WO2018120526A1 - 乳液聚合室温制备超高分子量聚合物的方法 - Google Patents

乳液聚合室温制备超高分子量聚合物的方法 Download PDF

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WO2018120526A1
WO2018120526A1 PCT/CN2017/081177 CN2017081177W WO2018120526A1 WO 2018120526 A1 WO2018120526 A1 WO 2018120526A1 CN 2017081177 W CN2017081177 W CN 2017081177W WO 2018120526 A1 WO2018120526 A1 WO 2018120526A1
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molecular weight
polymer
room temperature
polymerization
emulsion polymerization
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PCT/CN2017/081177
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French (fr)
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黄文艳
蒋必彪
薛小强
杨宏军
蒋其民
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常州大学
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Priority claimed from CN201611258871.9A external-priority patent/CN106674390B/zh
Priority claimed from CN201611258844.1A external-priority patent/CN106674393A/zh
Priority claimed from CN201611263551.2A external-priority patent/CN106632773A/zh
Application filed by 常州大学 filed Critical 常州大学
Priority to US15/742,407 priority Critical patent/US20180371143A1/en
Publication of WO2018120526A1 publication Critical patent/WO2018120526A1/zh
Priority to US17/188,760 priority patent/US11866539B2/en

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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
    • 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
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • C08F293/005—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 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/06—Hydrocarbons
    • C08F112/08—Styrene
    • 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
    • C08F118/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F118/02—Esters of monocarboxylic acids
    • C08F118/04—Vinyl esters
    • C08F118/08—Vinyl acetate
    • 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
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/02—Esters of monocarboxylic acids
    • C08F18/04—Vinyl esters
    • C08F18/08—Vinyl acetate
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]

Definitions

  • the invention belongs to the field of preparation of functional polymers in polymer synthesis, and in particular relates to an emulsion polymerization synthesis technology for preparing ultrahigh molecular weight polymers at room temperature.
  • thermoplastic resins such as polystyrene, polymethyl methacrylate (PMMA) and polyvinyl acetate have disadvantages such as low impact strength and low heat resistance, and their applications are greatly limited.
  • the performance of polymers has been improved by increasing the molecular weight thereof, and preparation of ultrahigh molecular weight polymers has been one of the research directions in recent years.
  • the ultra-high molecular weight polymer retains the excellent optical properties unique to the general-purpose polymer, is easy to process, and has high mechanical strength and heat resistance. Therefore, the development and enrichment of synthetic methods for ultrahigh molecular weight polymers is of great value.
  • polysubstituted bibenzyl compounds are mainly used as initiators to initiate styrene bulk solution polymerization; rare earth catalysts, ternary complexes of calixarene and Mg(n-Bu) 2 , HMPA The catalyst is coordinated by high pressure under high pressure; the azo compound is an initiator, and the organic hydrazine is a chain transfer agent, and the ultra-high molecular weight polystyrene is prepared by initiating the styrene by the free radical soap-free emulsion polymerization.
  • the preparation of ultrahigh molecular weight PMMA is generally carried out by suspension polymerization, low temperature plasma polymerization and coordination polymerization.
  • the initiation system is complicated, the initiation efficiency is low, and more impurities are introduced into the product.
  • the suspension polymerization method requires a large amount of water as a continuous phase, and has low production efficiency, and impurities such as a dispersant and a stabilizer contained in the prepared polymer product.
  • the low-temperature plasma polymerization method has high requirements on production equipment, and the prepared polymer has a wide molecular weight distribution and is prone to cross-linking reaction, resulting in deterioration of polymer solubility, toughness, and impact resistance.
  • the coordination polymerization system is complicated, the operation is difficult, and the conditions are harsh.
  • polyvinyl acetate is prepared by conventional free radical emulsion polymerization, using nonionic emulsifier, polyvinyl alcohol (PVA) as protective colloid, polymerization temperature is 60-90 ° C, high energy consumption for polymerization, and prone to active chain Upon transfer, the resulting polymer has a low molecular weight.
  • the redox initiation system can be used to polymerize relatively high molecular weight polyvinyl acetate at relatively low temperature, but the reaction system is complicated, and the reaction system and polymer properties are limited by the optimal ratio of reducing agent to oxidant. The extent also limits the development of large-scale applications of polyvinyl acetate.
  • the reaction system is simple and easy to operate, has a high polymerization rate, a high monomer conversion rate, and has a high molecular weight and a narrow molecular weight distribution.
  • the invention is characterized in that the polymerization monomer is initiated at room temperature under the emulsion polymerization condition by using potassium persulfate or ammonium persulfate as an initiator.
