WO2021114484A1 - 一种包水型热膨胀发泡微球及其制备方法 - Google Patents

一种包水型热膨胀发泡微球及其制备方法 Download PDF

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WO2021114484A1
WO2021114484A1 PCT/CN2020/076802 CN2020076802W WO2021114484A1 WO 2021114484 A1 WO2021114484 A1 WO 2021114484A1 CN 2020076802 W CN2020076802 W CN 2020076802W WO 2021114484 A1 WO2021114484 A1 WO 2021114484A1
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water
microspheres
microsphere
reaction
emulsion
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French (fr)
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陈海贤
唐华东
吴超
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陈海贤
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/125—Water, e.g. hydrated salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/10—Water or water-releasing compounds

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a water-inclusive thermally expandable foamed microsphere and a preparation method thereof.
  • Thermally expandable microspheres are also called physical foamed microspheres.
  • the size of the microspheres is generally between 5-500 ⁇ m.
  • the thermally expandable microspheres usually have a core-shell structure, and the core material is a low-boiling organic solvent (such as butane, pentane, etc.).
  • the shell material is a thermoplastic polymer (such as polyacrylonitrile, etc.).
  • the volume of the microspheres increases to several to several tens of times the original volume.
  • the toughness of the microsphere shell polymer matches the expansion pressure in the shell properly, the microspheres can maintain the expanded state, and the microspheres will not shrink significantly when returned to room temperature, but the microspheres will be vaporized by organic solvents at excessively high temperatures. After bursting, the collapsed structure of the microspheres was destroyed.
  • the heat-expandable microspheres are large in volume and light in weight after being heated and expanded, which makes the density of the expanded microspheres very low. After blending and adding to other products, the weight of the product can be significantly reduced, and the softness and elasticity of the product are improved. The application prospects of vibration, sound insulation, heat insulation, insulation, packaging and other fields are very broad.
  • thermal expansion foamed microsphere technology developed rapidly in the 1970s. The Dow Chemical Company and Akzo Nobel of Sweden have done a lot of research work on thermally expanding physical foamed microspheres. Akzo Nobel and Sekisui Chemical Co., Ltd. The club has gradually become a major supplier of heat-expandable microspheres in the world.
  • the existing domestic and foreign thermal expansion foamed microsphere technology mostly uses polyacrylonitrile and its copolymers, and polyvinylidene chloride and its copolymers as the main microsphere shell materials, and the low boiling point alkane is used as the coating material.
  • the core of the microsphere low boiling point alkanes (such as butane and pentane) are volatile, flammable, and explosive hazardous chemicals.
  • Acrylonitrile and vinylidene chloride are both flammable, highly toxic, and distorted controlled hazardous chemicals. These Hazardous chemicals make heat-expandable microspheres have great safety hazards during storage, transportation, production and use.
  • the technical problem to be solved by the present invention is to provide a water-inclusive thermally expandable foamed microsphere and a preparation method thereof, without the use of flammable and explosive low-boiling alkane and highly toxic acrylonitrile, vinylidene chloride and other monomers. It has the characteristics of simple synthesis process, low product cost, and safe production, storage, transportation and use.
  • the present invention provides a water-encapsulated thermally expandable foamed microsphere.
  • the thermally expandable microsphere has a core-shell structure with polymethyl methacrylate as the outer shell and water as the core.
  • the average particle size of the water-inclusive thermally expandable foamed microspheres is 50-90 ⁇ m, the concentrated foaming temperature is 140-200°C, and the foaming expansion ratio of the microspheres is 7-20 times.
  • the present invention provides a method for preparing the above-mentioned water-inclusive thermally expandable microspheres, which includes the following steps:
  • step B) Mix the W/O emulsion obtained in step A) with a reducing agent, and react at a temperature below 0°C;
  • step C) Mix the emulsion after the reaction by adding the reducing agent in step B) and emulsify to obtain a W/O/W emulsion.
  • the system is heated to 5°C for reaction, and then heated to room temperature to stop the reaction;
  • the mass ratio of the methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, crosslinking agent, emulsifier, oxidizing agent, water, reducing agent, and the water phase in step C) is preferably 100:5 ⁇ 15: 3 ⁇ 10:0.1 ⁇ 1:1:3:5 ⁇ 15:2:800 ⁇ 1200.
  • methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, crosslinking agent, emulsifier, oxidant and water are mixed into an oil phase, and emulsified below 0°C to obtain a W/O emulsion .
  • the crosslinking agent is preferably one of 1,4-butanediol dimethacrylate and 1,3-butanediol dimethacrylate or a mixture of two in any ratio.
  • the emulsifier is preferably one of Spiral 60 or Spiral 80 or a mixture of both in any ratio.
  • the oxidizing agent is preferably one of dibenzoyl peroxide and lauroyl peroxide or a mixture of two in any ratio.
  • the present invention does not specifically limit the ratio of each component in the mixture, and can be adjusted by itself according to experimental conditions.
  • the rotation speed of the emulsification is preferably 300-600 rpm, and the emulsification time is preferably 10 min.
  • the W/O emulsion obtained above is mixed with a reducing agent and reacted below 0°C.
  • the reducing agent is preferably one of N,N-dimethyl-p-toluidine and N,N-dihydroxyethyl-p-toluidine or a mixture of two in any ratio.
  • the present invention does not specifically limit the ratio of N,N-dimethyl-p-toluidine and N,N-dihydroxyethyl-p-toluidine, and can be adjusted according to experimental conditions.
  • the conditions of the above reaction are preferably a stirring reaction, the rotation speed of the stirring is preferably 300-600 rpm, and the reaction time is preferably 0.5-1.5 h.
