire coating, a hot air duct, an automobile engine lining.
  • Tg glass transition temperature
  • the synthesis methods of the conventional styrenic block copolymers mainly include anionic polymerization and cationic polymerization.
  • the two polymerization methods require high purity of the reaction raw materials, and the reaction process requires high vacuum conditions and is generally carried out at a low temperature; on the other hand, there are few studies on ion copolymerization, and the practical application thereof is limited to a small amount of second.
  • the monomer is modified, and the preparation of the block copolymer directly from the vinyl monomer is still a great challenge for anionic polymerization or cationic polymerization. Therefore, compared with free radical polymerization, anionic polymerization and cationic polymerization have great disadvantages in terms of energy conservation and environmental protection, and in terms of polymerization implementation conditions.
  • Controlled/living radical polymerization (CLRP) technology which was developed in the 1990s, has become a hot topic in academic research and has received extensive attention in the industry.
  • RAFT reversible addition fragmentation chain transfer radical polymerization
  • Polymerization technology can very effectively control the polymerization of monomers by increasing the reversible deuteration transfer of free radicals.
  • the polymer microstructure such as synthetic block copolymer
  • the degree of polymerization can be controlled.
  • reaction conditions are the same as those of the conventional radical polymerization, and are suitable for bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization. And a variety of reaction systems.
  • the emulsion polymerization system is mostly used in the industrial free radical polymerization process, because the emulsion system has many advantages, such as water as a medium, which is good for heat transfer, environmental protection and safety, low viscosity of latex, convenient for pipeline transportation and continuous production;
  • the micelle or colloidal particles are separated in the phase, so the free radicals have a long life and are characterized by high speed and high degree of polymerization.
  • the latex obtained by the reaction can be directly used, for example, as a water emulsion, binder, paper, leather, fabric treatment. Agents, etc.
  • the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent is obtained by polymerizing a hydrophilic monomer and a lipophilic monomer by a small molecule reversible addition fragmentation chain transfer reagent. Due to its amphiphilic nature, the macromolecular reversible addition fragmentation
  • the chain transfer reagent can act as both a chain transfer agent and an emulsifier. It can be used in emulsion polymerization systems to avoid the use of traditional emulsifiers, thereby preventing the generation of bubbles and reducing costs during production. Therefore, if the combination of RAFT technology and emulsion system can be combined, it is expected to provide a green, environmentally friendly, product-controllable polymerization route for the preparation of highly heat-resistant styrenic block copolymers.
  • the RAFT emulsion polymerization system has problems such as colloidal instability, retardation and inhibition, broad molecular weight distribution, and significant deviation between the actual molecular weight and the theoretical molecular weight.
  • Gilbert et al. used a polyacrylic acid-polybutyl acrylate amphiphilic macromolecular reversible addition fragmentation chain transfer reagent to carry out RAFT semi-continuous emulsion polymerization of styrene by starvation method, which solved the problem of emulsion instability, but the process is complicated and The deviation between the actual molecular weight and the theoretical molecular weight is large, and the block copolymer cannot be prepared.
  • Chain transfer reagent polyethylethyl methacrylate monoblock reversible addition fragmentation chain transfer reagent, poly(ethylene oxide-polyethylethyl methacrylate) two-block reversible addition fragmentation chain transfer reagent, etc. None of them showed any controllability to the molecular weight.
  • the main reason for the failure of styrene RAFT emulsion polymerization in the literature report is that the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent has a poorly designed hydrophilic-lipophilic chain length ratio, which must be neutralized by alkali addition to dissolve in water.
  • Luo Yingwu et al. designed and synthesized a polyacrylic-polystyrene amphiphilic macromolecular reversible addition fragmentation chain transfer reagent with a longer hydrophilic segment, which can be dissolved in water without neutralization, by emulsion polymerization.
  • the lye is added to make the carboxyl group of the hydrophilic segment ionize, resulting in electrostatic stabilization, improving the stability of the latex particles, the process reaction rate is fast and the final conversion rate is high, and the product actually
  • the molecular weight conforms to the theoretical design value and the molecular weight distribution is narrow, and poly(styrene-b-butyl acrylate-b-styrene) triblock copolymer has been successfully prepared.
  • the glass transition temperature of its polystyrene block is only about 100 ° C, this will greatly limit the application of such materials in the high temperature field.
  • the object of the present invention is to provide a block copolymer having a glass transition temperature higher than the ioo°c block and a preparation method thereof in view of the deficiencies of the prior art.
  • a reversible addition fragmentation chain transfer emulsion polymerization process for preparing a block copolymer latex comprising a block having a glass transition temperature greater than 100 ° C comprising the steps of:
  • First step 0.6-2.4 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent is stirred and dissolved in 30-90 parts by weight of water to form a uniform aqueous phase, and then from 3.4 to 11 parts by weight of St, 1.8- 9 parts by weight of the oil phase consisting of MeMBL was poured into the reactor and stirred and mixed.
  • the reactor temperature is raised to 50-80 ° C, stirring is maintained, after adding nitrogen gas for 30-60 minutes, 0.01-0.04 parts by weight of water-soluble initiator is added, and the polymerization is carried out for 10-25 minutes, and 0.07-0.27 parts by weight is added.
  • the aqueous solution of the base is further reacted for 15-40 minutes to obtain an AAm-b-St ⁇ -b MeMBL-co-St ⁇ -R polymer.
  • Step 2 After the first step of the reaction, 7-25 parts by weight of water is added, and 14-36 parts by weight of the nBA monomer is added dropwise at a rate of 0.4-1.4 parts by weight/minute, and the reaction is continued, and the reaction is supplemented. 0-30 parts by weight of water is diluted, and the addition time and reaction time are 60-120 minutes to obtain AA nl -b-St n2 -b-(MeMBL-co-St) n3 -b-nBA n4 -R block Copolymer.
  • Step 3 After the second step, add 0-10 parts by weight of water to 0.1-0.6 parts by weight/min. The reaction rate of 3.4-12 parts by weight of St and 1.9-9.5 parts by weight of MeMBL is added dropwise at the rate of the clock, and the reaction is continued for 90-140 minutes to obtain AA nl -b-St n2 -b-( MeMBL-co-St) n3 -b-nBA n4 -b-(MeMBL-co-St) n5 -R block copolymer latex.
  • the invention has the beneficial effects that the invention utilizes an emulsion system combined with a reversible addition fragmentation chain transfer living radical polymerization technique to prepare a block having a controlled molecular weight and a high colloidal stability and a block having a glass transition temperature greater than 100 ° C. Copolymer latex.
  • the invention utilizes an emulsion system combined with a reversible addition fragmentation chain transfer living radical polymerization technique to prepare a block having a controlled molecular weight and a high colloidal stability and a block having a glass transition temperature greater than 100 ° C. Copolymer latex.
  • amphiphilic macromolecular reversible addition fragmentation chain transfer reagent used in the method has the dual functions of chain transfer reagent and emulsifier, which not only achieves good control of monomer polymerization, but also avoids the use of traditional emulsifier;
  • the reaction has no inhibition period, the reaction speed is fast, and the conversion rate of each unit is high, which is beneficial to improve production efficiency;
  • the stability of the emulsion is improved by adding lye in the middle of the first reaction, the growth of the rubber particles is stable, the number of particles is kept constant, there is no secondary nucleation phenomenon and the particle size distribution is narrow;
  • the glass transition temperature of the hard segment of the copolymer prepared by the method is higher than 100 ° C (the Tg of the hard segment can be controlled by copolymerization, up to 155 ° C), and has good application prospect in the field of high heat resistant thermoplastic elastomer. ;
  • the latex obtained by the reaction can be directly used as a water emulsion, a binder, paper, leather, fabric treatment agent, and the like.
  • Figure 1 is a GPC graph of a polymer obtained in three steps of Example 1 of the present invention.
  • Figure 2 is an infrared spectrum diagram of the block copolymer obtained in Example 1 of the present invention.
  • Figure 3 is a transmission electron micrograph of the block copolymer latex obtained in Example 1 of the present invention.
  • Fig. 4 is a DSC chart of the block copolymer obtained in Example 1-7 of the present invention.
  • the invention provides a method for preparing a block copolymer latex having a glass transition temperature higher than ioo°c block by reversible addition fragmentation chain transfer emulsion polymerization, comprising the following steps:
  • First step 0.6-2.4 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent is stirred and dissolved in 30-90 parts by weight of water to form a uniform aqueous phase, and then from 3.4 to 11 parts by weight of St, 1.8- 9 parts by weight of the oil phase consisting of MeMBL was poured into the reactor and stirred and mixed.