  • the ultrahigh molecular weight polymer is directly produced, the polymerization system is simple and stable, the operation is easy, the reaction time is short, and the monomer conversion rate is high, the molecular weight of the obtained polymer is high and the molecular weight distribution is narrow, and the molecular weight of the polymer can be adjusted according to the polymerization conditions.
  • a method for preparing an ultrahigh molecular weight polymer by emulsion polymerization at room temperature comprising: using persulfate as an initiator, water as a medium, anionic surfactant as an emulsifier, sodium hydrogencarbonate as a pH adjuster, styrene, vinyl acetate
  • An ester or a (meth)acrylic acid methyl ester or the like is a polymerizable monomer, and is subjected to radical emulsion polymerization to obtain an ultrahigh molecular weight polymer at room temperature.
  • the initiator is potassium persulfate or ammonium persulfate
  • the initiator the polymerization monomer has a molar mass ratio of 1 to 5:100;
  • the mass ratio of water: polymerized monomer is 2 to 5:1;
  • the polymerization temperature is: room temperature; the polymerization reaction time is controlled to 1-6 hours;
  • the polymerization method is emulsion polymerization, and the polymerization mechanism is radical polymerization;
  • the surfactant is an anionic surfactant sodium dodecylbenzenesulfonate or sodium lauryl sulfate;
  • the mass ratio of the surfactant: polymerized monomer is 4-6%
  • the pH adjuster sodium hydrogencarbonate is used in an amount of 2 to 4% by weight of the polymerized monomer to ensure a stable polymerization system and a pH of 7 to 8 which is weakly alkaline.
  • styrene, vinyl acetate or (meth)acrylic acid methyl ester is initiated at room temperature under normal pressure under an emulsion polymerization condition using a persulfate as an initiator to form an ultrahigh molecular weight polymer.
  • emulsion polymerization uses water as the reaction medium, which is safe and reliable, which not only saves cost but also improves the environmental impact; using suitable emulsion polymerization conditions, the persulfate is decomposed at room temperature and pressure to initiate styrene, vinyl acetate.
  • the ester or (meth)acrylic acid methyl ester polymerizes, the polymerization rate is fast, the reaction time is short, and the monomer conversion rate is high, the molecular weight of the obtained polymer is high and the molecular weight distribution is narrow, and the molecular weight and molecular weight distribution can be adjusted according to the polymerization reaction conditions.
  • the whole system is simple and stable, the conditions are mild, and the operation is easy, which is suitable for the promotion of large-scale applications.
  • the present invention has the following beneficial technical effects:
  • the use of the commercially available initiator in the method of the invention greatly reduces the polymerization cost; the whole reaction system is simple and stable, the reaction condition is mild, no temperature control is required, the operation is simple and easy, the impact on the environment is small, and the energy consumption is low. Suitable for industrialized mass production.
  • the method of the invention has short reaction time and high monomer conversion rate, and the obtained polymer has high molecular weight and narrow molecular weight distribution, and the molecular weight and molecular weight distribution can be regulated in a wide range, which is advantageous for accurately controlling ultra-high molecular weight polymerization.
  • Example 1 is a molecular weight differential distribution curve of the ultrahigh molecular weight polystyrene obtained in Example 1.
  • Example 2 is a molecular weight differential distribution curve of the ultrahigh molecular weight polymethyl methacrylate obtained in Example 7.
  • Example 3 is a molecular weight differential distribution curve of the ultrahigh molecular weight polyvinyl acetate obtained in Example 13.
  • Styrene (5.0002 g, 0.0480 mol) was added to dissolve sodium lauryl sulfate (0.2500 g, 5 wt% styrene), sodium bicarbonate (0.1500 g, 3 wt% styrene), potassium persulfate (0.4321 g, In a reaction flask of 0.0016 mol) and water (20.0053 g, 400 wt% styrene), the mixture was stirred well, and after evacuating under vacuum, the reaction was carried out at 35 ° C for 4 hours, and the conversion of styrene was determined to be 90.27%.
  • Styrene (5.0002 g, 0.0480 mol) was added to dissolve sodium lauryl sulfate (0.3003 g, 6 wt% styrene), sodium bicarbonate (0.2001 g, 4 wt% styrene), ammonium persulfate (0.5472 g, The reaction flask of 0.0024 mol) and water (25.0005 g, 500 wt% styrene) was uniformly stirred, and after evacuating under vacuum, the reaction was carried out at 35 ° C for 1 hour, and the conversion of styrene was 89.77%.
