微胶囊

resin

Preparation of microencapsulated APP

Synthesis of prepolymer: PVA (6, 9, 12, 15, or 18 g), melamine(4 g), and distilled water (200 ml) were put into a three necked bottle with a stirrer. The mixture was adjusted to pH 4–5 with acetic acid, heated to about 90C, and kept at that temperature for 1.5 hr. Then the pH was adjusted to pH 8–9 with 10% Na2CO3 solution, then 4 g melamine and 10 ml 37% formaldehyde solution were added into the system. The temperature was kept at 90C for 1 hr. The prepolymer solution was then prepared and it was ready for the next step.

Preparation of microencapsulated APP: 40 g APP was first dispersed in 100ml ethanol with a stirrer (1000 rpm, 5min). The prepolymer solution obtained from the above step was added to the mixture, and the pH of the mixture was adjusted to pH 4–5 with sulfuric acid. The resulting mixture was heated at 80C for 3 hr with stirring (300 rpm). After that, the mixture was filtered, washed with distilled water, and dried at 80C, and the VMFAPP powder was finally obtained. The D50 value of the microcapsules was about 20mm. 表征手段：TGA，SEM，LOI-UL94，FTIR，XPS，锥形量热法，吸水率的影响 CONCLUSIONS:

In this work, APP was microencapsulated with VMF resin by an in situ polymerization method.

Microencapsulated APP (VMFAPP) decreases its water absorption and increases its water resistance in PP matrix. The LOI values of the PP/ VMFAPP composites increase compared with those of the PP/APP

composites at the same loading. It has been found that APP used alone in PP does not reach the UL 94 V-0 rating and VMFAPP used alone in PP can reach V-0 at the additive level of 30%. Moreover, after water treatment at 50C for 24 hr, the composites containing VMFAPP could still maintain good flame retardant properties. These results show that microencapsulation gives better water resistance and flame retardance compared with APP in PP. The cone calorimeter results show that VMFAPP is an effective flame retardant in PP compared with APP owing to the shell which can be used as blowing and carbonization agent. It is observed from the TG and dynamic FTIR study that VMFAPP can form a more stable charred layer which can prevent the underlying polymer from further combustion in the condensed phase compared with APP in PP.

2. Synthesis of In Situ Encapsulated Intumescent Flame Retardant and the Flame Retardancy in Polypropylene

Preparation of the Encapsulated MP

PA6 resin was dissolved in excessive H3PO4 solution, and melamine was added to react with H3PO4 to produce MP (PA6/MP wt ratio: 1.0/5.7). With the consumption of H3PO4, the pH value increased and the dissolved PA6 gradually precipitated on the MP surface to obtain the encapsulated flame retardant, which was filtrated and dried before being filled into PP. Preparation of the Flame Retardant PP

MP (encapsulated), PER (MP/PER wt ratio: 232/136), and PP were mixed in a certain proportion in a high-speed mixer. Then the mixture were extruded and injectionmolded in a twin-screw extruder (Φ 30 mm, L/D: 32, model: SLJ-30, Longchang Chemical Engineering Equipment

Factory, China) and an injector (K-TEC 40 Terromatik Milacron Corporation, Germany), respectively CONCLUSION

The flame retardant MP was synthesized in the PA6/H3PO4 solution, and H3PO4 acted as the solvent of PA6,

as well as the reactant. With the consumption of H3PO4 converting into the product, the system acidity decreased and the dissolved PA6 precipitated on the surface of the obtained MP particles, thus obtaining an encapsulated flame retardant. This encapsulated MP was incorporated with PER to compose an intumescent system used in PP. As the result of the isolating effects of macromolecular charring agentPA6 on MP, the MP–PER reaction temperature enhanced from 190 to 210°C, thus successfully solving the problem with regard to the MP–PER reaction temperature overlapping the processing temperature of PP. The TG and residual char morphology of the flame retardant materials indicated that the incorporation of a small

molecular agent, PER, and a macromolecular charring agent, PA6, improved the charring properties of the materials compared with that of the intumescent system of MP with only PER. PP/encapsulated

MP/PER showed obviously better flame retardancy, as well as better mechanical properties, than those of PP/MP/PER, thus possessing higher commercial merits.

3. 王正洲，Microencapsulated ammonium polyphosphate with urea–melamine–formaldehyde shell

Preparation of microencapsulated APP UMF prepolymer synthesis

The mixture (10 g) of urea and MEL with different mass ratio (3:1, 1:1, or 1:3), 50 ml distilled water and 37% formaldehyde solution (with a mole ratio of 3:1) were put into a three-neck bottle with a stir. The mixture was adjusted to pH 8–9 with 10% Na2CO3 solution, heated to about 80C, and kept at that temperature for 1 hr. The UMF prepolymer solution was prepared. Preparation of microencapsulated APP

The mixture of APP (40 g) and ethanol (100 ml) was first stirred at 1000 rpm for 5 min at room temperature. Then the above UMF prepolymer solution was added into the mixture, and the pH of the mixture was adjusted to 4–5 with sulfuric acid. The resulting mixture was heated to 80C and incubated at the same temperature for 3 hr with stirring(300 rpm). After that, the mixture was cooled to room temperature, filtered, washed with distilled water, and dried at 105C. The MCU-APP microcapsules were finallyobtained. The D50 value of the microcapsules is about 15 mm. 表征方法：

X-ray photoelectron spectroscopy spectra，FTIR Solubility in water

Scanning electron microscopy

Content of the UMF resin measurement- inductively coupled plasma atomic emission spectrometry (Atomscan

Advantage, Thermo Jarrell Ash Corporation, USA)

UL-94 testing ，Limiting oxygen index Cone calorimeter

Water resistance of FR PP composites Thermogravimetry (TG)

4. 四川大学，Microencapsulation of decabromodiphenyl ether byin situ polymerization

2.2.1. Preparation of MF resin prepolymer

Into a three-necked flask were added 4.5 g melamine, 6.9 g 37% formaldehyde and 30 ml deionized water. The pH value was adjusted to 8.5 with 10% NaHCO3 aqueous solution. Melamine-formaldehyde prepolymer can be obtained in weak alkali conditions. The preferred pH range for this step is from about 7.0 to 9.0. It was prepared by stirring at 70 _C for 10 min until the mixture became transparent.

