WO2023082116A1 - 一种pmma共聚功能树脂及其制备方法 - Google Patents

一种pmma共聚功能树脂及其制备方法 Download PDF

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WO2023082116A1
WO2023082116A1 PCT/CN2021/129923 CN2021129923W WO2023082116A1 WO 2023082116 A1 WO2023082116 A1 WO 2023082116A1 CN 2021129923 W CN2021129923 W CN 2021129923W WO 2023082116 A1 WO2023082116 A1 WO 2023082116A1
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pmma
functional resin
preparation
monomers
methyl methacrylate
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PCT/CN2021/129923
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English (en)
French (fr)
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朱从山
段浩
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佳易容聚合物(上海)有限公司
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Priority to PCT/CN2021/129923 priority Critical patent/WO2023082116A1/zh
Priority to KR1020237029074A priority patent/KR20230132589A/ko
Publication of WO2023082116A1 publication Critical patent/WO2023082116A1/zh

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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
    • C08F2/18—Suspension polymerisation
    • 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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/04—Azo-compounds
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a PMMA copolymerization functional resin and a preparation method thereof, in particular to a binary copolymerization resin formed by copolymerization of methyl methacrylate monomer and glycidyl methacrylate monomer. Resin and its preparation process.
  • PMMA Polymethyl methacrylate
  • acrylic or plexiglass is a transparent material with superior properties.
  • PMMA is also a very beautiful material with good processing performance and is widely used in aviation, construction, optical instruments, medical consumables and other fields.
  • PMMA needs to be blended with other materials, such as PC, ABS, etc. for modification. Since PMMA is incompatible with most polymers, direct blending modification is difficult to improve their mechanical properties or appearance properties, so it is necessary to directly add functional copolymer resin as a compatibilizer in the polymer blending process In order to improve the overall performance of the product.
  • the polymerization based on methyl methacrylate monomer has a remarkable feature - gel effect.
  • the polymerization rate increases significantly, and the viscosity rises rapidly, so that local overheating occurs, and even "burst polymerization" occurs.
  • the gel effect occurs in the polymerization process of many monomers, but in the bulk polymerization of MMA, the gel effect is very obvious. This feature will increase the polymerization reaction rate significantly, and the automatic acceleration effect will appear, and the molecular weight distribution will be broadened. .
  • free radical polymerization production technologies include bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, etc.
  • the investment in bulk polymerization equipment is large; solution polymerization uses solvents, and the post-treatment is complicated; emulsion polymerization contains a large amount of emulsifiers, and the washing water consumption is large;
  • emulsion polymerization contains a large amount of emulsifiers, and the washing water consumption is large;
  • conventional suspension polymerization in order to control the heat release, the water ratio is very large, and the yield of a single tank of equipment is very low.
  • the purpose of the present invention is to provide a PMMA copolymerized functional resin and a preparation method thereof.
  • the P(MMA-co-GMA) copolymer resin of the present invention is prepared by a low-temperature suspension method, the production process is simple, a relatively low reaction temperature of 68-72°C is adopted, the water ratio can be controlled within 2, and the heat release of the polymerization reaction is stable. On the one hand, it can increase the single-pot yield while avoiding "explosion polymerization" in industrial production; on the other hand, the reaction temperature is controlled stably, and the molecular weight distribution of the finished product is narrow.
  • a small amount of GMA functional group is copolymerized with MMA monomer to synthesize P(MMA-co-GMA).
  • P(MMA-co-GMA) can be used in PMMA/PC alloys, and a small amount of GMA functional groups can react with carboxyl or hydroxyl groups on PC or polyester to generate PC-PMMA graft polymers in situ, increasing PMMA/PC Compatibility of PC alloys.
  • a kind of PMMA copolymerization functional resin its preparation method comprises the following steps, methyl methacrylate, glycidyl methacrylate, auxiliary agent, water are mixed, in 68 ⁇ 72 Reaction at °C for 2-5 hours, and then curing to obtain PMMA copolymerization functional resin.