  • Styrene (5.0002 g, 0.0480 mol) was added to dissolve sodium lauryl sulfate (0.2003 g, 4 wt% styrene), sodium bicarbonate (0.1002 g, 2 wt% styrene), potassium persulfate (0.1309 g,
  • the reaction flask of 0.0005 mol) and water (10.0006 g, 200 wt% styrene) was uniformly stirred, and after evacuating under vacuum, the reaction was carried out at 35 ° C for 6 hours, and the conversion of styrene was 88.65%. Demulsification with ethanol, drying after three times of washing, and then three times of purification and drying to obtain a polymer.
  • Styrene (5.0001 g, 0.0480 mol) was added to dissolve sodium lauryl sulfate (0.2502 g, 5 wt% styrene), sodium bicarbonate (0.1500 g, 3 wt% styrene), potassium persulfate (0.4322 g, In a reaction flask of 0.0016 mol) and water (20.0007 g, 400 wt% styrene), the mixture was stirred well, and after evacuating under vacuum, the reaction was carried out at 25 ° C for 4 hours, and the styrene conversion was 88.97%.
  • Styrene (5.0001 g, 0.0480 mol) was added to dissolve sodium lauryl sulfate (0.2500 g, 5 wt% styrene), sodium bicarbonate (0.1500 g, 3 wt% styrene), potassium persulfate (0.3242 g, In a reaction flask of 0.0012 mol) and water (20.0053 g, 400 wt% styrene), the mixture was stirred well, and after evacuating under vacuum, the reaction was carried out at 35 ° C for 6 hours, and the conversion of styrene was found to be 92.74%.
  • Methyl methacrylate (MMA) (5.0002 g, 0.0500 mol) was added to dissolve sodium lauryl sulfate (0.2501 g, 5 wt% MMA), sodium bicarbonate (0.1500 g, 3 wt% MMA), potassium persulfate (0.4591 g, 0.0017 mol) and water (20.0042 g, 400 wt% MMA) in a reaction flask, stirred uniformly, and evacuated under vacuum, and then reacted at 35 ° C for 4 hours, and the conversion of MMA was measured to be 95.00%. Demulsification with ethanol, drying after three times of washing, and then three times of purification and drying to obtain a polymer.
  • MMA 5.0002 g, 0.0500 mol was added to dissolve sodium lauryl sulfate (0.3001 g, 6 wt% (MMA), sodium bicarbonate (0.2000 g, 4 wt% MMA), ammonium persulfate (0.5712 g, 0.0025 mol)
  • sodium lauryl sulfate 0.3001 g, 6 wt% (MMA), sodium bicarbonate (0.2000 g, 4 wt% MMA), ammonium persulfate (0.5712 g, 0.0025 mol
  • MMA (5.0002 g, 0.0500 mol) was added to dissolve sodium lauryl sulfate (0.2003 g, 4 wt% MMA), sodium hydrogencarbonate (0.1002 g, 2 wt% MMA), potassium persulfate (0.1308 g, 0.0005 mol)
  • a reaction flask with water (10.0006 g, 200 wt% MMA)
  • the mixture was stirred well, and after evacuating under vacuum, the reaction was carried out at 35 ° C for 6 hours, and the MMA conversion was measured to be 93.65%.
  • MMA 5.0001 g, 0.0500 mol was added to dissolve sodium lauryl sulfate (0.2502 g, 5 wt% MMA), sodium bicarbonate (0.1500 g, 3 wt% MMA), potassium persulfate (0.4592 g, 0.0017 mol)
  • a reaction flask with water 20.0001 g, 400 wt% MMA
  • the mixture was stirred well, and after evacuating under vacuum, the reaction was carried out at 25 ° C for 4 hours, and the MMA conversion was measured to be 95.05%.
  • MMA 5.0001 g, 0.0500 mol was added to dissolve sodium lauryl sulfate (0.2502 g, 5 wt% MMA), sodium hydrogencarbonate (0.1500 g, 3 wt% MMA), potassium persulfate (0.3375 g, 0.0013 mol)
  • a reaction flask with water 20.0053 g, 400 wt% MMA
  • the mixture was stirred well, and after evacuating under vacuum, the reaction was carried out at 35 ° C for 6 hours, and the MMA conversion was 98.21%.