  • the reactor temperature is raised to 50-80 ° C, stirring is maintained, after adding nitrogen gas for 30-60 minutes, 0.01-0.04 parts by weight of water-soluble initiator is added, and the polymerization is carried out for 10-25 minutes, and 0.07-0.27 parts by weight is added.
  • the aqueous solution of the base is further reacted for 15-40 minutes to obtain an AA nl -b-St n2 -b-(MeMBL-co-St) n3 -R polymer.
  • Step 2 After the first step of the reaction, add 7-25 parts by weight of water to 0.4-1.4 parts by weight per minute. The reaction is continued after the dropwise addition of 14-36 parts by weight of the nBA monomer, and the reaction is carried out by adding 0-30 parts by weight of water for dilution, and the addition time and reaction time are 60-120 minutes to obtain AA nl -b. - St n2 -b-(MeMBL-co-St) n3 -b-nBA n4 -R block copolymer.
  • Step 3 After the second step is completed, 0-10 parts by weight of water is added, and 3.4-12 parts by weight of St and 1.9-9.5 parts by weight of MeMBL mixed monomer are added dropwise at a rate of 0.1-0.6 parts by weight/minute. After the reaction was continued, the addition time and the reaction time were 90-140 minutes to obtain AAn b-Stns-b-CMeMBL-co-S ⁇ -b-nBA ⁇ -b-CMeMBL-co-S ns-R block copolymer. latex.
  • step 1 the chemical structure of the reversible addition fragmentation chain transfer reagent of the amphiphilic macromolecule is:
  • St is a styrene monomer unit
  • AA is a methacrylic monomer unit or an acrylic monomer unit
  • Z is a thiol group, a fluorenyl group, a phenyl group or a benzyl group having a carbon number of from four to twelve
  • X is an Propionic acid group, acetic acid group, 2-cyanoacetic acid group or 2-aminoacetic acid group
  • the water-soluble initiator is a derivative of potassium persulfate, ammonium persulfate, hydrogen peroxide or hydrogen peroxide.
  • the base is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate.
  • the monomer conversion rate of each step is measured by the gravimetric method.
  • the particle size and particle size distribution of each step of the latex particles were tested on a Malvern ZETASIZER 3000 HAS pellet.
  • the number of latex particles is calculated by:
  • + is the number of latex particles, the mass of the polymer (gd), the density of the polymer, and the volume average particle diameter.
  • the particle size distribution coefficient is a ratio of the volume average particle diameter to the number average particle diameter.
  • the molecular weight of the design is calculated by: Ten M:.
  • !BAFTI where, refers to the design value of the molecular weight of the polymer in the emulsion at the end of each reaction, m is the total mass of the monomer added in this step, X is the conversion, and FF] is the amphiphilic reversible before the start of the reaction.
  • the amount of the substance to which the fragmentation chain transfer reagent is added, and the molecular weight of the molecular polymer which is an amphiphilic reversible addition fragmentation chain transfer reagent, is carried out on a gel permeation chromatography Watersl 525-2414-717 GPC apparatus, and the eluent is tetrahydrofuran. Calibration was performed with narrowly distributed polystyrene standards.
  • the characteristic functional groups of the block copolymer were characterized by a Ni CO let 5700 infrared spectrometer.
  • the morphology of the polymer latex particles was characterized by a JOEL JEMACRO-123 transmission electron microscope with a test voltage of 80 kV.
  • the Tg measurement of the block copolymer was carried out on a TA Q200 apparatus, and heated from -80 ° C to 200 ° C at a heating rate of 10 ° C / mi n using a nitrogen atmosphere.
  • the block copolymer prepared by the invention has a glass transition temperature of higher than 100 ° C and a maximum of 155 ° C, and has a good application prospect in the field of high heat resistant thermoplastic elastomer; it can be directly used as a water emulsion. Used as binder, paper, leather, fabric treatment agent, etc.
  • amphiphilic macromolecular reversible addition fragmentation chain transfer reagent used in the examples of the present invention is:
  • Example 1 ((MeMBL-co-St) n3 -b-nBA n4 -b-(MeMBL-co-St) n5 triblock design molecular weight is 30K-25K-30K, wherein the ratio of MeMBL to St unit number is 1:2 ):
  • First step 1.9 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent (1) is stirred and dissolved in 85 parts by weight of water to form a homogeneous aqueous phase, and then composed of 11 parts by weight of St, 6 parts by weight of MeMBL.
  • the oil phase was poured into the reactor and stirred to mix.
  • the temperature of the reactor was raised to 70 ° C, and stirring was maintained.
  • nitrogen gas was passed for 30 minutes, 0.03 parts by weight of potassium persulfate was added, and when the polymerization was initiated for 20 minutes, an aqueous solution containing 0.2 part by weight of sodium hydroxide was added, and the reaction was continued for 20 minutes to obtain a reaction.
  • AAn!-bS b-CMeMBL-co-St ⁇ -R polymer AAn!-bS b-CMeMBL-co-St ⁇ -R polymer.
  • Step 2 After the first step of the reaction, 10 parts by weight of water is added, and 15 parts by weight of nBA monomer is added dropwise at a rate of 1 part by weight/minute, and the reaction is carried out for 66 minutes (including the monomer dropping time) to obtain AAn.
  • b-Stns-b-CMeMBL-co-S ⁇ -b-nBA ⁇ -R block copolymer After the first step of the reaction, 10 parts by weight of water is added, and 15 parts by weight of nBA monomer is added dropwise at a rate of 1 part by weight/minute, and the reaction is carried out for 66 minutes (including the monomer dropping time) to obtain AAn.
  • b-Stns-b-CMeMBL-co-S ⁇ -b-nBA ⁇ -R block copolymer After the first step of the reaction, 10 parts by weight of water is added, and 15 parts by weight of nBA monomer is added dropwise at a rate of 1 part by weight/minute, and the
  • the third step After the second step, the mixed monomer of 12 parts by weight of St and 6.5 parts by weight of MeMBL is added dropwise at a rate of 0.3 parts by weight per minute, and the reaction is carried out for 116 minutes (including the monomer dropping time) to obtain AAn b. - Stns-b-CMeMBL-co-S ⁇ -b-nBA ⁇ -b-CMeMBL-co-S ns-R block copolymer latex.
  • Example 1 in Table 1 the reaction time of each step is short and the conversion rate is high. As the reaction progresses, the particle size of the latex particles is continuously increased, while the number of particles is kept constant and the particle size distribution is very high. Narrow, proves that the system is stable and there is no secondary nucleation. From the data of Example 1 in Table 2, the measured values of the molecular weight of the polymer obtained in each step are in accordance with the design value, the molecular weight of the copolymer is gradually increasing, and the final molecular weight distribution is relatively narrow, indicating that the method well controls the polymerization of the monomer. As shown in Fig.
  • Example 2 ((MeMBL-co-St) n3 -b-nBA n4 -b-(MeMBL-co-St) n5 triblock design molecular weight is 30K-70K-30K, wherein the ratio of MeMBL to St unit number is 1:2 ):
  • First step 1.3 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent (1) is stirred and dissolved in 62 parts by weight of water to form a homogeneous aqueous phase, and then composed of 7.5 parts by weight of St, 4 parts by weight of MeMBL.
  • the oil phase was poured into the reactor and stirred to mix.
  • the temperature of the reactor was raised to 70 ° C, and stirring was continued.
  • nitrogen gas was passed for 40 minutes, 0.02 parts by weight of potassium persulfate was added, and when the polymerization was initiated for 20 minutes, an aqueous solution containing 0.17 parts by weight of sodium hydroxide was added, and the reaction was continued for 20 minutes to obtain AAn.
  • b-Stns-b-CMeMBL-co-S ⁇ -R polymer 1.3 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent (1) is stirred and dissolved in 62 parts by weight
  • Step 2 After the first step of the reaction, 7 parts by weight of water is added, and 15 parts by weight of nBA monomer is added dropwise at a rate of 1.4 parts by weight per minute, and 14 parts by weight of water is added for dilution, and the reaction is carried out for 73 minutes.
  • AA ⁇ -b-St ⁇ -b ⁇ MeMBL-co-St-b-nBA ⁇ -R block copolymer was obtained after including the monomer dropwise addition time.