  • the emulsion after the reaction by adding the reducing agent is mixed with the water phase and emulsified to obtain a W/O/W emulsion.
  • the system is heated to 5°C for reaction, and then heated to room temperature to stop the reaction;
  • the rotation speed of the emulsification is preferably 100 to 300 rpm, and the reaction time is preferably 8 to 12 hours.
  • a certain amount of stabilizer such as one or more of polyvinyl alcohol and carboxymethyl cellulose, can be further dissolved in the water phase.
  • the addition ratio of the stabilizer can be based on actual conditions. It needs to be determined that the aqueous phase in step C) is preferably an aqueous solution containing 0.5% (mass ratio) of polyvinyl alcohol.
  • sodium chloride can also be added to the water phase.
  • the ratio of sodium chloride can be added according to actual needs. Without making specific restrictions.
  • the method for removing oxygen in the reactor is preferably: evacuating the reactor to a vacuum degree of less than 200 Pa, then filling it with 1 atmosphere of nitrogen, cyclically performing the above-mentioned vacuuming and nitrogen filling process several times, and finally filling the reactor 1 atmosphere of nitrogen.
  • the method for removing oxygen from the oil phase is preferably: after the oil phase is configured, nitrogen is bubbled into the oil phase to remove oxygen, and the bubbling time is determined according to actual needs, which is not specifically limited here.
  • the method for removing oxygen from the water phase is preferably: after the water phase is configured, nitrogen is introduced into the water phase for bubbling to remove oxygen, and the bubbling time is determined according to actual needs, which is not specifically limited here.
  • the composition of the oil phase is 100 parts of methyl methacrylate, 10 parts of phenyl methacrylate, 5 parts of glycidyl methacrylate, and crosslinking agent.
  • step (2) add 2 parts of reducing agent (N,N-dimethyl-p-toluidine) to the W/O emulsion and continue to stir the reaction at a rotating speed of 450 rpm at 0°C 1 hour; in step (3), 1000 parts of the water phase are added to the W/O emulsion, emulsified at 200 rpm to form a W/O/W emulsion, and then reacted at 5° C. for 10 hours, and the reaction is stopped after naturally warming to room temperature.
  • reducing agent N,N-dimethyl-p-toluidine
  • the powder is obtained by filtration, and the water-inclusive heat-expandable microspheres are obtained after drying.
  • the reaction liquid is centrifuged to collect the solid powder, and then the solid powder is washed several times with water, and finally the solid powder is dried to prepare the thermally expandable foamed microspheres.
  • the present invention provides a thermal expansion physical expansion process that adopts a normal temperature suspension polymerization process, uses polymethyl methacrylate as the main shell material, and uses low-cost, flame-retardant and fire-extinguishing water (H 2 O) as the core foaming agent.
  • Bubble microspheres avoid the use of flammable and explosive low-boiling alkanes and highly toxic monomers such as acrylonitrile and vinylidene chloride, and do not produce flammable and explosive low-boiling alkane gases.
  • the water contained in the microspheres can extinguish and suppress explosions. Therefore, the water-encapsulated thermally expandable foamed microspheres have the characteristics of simple synthesis process, low product cost, safe production, storage, transportation, use, flame retardancy and explosion suppression.
  • Figure 1 is a microscopic morphology of W/O emulsion particles prepared by the present invention
  • Figure 2 is a morphology diagram of W/O/W emulsion particles prepared by the present invention under a microscope
  • Fig. 3 is an infrared absorption spectrum diagram of the water-inclusive thermally expandable foamed microsphere particles prepared by the present invention
  • Fig. 4 is a morphology diagram of the water-inclusive thermally-expandable foamed microsphere particle product prepared by the present invention under a microscope;
  • Figure 5 is a microscopic morphology of the water-inclusive thermally expandable foamed microsphere particles prepared by the present invention after thermal expansion and foaming;
  • Figure 6 is a picture of the water-in-capable thermally-expandable foamed microspheres prepared by the present invention that does not burn when exposed to flame (the left picture is before the flame is exposed, and the right picture is after the flame is exposed);
  • Figure 7 is a picture of traditional thermally expanded foamed microspheres coated with low-boiling alkane burning violently when exposed to flame (the left picture is before the flame, and the right picture is after the flame).
  • step (1) Add 2 parts of reducing agent to the W/O emulsion in step (1), and continue to stir and react for 0.5-1.5 hours at 300-600 rpm at 0°C.
  • step (3) Add 800-1200 parts of the water phase to the W/O emulsion of step (2), emulsify at 100-300 rpm to form a W/O/W emulsion.
  • the reaction system is heated to 5°C to continue the reaction for 8-12 hours, and then naturally The reaction was stopped after warming to room temperature.
  • the reaction product is taken out for centrifugal separation, the solid powder product is collected, and then the solid powder is washed several times with water, and finally the solid powder is dried to prepare the thermally expandable foamed microspheres.
  • the microsphere products are packaged and stored, and tested and characterized.
  • Observation of emulsion particle morphology take a small amount of W/O emulsion or W/O/W emulsion and place it on the glass slide of the hot stage microscope (Jiangnan Yongxin XP-213 hot stage polarizing microscope), and select the appropriate one according to the size of the emulsion particles Combine the eyepiece and objective lens, adjust the focus, observe and record the morphology and size of W/O emulsion or W/O/W emulsion particles through computer software.
  • microspheres before and after foaming Take a small amount of microsphere powder and place it on the glass slide of the hot stage microscope. According to the particle size of the microspheres, select the appropriate combination of eyepiece and objective lens, adjust the focus, and observe and record the shape and shape of the microspheres through computer software. size.