  • N-butyl methacrylate (5.0000 g, 0.0352 mol) was added to dissolve sodium dodecylbenzenesulfonate (0.3000 g, 6 wt% n-butyl methacrylate), sodium bicarbonate (0.1500 g, 3 wt% A)
  • sodium dodecylbenzenesulfonate 0.3000 g, 6 wt% n-butyl methacrylate
  • sodium bicarbonate 0.1500 g, 3 wt% A
  • Vinyl acetate (5.0002 g, 0.0582 mol) was added to dissolve sodium lauryl sulfate (0.2502 g, 5 wt% vinyl acetate), sodium bicarbonate (0.1501 g, 3 wt% vinyl acetate), potassium persulfate ( 0.6211g, 0.0023mol) and water (20.0008g, 400wt% vinyl acetate) in the reaction flask, stirred evenly, vacuumed and discharged, placed at 35 ° C for 4 hours, measured vinyl acetate conversion rate of 87.88 %. Demulsification with ethanol, drying after three times of washing, and then three times of purification and drying to obtain a polymer.
  • Vinyl acetate (5.0000 g, 0.0581 mol) was added to dissolve sodium lauryl sulfate (0.3003 g, 6 wt% vinyl acetate), sodium bicarbonate (0.2001 g, 4 wt% vinyl acetate), ammonium persulfate ( 0.6612g, 0.0029mol) and water (25.0009g, 500wt% vinyl acetate) in a reaction flask, stirred evenly, vacuumed and discharged, placed at 35 ° C for 1 hour, measured vinyl acetate conversion rate of 90.71 %. Demulsification with ethanol, drying after three times of washing, and then three times of purification and drying to obtain a polymer.
  • Vinyl acetate (5.0003 g, 0.0582 mol) was added to dissolve sodium lauryl sulfate (0.2003 g, 4 wt% vinyl acetate), sodium bicarbonate (0.2002 g, 4 wt% vinyl acetate), potassium persulfate ( In a reaction flask of 0.1566 g, 0.0006 mol) and water (10.0026 g, 200 wt% vinyl acetate), the mixture was stirred well, and after evacuating under vacuum, the reaction was carried out at 35 ° C for 6 hours, and the conversion of vinyl acetate was measured to be 90.45. %. Demulsification with ethanol, drying after three times of washing, and then three times of purification and drying to obtain a polymer.
  • Vinyl acetate (5.0001 g, 0.0581 mol) was added to dissolve sodium lauryl sulfate (0.2502 g, 5 wt% vinyl acetate), sodium bicarbonate (0.1500 g, 3 wt% vinyl acetate), potassium persulfate ( 0.5224g, 0.0019mol) and water (20.0018g, 400wt% vinyl acetate) in a reaction flask, stirred evenly, vacuumed and discharged, placed at 25 ° C for 4 hours, measured vinyl acetate conversion rate of 85.06 %. Demulsification with ethanol, drying after three times of washing, and then three times of purification and drying to obtain a polymer.
  • Vinyl acetate (5.0001 g, 0.0581 mol) was added to dissolve sodium lauryl sulfate (0.2500 g, 5 wt% vinyl acetate), sodium bicarbonate (0.1500 g, 3 wt% vinyl acetate), potassium persulfate ( 0.3923g, 0.0015mol) and water (20.0012g, 400wt% vinyl acetate) in a reaction flask, stirred evenly, vacuumed and discharged, placed at 35 ° C for 6 hours, measured vinyl acetate conversion rate of 93.15 %. Demulsification with ethanol, drying after three times of washing, and then three times of purification and drying to obtain a polymer.
  • Vinyl acetate (5.0002 g, 0.0582 mol) was added to dissolve sodium dodecylbenzenesulfonate (0.3002 g, 6 wt% vinyl acetate), sodium bicarbonate (0.1503 g, 3 wt% vinyl acetate), persulfuric acid
  • sodium dodecylbenzenesulfonate (0.3002 g, 6 wt% vinyl acetate
  • sodium bicarbonate 0.1503 g, 3 wt% vinyl acetate
  • persulfuric acid In a reaction flask of potassium (0.5235 g, 0.0019 mol) and water (20.0006 g, 400 wt% vinyl acetate), the mixture was stirred well, and after evacuating under vacuum, the reaction was carried out at 25 ° C for 4 hours, and the conversion of vinyl acetate was measured. It is 87.75%.
  • the emulsion was demulsified with ethanol, washed three times with water, dried, and then purified by three times to obtain a polymer.