  • the third step after the end of the second step, 10 parts by weight of water is added, and 7.5 parts by weight of St and 4.2 parts by weight of MeMBL mixed monomer are added dropwise at a rate of 0.4 parts by weight per minute for 93 minutes (including monomer After adding time)
  • Example 3 ((MeMBL-co-St) n3 -b-nBA n4 -b-(MeMBL-co-St)
  • the molecular weight of the n5 triblock design is 30K-90K-30K, wherein the ratio of the number of units of MeMBL to St is 1:2 ):
  • First step 1.3 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent (1) is stirred and dissolved in 62 parts by weight of water to form a homogeneous aqueous phase, and then composed of 7.5 parts by weight of St, 4 parts by weight of MeMBL.
  • the oil phase was poured into the reactor and stirred to mix.
  • the temperature of the reactor was raised to 70 ° C, and stirring was maintained.
  • nitrogen gas was passed for 30 minutes, 0.02 parts by weight of potassium persulfate was added, and when the polymerization was initiated for 20 minutes, an aqueous solution containing 0.16 parts by weight of sodium hydroxide was added, and the reaction was continued for 20 minutes to obtain AA.
  • nl -b-St n2 -b- (MeMBL -co-St) n3 -R polymer 1.
  • Step 2 After the first step of the reaction, 10 parts by weight of water is added, 20 parts by weight of nBA monomer is added dropwise at a rate of 1 part by weight/minute, and 30 parts by weight of water is added for dilution, and the reaction is carried out for 94 minutes.
  • AA ⁇ -b-St ⁇ -b-MeMBL-co-St ⁇ -b-nBA ⁇ -R block copolymer was obtained after including the monomer dropwise addition time.
  • the third step after the end of the second step, 10 parts by weight of water is added, and 7.5 parts by weight of St and 4 parts by weight of MeMBL mixed monomer are added dropwise at a rate of 0.4 parts by weight per minute for 138 minutes (including monomer After adding time)
  • the reaction time, conversion rate, latex particle size, particle number and particle size distribution of each step are shown in Table 1.
  • the designed molecular weight, measured molecular weight and molecular weight distribution of the polymer obtained in each step are shown in Table 2.
  • the DSC curve is shown in Figure 4.
  • Example 4 ((MeMBL-co-St) n3 -b-nBA n4 -b-(MeMBL-co-St) n5 triblock design molecular weight is 15K-70K-15K, wherein the ratio of MeMBL to St unit number is 1:2 ):
  • First step 1.6 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent (1) is stirred and dissolved in 38 parts by weight of water to form a homogeneous aqueous phase, and then composed of 4.7 parts by weight of St and 2.7 parts by weight of MeMBL.
  • the oil phase was poured into the reactor and stirred to mix.
  • the temperature of the reactor was raised to 70 ° C, and stirring was maintained.
  • nitrogen gas was applied for 60 minutes, 0.03 parts by weight of potassium persulfate was added, and when the polymerization was initiated for 20 minutes, an aqueous solution containing 0.17 parts by weight of sodium hydroxide was added, and the reaction was continued for 20 minutes to obtain AA.
  • nl -b-St n2 -b- (MeMBL -co-St) n3 -R polymer 1.
  • Second step After the first step of the reaction, 20 parts by weight of water is added, 35 parts by weight of nBA monomer is added dropwise at a rate of 1 part by weight/minute, and 30 parts by weight of water is added for dilution, and the reaction is carried out for 75 minutes.
  • AA ⁇ -b-St ⁇ -b-MeMBL-co-St ⁇ -b-nBA ⁇ -R block copolymer was obtained after including the monomer dropwise addition time.
  • Step 3 After the second step, add 9 parts by weight of water to a rate of 0.4 parts by weight per minute.
  • the mixed monomer of 4.9 parts by weight of St and 2.7 parts by weight of MeMBL was added dropwise, and the reaction was carried out for 95 minutes (including the monomer dropping time).
  • the reaction time, conversion rate, latex particle size, particle number and particle size distribution of each step are shown in Table 1.
  • the designed molecular weight, measured molecular weight and molecular weight distribution of the polymer obtained in each step are shown in Table 2.
  • the DSC curve is shown in Figure 4.
  • Example 5 ((MeMBL-co-St) n3 -b-nBA n4 -b-(MeMBL-co-St) n5 triblock design molecular weight is 15K-35K-15K, wherein the ratio of MeMBL to St unit number is 1:2 ):
  • First step 2.4 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent (1) is stirred and dissolved in 57 parts by weight of water to form a homogeneous aqueous phase, and then composed of 7 parts by weight of St, 3.8 parts by weight of MeMBL.
  • the oil phase was poured into the reactor and stirred to mix.
  • the temperature of the reactor was raised to 70 ° C, and stirring was maintained.
  • 0.04 parts by weight of potassium persulfate was added to initiate polymerization for 20 minutes, and an aqueous solution containing 0.27 parts by weight of sodium hydroxide was added to continue the reaction for 20 minutes to obtain AA.
  • nl -b-St n2 -b- (MeMBL -co-St) n3 -R polymer 1.
  • Step 2 After the first step of the reaction, 10 parts by weight of water is added, and 26 parts by weight of nBA monomer is added dropwise at a rate of 1 part by weight/minute, and 15 parts by weight of water is added for dilution, and the reaction is carried out for 64 minutes.
  • AA ⁇ -b-St ⁇ -b-MeMBL-co-St ⁇ -b-nBA ⁇ -R block copolymer was obtained after including the monomer dropwise addition time.
  • the third step after the end of the second step, 8 parts by weight of water is added, and 7.4 parts by weight of St and 4 parts by weight of MeMBL mixed monomer are added dropwise at a rate of 0.3 parts by weight per minute for 97 minutes (including monomer After the dropwise addition time, AA nl -b-St n2 -b-(MeMBL-co-St) n3 -b-nBA n4 -b-(MeMBL-co-St) n5 -R block copolymer latex was obtained.
  • the reaction time, conversion rate, latex particle size, particle number and particle size distribution of each step are shown in Table 1.
  • the designed molecular weight, measured molecular weight and molecular weight distribution of the polymer obtained in each step are shown in Table 2.
  • the DSC curve is shown in Figure 4.
  • Example 6 ((MeMBL-co-St) n3 -b-nBA n4 -b-(MeMBL-co-St) n5 triblock design molecular weight is 30K-25K-30K, wherein the ratio of MeMBL to St unit number is 1:1):
  • Second step 2 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent (1) is stirred and dissolved in 65 parts by weight of water to form a homogeneous aqueous phase, and then composed of 8.4 parts by weight of St, 9 parts by weight of MeMBL.
  • the oil phase was poured into the reactor and stirred to mix.
  • the temperature of the reactor was raised to 70 ° C, and stirring was maintained.
  • nitrogen gas was passed for 40 minutes, 0.03 parts by weight of potassium persulfate was added, and when the polymerization was initiated for 15 minutes, an aqueous solution containing 0.26 parts by weight of sodium hydroxide was added, and the reaction was continued for 15 minutes to obtain AA.
  • nl -b-St n2 -b- (MeMBL -co-St) n3 -R polymer 2 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent (1) is stirred and
  • Step 2 After the first step of the reaction, add 10 parts by weight of water to a rate of 1.2 parts by weight per minute. Add 15 parts by weight of nBA monomer dropwise, and react for 65 minutes (including monomer dropping time) to obtain AA nl -b-St n2 -b-(MeMBL-co-St) n3 -b-nBA n4 -R Segment copolymer.
  • the third step After the end of the second step, 8.7 parts by weight of St and 9.5 parts by weight of MeMBL mixed monomer were added dropwise at a rate of 0.3 parts by weight per minute, and reacted for 97 minutes (including monomer dropping time) to obtain AA nl -b-St n2 -b-(MeMBL-co-St) n3 -b-nBA n4 -b-(MeMBL-co-St) n5 -R block copolymer latex.
  • Example 7 ((MeMBL-co-St) n3 -b-nBA n4 -b-(MeMBL-co-St) n5 triblock design molecular weight is 30K-70K-30K, wherein the ratio of MeMBL to St unit number is 1 :4 ) :
  • First step 1.3 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent (1) is stirred and dissolved in 60 parts by weight of water to form a homogeneous aqueous phase, and then composed of 9 parts by weight of St and 2.4 parts by weight of MeMBL.
  • the oil phase was poured into the reactor and stirred to mix.