  • Infrared spectroscopy measurement of microspheres Take a small amount of microsphere powder and place it on the Specac Attenuated Total Reflectance (ATR) accessory of Shimadzu IRAffinity-1S infrared spectrometer to measure the infrared absorption spectrum of thermally expandable microspheres.
  • Test conditions horizontal Specac ATR accessory, Zn-Se crystal; scan wave number range 500-4000cm -1 ; resolution 2cm -1 ; scan times 32 times; test at room temperature.
  • the water phase in the following examples is an aqueous solution containing 0.5% (mass ratio) of polyvinyl alcohol.
  • the oil phase composition is 100 parts of methyl methacrylate, 10 parts of phenyl methacrylate, 5 parts of glycidyl methacrylate, and 1,4-dimethacrylate.
  • step (2) In the W/O emulsion, add 2 parts of N,N-dimethyl-p-toluidine and continue to stir and react for 1 hour at 0°C at 450 pm; in step (3), add 1000 parts of water to the W/O emulsion Phase, emulsify at 200 rpm to form a W/O/W emulsion, then increase the temperature to 5° C. to continue the reaction for 10 hours, and stop the reaction after the natural temperature rises to room temperature.
  • the W/O emulsion particles formed by water in the methacrylate oil phase are spherical in shape, and the particle size of the water in the internal phase is about 5-20 ⁇ m, and the distribution is relatively uniform. .
  • reaction step (3) when a large amount of water phase is added to the W/O emulsion to form a W/O/W emulsion, the morphology of the W/O/W emulsion particles under the microscope ( ⁇ 100) is shown in Figure 2 .
  • the methacrylate oil phase particles in the W/O/W emulsion are spherically distributed in the water phase, with a particle size of about 20-100 ⁇ m, and the distribution is relatively uniform.
  • the oil phase particles also contain many Small-sized spherical water particles form a typical W/O/W emulsion structure.
  • the infrared absorption spectrum test was performed on the microsphere particle product obtained after the microsphere preparation reaction was completed, and the test result is shown in FIG. 3. It can be seen from the analysis of Fig. 3 that the broad absorption peak at 3644 cm -1 corresponds to the stretching vibration peak of the water hydroxyl group wrapped inside the microsphere particles.
  • the strong absorption peaks at 2991cm -1 and 2945cm -1 are caused by the stretching vibrations of the methyl and methylene groups of the polymethyl methacrylate polymer.
  • the absorption peak at 1145 cm -1 corresponds to the ester stretching vibration peak of polymethyl methacrylate.
  • microsphere particles there is no characteristic absorption peak of cyano group in the microsphere particles between 2100cm -1 -2300cm -1 , indicating that the prepared thermally expandable foamed microspheres do not contain polyacrylonitrile substances, and the microsphere products are mainly composed of It is composed of polymethyl methacrylate polymer material and does not need to use hazardous chemicals such as acrylonitrile and low boiling point alkanes in the preparation of microspheres.
  • the morphology of the microsphere particle product prepared by the present invention under the microscope ( ⁇ 100) is shown in FIG. 4. It can be seen from Figure 4 that the microsphere particles exhibit a spherical multi-core core-shell structure under the microscope at room temperature, and the particle size distribution is uneven. The average particle size of the statistical microspheres is 77.2 ⁇ m.
  • the multi-nuclear structure inside the microsphere particles is a small particle size spherical particle that is wrapped with water. These water particles can vaporize when the heating temperature of the microsphere exceeds its boiling point, forming an internal pressure that promotes the expansion and expansion of the microsphere particles, resulting in foaming. .
  • the morphology of the microspheres after being expanded and foamed by heating is shown in Figure 5 under the microscope ( ⁇ 100). It can be seen from Figure 5 that when the microspheres are heated, the outer polymethacrylic resin softens, and the small-sized water particles wrapped in the microspheres vaporize, which causes the microspheres to expand and increase, and the particle size increases significantly.
  • Statistics The average particle size of the foamed microspheres is 197.7 ⁇ m, and the expansion ratio of the foamed microspheres is calculated to be 17 times.
  • the prepared water-inclusive thermally expandable microsphere particles present a multi-core core-shell structure; the average particle size is 77.2 ⁇ m, the concentrated foaming temperature of the microspheres is 165°C, and the expansion ratio of the microspheres is 17 Times.
  • the thermally expandable foamed microspheres prepared by the present invention contact the flame of a lighter, since the vaporization of water needs to absorb a large amount of heat and the vaporized water vapor can isolate oxygen and play a role in preventing the combustion of the microspheres, the water-incorporated thermal expansion
  • the foamed microspheres will not burn or burst when exposed to flame (as shown in Figure 6), and the microsphere particles remain stable, indicating that the water-inclusive thermally expandable foamed microspheres have the function of flame retardancy and explosion suppression, so the thermally expandable microspheres have The synthesis process is simple, the production cost is low, and the transportation and storage are safe.
  • the oil phase composition is 100 parts of methyl methacrylate, 5 parts of phenyl methacrylate, 8 parts of glycidyl methacrylate, and 1,3-dimethacrylate.
  • step (2) In the W/O emulsion, add 2 parts of N,N-dihydroxyethyl-p-toluidine and continue to react with stirring at 600 pm at 0°C for 0.5 hours; in step (3), add 1200 parts of the W/O emulsion
  • the water phase was emulsified at 300 rpm to form a W/O/W emulsion, then the temperature was raised to 5° C. to continue the reaction for 8 hours, and the reaction was stopped after the temperature was naturally raised to room temperature.