  • the weight sum of methyl methacrylate and glycidyl methacrylate is 100%, wherein the weight of methyl methacrylate is 90-99.5%; the weight of water is 100%-200%; the weight of additives is 0.2%-5%.
  • the preparation method of the functional copolymer resin provided by the present invention is a low-temperature suspension polymerization process, which can be carried out under normal pressure; specifically, the following steps are as follows: taking the total weight of the monomer as 100% as a benchmark, and 90% methyl methacrylate monomer ⁇ 99.5wt%, glycidyl methacrylate monomer 0.5 ⁇ 10wt%, initiator 0.2 ⁇ 0.5wt%, molecular weight regulator 0.2 ⁇ 2wt%, dispersant 0.01 ⁇ 2wt%, and the total weight ratio of the monomer is (1 ⁇ 2) : 1 deionized water is mixed in the reaction kettle, reacted at 68-72°C for 2-5 hours under conventional stirring, and then heated to 85°C-110°C for 0.5-2 hours; then discharging, filtering, cleaning, The obtained particles are dried at 85° C. to 110° C. to obtain PMMA copolymerization functional resin.
  • the ratio of deionized water to the total weight of the monomer is 1.5:1, which is 3:1 in the prior art, which can double the production capacity of a single tank and greatly reduce water consumption.
  • the reaction temperature is 70°C.
  • the aging temperature is 95°C.
  • the auxiliary agent includes an initiator, a molecular weight regulator, and a dispersant; preferably, the initiator is an azo initiator, preferably azobisisobutyronitrile (AIBN).
  • the molecular weight regulator is a mercaptan molecular weight regulator or an ⁇ -methylstyrene dimer molecular weight regulator; wherein the mercaptan molecular weight regulator is preferably dodecyl mercaptan.
  • the dispersant is an inorganic dispersant or an organic dispersant;
  • the inorganic dispersant includes active calcium phosphate (TPC);
  • the organic dispersant includes hydroxyethyl cellulose (CMC), polyvinyl alcohol (PVA) ;
  • the amount of the organic dispersant is 0.01 to 0.5wt% of the total weight of the monomers.
  • the suspension polymerization process is generally that the monomer is dispersed into droplets under the action of shear, and is stably suspended in the aqueous solution of the dispersant, and the oil-soluble initiator is used to polymerize in the droplets.
  • the general requirements of the suspension polymerization lower than other aggregates. Concrete operations involved in the present invention, such as stirring, discharging, filtering and cleaning are all existing conventional technologies.
  • the reaction temperature of the present invention is 68-72° C., the preferred reaction temperature is 70° C., and the corresponding reaction period is 2-5 hours.
  • the reaction rate is not reduced, and the polymerization time is shortened without causing the reaction to run out of control and "implosion"; and the water consumption is small, and the molecular weight distribution of the product is narrow.
  • Fig. 1 is the infrared spectrum of embodiment 1 product.
  • Fig. 2 is the physical photograph of embodiment 1 product.
  • Fig. 3 is the physical photograph of embodiment 2 products.
  • Fig. 4 is the GPC curve of embodiment 1 product.
  • Fig. 5 is the GPC curve of embodiment 2 products.
  • Fig. 6 is the GPC curve of comparative example 2 product.
  • the present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
  • the raw materials of the present invention are all existing commercially available products, and the specific operation method and testing method are all conventional techniques, and the temperature control of the reactor is prior art, and without special instructions, all operations are carried out under conventional conditions.
  • the structural elucidation used infrared spectroscopy (IR method). Yield product quality after drying/total weight of monomers fed; with methyl methacrylate and glycidyl methacrylate as monomers, the sum of the two weights is the total weight of monomers.