  • the temperature of the reactor was raised to 70 ° C, and stirring was maintained.
  • nitrogen gas was passed for 30 minutes, 0.02 parts by weight of potassium persulfate was added, and an aqueous solution containing 0.16 parts by weight of sodium hydroxide was added for 25 minutes to carry out polymerization, and the reaction was continued for 40 minutes to obtain AA.
  • nl -b-St n2 -b- (MeMBL -co-St) n3 -R polymer 1.3 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent (1) is stirred and
  • Second step After the first step of the reaction, 28 parts by weight of water was added, and 28 parts by weight of nBA monomer was added dropwise at a rate of 0.6 parts by weight/minute, and the reaction was carried out for 97 minutes (including the monomer dropping time) to obtain AA.
  • the third step after the end of the second step, 8 parts by weight of water is added, and 9.7 parts by weight of St and 2.6 parts by weight of MeMBL mixed monomer are added dropwise at a rate of 0.56 parts by weight per minute for 111 minutes (including monomer After adding time)
  • Example 8 ((MeMBL-co-St) n3 -b-nBA n4 -b-(MeMBL-co-St) n5 triblock design molecular weight is 45K-70K-45K, wherein the ratio of MeMBL to St unit number is 1 : 1 ) :
  • First step 0.7 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent (1) is stirred and dissolved in 55 parts by weight of water to form a homogeneous aqueous phase, and then composed of 4 parts by weight of St and 4.5 parts by weight of MeMBL.
  • the oil phase was poured into the reactor and stirred to mix.
  • the temperature of the reactor was raised to 50 ° C, and stirring was continued.
  • 0.01 part by weight of potassium persulfate was added, and when the polymerization was initiated for 10 minutes, an aqueous solution containing 0.07 part by weight of sodium hydroxide was added, and the reaction was continued for 20 minutes to obtain AA.
  • nl -b-St n2 -b- (MeMBL -co-St) n3 -R polymer 0.7 parts by weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent (1) is stirred and dissolved in 55 parts by
  • Step 2 After the first step of the reaction, add 15 parts by weight of water to a rate of 0.4 parts by weight per minute. Adding 14 parts by weight of nBA monomer dropwise, and reacting for 74 minutes (including monomer dropping time) to obtain AA nl -b-St n2 -b-(MeMBL-co-St) n3 -b-nBA n4 -R Segment copolymer.
  • the third step after the end of the second step, 10 parts by weight of water is added, and 4 parts by weight of St and 4.5 parts by weight of MeMBL mixed monomer are added dropwise at a rate of 0.2 parts by weight per minute for 116 minutes (including monomer After adding time)
  • Example 9 ((MeMBL-co-St) n3 -b-nBA n4 -b-(MeMBL-co-St) n5 triblock design molecular weight is 30K-200K-30K, wherein the ratio of MeMBL to St unit number is 1:4):
  • First step 6 parts by weight of the amphiphilic macromolecule is reversibly added to the fragmentation chain transfer reagent (2), stirred and dissolved in 30 parts by weight of water to form a homogeneous aqueous phase, and then composed of 4 parts by weight of St and 1.1 parts by weight of MeMBL.
  • the oil phase was poured into the reactor and stirred to mix.
  • the temperature of the reactor was raised to 80 ° C, and stirring was maintained.
  • nitrogen gas was passed for 30 minutes, 0.01 part by weight of potassium persulfate was added, and when the polymerization was initiated for 20 minutes, an aqueous solution containing 0.07 parts by weight of sodium hydroxide was added, and the reaction was continued for 40 minutes to obtain AA.
  • nl -b-St n2 -b- (MeMBL -co-St) n3 -R polymer 6 parts by weight of the amphiphilic macromolecule is reversibly added to the fragmentation chain transfer reagent (2), stir
  • the second step After the first step of the reaction, 25 parts by weight of water is added, 36 parts by weight of nBA monomer is added dropwise at a rate of 0.4 parts by weight per minute, and 15 parts by weight of water is added for dilution, and the reaction is carried out for 120 minutes.
  • AA nl -b-St n2 -b-(MeMBL-co-St) n3 -b-nBA n4 -R block copolymer was obtained after including the monomer dropwise addition time.