  • the composition of the oil phase in step (1) is 100 parts of methyl methacrylate, 15 parts of phenyl methacrylate, 3 parts of glycidyl methacrylate, 0.3 parts of 1,4-butanediol dimethacrylate, general 60 emulsifier 1 part, lauroyl peroxide 3 parts, water 8 parts, the oil phase is emulsified at 0°C at 300 rpm for 10 min to obtain W/O emulsion; in step (2), 2 parts of N are added to the W/O emulsion , N-dimethyl-p-toluidine and continue to stir and react for 1.5 hours at 0°C at 300 pm; in step (3), add 800 parts of the water phase to the W/O emulsion and emulsify at 100 rpm to form W/O/ W emulsion, then the temperature was raised to 5°C to continue the reaction for 12 hours, and the reaction was stopped after the temperature was naturally raised to room temperature.
  • the oil phase composition is 100 parts of methyl methacrylate, 7 parts of phenyl methacrylate, 10 parts of glycidyl methacrylate, and 1,4-dimethacrylate.
  • step (2) In the W/O emulsion, add 2 parts of N,N-dimethyl-p-toluidine and continue to stir and react at 450 rpm at 0°C for 0.5 hours; in step (3), add 800 parts of water to the W/O emulsion.
  • step (3) emulsify at 200 rpm to form a W/O/W emulsion, then increase the temperature to 5° C. to continue the reaction for 9 hours, and stop the reaction after the temperature is naturally raised to room temperature.
  • the oil phase composition is 100 parts of methyl methacrylate, 8 parts of phenyl methacrylate, 3 parts of glycidyl methacrylate, and 1,3-dimethacrylate.
  • step (2) In the W/O emulsion, add 2 parts of N,N-dihydroxyethyl p-toluidine and continue to stir and react at 400 rpm at 0°C for 1 hour; in step (3), add 900 parts of the W/O emulsion
  • the water phase is emulsified at 250 rpm to form a W/O/W emulsion, and then the temperature is raised to 5° C. to continue the reaction for 10 hours, and the reaction is stopped after the temperature is naturally raised to room temperature.
  • the water-encapsulated thermally expandable foamed microspheres prepared by the present invention have the function of extinguishing and suppressing explosions, and are safe for transportation and storage.

Abstract