  • Embodiment 1 Methyl methacrylate accounting for 99.5% of the total amount of monomers, glycidyl methacrylate accounting for 0.5% of the total amount of monomers, and all oil-soluble initiator azobis Isobutyronitrile, all the molecular weight regulator dodecyl mercaptan accounting for 1% of the total amount of monomers, all the dispersant active calcium phosphate accounting for 1.5% of the total amount of monomers, and deionized water 1.5 times the total weight of monomers were mixed in In the reaction kettle, react at 70°C for 3 hours under conventional stirring, and then heat up to 95°C for aging for 1 hour; then discharge the material in the storage tank, filter it routinely and wash it with deionized water, and then dry the obtained product at 90°C until constant Weight, to get the final product PMMA functional copolymer resin.
  • azobis Isobutyronitrile all the molecular weight regulator dodecyl mercaptan accounting for 1% of the
  • Embodiment 2 the methyl methacrylate that accounts for 90% of the total amount of monomers, the glycidyl methacrylate that accounts for 10% of the total amount of monomers, and the whole oil-soluble initiator azobis that account for 0.3% of the total amount of monomers Isobutyronitrile, all the molecular weight regulator dodecyl mercaptan accounting for 1% of the total amount of monomers, all the dispersant active calcium phosphate accounting for 1.5% of the total amount of monomers, and deionized water 1.5 times the total weight of monomers were mixed in In the reaction kettle, react at 70°C for 4 hours under conventional stirring, then raise the temperature to 95°C and mature for 1 hour; then discharge the material in the storage tank, filter it routinely and wash it with deionized water, and then dry the obtained product at 90°C until constant Weight, to get the final product functional copolymer resin.
  • Comparative example 1 Methyl methacrylate accounting for 99.5% of the total amount of monomers, glycidyl methacrylate accounting for 0.5% of the total amount of monomers, and all oil-soluble initiator azobis Isobutyronitrile, all the molecular weight regulator dodecyl mercaptan accounting for 1% of the total amount of monomers, all the dispersant active calcium phosphate accounting for 1.5% of the total amount of monomers, and deionized water 1.5 times the total weight of monomers were mixed in In the reaction kettle, react at 75°C under conventional stirring, and detonation occurs. It can be seen that, on the basis of Example 1, Comparative Example 1 only increases the reaction temperature, resulting in detonation. Similarly, on the basis of Example 2, when the reaction temperature was increased to 75° C., implosion also occurred.
  • Comparative example 2 Methyl methacrylate accounting for 99.5% of the total amount of monomers, glycidyl methacrylate accounting for 0.5% of the total amount of monomers, and all oil-soluble initiators azodicarbonate accounting for 0.3% of the total amount of monomers Isobutyronitrile, all the molecular weight regulator dodecyl mercaptan accounting for 1% of the total amount of monomers, all the dispersant active calcium phosphate accounting for 1.5% of the total amount of monomers, and deionized water 3 times the total weight of monomers were mixed in In the reaction kettle, react at 75°C for 3 hours under conventional stirring, and then heat up to 95°C for 1 hour of aging. Then the material is discharged into the storage tank, filtered and washed with deionized water, and then the obtained product is dried at 90° C. to constant weight to obtain the final functional copolymer resin.
  • the formulations and results of Examples 1-2 and Comparative Examples 1 and 2 are shown in Table 1.
  • the results in Table 1 show that under the same equipment conditions, when the reaction temperature is set at 70° C., the reaction process of the example is stable, and the molecular weight distribution of the obtained polymer is narrow.
  • Comparative Example 1-2 the reaction temperature was set at 75°C, and the reaction process was unstable, which resulted in "implosion” in Comparative Example 1.
  • Comparative Example 2 did not "implode” due to the high water ratio, the molecular weight distribution of the product was too high.
  • the reaction temperature is set at a lower temperature and the formula is limited, so that the reaction rate is controlled, and the implementation and control of the PMMA-based functional resin in the suspension polymerization system are easier.