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Abstract

乳液聚合室温制备超高分子量聚合物的方法，属于聚合物合成领域。以过硫酸盐为引发剂，水为介质，阴离子型表面活性剂为乳化剂，碳酸氢钠为pH调节剂，苯乙烯，(甲基)丙烯酸酯类聚合物或者醋酸乙烯酯为单体，在室温常压下聚合反应1-6小时，单体转化率达85％以上，成功得到重均分子量大于100×10 4g/mol的超高分子量聚合物。该聚合体系简单且稳定，商品化反应原料的使用，极大地降低聚合成本，操作易行，条件温和，对环境的影响较小，反应无需控温加压，能耗低，反应时间短且单体转化率高，所得超高分子量聚合物的分子量高及分子量分布窄，且其在较宽范围内进行调控。

Description

乳液聚合室温制备超高分子量聚合物的方法 技术领域
本发明属于高分子合成中功能聚合物制备领域，具体涉及一种室温制备超高分子量聚合物的乳液聚合合成技术。
背景技术
聚苯乙烯，聚甲基丙烯酸甲酯(PMMA)和聚醋酸乙烯酯这些普通的热塑性树脂，均具有抗冲击强度低，耐热性不高等缺点，其应用大大地受到限制。近年来，通过提高聚合物的分子量来改善其性能，其中制备超高分子量聚合物是近年的研究方向之一。超高分子量聚合物既保留了通用型聚合物所特有的优异光学性能，易加工性能，又具有较高的机械强度和耐热性。因此，发展和丰富超高分子量聚合物的合成方法具有重要价值。
目前主要采用多取代联苄类化合物(碳-碳键型化合物)为引发剂引发苯乙烯本体溶液聚合；稀土催化剂，杯芳烃钕与Mg(n-Bu)2、HMPA所组成的三元络合催化剂在高压下经配位聚合；偶氮类化合物为引发剂，有机碲为链转移剂，经活性自由基无皂乳液聚合，引发苯乙烯制备得超高分子量聚苯乙烯。制备超高分子量的PMMA一般采用悬浮聚合法，低温等离子体聚合法和配位聚合法来合成。引发体系复杂，引发效率较低，产物中引入较多杂质。悬浮聚合法需用大量的水做连续相，生产效率较低，制备得到的聚合物产品中含有的分散剂、稳定剂等杂质。低温等离子体聚合法对生产设备要求高，制备得到的聚合物分子量分布较宽、容易发生交联反应而导致聚合物溶解性变差和韧性、抗冲击性能下降。配位聚合体系复杂，操作困难，条件苛刻。上述聚合反应体系复杂，对生产工艺及设备要求高，聚合反应成本高，高单体转化率所需聚合时间较长，所得聚合物的分子量受各种因素影响，这些不足一定程度上限制了超高分子量聚合物规模化应用的发展。聚醋酸乙烯酯一般只能通过自由基聚合而成，因为醋酸乙烯酯单体上的吸电子基团，使得它不能进行阴离子聚合，又因为醋酸乙烯酯的自由基活性过高，链转移常数过大，所以采用本体溶液聚合，很难得到高分子量的聚醋酸乙烯酯。目前，采用常规自由基乳液聚合制备聚醋酸乙烯酯，采用非离子型乳化剂，聚乙烯醇(PVA)为保护胶体，聚合温度为60-90℃，聚合反应能耗高，且易发生活性链转移，所得聚合物分子量低。采用氧化还原引发体系，可以在相对较低温度下聚合得到相对高分子量的聚醋酸乙烯酯，但是反应体系复杂，反应体系与聚合物性能受还原剂与氧化剂最佳配比的限制，这些不足一定程度上也限制了聚醋酸乙烯酯规模化应用的发展。
发明内容
本发明的目的在于提供了一种乳液聚合室温制备超高分子量聚合物的方法，该方法反应体系简单易操作，聚合速率快，单体转化率高，所得聚合物分子量高且分子量分布窄。其特征是以过硫酸钾或过硫酸铵为引发剂，在乳液聚合条件下，室温引发聚合单体， 直接生成超高分子量聚合物，聚合体系简单且稳定，操作易行，反应时间短且单体转化率高，所得聚合物的分子量高及分子量分布窄，且可以根据聚合条件调节聚合物的分子量。
一种乳液聚合室温制备超高分子量聚合物的方法，包括：采用过硫酸盐为引发剂，水为介质，阴离子型表面活性剂为乳化剂，碳酸氢钠为pH调节剂，苯乙烯，醋酸乙烯酯或者(甲基)丙烯酸类甲酯等为聚合单体，通过自由基乳液聚合，在室温下反应得到超高分子量聚合物。
优选的技术方案中，所述的引发剂为过硫酸钾或者过硫酸铵；
优选的技术方案中，所述的引发剂:聚合单体的摩尔质量比为1～5:100；
优选的技术方案中，所述的水:聚合单体的质量比为2～5:1；
优选的技术方案中，聚合反应温度：室温；聚合反应时间控制为1-6小时；
优选的技术方案中，所述的聚合方法为乳液聚合，聚合机理为自由基聚合；
优选的技术方案中，所述的表面活性剂为阴离子型表面活性剂十二烷基苯磺酸钠或十二烷基硫酸钠；
优选的技术方案中，所述的表面活性剂:聚合单体的质量比为4-6％；
优选的技术方案中，所述的pH调节剂碳酸氢钠的用量为聚合单体的2～4wt％，保证聚合体系稳定且pH值为7～8呈弱碱性。
本发明中，以过硫酸盐为引发剂，在乳液聚合条件下，室温常压引发苯乙烯，醋酸乙烯酯或者(甲基)丙烯酸类甲酯，生成超高分子量聚合物。其中，乳液聚合以水作为反应介质，安全可靠，既节省了成本，又改善了对环境的影响；采用合适的乳液聚合反应条件，使得过硫酸盐在室温常压下分解引发苯乙烯，醋酸乙烯酯或者(甲基)丙烯酸类甲酯聚合，聚合速度快，反应时间短且单体转化率高，所得聚合物的分子量高及分子量分布窄，分子量以及分子量分布可根据聚合反应条件调节。整个体系简单且稳定，条件温和，操作易行，适用于进行规模化应用的推广。