本发明提供了一种包水型热膨胀发泡微球，所述热膨胀微球为以聚甲基丙烯酸甲酯为外壳，以水作为内核的核壳结构。本发明提供了一种采用常温悬浮聚合工艺，以聚甲基丙烯甲酯为主要壳层材料，以低成本、具有阻燃灭火性能的水(H2O)为内核发泡剂的热膨胀物理发泡微球。该微球避开使用易燃、易爆的低沸点烷烃以及高毒性丙烯腈、偏氯乙烯等单体，不产生易燃、易爆的低沸点烷烃气体，微球包裹的水分具有灭火抑爆功能，因此，该包水型热膨胀发泡微球具有合成工艺简单，产品成本低廉，生产、存储、运输、使用安全、阻燃抑爆的特点。

Description

一种包水型热膨胀发泡微球及其制备方法
本申请要求于2019年12月12日提交中国专利局、申请号为201911273691.1、发明名称为“一种包水型热膨胀发泡微球及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及高分子材料技术领域，尤其涉及一种包水型热膨胀发泡微球及其制备方法。
背景技术
热膨胀微球又称物理发泡微球，微球大小一般在5-500μm之间，热膨胀微球通常具有核壳结构，其核材为低沸点的有机溶剂(如丁烷、戊烷等)，壳材为热塑性高分子聚合物(如聚丙烯腈等)。当微球被加热超过一定温度时(高于有机溶剂的沸点以及壳材的玻璃化转变温度T g)，微球外壳软化内部低沸点有机溶剂迅速汽化，产生内压力迫使微球外壳膨胀涨大，使微球体积增大到原始体积的几倍到几十倍。只要微球外壳聚合物的韧性与壳内膨胀压力匹配适当，微球可以保持膨胀状态，回到室温下微球不会发生明显的回缩，但在过高温度下微球会被有机溶剂蒸汽涨破，微球塌陷结构遭到破坏。
热膨胀微球受热膨胀后体积大而质量轻，使得膨胀微球的密度很低，共混添加到其它产品中后可显著减轻产品的重量，提升产品的柔软性与弹性，因而热膨胀微球在减震、隔音、隔热、绝缘、包装等多个领域的应用前景十分广泛。历史上热膨胀发泡微球技术在上世纪70年代发展十分迅速，陶氏化学公司与瑞典Akzo Nobel公司对热膨胀物理发泡微球做了大量的研究工作，Akzo Nobel公司与日本积水化学工业株式会社逐渐成为了全球热膨胀微球的主要供应商。国内对热膨胀发泡微球的研究起步很晚、进展缓慢。2002年吴明华等合成了基于聚丙烯腈、聚偏二氯乙烯材料的热膨胀微球用于立体印花；2007年江尻哲男等申请了用丙烯腈等单体制备热膨胀发泡微球的专利；2012年缪克存等以丙烯腈和N,N-二甲基丙烯酰胺为单体制备了热膨胀微球；2014年林宏等发明了基于聚甲基丙烯腈材料的中低温热膨胀微球的合成方法。2016年周凯军开发了低温发泡热膨胀微球的制备技术并对低温发泡热膨胀微球的发泡性能进行了研究。
现有国内外热膨胀发泡微球技术为满足微球的机械性能大多采用聚丙烯腈及其共聚物、以及聚偏氯乙烯及其共聚物作为主要的微球壳层材料，包裹低沸点烷烃作为微球的内核。但低沸点烷烃(如丁烷、戊烷)是易挥发、易燃、易爆的危化品，丙烯腈与偏氯乙烯皆属易燃、强毒性、有致畸变风险的管控危险化学品，这些危化品使得热膨胀微球在存储、运输、生产和使用过程中存在很大的安全隐患，同时在生产和使用过程中产生的废液、废渣、废气需要排放处理，对生态环境的影响也需受到严格的监管控制，从而给生产企业带来了高昂的生产成本，这些问题一定程度上阻碍了国内高质量热膨胀发泡微球技术的大规模产业化进程，使得进口的热膨胀发泡微球产品占据了国内的大部分市场。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种包水型热膨胀发泡微球及其制备方法，无需使用易燃、易爆的低沸点烷烃以及高毒性丙烯腈、偏氯乙烯等单体，具有合成工艺简单，产品成本低廉，生产、存储、运输、使用安全的特点。
为解决以上技术问题，本发明提供了一种包水型热膨胀发泡微球，所述热膨胀微球为以聚甲基丙烯酸甲酯为外壳，以水作为内核的核壳结构。
所述包水型热膨胀发泡微球的平均粒径为50～90μm，集中发泡温度为140～200℃，微球的发泡膨胀倍率为7～20倍。
本发明提供了上述包水型热膨胀微球的制备方法，包括以下步骤：
A)将甲基丙烯酸甲酯、甲基丙烯酸苯酯、甲基丙烯酸缩水甘油酯、交联剂、乳化剂、氧化剂和水混匀成油相，在0℃以下乳化，得到W/O乳液；
B)将步骤A)得到的W/O乳液与还原剂混合，并在0℃以下反应；
C)将步骤B)添加还原剂反应后的乳液与水相混合，乳化，得到W/O/W乳液，体系升温至5℃进行反应，然后升温至室温，停止反应；
D)过滤得到粉末，干燥后得到包水型热膨胀微球。
所述甲基丙烯酸甲酯、甲基丙烯酸苯酯、甲基丙烯酸缩水甘油酯、交联剂、乳化剂、氧化剂、水、还原剂、步骤C)中的水相的质量比优选为100：5～15： 3～10：0.1～1：1：3：5～15：2：800～1200。
本发明首先将甲基丙烯酸甲酯、甲基丙烯酸苯酯、甲基丙烯酸缩水甘油酯、交联剂、乳化剂、氧化剂和水混匀成油相，在0℃以下乳化，得到W/O乳液。
所述交联剂优选为二甲基丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,3-丁二醇酯的一种或两种任意比例的混合物。
所述乳化剂优选为司般60或司般80的一种或两种的任意比例混合物。
所述氧化剂优选为过氧化二苯甲酰、过氧化月桂酰的一种或两种的任意比例混合物。
当所述交联剂、乳化剂或氧化剂为混合物时，本发明对所述混合物中各组分的比例并无特殊限定，可以根据实验条件自行调整。
所述乳化的转速优选为300～600rpm，乳化的时间优选为10min。
然后将上述得到的W/O乳液与还原剂混合，并在0℃以下反应。
所述还原剂优选为N,N-二甲基对甲苯胺、N,N-二羟乙基对甲苯胺的一种或两种的任意比例混合物。