  • Embodiment 3 Methyl methacrylate accounting for 98% of the total amount of monomers, glycidyl methacrylate accounting for 2% of the total amount of monomers, and all oil-soluble initiator azobis methacrylates accounting for 0.35% of the total amount of monomers Isobutyronitrile, all the molecular weight regulator dodecyl mercaptan accounting for 1% of the total amount of monomers, all the dispersant active calcium phosphate accounting for 1.1% of the total amount of monomers, and deionized water 1.5 times the total weight of monomers were mixed in In the reaction kettle, react at 71°C for 3 hours under conventional stirring, then raise the temperature to 95°C and mature for 1 hour; then discharge the material in the storage tank, filter it routinely and wash it with deionized water, and then dry the obtained product at 90°C until constant Weight, to get the final product PMMA functional copolymer resin.
  • Embodiment 4 the methyl methacrylate that accounts for 92% of the total amount of monomers, the glycidyl methacrylate that accounts for 8% of the total amount of monomers, and the whole oil-soluble initiator azobis that account for 0.25% of the total amount of monomers Isobutyronitrile, all the molecular weight regulator dodecyl mercaptan accounting for 1% of the total amount of monomers, all the dispersant active calcium phosphate accounting for 0.8% of the total amount of monomers, and deionized water of 1 times the total weight of monomers were mixed in In the reaction kettle, react at 69°C for 5 hours under conventional stirring, and then heat up to 95°C for aging for 1 hour; then discharge the material in the storage tank, filter it routinely and wash it with deionized water, and then dry the obtained product at 90°C until constant Weight, to get the final product functional copolymer resin.
  • Embodiment 5 Methyl methacrylate accounting for 95% of the total amount of monomers, glycidyl methacrylate accounting for 5% of the total amount of monomers, and all oil-soluble initiator azobis-acids accounting for 0.3% of the total amount of monomers Isobutyronitrile, all the molecular weight regulator dodecyl mercaptan accounting for 1.2% of the total monomer weight, all the dispersant active calcium phosphate accounting for 1.5% of the total monomer weight, and deionized water 1.5 times the total monomer weight were mixed in In the reaction kettle, react at 71°C for 3.5 hours under conventional stirring, and then heat up to 95°C for aging for 1 hour; then the material is discharged into the storage tank, filtered and cleaned with deionized water, and then the obtained product is dried at 90°C until constant Weight, to get the final product PMMA functional copolymer resin.
  • Comparative example 3 adjust the total molecular weight of methyl methacrylate accounting for 100% of the total amount of monomers, all oil-soluble initiators azobisisobutyronitrile accounting for 0.3% of the total amount of monomers, and 1% of the total amount of monomers Dodecyl mercaptan, all the dispersant active calcium phosphate accounting for 1.5% of the total amount of monomers, and deionized water 1.5 times the total weight of the monomers were mixed in the reactor, and reacted at 70°C for 3 hours under conventional stirring, and then heated up Matured at 95°C for 1 hour; then discharged into the storage tank, routinely filtered and washed with deionized water, and then dried at 90°C to constant weight to obtain the final product with a yield of 97% and a molecular weight distribution of 2.6.