与现有技术相比，本发明具有以下有益的技术效果：
1、本发明方法中商品化的引发剂的使用极大地降低聚合成本；整个反应体系简单且稳定，反应条件温和，勿需控温，操作简单易行，对环境的影响较小，能耗低，适合应用于工业化大规模生产。
2、本发明方法中反应时间短且单体转化率高，所得聚合物的分子量高及分子量分布窄，且其分子量以及分子量分布可以在较宽范围内进行调控，有利于精确控制超高分子量聚合物合成工艺，从而制备能够满足于不同需求的超高分子量聚合物产品。这对于超高分子量聚合物合成工艺的理论研究同样也具有重要意义。
附图说明
图1为实施例1所得超高分子量聚苯乙烯的分子量微分分布曲线。
图2为实施例7所得超高分子量聚甲基丙烯酸甲酯的分子量微分分布曲线。
图3为实施例13所得超高分子量聚醋酸乙烯酯的分子量微分分布曲线。
具体实施方式
实施例1
将苯乙烯(5.0002g，0.0480mol)加入到溶有十二烷基硫酸钠(0.2500g，5wt％苯乙烯)、碳酸氢钠(0.1500g，3wt％苯乙烯)、过硫酸钾(0.4321g，0.0016mol)和水(20.0053g，400wt％苯乙烯)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应4小时，测得苯乙烯转化率为90.27％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝2693000g/mol，分子量分布PDI＝3.60。图1为实施例1所得超高分子量聚苯乙烯的分子量微分分布曲线。
实施例2
将苯乙烯(5.0002g，0.0480mol)加入到溶有十二烷基硫酸钠(0.3003g，6wt％苯乙烯)、碳酸氢钠(0.2001g，4wt％苯乙烯)、过硫酸铵(0.5472g，0.0024mol)和水(25.0005g，500wt％苯乙烯)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应1小时，测得苯乙烯转化率为89.77％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝3730000g/mol，分子量分布PDI＝2.07。
实施例3
将苯乙烯(5.0002g，0.0480mol)加入到溶有十二烷基硫酸钠(0.2003g，4wt％苯乙烯)、碳酸氢钠(0.1002g，2wt％苯乙烯)、过硫酸钾(0.1309g，0.0005mol)和水(10.0006g，200wt％苯乙烯)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应6小时，测得苯乙烯转化率为88.65％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝5847000g/mol，分子量分布PDI＝2.06。
实施例4
将苯乙烯(5.0001g，0.0480mol)加入到溶有十二烷基硫酸钠(0.2502g，5wt％苯乙烯)、碳酸氢钠(0.1500g，3wt％苯乙烯)、过硫酸钾(0.4322g，0.0016mol)和水(20.0007g，400wt％苯乙烯)的反应瓶中，搅拌均匀，抽真空排氧后，置于25℃下反应4小时，测得苯乙烯转化率为88.97％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝5502000g/mol，分子量分布PDI＝2.25。
实施例5
将苯乙烯(5.0001g，0.0480mol)加入到溶有十二烷基硫酸钠(0.2500g，5wt％苯乙烯)、碳酸氢钠(0.1500g，3wt％苯乙烯)、过硫酸钾(0.3242g，0.0012mol)和水(20.0053g，400wt％苯乙烯)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应6小时，测得苯乙烯转化率为92.74％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝3558000g/mol，分子量分布PDI＝4.20。
实施例6
将苯乙烯(5.0002g，0.0480mol)加入到溶有十二烷基苯磺酸钠(0.3000g，6wt％苯乙烯)、碳酸氢钠(0.1500g，3wt％苯乙烯)、过硫酸钾(0.4321g，0.0016mol)和水(20.0053g，400wt％苯乙烯)的反应瓶中，搅拌均匀，抽真空排氧后，置于25℃下反应4小时，测得苯乙烯转化率为91.54％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝4331000g/mol，分子量分布PDI＝2.40。