当所述还原剂为混合物时，本发明对所述N,N-二甲基对甲苯胺和N,N-二羟乙基对甲苯胺的比例并无特殊限定，可以根据实验条件自行调整。
上述反应的条件优选为搅拌反应，所述搅拌的转速优选为300～600rpm，反应的时间优选为0.5～1.5h。
然后将上述添加还原剂反应后的乳液与水相混合，乳化，得到W/O/W乳液，体系升温至5℃进行反应，然后升温至室温，停止反应；
所述乳化的转速优选为100～300rpm，所述反应的时间优选为8～12h。
为了提高悬浮聚合反应体系的稳定性，还可进一步在水相中溶解一定量的稳定剂，比如聚乙烯醇和羧甲基纤维素中的一种或多种等，稳定剂的添加比例可以根据实际需要确定，所述步骤C)中的水相优选为含聚乙烯醇0.5％(质量比)的水溶液。
同时为了降低有机单体在水相中的溶解度，减少单体在水相中发生聚合的副反应，还可在水相中添加氯化钠，同样地，添加氯化钠的比例可以根据实际需要而不做具体限定。
由于自由基聚合反应中氧气具有显著的阻聚作用，所以优选将反应体系中 的氧气除去，使聚合反应在无氧环境下顺利进行。除去反应器内氧气的方法优选为：将反应器内抽真空至真空度小于200Pa，随后充入1个大气压的氮气，循环进行上述抽真空、充氮气的过程数次，最后使反应器内充满1个大气压的氮气。油相除去氧气的方法优选为：油相配置完成后，将氮气通入油相中鼓泡除氧，鼓泡时间根据实际需要确定，在此不做具体限定。水相除去氧气的方法优选为：水相配置完成后，将氮气通入水相中鼓泡除氧，鼓泡时间根据实际需要确定，在此不做具体限定。
在本发明的一些具体实施例中，所述步骤(1)中，油相组成为甲基丙烯酸甲酯100份、甲基丙烯酸苯酯10份、甲基丙烯酸缩水甘油酯5份、交联剂(二甲基丙烯酸1,4-丁二醇酯)0.5份、司般80乳化剂1份、氧化剂(过氧化二苯甲酰)3份、水10份，油相在0℃下以450rpm的转速乳化10min得到W/O乳液；在步骤(2)中，W/O乳液中加入2份还原剂(N,N-二甲基对甲苯胺)并继续在0℃下以450rpm的转速搅拌反应1小时；在步骤(3)中，W/O乳液中加入1000份水相，以200rpm转速乳化形成W/O/W乳液，然后在5℃反应10小时，自然升温到室温后停止反应。
反应结束后，对体系进行后处理。
优选地，过滤得到粉末，干燥后得到包水型热膨胀微球。
在本发明的一些具体实施例中，反应结束后，将反应液离心分离，收集固体粉末，然后用水洗涤所述固体粉末数次，最后将固体粉末干燥，制得所述热膨胀发泡微球。
本发明提供了一种采用常温悬浮聚合工艺，以聚甲基丙烯甲酯为主要壳层材料，以低成本、具有阻燃灭火性能的水(H 2O)为内核发泡剂的热膨胀物理发泡微球。该微球避开使用易燃、易爆的低沸点烷烃以及高毒性丙烯腈、偏氯乙烯等单体，不产生易燃、易爆的低沸点烷烃气体，微球包裹的水分具有灭火抑爆功能，因此，该包水型热膨胀发泡微球具有合成工艺简单，产品成本低廉，生产、存储、运输、使用安全、阻燃抑爆的特点。
附图说明
图1是本发明制备的W/O乳液颗粒在显微镜下的形貌图；
图2是本发明制备的W/O/W乳液颗粒在显微镜下的形貌图；
图3是本发明制备的包水型热膨胀发泡微球颗粒的红外吸收光谱图；
图4是本发明制备的包水型热膨胀发泡微球颗粒产品在显微镜下的形貌图；
图5是本发明制备的包水型热膨胀发泡微球颗粒受热膨胀发泡后在显微镜下的形貌图；
图6是本发明制备的包水型热膨胀发泡微球接触火焰不燃烧图片(左图为接触火焰前，右图为接触火焰后)；
图7是传统包裹低沸点烷烃的热膨胀发泡微球接触火焰剧烈燃烧图片(左图为接触火焰前，右图为接触火焰后)。
具体实施方式
为了进一步说明本发明，下面结合实施例对本发明提供的包水型热膨胀发泡微球及其制备方法进行详细描述。
【01】以下制备实施例热膨胀发泡微球的制备反应步骤如下：
(1)取甲基丙烯酸甲酯100份、甲基丙烯酸苯酯5-15份、甲基丙烯酸缩水甘油酯3-10份、交联剂0.1-1份、乳化剂1份、氧化剂3份、水5-15份混匀成油相，在0℃下以300-600rpm的转速乳化10min得到W/O乳液；
(2)向步骤(1)中的W/O乳液加入2份还原剂，继续在0℃下以300-600rpm的转速搅拌反应0.5-1.5小时。
(3)向步骤(2)的W/O乳液加入800-1200份水相，以100-300rpm转速乳化形成W/O/W乳液，反应体系升温至5℃继续反应8～12小时，然后自然升温到室温后停止反应。
【02】热膨胀发泡微球产品后处理步骤如下：
反应结束后，取出反应产物进行离心分离，收集固体粉末产品，然后用水洗涤所述固体粉末数次，最后将固体粉末干燥，制得所述热膨胀发泡微球。将微球产品封装保存，并进行测试表征。
【03】热膨胀发泡微球产品测试表征方法如下：
乳液颗粒形貌观察：取少量W/O乳液或W/O/W乳液置于热台显微镜(江 南永新XP-213热台偏光显微镜)的载玻片上，根据乳液颗粒粒径大小，选取合适目镜物镜组合，调好焦距，通过电脑软件观察记录W/O乳液或W/O/W乳液颗粒的形貌和大小。
微球发泡前后形态观察：取少量微球粉末置于热台显微镜的载玻片上，根据微球粒径大小，选取合适目镜物镜组合，调好焦距，通过电脑软件观察记录微球的形态和大小。
微球发泡膨胀倍率测试：取少量微球粉末置于热台显微镜的载玻片上，根据微球粒径大小，选取不同目镜物镜组合，调好焦距，通过电脑软件观察记录微球在加热过程中的发泡膨胀情况，软件统计微球膨胀前后的平均粒径大小，计算微球膨胀前后的体积。根据温控仪上的温度确定微球的集中发泡温度，计算微球的发泡膨胀倍率(膨胀倍率＝集中发泡温度下微球体积/室温下微球的初始体积)。