  • the third step after the end of the second step, 9 parts by weight of water is added, and 4 parts by weight of St and 1.1 parts by weight of MeMBL mixed monomer are added dropwise at a rate of 0.1 parts by weight per minute for 110 minutes (including monomer After adding time)

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Abstract

本发明公开了一种含玻璃化温度高于100°C嵌段的嵌段共聚物及制备方法，本发明采用乳液聚合体系，运用可逆加成断裂链转移自由基聚合技术，以丙烯酸正丁酯为软段，苯乙烯与γ-甲基-α-亚甲基-γ-丁内酯的无规共聚物为硬段，制备得到嵌段共聚物胶乳。本发明流程设备简单，过程环保节能；采用两亲性大分子可逆加成断裂链转移试剂，其兼具链转移试剂与乳化剂双重功能，既实现了对单体聚合的良好控制，又避免了传统乳化剂的使用；反应无阻聚期，反应速度快且最终转化率高；过程胶粒增长稳定；产物硬段玻璃化温度最高可达155°C，在高耐热性热塑性弹性体领域有良好的应用前景。

Description

说 明 书 含玻璃化温度高于 locrc嵌段的嵌段共聚物及制备方法 技术领域
本发明涉及一种嵌段共聚物材料， 尤其涉及一种可逆加成断裂链转移乳液 聚合制备含玻璃化温度高于 100 °c嵌段的嵌段共聚物胶乳的方法。
背景技术
热塑性弹性体作为一类在室温下具有橡胶弹性， 高温下又具有塑料加工方 便特点的聚合物材料， 其市场需求增长快速， 其中尤以苯乙烯类嵌段共聚物的 需求最大。 据报道， 2013年苯乙烯类嵌段共聚物的市场需求预计将达到 200万 吨 /年， 接近全球热塑性弹性体市场需求的一半。 但是， 苯乙烯类嵌段共聚物的 耐热温度受限于聚苯乙烯链段的玻璃化温度（100°C )， 当温度接近 100°C时， 聚 合物的力学性能急剧下降， 因此合成具有更高玻璃化温度 （Tg) 硬段的嵌段共 聚物是拓宽其应用领域的关键， 本专利通过引进 甲基- « -亚甲基 -丁内酯 γ -methyl- a -methylene- γ -butyrolactone， MeMBL ) 单体与苯乙烯共聚的方法来实 现。 MeMBL是一种可由生物质原料制备的新型单体， 该单体均聚物的玻璃化温 度高达 210-227°C，若将其与苯乙烯共聚，可以提高聚苯乙烯硬段的玻璃化温度， 进而合成出具有更高玻璃化温度 （Tg) 硬段的苯乙烯类嵌段共聚物， 有望作为 高耐热性的热塑性弹性体来使用， 在电线包覆层、 热空气导管、 汽车发动机衬 垫和密封圈等领域拥有巨大的市场前景。
传统苯乙烯类嵌段共聚物的合成方法主要有阴离子聚合与阳离子聚合。 但 是， 这两种聚合方法对反应原料的纯度要求较高， 反应过程需要高真空条件且 一般要在低温下进行； 另一方面， 离子共聚的研究较少， 其实际应用多限于用 少量第二单体进行改性， 而直接由乙烯基单体来制备嵌段共聚物对于阴离子聚 合或阳离子聚合而言仍然是极大的挑战。 因此， 与自由基聚合相比， 阴离子聚 合与阳离子聚合无论在节能环保方面， 还是在聚合实施条件方面都存在着巨大 的劣势。
而在二十世纪 90年代才发展起来的可控 /活性自由基聚合 （controlled/living radical polymerization, CLRP ) 技术， 已经成为学术研究热点并受到工业界的广 泛关注。 其中， 可逆加成断裂链转移自由基聚合法 （reversible addition fragmentation chain transfer radical polymerization, RAFT) 以其广泛的单体适用 范围和温和的反应条件而被誉为是当今最有工业化前景的活性自由基聚合技 术。 RAFT 技术通过增长自由基的可逆蜕化转移可以非常有效地控制单体的聚 合， 实现聚合物微结构 （如合成嵌段共聚物等） 及聚合度的可控调节。 其可应 用于多种单体的均聚与共聚体系， 几乎对所有的乙烯基单体都适用， 并且反应 条件与传统自由基聚合无异， 适用于本体聚合、 溶液聚合、 乳液聚合、 悬浮聚 合等多种反应体系。 其中， 工业上自由基聚合过程中多采用乳液聚合体系， 因 为乳液体系具有许多优点， 如以水为介质， 利于传热， 环保安全， 乳胶粘度低， 便于管道输送和连续生产； 分子链增长在胶束或胶粒的隔离相中进行， 因此自 由基寿命长， 兼具高速与高聚合度的特点； 反应得到的胶乳可直接使用， 例如 作为水乳胶、 粘结剂、 纸张、 皮革、 织物处理剂等。 两亲性大分子可逆加成断 裂链转移试剂是由小分子可逆加成断裂链转移试剂依次与亲水性单体和亲油性 单体聚合得到， 由于自身的两亲性， 大分子可逆加成断裂链转移试剂既可以充 当链转移试剂又可以充当乳化剂， 应用于乳液聚合体系中可以避免传统乳化剂 的使用， 从而防止生产过程中泡沬的产生并降低成本。 因此， 若能将 RAFT技 术与乳液体系两者相结合， 便有望为制备高耐热性苯乙烯类嵌段共聚物提供一 条绿色环保、 产物可控， 具有良好工业化应用前景的聚合路线。
然而， RAFT乳液聚合体系却存在着诸如胶体失稳、 缓聚与阻聚、 分子量分 布较宽以及实际分子量与理论分子量之间存在明显偏差等问题。 Gilbert等人利 用聚丙烯酸-聚丙烯酸丁酯两亲性大分子可逆加成断裂链转移试剂， 以饥饿法进 料进行苯乙烯的 RAFT半连续乳液聚合， 解决了乳液失稳问题， 但过程复杂且 实际分子量与理论分子量之间偏差较大，没能制备出嵌段共聚物； Charieux等人 利用含聚环氧乙垸大分子可逆加成断裂链转移试剂进行苯乙烯间歇乳液聚合， 反应 22.7小时时最终转化率只有 66.7%。 而其他文献报道的苯乙烯间歇乳液聚 合体系中所采用的两亲性大分子可逆加成断裂链转移试剂如聚苯乙烯-聚乙烯基 苯基三乙基氯化铵两嵌段可逆加成断裂链转移试剂、 聚二乙基甲基丙烯酸乙胺 单嵌段可逆加成断裂链转移试剂、 聚环氧乙垸 -聚二乙基甲基丙烯酸乙胺两嵌段 可逆加成断裂链转移试剂等均未能表现出对分子量的任何可控性。 文献报道中 苯乙烯 RAFT乳液聚合失败的主要原因在于其采用的两亲性大分子可逆加成断 裂链转移试剂亲水亲油链段长度比例设计不当， 必须通过加碱中和才能溶于水 中， 反应结果表现为反应阻聚期长， 反应速度慢且最终转化率低， 产物分子量 失控且分子量分布较宽， 乳液体系失稳， 因而不能很好地合成高分子量聚合物 和嵌段共聚物。 而罗英武等设计并合成了具有较长亲水性链段的聚丙烯酸 -聚苯 乙烯两亲性大分子可逆加成断裂链转移试剂， 不需中和即可溶解在水中， 通过 在乳液聚合过程中后补加碱液， 使得其亲水性链段的羧基电离， 产生静电稳定 作用， 提高了胶乳粒子的稳定性， 过程反应速率快且最终转化率高， 产物实际 分子量符合理论量设计值且分子量分布较窄， 并已成功制备出了聚 （苯乙烯 -b- 丙烯酸丁酯 -b-苯乙烯） 三嵌段共聚物。 但是， 由于其聚苯乙烯嵌段的玻璃化温 度只有约 100 °C， 这将极大地限制该类材料在高温领域的应用。
发明内容
本发明的目的是针对现有技术的不足，提供一种含玻璃化温度高于 ioo°c嵌 段的嵌段共聚物及制备方法。
本发明的目的是通过以下技术方案来实现的：
一种含玻璃化温度高于 ioo°c嵌段的嵌段共聚物， 其结构式表达为： AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-b- (MeMBL-co-St)n5-R; 其中， AAnl中， AA 为甲基丙烯酸单体单元或丙烯酸单体单元， ηι为 AA 的平均聚合度， ηι= 20-60； Stn2中， St 为苯乙烯单体单元， n2为 St 的平均聚合度， n2=3-10 ; (MeMBL-co-St)n3中， MeMBL-co-St为 MeMBL与 St的无规共聚物， MeMBL为 γ-甲基 -α-亚甲基 -γ-丁内酯单体单元， St为苯乙烯单体单元， MeMBL与 St的单 元数之比为 1:4-1:1，n3为 MeMBL-co-St共聚物的平均聚合度，n3=130-500; nBAn4 中， nBA为丙烯酸正丁酯单体单元， n4为 nBA 的平均聚合度， n4=200-1600; (MeMBL-co-St)n5中， MeMBL-co-St为 MeMBL与 St的无规共聚物， MeMBL为 γ-甲基 -α-亚甲基 -γ-丁内酯单体单元， St为苯乙烯单体单元， MeMBL与 St的单 元数之比为 1:4-1 :1， n5为 MeMBL-co-St共聚物的平均聚合度， n5=130-500; R 为垸基二硫代酯基团或垸基三硫代酯基团， 上述嵌段共聚物以粒子形式稳定分 散在水中， 粒子平均体均直径为 80〜140 nm。
一种可逆加成断裂链转移乳液聚合制备含玻璃化温度大于 100 °C嵌段的嵌 段共聚物胶乳的方法， 包括如下步骤：
第一步： 将 0.6-2.4重量份的两亲性大分子可逆加成断裂链转移试剂搅拌溶 于 30-90重量份的水中形成均匀水相， 再与由 3.4-11 重量份 St、 1.8-9重量份 MeMBL组成的油相一起倒入反应器中搅拌混合。 将反应器温度升至 50-80°C， 保持搅拌， 通氮气 30-60分钟后加入 0.01-0.04重量份的水溶性引发剂， 弓 I发聚 合 10-25分钟时加入含 0.07-0.27重量份碱的水溶液， 继续反应 15-40分钟， 得 到 AAm-b-St^-b MeMBL-co-St^-R聚合物。