实施例7
将甲基丙烯酸甲酯(MMA)(5.0002g，0.0500mol)加入到溶有十二烷基硫酸钠(0.2501g，5wt％MMA)、碳酸氢钠(0.1500g，3wt％MMA)、过硫酸钾(0.4591g，0.0017mol)和水(20.0042g，400wt％MMA)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应4小时，测得MMA的转化率为95.00％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝3315000g/mol，分子量分布PDI＝2.39。图2为实施例7所得超高分子量PMMA的分子量微分分布曲线。
实施例8
将MMA(5.0002g，0.0500mol)加入到溶有十二烷基硫酸钠(0.3001g，6wt％(MMA)、碳酸氢钠(0.2000g，4wt％MMA)、过硫酸铵(0.5712g，0.0025mol)和水(25.0005g，500wt％MMA)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应1小时，测得MMA的转化率为90.97％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝3023000g/mol，分子量分布PDI＝3.13。
实施例9
将MMA(5.0002g，0.0500mol)加入到溶有十二烷基硫酸钠(0.2003g，4wt％MMA)、碳酸氢钠(0.1002g，2wt％MMA)、过硫酸钾(0.1308g，0.0005mol)和水(10.0006g，200wt％MMA)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应6小时，测 得MMA转化率为93.65％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝6082300g/mol，分子量分布PDI＝2.46。
实施例10
将MMA(5.0001g，0.0500mol)加入到溶有十二烷基硫酸钠(0.2502g，5wt％MMA)、碳酸氢钠(0.1500g，3wt％MMA)、过硫酸钾(0.4592g，0.0017mol)和水(20.0001g，400wt％MMA)的反应瓶中，搅拌均匀，抽真空排氧后，置于25℃下反应4小时，测得MMA转化率为95.05％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝5987000g/mol，分子量分布PDI＝2.76。
实施例11
将MMA(5.0001g，0.0500mol)加入到溶有十二烷基硫酸钠(0.2502g，5wt％MMA)、碳酸氢钠(0.1500g，3wt％MMA)、过硫酸钾(0.3375g，0.0013mol)和水(20.0053g，400wt％MMA)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应6小时，测得MMA转化率为98.21％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝6380000g/mol，分子量分布PDI＝2.97。
实施例12
将甲基丙烯酸正丁酯(5.0000g，0.0352mol)加入到溶有十二烷基苯磺酸钠(0.3000g，6wt％甲基丙烯酸正丁酯)、碳酸氢钠(0.1500g，3wt％甲基丙烯酸正丁酯)、过硫酸钾(0.3171g，0.0012mol)和水(20.0003g，400wt％甲基丙烯酸正丁酯)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应4小时，测得甲基丙烯酸正丁酯的转化率为94.06％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝3291000g/mol，分子量分布PDI＝2.76。
实施例13
将醋酸乙烯酯(5.0002g，0.0582mol)加入到溶有十二烷基硫酸钠(0.2502g，5wt％醋酸乙烯酯)、碳酸氢钠(0.1501g，3wt％醋酸乙烯酯)、过硫酸钾(0.6211g，0.0023mol)和水(20.0008g，400wt％醋酸乙烯酯)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应4小时，测得醋酸乙烯酯转化率为87.88％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝1022300g/mol，分子量分布PDI＝3.96。图3为实施例13所得超高分子量聚醋酸乙烯酯的分子量微分分布曲线。
实施例14