微球的红外光谱测定：取少量微球粉末，置于岛津IRAffinity-1S红外光谱仪Specac衰减全反射(ATR)附件上测定热膨胀微球的红外吸收光谱。测试条件：水平Specac ATR附件，Zn-Se晶体；扫描波数范围500-4000cm -1；分辨率2cm -1；扫描次数32次；室温下测试。
以下实施例中的水相为含聚乙烯醇0.5％(质量比)的水溶液。
实施例1
按照以上【01】所述方法制备包水型热膨胀发泡微球。
原料配方组成以及合成工艺条件如下：步骤(1)中油相组成为甲基丙烯酸甲酯100份、甲基丙烯酸苯酯10份、甲基丙烯酸缩水甘油酯5份、二甲基丙烯酸1,4-丁二醇酯0.5份、司般80乳化剂1份、过氧化二苯甲酰3份、水10份，油相在0℃下以450rpm的转速乳化10min得到W/O乳液；步骤(2)中，W/O乳液中加入2份N,N-二甲基对甲苯胺并继续在0℃下以450pm的转速搅拌反应1小时；步骤(3)中，W/O乳液中加入1000份水相，以200rpm转速乳化形成W/O/W乳液，然后升温至5℃继续反应10小时，自然升温到室温后停止反应。
反应后处理以及包水型热膨胀发泡微球的表征测试见【02】、【03】。
步骤(1)中W/O乳液颗粒在显微镜下(×100)的形貌如图1所示。
从图1中可看出，在反应步骤(1)中，水在甲基丙烯酸酯油相中形成的W/O乳液颗粒呈球形状，内相水粒径大小约5-20μm，分布较均匀。
在反应步骤(3)中，当向W/O乳液加入大量水相乳化后形成W/O/W乳液，W/O/W乳液颗粒在显微镜下(×100)的形貌如图2所示。
从图2中可看出，W/O/W乳液中甲基丙烯酸酯油相颗粒呈球状分布在水相中，粒径大小约20-100μm，分布较均匀，油相颗粒内部还包含了许多小粒径球形水颗粒，形成了典型的W/O/W乳液结构。
对微球制备反应完成后得到的微球颗粒产品进行红外吸收光谱测试，测试结果如图3所示。通过分析图3可看出，在3644cm -1处的宽吸收峰对应于微球颗粒内部所包裹水分羟基的伸缩振动峰。2991cm -1、2945cm -1处的中强吸收峰则是由聚甲基丙烯酸甲酯聚合物的甲基以及亚甲基的伸缩振动所引起。1728cm -1处的强吸收峰是聚甲基丙烯酸甲酯羰基-C＝O的伸缩振动峰。而1145cm -1处吸收峰则对应于聚甲基丙烯酸甲酯的酯基伸缩振动峰。同时可以看出，微球颗粒在2100cm -1-2300cm -1之间没有出现氰基的特征吸收峰，说明所制得热膨胀发泡微球中不含聚丙烯腈类物质，微球产品主要由聚甲基丙烯酸甲酯聚合物材料组成，在微球制备反应中不需要使用丙烯腈以及低沸点烷烃等危化品。
本发明制备得到的微球颗粒产品在显微镜下(×100)的形貌如图4所示。从图4可看出，室温下微球颗粒在显微镜下呈现球状多核核壳结构，粒径大小分布不均匀，统计微球的平均粒径为77.2μm。在微球颗粒内部多核结构为包裹了水的小粒径球形颗粒，这些水颗粒能够在微球受热温度超过它的沸点时发生汽化，形成内压力促使微球颗粒膨胀涨大而产生发泡现象。
微球受热(165℃)膨胀发泡后的形貌在显微镜下(×100)如图5所示。从图5可看出，当微球受热后外层聚甲基丙烯酸树脂软化，包裹在微球颗粒内部小粒径水颗粒发生汽化，使微球颗粒膨胀涨大，粒径显著增大，统计微球发泡的平均粒径为197.7μm，计算得到微球的发泡膨胀倍率为17倍。
由以上表征测试结果可知：所制得包水型热膨胀微球颗粒呈现多核核壳结构；平均粒径为77.2μm，微球的集中发泡温度为165℃，微球的发泡膨胀倍率为17倍。
本发明制备的包水型热膨胀发泡微球在接触打火机火焰时，由于水的汽化需要吸收大量热量并且汽化后的水蒸气能隔绝氧气而起到阻止微球燃烧的作用，所以包水型热膨胀发泡微球遇火焰不发生燃烧，也不会爆裂(如图6所示)，微球颗粒保持稳定，表明包水型热膨胀发泡微球具有阻燃抑爆功能，因此该热膨胀微球具有合成工艺简单、生产成本低廉、运输存储安全的特点。
作为对比，传统包裹低沸点烷烃的热膨胀发泡微球在接触打火机火焰一瞬间，即刻发生爆燃，发出噼啪的爆裂声，微球颗粒飞溅，燃烧十分剧烈(如图7所示)，表明传统包裹低沸点烷烃微球产品易燃、易爆，在生产、存储、运输、使用等过程中都应特别注意安全问题。
实施例2
制备热膨胀发泡微球的具体实验步骤见【01】。原料配方组成以及合成工艺条件如下：步骤(1)中油相组成为甲基丙烯酸甲酯100份、甲基丙烯酸苯酯5份、甲基丙烯酸缩水甘油酯8份、二甲基丙烯酸1,3-丁二醇酯1份、司般80乳化剂1份、过氧化二苯甲酰3份、水5份，油相在0℃下以600rpm的转速乳化10min得到W/O乳液；步骤(2)中，W/O乳液中加入2份N,N-二羟乙基对甲苯胺并继续在0℃下以600pm的转速搅拌反应0.5小时；步骤(3)中，W/O乳液中加入1200份水相，以300rpm转速乳化形成W/O/W乳液，然后升温至5℃继续反应8小时，自然升温到室温后停止反应。
微球产品的后处理与表征测试步骤见【02】【03】。由表征测试结果可知：所制得包水型热膨胀发泡微球颗粒呈现多核核壳结构；平均粒径58.6μm；微球的集中发泡温度，188℃；微球的发泡膨胀倍率，8.7倍。
实施例3
制备热膨胀发泡微球的具体实验步骤见【01】。原料配方组成以及合成工艺条件如下：