  • Comparative example 4 Methyl methacrylate accounting for 85% of the total amount of monomers, glycidyl methacrylate accounting for 15% of the total amount of monomers, and all oil-soluble initiators azodicarbonate accounting for 0.3% of the total amount of monomers Isobutyronitrile, all the molecular weight regulator dodecyl mercaptan accounting for 1% of the total amount of monomers, all the dispersant active calcium phosphate accounting for 1.5% of the total amount of monomers, and deionized water 1.5 times the total weight of monomers were mixed in In the reaction kettle, react at 70°C for 3 hours under conventional stirring, and then heat up to 95°C for aging for 1 hour; then discharge the material in the storage tank, filter it routinely and wash it with deionized water, and then dry the obtained product at 90°C until constant Weight, to get the final product functional copolymer resin, the yield is 89%, the molecular weight distribution is 2.38, and when used in the downstream, the transparency performance is

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Abstract

本发明公开了一种PMMA共聚功能树脂及其制备方法，将甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、助剂、水混合，加热反应，然后熟化，得到PMMA共聚功能树脂；具体的，将引发剂、链转移剂溶解到单体中，将分散剂加入到反应介质水中，然后将它们加入到反应釜中混合，并进行悬浮聚合。经分离，清洗，烘干后得到珠状的功能共聚微球。本发明采用低温悬浮聚合工艺，改善了反应体系的稳定性，降低了凝胶效应，同时通过独特的配方工艺调整，使得反应体系聚合速率适中，大大增加了甲基丙烯酸甲酯基体功能共聚树脂的悬浮聚合的稳定性。

Description

一种PMMA共聚功能树脂及其制备方法 技术领域
本发明涉及高分子材料技术领域，尤其涉及一种PMMA共聚功能树脂及其制备方法，具体涉及一种由甲基丙烯酸甲酯单体，甲基丙烯酸缩水甘油酯单体共聚而成的二元共聚树脂及其制备工艺。
 背景技术
聚甲基丙烯酸甲酯（PMMA），又称作亚克力或有机玻璃，是一种性能优越的透明材料。PMMA还是一种非常美观的材料，具有良好的加工性能，广泛应用到航空，建筑，光学仪器，医疗耗材等领域。但是由于PMMA的抗冲击性能较差，所以在某些应用的地方，PMMA需要与其它材料，例如PC、ABS等进行共混改性。由于PMMA与大多数聚合物之间是不相容的，直接共混改性很难提高他们的机械性能或者表观性能，因此在聚合物共混过程中需要直接加入功能共聚树脂作为相容剂以提高产物的综合性能。
以甲基丙烯酸甲酯单体为主的聚合有个显著的特点--凝胶效应。MMA在聚合过程中，当单体达到约20%时，聚合速率显著提高，粘度上升很快，以致发生局部过热，甚至产生“爆聚”。凝胶效应在很多单体聚合过程中都有发生，但在MMA的本体聚合中，凝胶效应甚为明显，这一特点会使聚合反应速率明显增加，出现了自动加速效应，分子量分布变宽。