第二步： 第一步反应结束后， 加入 7-25重量份的水， 以 0.4-1.4重量份 /分 钟的速率滴加 14-36重量份的 nBA单体后继续反应， 反应过程中补加 0-30重量 份的水进行稀释， 滴加时间和反应时间共 60-120 分钟， 得到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-R嵌段共聚物。
第三步： 第二步反应结束后， 补加 0-10重量份的水， 以 0.1-0.6重量份 /分 钟的速率滴加 3.4-12重量份 St与 1.9-9.5重量份 MeMBL的混合单体后继续反应， 滴 加 时 间 和 反 应 时 间 共 90-140 分 钟 ， 得 到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5-R嵌段共聚物胶乳。
本发明的有益效果是， 本发明利用乳液体系， 结合可逆加成断裂链转移活 性自由基聚合技术， 来制备分子量可控、 胶体稳定性高的含玻璃化温度大于 100°C嵌段的嵌段共聚物胶乳。 具有以下几个特点：
1、 以水为分散介质， 利于传热， 环保安全， 乳胶粘度低， 便于管道输送和 连续生产；
2、 方法所采用的两亲性大分子可逆加成断裂链转移试剂兼具链转移试剂与 乳化剂的双重功能， 既实现了对单体聚合的良好控制， 又避免了传统乳化剂的 使用；
3、 反应无阻聚期， 反应速度快， 各段单体转化率高， 有利于提高生产效率;
4、 通过在第一段反应中期补加碱液提高了乳液稳定性， 胶粒增长稳定， 粒 子数保持恒定， 不存在二次成核现象且粒径分布较窄；
5、方法制得的共聚物硬段玻璃化温度高于 100°C (硬段 Tg可由共聚组成进 行调控， 最高可达 155°C )， 在高耐热性热塑性弹性体领域有良好的应用前景；
6、 反应得到的胶乳可直接作为水乳胶， 粘结剂， 纸张、 皮革、 织物处理剂 等使用。
附图说明
图 1是本发明实施例 1三个步骤得到的聚合物的 GPC曲线图；
图 2是本发明实施例 1得到的嵌段共聚物的红外光谱图；
图 3是本发明实施例 1得到的嵌段共聚物胶乳的透射电镜图；
图 4是本发明实施例 1-7得到的嵌段共聚物的 DSC曲线图。
具体实施方式
本发明可逆加成断裂链转移乳液聚合制备含玻璃化温度高于 ioo°c嵌段的 嵌段共聚物胶乳的方法， 包括以下步骤：
第一步： 将 0.6-2.4重量份的两亲性大分子可逆加成断裂链转移试剂搅拌溶 于 30-90重量份的水中形成均匀水相， 再与由 3.4-11 重量份 St、 1.8-9重量份 MeMBL组成的油相一起倒入反应器中搅拌混合。 将反应器温度升至 50-80°C， 保持搅拌， 通氮气 30-60分钟后加入 0.01-0.04重量份的水溶性引发剂， 弓 I发聚 合 10-25分钟时加入含 0.07-0.27重量份碱的水溶液， 继续反应 15-40分钟， 得 到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-R聚合物。
第二步： 第一步反应结束后， 加入 7-25重量份的水， 以 0.4-1.4重量份 /分 钟的速率滴加 14-36重量份的 nBA单体后继续反应， 反应过程中补加 0-30重量 份的水进行稀释， 滴加时间和反应时间共 60-120 分钟， 得到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-R嵌段共聚物。
第三步： 第二步反应结束后， 补加 0-10重量份的水， 以 0.1-0.6重量份 /分 钟的速率滴加 3.4-12重量份 St与 1.9-9.5重量份 MeMBL的混合单体后继续反应， 滴 加 时 间 和 反 应 时 间 共 90-140 分 钟 ， 得 到 AAn b-Stns-b-CMeMBL-co-S ^-b-nBA^-b-CMeMBL-co-S ns-R嵌段共聚物胶乳。
步骤 1中， 两亲性大分子可逆加成断裂链转移试剂的化学结构通式为：
Figure imgf000007_0001
其中 St为苯乙烯单体单元， AA为甲基丙烯酸单体单元或丙烯酸单体单元， Z 为碳原子数从四到十二的垸硫基、 垸基、 苯基或苄基， X为异丙酸基、 乙酸基、 2—腈基乙酸基或 2—胺基乙酸基； n6为苯乙烯单体单元的平均聚合度， n6=3〜 10， 117为甲基丙烯酸单体单元或丙烯酸单体单元的平均聚合度， n7=20〜60。
所述的水溶性引发剂为过硫酸钾、 过硫酸铵、 过氧化氢或过氧化氢的衍生 物。 所述的碱为氢氧化钠、 氢氧化钾、 碳酸钠、 碳酸钾、 碳酸氢钠或碳酸氢钾。
各步的单体转化率由重量法测 ^曰.
各步乳胶粒子的粒径及粒径分布测试在 Malvern ZETASIZER 3000 HAS 粒
Figure imgf000007_0002
乳胶粒子数由下式计算：
Figure imgf000007_0003
式中， +为乳胶粒子数， 为聚合物质量（gd )， 为聚合物密度， 为 体均粒径。 粒径分布系数为体均粒径与数均粒径的比值。
设计分子量由下式计算：
Figure imgf000007_0004
十 M:.
!BAFTI 其中， 指各步反应结束时乳液中聚合物分子量的设计值， m为此步反 应所加单体的总质量， X为转化率， FF]为反应开始前所加的两亲性可逆加成 断裂链转移试剂的物质的量， ^为两亲性可逆加成断裂链转移试剂的分子 聚合物的分子量表征在凝胶渗透色谱 Watersl525-2414-717GPC仪器上进 行， 洗脱液为四氢呋喃， 以窄分布聚苯乙烯标样进行校正。 嵌段共聚物的特征官能团由 NiCOlet5700红外光谱仪表征得到。
聚合物乳胶粒形貌采用 JOEL JEMACRO- 123透射电子显微镜表征， 测试电 压为 80kV。
嵌段共聚物的 Tg测定在 TA Q200仪器上进行，使用氮气氛围， 以 10°C/min 的升温速率从 -80°C加热到 200 °C。
实验证明， 本发明制备的嵌段共聚物硬段玻璃化温度高于 100 °C， 最高可达 155°C , 在高耐热性热塑性弹性体领域有良好的应用前景； 可直接作为水乳胶， 粘结剂， 纸张、 皮革、 织物处理剂等使用。
下面根据附图和实施例详细描述本发明， 本发明的目的和效果将变得更加 明显。
本发明实施例中所用的两亲性大分子可逆加成断裂链转移试剂的化学结构 式为：
Figure imgf000008_0001
实施例 1 ((MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5三嵌段设计分子量 为 30K-25K-30K, 其中 MeMBL与 St的单元数之比为 1:2 ):
第一步： 将 1.9重量份的两亲性大分子可逆加成断裂链转移试剂 （1 ) 搅拌 溶于 85重量份的水中形成均匀水相， 再与由 11重量份 St、 6重量份 MeMBL组 成的油相一起倒入反应器中搅拌混合。 将反应器温度升至 70°C， 保持搅拌， 通 氮气 30分钟后加入 0.03重量份的过硫酸钾， 引发聚合 20分钟时加入含 0.2重 量 份 氢 氧 化 钠 的 水 溶 液 ， 继 续 反 应 20 分 钟 ， 得 到 AAn!-b-S b-CMeMBL-co-St^-R聚合物。
第二步： 第一步反应结束后， 加入 10重量份的水， 以 1重量份 /分钟的速率 滴加 15 重量份的 nBA 单体， 反应 66 分钟 （包括单体滴加时间） 后得到 AAn b-Stns-b-CMeMBL-co-S ^-b-nBA^-R嵌段共聚物。
第三步： 第二步反应结束后， 以 0.3重量份 /分钟的速率滴加 12重量份 St与 6.5重量份 MeMBL 的混合单体， 反应 116分钟 （包括单体滴加时间） 后得到 AAn b-Stns-b-CMeMBL-co-S ^-b-nBA^-b-CMeMBL-co-S ns-R嵌段共聚物胶乳。
如表 1 中实施例 1数据所示， 各步的反应时间较短且转化率很高， 随着反 应的进行， 乳胶粒的粒径在不断增大， 同时粒子数保持恒定且粒径分布很窄， 证明体系稳定， 不存在二次成核现象。 由表 2中实施例 1数据可知， 各步所得 聚合物分子量的实测值符合设计值， 共聚物的分子量在逐步增长， 且最终的分 子量分布相对较窄， 表明方法良好地控制了单体的聚合， 如图 1 所示， 各嵌段 的分子量呈现单峰且在逐步增长， 证明得到了嵌段共聚物。 图 2 中， 共聚物各 嵌段的特征官能团出峰明显， 证明产物为设计产物。 如图 3 所示， 反应最终得 到的是粒径均一、 形貌良好的乳胶粒子。 图 4 中 30K-25K-30K ( [MeMBL]:[St]=l :2) 的 DSC曲线在 -55°C附近与 135°C附近有明显的玻璃化转 变吸热峰， 也证明了产品为设计的结构， 且显示出高的硬段玻璃化温度。
实施例 2 ((MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5三嵌段设计分子量 为 30K-70K-30K, 其中 MeMBL与 St的单元数之比为 1:2 ):
第一步： 将 1.3重量份的两亲性大分子可逆加成断裂链转移试剂 （1 ) 搅拌 溶于 62重量份的水中形成均匀水相， 再与由 7.5重量份 St、 4重量份 MeMBL 组成的油相一起倒入反应器中搅拌混合。 将反应器温度升至 70°C， 保持搅拌， 通氮气 40分钟后加入 0.02重量份的过硫酸钾， 引发聚合 20分钟时加入含 0.17 重 量 份 氢 氧 化 钠 的 水 溶 液 ， 继 续 反 应 20 分 钟 ， 得 到 AAn b-Stns-b-CMeMBL-co-S ^-R聚合物。