将醋酸乙烯酯(5.0000g，0.0581mol)加入到溶有十二烷基硫酸钠(0.3003g，6wt％醋酸乙烯酯)、碳酸氢钠(0.2001g，4wt％醋酸乙烯酯)、过硫酸铵(0.6612g，0.0029mol)和水(25.0009g，500wt％醋酸乙烯酯)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应1小时，测得醋酸乙烯酯转化率为90.71％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝1001300g/mol，分子量分布PDI＝2.87。
实施例15
将醋酸乙烯酯(5.0003g，0.0582mol)加入到溶有十二烷基硫酸钠(0.2003g，4wt％醋酸乙烯酯)、碳酸氢钠(0.2002g，4wt％醋酸乙烯酯)、过硫酸钾(0.1566g，0.0006mol)和水(10.0026g，200wt％醋酸乙烯酯)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应6小时，测得醋酸乙烯酯转化率为90.45％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝2744000g/mol，分子量分布PDI＝3.16。
实施例16
将醋酸乙烯酯(5.0001g，0.0581mol)加入到溶有十二烷基硫酸钠(0.2502g，5wt％醋酸乙烯酯)、碳酸氢钠(0.1500g，3wt％醋酸乙烯酯)、过硫酸钾(0.5224g，0.0019mol)和水(20.0018g，400wt％醋酸乙烯酯)的反应瓶中，搅拌均匀，抽真空排氧后，置于25℃下反应4小时，测得醋酸乙烯酯转化率为85.06％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝1313000g/mol，分子量分布PDI＝3.34。
实施例17
将醋酸乙烯酯(5.0001g，0.0581mol)加入到溶有十二烷基硫酸钠(0.2500g，5wt％醋酸乙烯酯)、碳酸氢钠(0.1500g，3wt％醋酸乙烯酯)、过硫酸钾(0.3923g，0.0015mol)和水(20.0012g，400wt％醋酸乙烯酯)的反应瓶中，搅拌均匀，抽真空排氧后，置于35℃下反应6小时，测得醋酸乙烯酯转化率为93.15％。用乙醇破乳，经三次水洗后烘干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝1776000g/mol，分子量分布PDI＝3.13。
实施例18
将醋酸乙烯酯(5.0002g，0.0582mol)加入到溶有十二烷基苯磺酸钠(0.3002g，6wt％醋酸乙烯酯)、碳酸氢钠(0.1503g，3wt％醋酸乙烯酯)、过硫酸钾(0.5235g，0.0019mol)和水(20.0006g，400wt％醋酸乙烯酯)的反应瓶中，搅拌均匀，抽真空排氧后，置于25℃下反应4小时，测得醋酸乙烯酯转化率为87.75％。用乙醇破乳，经三次水洗后烘 干，再经三次提纯后烘干，得到聚合物。采用三检测体积排除色谱仪对聚合物进行分析，结果如下：光散射重均分子量Mw.MALLS＝2352000g/mol，分子量分布PDI＝2.97。

Claims (8)

  1. 乳液聚合室温制备超高分子量聚合物的方法，包括：采用过硫酸盐为引发剂，水为介质，阴离子型表面活性剂为乳化剂，碳酸氢钠为pH调节剂，苯乙烯，醋酸乙烯酯或者(甲基)丙烯酸酯类化合物为聚合单体，通过自由基乳液聚合，在室温下乳液聚合反应得到超高分子量聚苯乙烯，其重均分子量大于100×104g/mol。
  2. 根据权利要求1所述的乳液聚合室温制备超高分子量聚合物的方法，其特征在于所述的引发剂为过硫酸钾或者过硫酸铵。
  3. 根据权利要求1所述的乳液聚合室温制备超高分子量聚合物的方法，其特征在于所述的引发剂:聚合单体的摩尔质量比为1～5:100。
  4. 根据权利要求1所述的乳液聚合室温制备超高分子量聚合物的方法，其特征在于所述的水:聚合单体的质量比为2～5:1。
  5. 根据权利要求1所述的乳液聚合室温制备超高分子量聚合物的方法，其特征在于聚合反应温度为室温，聚合反应时间为1-6小时。
  6. 根据权利要求1所述的乳液聚合室温制备超高分子量聚合物的方法，其特征在于所述的表面活性剂为十二烷基苯磺酸钠或十二烷基硫酸钠。
  7. 根据权利要求1所述的乳液聚合室温制备超高分子量聚合物的方法，其特征在于所述的表面活性剂:聚合单体的质量比为4-6％。
  8. 根据权利要求1所述的乳液聚合室温制备超高分子量聚合物的方法，其特征在于所述的pH调节剂碳酸氢钠的用量为聚合单体的2～4wt％，保证聚合体系稳定且pH值为7～8呈弱碱性。
PCT/CN2017/081177 2016-12-30 2017-04-20 乳液聚合室温制备超高分子量聚合物的方法 WO2018120526A1 (zh)

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