步骤(1)中油相组成为甲基丙烯酸甲酯100份、甲基丙烯酸苯酯15份、甲基丙烯酸缩水甘油酯3份、二甲基丙烯酸1,4-丁二醇酯0.3份、司般60乳化剂1份、过氧化月桂酰3份、水8份，油相在0℃下以300rpm的转速乳化10min得到W/O乳液；步骤(2)中，W/O乳液中加入2份N,N-二甲基对甲苯胺并继续在0℃下以300pm的转速搅拌反应1.5小时；步骤(3)中，W/O乳 液中加入800份水相，以100rpm转速乳化形成W/O/W乳液，然后升温至5℃继续反应12小时，自然升温到室温后停止反应。
微球产品的后处理与表征测试步骤见【02】【03】。由表征测试结果可知：所制得包水型热膨胀发泡微球颗粒呈现多核核壳结构；平均粒径85.9μm；微球的集中发泡温度，162℃；微球的发泡膨胀倍率，12.3倍。
实施例4
制备热膨胀发泡微球的具体实验步骤见【01】。原料配方组成以及合成工艺条件如下：步骤(1)中油相组成为甲基丙烯酸甲酯100份、甲基丙烯酸苯酯7份、甲基丙烯酸缩水甘油酯10份、二甲基丙烯酸1,4-丁二醇酯0.1份、司般80乳化剂1份、过氧化二苯甲酰3份、水15份，油相在0℃下以450rpm的转速乳化10min得到W/O乳液；步骤(2)中，W/O乳液中加入2份N,N-二甲基对甲苯胺并继续在0℃下以450rpm的转速搅拌反应0.5小时；步骤(3)中，W/O乳液中加入800份水相，以200rpm转速乳化形成W/O/W乳液，然后升温至5℃继续反应9小时，自然升温到室温后停止反应。
微球产品的后处理与表征测试步骤见【02】【03】。由表征测试结果可知：所制得包水型热膨胀发泡微球颗粒呈现多核核壳结构；平均粒径75.4μm；微球的集中发泡温度，153℃；微球的发泡膨胀倍率，16.7倍。
实施例5
制备热膨胀微球的具体实验步骤见【01】。原料配方组成以及合成工艺条件如下：步骤(1)中油相组成为甲基丙烯酸甲酯100份、甲基丙烯酸苯酯8份、甲基丙烯酸缩水甘油酯3份、二甲基丙烯酸1,3-丁二醇酯0.5份、司般60乳化剂1份、过氧化二苯甲酰3份、水12份，油相在0℃下以400rpm的转速乳化10min得到W/O乳液；步骤(2)中，W/O乳液中加入2份N,N-二羟乙基对甲苯胺并继续在0℃下以400rpm的转速搅拌反应1小时；步骤(3)中，W/O乳液中加入900份水相，以250rpm转速乳化形成W/O/W乳液，然后升温至5℃继续反应10小时，自然升温到室温后停止反应。
微球产品的后处理与表征测试步骤见【02】【03】。由表征测试结果可知：所制得包水型热膨胀发泡微球颗粒呈现多核核壳结构；平均粒径70.4μm；微球的集中发泡温度，168℃；微球的发泡膨胀倍率，14.1倍。
由上述实施例可知，本发明制备的包水型热膨胀发泡微球具有灭火抑爆功能，运输存储安全。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (10)

  1. 一种包水型热膨胀发泡微球，其特征在于，所述热膨胀微球为以聚甲基丙烯酸甲酯为外壳，以水作为内核的核壳结构。
  2. 权利要求1所述的包水型热膨胀微球的制备方法，其特征在于，包括以下步骤：
    A)将甲基丙烯酸甲酯、甲基丙烯酸苯酯、甲基丙烯酸缩水甘油酯、交联剂、乳化剂、氧化剂和水混匀成油相，在0℃以下乳化，得到W/O乳液；
    B)将步骤A)得到的W/O乳液与还原剂混合，并在0℃以下反应；
    C)将步骤B)添加还原剂反应后的乳液与水相混合，乳化，得到W/O/W乳液，体系升温至5℃进行反应，然后升温至室温，停止反应；
    D)过滤得到粉末，干燥后得到包水型热膨胀微球。
  3. 根据权利要求2所述的制备方法，其特征在于，所述甲基丙烯酸甲酯、甲基丙烯酸苯酯、甲基丙烯酸缩水甘油酯、交联剂、乳化剂、氧化剂、水、还原剂、步骤C)中的水相的质量比为100：5～15：3～10：0.1～1：1：3：5～15：2：800～1200。
  4. 根据权利要求2所述的制备方法，其特征在于，所述交联剂为二甲基丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,3-丁二醇酯的一种或两种任意比例的混合物；所述乳化剂为司般60或司般80的一种或两种的任意比例混合物；所述氧化剂为过氧化二苯甲酰、过氧化月桂酰的一种或两种的任意比例混合物；所述还原剂为N,N-二甲基对甲苯胺、N,N-二羟乙基对甲苯胺的一种或两种的任意比例混合物。
  5. 根据权利要求2所述的制备方法，其特征在于，所述步骤A)中，乳化的转速为300～600rpm，乳化的时间为10min。
  6. 根据权利要求2所述的制备方法，其特征在于，所述步骤B)中，反应的条件为搅拌反应，所述搅拌的转速为300～600rpm，反应的时间为0.5～1.5h。
  7. 根据权利要求2所述的制备方法，其特征在于，所述步骤C)中，乳化的转速为100～300rpm，所述反应的时间为8～12h。
  8. 根据权利要求2所述的制备方法，其特征在于，所述步骤C)中的水 相还包括稳定剂。
  9. 根据权利要求8所述的制备方法，其特征在于，所述稳定剂为聚乙烯醇和羧甲基纤维素中的一种或多种。
  10. 根据权利要求2或8所述的制备方法，其特征在于，所述步骤C)中的水相还包括氯化钠。
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