第二步： 第一步反应结束后， 加入 7重量份的水， 以 1.4重量份 /分钟的速 率滴加 15重量份的 nBA单体，过程补加 14重量份的水进行稀释，反应 73分钟 (包括单体滴加时间） 后得到 AA^-b-St^-b^MeMBL-co-St -b-nBA^-R嵌段共 聚物。
第三步： 第二步反应结束后， 补加 10重量份的水， 以 0.4重量份 /分钟的速 率滴加 7.5重量份 St与 4.2重量份 MeMBL的混合单体， 反应 93分钟 （包括单 体滴加时间） 后得到
AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5-R嵌段共聚物胶乳。 各步的反应时间、 转化率、 乳胶粒粒径、 粒子数及粒径分布如表 1 所示。 各步所得聚合物的设计分子量、 实测分子量及分子量分布如表 2所示。 DSC曲 线如图 4所示。
实施例 3 ((MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5三嵌段设计分子量 为 30K-90K-30K, 其中 MeMBL与 St的单元数之比为 1:2 ):
第一步： 将 1.3重量份的两亲性大分子可逆加成断裂链转移试剂 （1 ) 搅拌 溶于 62重量份的水中形成均匀水相， 再与由 7.5重量份 St、 4重量份 MeMBL 组成的油相一起倒入反应器中搅拌混合。 将反应器温度升至 70°C， 保持搅拌， 通氮气 30分钟后加入 0.02重量份的过硫酸钾， 引发聚合 20分钟时加入含 0.16 重 量 份 氢 氧 化 钠 的 水 溶 液 ， 继 续 反 应 20 分 钟 ， 得 到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-R聚合物。
第二步： 第一步反应结束后， 加入 10重量份的水， 以 1重量份 /分钟的速率 滴加 20重量份的 nBA单体，过程补加 30重量份的水进行稀释，反应 94分钟（包 括单体滴加时间）后得到 AA^-b-St^-b- MeMBL-co-St^-b-nBA^-R嵌段共聚物。
第三步： 第二步反应结束后， 补加 10重量份的水， 以 0.4重量份 /分钟的速 率滴加 7.5重量份 St与 4重量份 MeMBL的混合单体， 反应 138分钟 （包括单 体滴加时间） 后得到
AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5-R嵌段共聚物胶乳。
各步的反应时间、 转化率、 乳胶粒粒径、 粒子数及粒径分布如表 1 所示。 各步所得聚合物的设计分子量、 实测分子量及分子量分布如表 2所示。 DSC曲 线如图 4所示。
实施例 4 ((MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5三嵌段设计分子量 为 15K-70K-15K, 其中 MeMBL与 St的单元数之比为 1:2 ):
第一步： 将 1.6重量份的两亲性大分子可逆加成断裂链转移试剂 （1 ) 搅拌 溶于 38重量份的水中形成均匀水相， 再与由 4.7重量份 St、 2.7重量份 MeMBL 组成的油相一起倒入反应器中搅拌混合。 将反应器温度升至 70°C， 保持搅拌， 通氮气 60分钟后加入 0.03重量份的过硫酸钾， 引发聚合 20分钟时加入含 0.17 重 量 份 氢 氧 化 钠 的 水 溶 液 ， 继 续 反 应 20 分 钟 ， 得 到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-R聚合物。
第二步： 第一步反应结束后， 加入 20重量份的水， 以 1重量份 /分钟的速率 滴加 35重量份的 nBA单体，过程补加 30重量份的水进行稀释，反应 75分钟（包 括单体滴加时间）后得到 AA^-b-St^-b- MeMBL-co-St^-b-nBA^-R嵌段共聚物。
第三步： 第二步反应结束后， 补加 9重量份的水， 以 0.4重量份 /分钟的速 率滴加 4.9重量份 St与 2.7重量份 MeMBL的混合单体， 反应 95分钟 （包括单 体滴加时间） 后得到
AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5-R嵌段共聚物胶乳。
各步的反应时间、 转化率、 乳胶粒粒径、 粒子数及粒径分布如表 1 所示。 各步所得聚合物的设计分子量、 实测分子量及分子量分布如表 2所示。 DSC曲 线如图 4所示。
实施例 5 ((MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5三嵌段设计分子量 为 15K-35K-15K, 其中 MeMBL与 St的单元数之比为 1:2 ):
第一步： 将 2.4重量份的两亲性大分子可逆加成断裂链转移试剂 （1 ) 搅拌 溶于 57重量份的水中形成均匀水相， 再与由 7重量份 St、 3.8重量份 MeMBL 组成的油相一起倒入反应器中搅拌混合。 将反应器温度升至 70°C， 保持搅拌， 通氮气 30分钟后加入 0.04重量份的过硫酸钾， 引发聚合 20分钟时加入含 0.27 重 量 份 氢 氧 化 钠 的 水 溶 液 ， 继 续 反 应 20 分 钟 ， 得 到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-R聚合物。
第二步： 第一步反应结束后， 加入 10重量份的水， 以 1重量份 /分钟的速率 滴加 26重量份的 nBA单体，过程补加 15重量份的水进行稀释，反应 64分钟（包 括单体滴加时间）后得到 AA^-b-St^-b- MeMBL-co-St^-b-nBA^-R嵌段共聚物。
第三步： 第二步反应结束后， 补加 8重量份的水， 以 0.3重量份 /分钟的速 率滴加 7.4重量份 St与 4重量份 MeMBL的混合单体， 反应 97分钟（包括单体 滴加时间 )后得到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5-R 嵌段共聚物胶乳。
各步的反应时间、 转化率、 乳胶粒粒径、 粒子数及粒径分布如表 1 所示。 各步所得聚合物的设计分子量、 实测分子量及分子量分布如表 2所示。 DSC曲 线如图 4所示。
实施例 6 ((MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5三嵌段设计分子量 为 30K-25K-30K, 其中 MeMBL与 St的单元数之比为 1:1 ):
第一步： 将 2重量份的两亲性大分子可逆加成断裂链转移试剂 （1 ) 搅拌溶 于 65重量份的水中形成均匀水相， 再与由 8.4重量份 St、 9重量份 MeMBL组 成的油相一起倒入反应器中搅拌混合。 将反应器温度升至 70°C， 保持搅拌， 通 氮气 40分钟后加入 0.03重量份的过硫酸钾， 引发聚合 15分钟时加入含 0.26重 量 份 氢 氧 化 钠 的 水 溶 液 ， 继 续 反 应 15 分 钟 ， 得 到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-R聚合物。
第二步： 第一步反应结束后， 加入 10重量份的水， 以 1.2重量份 /分钟的速 率滴加 15 重量份的 nBA 单体， 反应 65 分钟 （包括单体滴加时间） 后得到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-R嵌段共聚物。
第三步： 第二步反应结束后， 以 0.3重量份 /分钟的速率滴加 8.7重量份 St 与 9.5重量份 MeMBL的混合单体， 反应 97分钟 （包括单体滴加时间） 后得到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5-R嵌段共聚物胶乳。
图 4中 30K-25K-30K( [MeMBL]:[St]=l : l )的 DSC曲线在 -55 °C附近与 155°C 附近有明显的玻璃化转变吸热峰， 显示出高的硬段玻璃化温度。
实施例 7 ((MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5三嵌段设计分子量 为 30K-70K-30K, 其中 MeMBL与 St的单元数之比为 1 :4 ) :
第一步： 将 1.3重量份的两亲性大分子可逆加成断裂链转移试剂 （1 ) 搅拌 溶于 60重量份的水中形成均匀水相， 再与由 9重量份 St、 2.4重量份 MeMBL 组成的油相一起倒入反应器中搅拌混合。 将反应器温度升至 70°C， 保持搅拌， 通氮气 30分钟后加入 0.02重量份的过硫酸钾， 引发聚合 25分钟时加入含 0.16 重 量 份 氢 氧 化 钠 的 水 溶 液 ， 继 续 反 应 40 分 钟 ， 得 到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-R聚合物。
第二步： 第一步反应结束后， 加入 28重量份的水， 以 0.6重量份 /分钟的速 率滴加 28 重量份的 nBA 单体， 反应 97 分钟 （包括单体滴加时间） 后得到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-R嵌段共聚物。
第三步： 第二步反应结束后， 补加 8重量份的水， 以 0.56重量份 /分钟的速 率滴加 9.7重量份 St与 2.6重量份 MeMBL的混合单体， 反应 111分钟（包括单 体滴加时间） 后得到