另外，自由基聚合生产技术有本体聚合、悬浮聚合、溶液聚合、乳液聚合等，其中本体聚合设备投资大；溶液聚合采用溶剂，后处理复杂；乳液聚合含有大量的乳化剂，洗涤耗水量大；常规悬浮聚合，为了控制放热，水比很大，设备单釜产率很低。
 技术问题
针对现有技术的缺陷，本发明的目的是提供一种PMMA共聚功能树脂及其制备方法。本发明的P(MMA-co-GMA)共聚树脂采用低温悬浮法制备，生产工艺简单，采用相对较低的反应温度68～72℃，水比可以控制在2以内，聚合反应放热平稳，一方面可以在提高单釜产率的同时，避免工业生产“爆聚”；另外一方面反应温度控制平稳，制成的成品分子量分布较窄。本发明将少量GMA官能团与MMA单体进行共聚，合成出P(MMA-co-GMA)。P(MMA-co-GMA)可以用到PMMA/PC合金中，少量的GMA官能团可以与PC或者聚酯上的羧基或者羟基进行反应，原位反应生成PC-PMMA接枝聚合物，增加PMMA/PC合金的相容性。
 技术解决方案
本发明的目的是通过以下技术方案实现的：一种PMMA共聚功能树脂，其制备方法包括以下步骤，将甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、助剂、水混合，于68～72℃下反应2～5小时，然后熟化，得到PMMA共聚功能树脂。
本发明中，以甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯为单体，以甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯的重量和为100%，其中甲基丙烯酸甲酯的重量为90～99.5%；水的重量为100%～200%；助剂的重量为0.2%～5%。
本发发明提供的功能性共聚树脂的制备方法为低温悬浮聚合工艺，在常压即可进行；具体为以下步骤：以单体总重量为100%做基准，将甲基丙烯酸甲酯单体90～99.5wt%、甲基丙烯酸缩水甘油酯单体0.5～10wt%、引发剂0.2～0.5wt%、分子量调节剂0.2～2wt%、分散剂0.01～2wt%、与单体总重量比为(1～2)∶1的去离子水混合于反应釜中，常规搅拌下68～72℃反应2～5小时，然后升温到85℃～110℃熟化0.5～2小时；然后出料、过滤、清洗，将所得粒子于85℃～110℃下干燥，得到PMMA共聚功能树脂。
优选地，去离子水与单体总重量的比为1.5:1，比现有技术中3:1，可以提高1倍的单釜产能，且极大的降低了水消耗。
优选地，所述反应的温度为70℃。
优选地，所述熟化的温度为95℃。
本发明中，助剂包括引发剂、分子量调节剂、分散剂；优选地，所述引发剂为偶氮类引发剂，优选为偶氮二异丁腈（AIBN）。优选地，所述分子量调节剂为硫醇类分子量调节剂或者α-甲基苯乙烯二聚体分子量调节剂；其中硫醇类分子量调节剂优选十二烷基硫醇。优选地，所述分散剂为无机分散剂或者有机分散剂；所述无机分散剂包括活性磷酸钙 (TPC)；所述有机分散剂包括羟乙基纤维素(CMC) 、聚乙烯醇(PVA)；优选的，有机分散剂的用量为单体总重量的0.01～0.5wt%。
悬浮聚合过程一般是单体在剪切作用下分散成液滴，稳定悬浮在分散剂水溶液中，采用油溶性引发剂，在液滴中进行聚合，在对反应器的要求方面，悬浮聚合一般要求较其他聚合低。本发明涉及的具体操作，比如搅拌、出料、过滤、清洗都为现有常规技术。
本发明反应温度为68～72℃，优选的反应温度在70℃，对应反应周期为2～5小时。可以在控制反应速率的情况下，不降低反应速率，缩短聚合时间又不至于反应失控“爆聚”；并且水用量少，产品分子量分布窄。
 附图说明
图1为实施例1产品的红外光谱。
图2为实施例1产品的实物照片。
图3为实施例2产品的实物照片。
图4为实施例1产品的GPC曲线。
图5为实施例2产品的GPC曲线。
图6为对比例2产品的GPC曲线。
 本发明的实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。本发明的原料都是现有市售产品，具体操作方法以及测试方法都是常规技术，反应釜温控为现有技术，没有特殊说明下，所有操作都在常规环境下进行。下面实施例中的百分数为以甲基丙烯酸甲酯单体+甲基丙烯酸缩水甘油酯单体＝100%为基准。结构解析使用红外光谱法(IR 法)。产率=干燥后产物质量/投料单体总重量；以甲基丙烯酸甲酯和甲基丙烯酸缩水甘油酯为单体，两者重量和为单体总重量。