AAn b-Stns-b-CMeMBL-co-S ^-b-nBA^-b-CMeMBL-co-S ns-R嵌段共聚物胶乳。
图 4中 30K-70K-30K( [MeMBL]:[St]=l :4 )的 DSC曲线在 -55 °C附近与 115°C 附近有明显的玻璃化转变吸热峰， 显示出高的硬段玻璃化温度。
实施例 8 ((MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5三嵌段设计分子量 为 45K-70K-45K, 其中 MeMBL与 St的单元数之比为 1 : 1 ) :
第一步： 将 0.7重量份的两亲性大分子可逆加成断裂链转移试剂 （1 ) 搅拌 溶于 55重量份的水中形成均匀水相， 再与由 4重量份 St、 4.5重量份 MeMBL 组成的油相一起倒入反应器中搅拌混合。 将反应器温度升至 50°C， 保持搅拌， 通氮气 50分钟后加入 0.01重量份的过硫酸钾， 引发聚合 10分钟时加入含 0.07 重 量 份 氢 氧 化 钠 的 水 溶 液 ， 继 续 反 应 20 分 钟 ， 得 到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-R聚合物。
第二步： 第一步反应结束后， 加入 15重量份的水， 以 0.4重量份 /分钟的速 率滴加 14 重量份的 nBA 单体， 反应 74 分钟 （包括单体滴加时间） 后得到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-R嵌段共聚物。
第三步： 第二步反应结束后， 补加 10重量份的水， 以 0.2重量份 /分钟的速 率滴加 4重量份 St与 4.5重量份 MeMBL的混合单体， 反应 116分钟 （包括单 体滴加时间） 后得到
AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5-R嵌段共聚物胶乳。
实施例 9 ((MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5三嵌段设计分子量 为 30K-200K-30K, 其中 MeMBL与 St的单元数之比为 1:4):
第一步： 将 6重量份的两亲性大分子可逆加成断裂链转移试剂 （2) 搅拌溶 于 30重量份的水中形成均匀水相， 再与由 4重量份 St、 1.1重量份 MeMBL组 成的油相一起倒入反应器中搅拌混合。 将反应器温度升至 80°C， 保持搅拌， 通 氮气 30分钟后加入 0.01重量份的过硫酸钾， 引发聚合 20分钟时加入含 0.07重 量 份 氢 氧 化 钠 的 水 溶 液 ， 继 续 反 应 40 分 钟 ， 得 到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-R聚合物。
第二步： 第一步反应结束后， 加入 25重量份的水， 以 0.4重量份 /分钟的速 率滴加 36重量份的 nBA单体， 过程补加 15重量份的水进行稀释， 反应 120分 钟 （包括单体滴加时间） 后得到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-R嵌段 共聚物。
第三步： 第二步反应结束后， 补加 9重量份的水， 以 0.1重量份 /分钟的速 率滴加 4重量份 St与 1.1重量份 MeMBL的混合单体， 反应 110分钟 （包括单 体滴加时间） 后得到
AAn b-Stns-b-CMeMBL-co-S ^-b-nBA^-b-CMeMBL-co-S ns-R嵌段共聚物胶乳。 表 h 嵌段共聚物胶乳制备过程各步的转化率及乳胶粒子演变情况
粒子数
反应时间
实施例 转化率 粒径 /nm 粒径分布
/min (LogNpy
一少 40 91% 71.3 14.82 1.13
1 一
一少 66 100% 84.5 14.81 1.10 二少 116 94% 95.9 14.80 1.03 一少 40 92% 68.8 14.85 1.16
2 一
一少 73 96% 91.9 14.83 1.13 二少 93 87% 100.4 14.75 1.08 一少 40 94% 75.1 14.74 1.07 一
3 一少 94 100% 100.9 14.72 1.11
二少 138 96% 107.8 14.67 1.14
4 一少 40 94% 61.5 14.96 1.03 一
一少 75 97% 91.4 14.83 1.01 二少 95 100% 94.1 14.82 1.03 一少 40 95% 61 14.99 1.03
5 一
一少 64 100% 82.7 14.94 1.02 二少 97 95% 89.5 14.89 1.01 表 2: 嵌段共聚物胶乳制备过程各步分子量的演变情况
Figure imgf000014_0001
上述实施例用来解释说明本发明， 而不是对本发明进行限制， 在本发明的 精神和权利要求的保护范围内， 对本发明作出的任何修改和改变， 都落入本发 明的保护范围。

Claims

权 利 要 求 书
1. 一种含玻璃化温度高于 ioo°c嵌段的嵌段共聚物， 其特征在于， 其结构式表 达为： AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-b- (MeMBL-co-St)n5-R;其中， AAnl 中， AA为甲基丙烯酸单体单元或丙烯酸单体单元， 为入入的平均聚合度， ηι= 20-60； 中， St 为苯乙烯单体单元， n2为 St 的平均聚合度， n2=3-10 ; (MeMBL-co-St)n3中， MeMBL-co-St为 MeMBL与 St的无规共聚物， MeMBL为 γ-甲基 -α-亚甲基 -γ-丁内酯单体单元， St为苯乙烯单体单元， MeMBL与 St的单 元数之比为 1:4-1:1，n3为 MeMBL-co-St共聚物的平均聚合度，n3=130-500; nBAn4 中， nBA为丙烯酸正丁酯单体单元， n4为 nBA 的平均聚合度， n4=200-1600; (MeMBL-co-St)n5中， MeMBL-co-St为 MeMBL与 St的无规共聚物， MeMBL为 γ-甲基 -α-亚甲基 -γ-丁内酯单体单元， St为苯乙烯单体单元， MeMBL与 St的单 元数之比为 1:4-1 :1， n5为 MeMBL-co-St共聚物的平均聚合度， n5=130-500; R 为垸基二硫代酯基团或垸基三硫代酯基团， 上述嵌段共聚物以粒子形式稳定分 散在水中， 粒子平均体均直径为 80〜140 nm。
2. 一种权利要求 1所述含玻璃化温度高于 100°C嵌段的嵌段共聚物的可逆加成 断裂链转移乳液聚合制备方法， 其特征在于， 包括如下步骤：
( 1 ) :将 0.6-2.4重量份的两亲性大分子可逆加成断裂链转移试剂搅拌溶于 30-90 重量份的水中形成均匀水相， 再与由 3.4-11重量份 St、 1.8-9重量份 MeMBL组 成的油相一起倒入反应器中搅拌混合； 将反应器温度升至 50-80°C， 保持搅拌， 通氮气 30-60分钟后加入 0.01-0.04重量份的水溶性引发剂， 引发聚合 10-25分 钟时加入含 0.07-0.27 重量份碱的水溶液， 继续反应 15-40 分钟， 得到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-R聚合物；
(2)： 第一步反应结束后， 加入 7-25重量份的水， 以 0.4-1.4重量份 /分钟的速 率滴加 14-36重量份的 nBA单体后继续反应， 反应过程中补加 0-30重量份的水 进 行 稀 释 ， 滴 加 时 间 和 反 应 时 间 共 60-120 分 钟 ， 得 到 AAn b-Stns-b-CMeMBL-co-S ^-b-nBA^-R嵌段共聚物；
(3 )： 第二步反应结束后， 补加 0-10重量份的水， 以 0.1-0.6重量份 /分钟的速 率滴加 3.4-12重量份 St与 1.9-9.5重量份 MeMBL的混合单体后继续反应，滴加 时 间 和 反 应 时 间 共 90-140 分 钟 ， 得 到 AAnl-b-Stn2-b-(MeMBL-co-St)n3-b-nBAn4-b-(MeMBL-co-St)n5-R嵌段共聚物胶乳。
3. 根据权利要求 2所述的可逆加成断裂链转移乳液聚合制备方法，其特征在于， 所述的两亲性大分子可逆加成断裂链转移试剂的化学结构通式为
Figure imgf000016_0001
其中 St为苯乙烯单体单元， AA为甲基丙烯酸单体单元或丙烯酸单体单元， Z 为碳原子数从四到十二的垸硫基、 垸基、 苯基或苄基， X为异丙酸基、 乙酸基、 2—腈基乙酸基或 2—胺基乙酸基； n6为苯乙烯单体单元的平均聚合度， n6=3〜 10， 117为甲基丙烯酸单体单元或丙烯酸单体单元的平均聚合度， n7=20〜60。
4. 根据权利要求 3所述的可逆加成断裂链转移乳液聚合方法， 其特征在于， 所 述的两亲性大分子可逆加成断裂链转移试剂为分子量在 1000〜6000之间的两亲 性齐聚物。
5. 根据权利要求 2所述的可逆加成断裂链转移乳液聚合， 其特征在于， 所述的 水溶性引发剂为过硫酸钾、 过硫酸铵、 过氧化氢或过氧化氢的衍生物。
6. 根据权利要求 2所述的可逆加成断裂链转移乳液聚合， 其特征在于所述的碱 为氢氧化钠、 氢氧化钾、 碳酸钠、 碳酸钾、 碳酸氢钠或碳酸氢钾。
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