实施例1：将占单体总量99.5%的甲基丙烯酸甲酯、占单体总量0.5%的甲基丙烯酸缩水甘油酯、占单体总量0.3%的全部油溶性引发剂偶氮二异丁腈、占单体总量1%的全部分子量调节剂十二烷基硫醇、占单体总量1.5%的全部分散剂活性磷酸钙、单体总重量1.5倍的去离子水混合于反应釜中，常规搅拌下70℃反应3小时，再升温至95℃熟化1小时；然后出料于储料槽中，常规过滤并用去离子水清洗，然后将所得产物于90℃下干燥至恒重，得最终产品PMMA功能共聚树脂。
图1为实施例1的产品PMMA共聚GMA功能树脂的红外光谱，在1620～1680cm -1区域没有特征峰出现，说明聚合产物中无C＝C双键，这一方面证明聚合反应是完全的，另一方面证明了GMA也是以双键参与反应的，1720cm -1证明酯基的存在，在1269cm -1(环氧基团的对称振动吸收峰)、911cm -1 和 840cm -1(环氧基团的不对称振动的两个吸收峰) 处的吸收峰，表明了环氧基团的存在。
实施例2：将占单体总量90%的甲基丙烯酸甲酯、占单体总量10%的甲基丙烯酸缩水甘油酯、占单体总量0.3%的全部油溶性引发剂偶氮二异丁腈、占单体总量1%的全部分子量调节剂十二烷基硫醇、占单体总量1.5%的全部分散剂活性磷酸钙、单体总重量1.5倍的去离子水混合于反应釜中，常规搅拌下70℃反应4小时，再升温至95℃熟化1小时；然后出料于储料槽中，常规过滤并用去离子水清洗，然后将所得产物于90℃下干燥至恒重，得最终产品功能共聚树脂。
对比例1：将占单体总量99.5%的甲基丙烯酸甲酯、占单体总量0.5%的甲基丙烯酸缩水甘油酯、占单体总量0.3%的全部油溶性引发剂偶氮二异丁腈、占单体总量1%的全部分子量调节剂十二烷基硫醇、占单体总量1.5%的全部分散剂活性磷酸钙、单体总重量1.5倍的去离子水混合于反应釜中，常规搅拌下75℃反应，发生爆聚。可以看出，在实施例1的基础上，对比例1仅仅是反应温度提升，出现爆聚。同样的，在实施例2的基础上，反应温度提升至75℃，也出现爆聚。
对比例2：将占单体总量99.5%的甲基丙烯酸甲酯、占单体总量0.5%的甲基丙烯酸缩水甘油酯、占单体总量0.3%的全部油溶性引发剂偶氮二异丁腈、占单体总量1%的全部分子量调节剂十二烷基硫醇、占单体总量1.5%的全部分散剂活性磷酸钙、单体总重量3倍的去离子水混合于反应釜中，常规搅拌下75℃反应3小时，再升温至95℃熟化1小时。然后出料于储料槽中，常规过滤并用去离子水清洗，然后将所得产物于90℃下干燥至恒重，得最终产品功能共聚树脂。
图2、图3分别为实施例1、实施例2产品的实物照片；图4、图5、图6分别为实施例1、实施例2、对比例2的产品GPC曲线。实施例1～2和对比例1、2的配方及结果如表1所示。表1结果表明，在同样的设备条件下，反应温度设定在70℃时候， 实施例的反应过程中稳定，所得的聚合物分子量分布窄。对比例1-2，反应温度设定在75℃，反应过程不稳定，结果导致对比例1“爆聚”，对比例2虽然由于很高的水比没有“爆聚”，但是产品分子量分布太宽，且单釜产率太低，耗水量大。本发明反应温度设置在较低的温度和限定配方，控制了反应速率，使PMMA基功能树脂在悬浮聚合体系实施更容易，更容易控制。
Figure 502327dest_path_image001
。
实施例3：将占单体总量98%的甲基丙烯酸甲酯、占单体总量2%的甲基丙烯酸缩水甘油酯、占单体总量0.35%的全部油溶性引发剂偶氮二异丁腈、占单体总量1%的全部分子量调节剂十二烷基硫醇、占单体总量1.1%的全部分散剂活性磷酸钙、单体总重量1.5倍的去离子水混合于反应釜中，常规搅拌下71℃反应3小时，再升温至95℃熟化1小时；然后出料于储料槽中，常规过滤并用去离子水清洗，然后将所得产物于90℃下干燥至恒重，得最终产品PMMA功能共聚树脂。
实施例4：将占单体总量92%的甲基丙烯酸甲酯、占单体总量8%的甲基丙烯酸缩水甘油酯、占单体总量0.25%的全部油溶性引发剂偶氮二异丁腈、占单体总量1%的全部分子量调节剂十二烷基硫醇、占单体总量0.8%的全部分散剂活性磷酸钙、单体总重量1倍的去离子水混合于反应釜中，常规搅拌下69℃反应5小时，再升温至95℃熟化1小时；然后出料于储料槽中，常规过滤并用去离子水清洗，然后将所得产物于90℃下干燥至恒重，得最终产品功能共聚树脂。
实施例5：将占单体总量95%的甲基丙烯酸甲酯、占单体总量5%的甲基丙烯酸缩水甘油酯、占单体总量0.3%的全部油溶性引发剂偶氮二异丁腈、占单体总量1.2%的全部分子量调节剂十二烷基硫醇、占单体总量1.5%的全部分散剂活性磷酸钙、单体总重量1.5倍的去离子水混合于反应釜中，常规搅拌下71℃反应3.5小时，再升温至95℃熟化1小时；然后出料于储料槽中，常规过滤并用去离子水清洗，然后将所得产物于90℃下干燥至恒重，得最终产品PMMA功能共聚树脂。
实施例3至实施例5的产品收率都超过97%，分子量分布在2.1～2.2。
对比例3：将占单体总量100%的甲基丙烯酸甲酯、占单体总量0.3%的全部油溶性引发剂偶氮二异丁腈、占单体总量1%的全部分子量调节剂十二烷基硫醇、占单体总量1.5%的全部分散剂活性磷酸钙、单体总重量1.5倍的去离子水混合于反应釜中，常规搅拌下70℃反应3小时，再升温至95℃熟化1小时；然后出料于储料槽中，常规过滤并用去离子水清洗，然后将所得产物于90℃下干燥至恒重，得最终产品，收率97%，分子量分布2.6。
对比例4：将占单体总量85%的甲基丙烯酸甲酯、占单体总量15%的甲基丙烯酸缩水甘油酯、占单体总量0.3%的全部油溶性引发剂偶氮二异丁腈、占单体总量1%的全部分子量调节剂十二烷基硫醇、占单体总量1.5%的全部分散剂活性磷酸钙、单体总重量1.5倍的去离子水混合于反应釜中，常规搅拌下70℃反应3小时，再升温至95℃熟化1小时；然后出料于储料槽中，常规过滤并用去离子水清洗，然后将所得产物于90℃下干燥至恒重，得最终产品功能共聚树脂，收率89%，分子量分布2.38，且在下游应用的时候，透明性能略差。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。

Claims (10)

  1. 一种PMMA共聚功能树脂，其特征在于，所述PMMA共聚功能树脂的制备方法包括以下步骤，将甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、助剂、水混合，于68～72℃下反应2～5小时，然后熟化，得到PMMA共聚功能树脂。
  2. 根据权利要求1所述PMMA共聚功能树脂，其特征在于，以甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯的重量和为100%，其中甲基丙烯酸甲酯的重量为90～99.5%；水的重量为100%～200%；助剂的重量为0.2%～5%。
  3. 根据权利要求1所述PMMA共聚功能树脂，其特征在于，助剂包括引发剂、分子量调节剂、分散剂；以甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯的重量和为100%，其中引发剂的重量为0.2～0.5wt%，分子量调节剂的重量为0.2～2wt%，分散剂的重量为0.01～2wt%。
  4. 根据权利要求3所述PMMA共聚功能树脂，其特征在于，所述引发剂为偶氮类引发剂；所述分子量调节剂为硫醇类分子量调节剂或者α-甲基苯乙烯二聚体分子量调节剂；所述分散剂为无机分散剂或者有机分散剂。
  5. 权利要求1所述PMMA共聚功能树脂的制备方法，其特征在于，包括以下步骤，将甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、助剂、水混合，于68～72℃下反应2～5小时，然后熟化，得到PMMA共聚功能树脂。
  6. 根据权利要求5所述PMMA共聚功能树脂的制备方法，其特征在于，反应的温度为70℃；熟化的温度为95℃，时间为0.5～2小时。
  7. 根据权利要求5所述PMMA共聚功能树脂的制备方法，其特征在于，熟化结束后，出料、过滤、清洗、干燥，得到PMMA共聚功能树脂。
  8. 根据权利要求5所述PMMA共聚功能树脂的制备方法，其特征在于，反应在常压下进行。
  9. 权利要求1所述PMMA共聚功能树脂在制备合金塑料中的应用。
  10. 权利要求1所述PMMA共聚功能树脂在制备透明塑料中的应用。
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