2.2.2. Preparation of MF microcapsules with DBDPO core

The second step was to prepare the MF microcapsule with DBDPO core. The above prepolymer was added into a three necked flask containing 40 g DBDPO powder and 300 ml deionized water and 2.5 g Tween 80. The second melamine-formaldehyde precondensate was affected by decreasing the pH value to about 4.0 and heating. The pH was lowered by adding acetic acid to the mixture and the mixture was stirred at 70 _C for 2 h with an impeller (Model JJ-1, Jintan Co. Ltd,China) the maximal power of which is 40 W, and the stirring rate is 2000 rpm. The obtained microcapsules were centrifuged and washed with deionized water until they became neutral and then were dried in an oven to constant weight at 100 _C.

Reaction between melamine and formaldehyde at 70 _C leads to formation of tri- and hexa-methylomelamine as shown in Fig. 1 [13]. Further heating and acidification condense the methylolmelamine, and precipitate the resin. Through polycondensation reaction at acidic condition between methylols or between methylol and amidogen or imine group, the prepolymer was cross-linked either by ether linkage or methylene as shown in Fig. 2 [14].

5. 王正洲，Study on Flame Retardance of Co-Microencapsulated Ammonium Polyphosphate and Dipentaerythritol in Polypropylene

Preparation of Microcapsules

Preparation of the MF prepolymer: melamine and 37% formaldehyde solution (with a mole ratio of 3:1) were put into a three-neck bottle with a stir. The mixture was adjusted to pH 8–9 with 10% Na2CO3 solution, heated to about 80C and kept at that temperature for 1 h. The MF prepolymer solution was prepared and ready for use of the microencapsulation.

Preparation of microencapsulated additives: APP, DPER, or a mixture of APP and DPER with different mass ratios of 3/1, 1/1, and 1/3 (60 g) was first dispersed in 150 ml ethanol. Then suitable amount of the MF prepolymer solution was added into the mixture, and the pH of the mixture was adjusted to 4–5 with sulfuric acid. The resulting mixture was heated at 80C for 2 h. After that, the mixture was cooled to room temperature, filtered, washed with distilled water, and dried at 105C. The microencapsulated additives were finally

obtained.

Preparation of Flame Retarded PP Composites All flame retarded PP composites were mixed in a Brabender-like apparatus at a temperature about 180C for 15 min. After the mixing, the samples were hot-pressed at about 180C under 10 MPa for 10 min into sheets of suitable thickness for analysis

6.中科大， Synergistic effect between a char forming agent (CFA) and microencapsulated ammonium polyphosphate

Synthesis of CFA15 参考专利-李斌，大分子三嗪成炭剂合成

Cyanuric chloride (1.0 mol) and water (400 ml) were fed into 1000 ml four-neck flask which was equipped with a stirrer, thermometer, dropping funnel, and reflux condenser. Ethanolamine (1.0 mol) and NaOH (1.0 mol) were mixed together in water and then the mixed solution was added dropwise into the flask, and regulated the pH to 5–8 by the speed of the dropwise. The reaction was kept at 0–5C for 3 hr. After that, a water solution of ethylenediamine (0.5 mol) and NaOH (1.0 mol) was added to the above reactive system containing intermediate I and kept at pH=5–8 by the speed of the dropwise of the alkali solution. The reaction was kept at 40–50C for 10 hr. Finally, another mixed water solution of both ethylenediamine (0.5 mol) and NaOH (1.0 mol) was added to the above system containing intermediate II and was refluxed for 10 hr. It was then cooled to room temperature, and the product was filtered and washed with acetone and water. In this way the char forming agent was obtained (Scheme 1).

The elemental analysis of CFA shows the mol ratio C/N/H=6.0/7.01/13.01, which is similar to calculated values of C/N/H=6/7/12.

7.（1115.ftp）中科大瞿保君，Preparation and characterization of microcapsulated red phosphorus

Preparation of microcapsulated red phosphorus

The following two-step method were used to prepare the MRP sample. The first step was to prepare the oligomer of melamine–formaldehyde resin. 4.5 g of melamine, 4.0 g of formaldehyde, and 40ml of distilled water were put into a three-necked flask. The pH value of their suspension was adjusted to 7.5 with sodium bicarbonate and the reaction mixture was heated to 70 ◦C. After the suspension became transparent and it was kept for 30 min at the same temperature and the solution was then cooled to room temperature in air. The oligomer solution of melamine–formaldehyde was ready for the next step.

The second step was to prepare the MRP sample. The above oligomer was added into a three-necked flask containing 40 g of red phosphorus powder and 100 ml of distilled water. The pH of the mixture was

adjusted to 4.5–5.0 with aqueous hydrochloric acid. The mixture was stirred for 30 min and heated to

70–80 ◦C for 40 min. The reaction mixture was kept at the same temperature for 1 h, and then left to cool to room temperature. The product was filtered, washed three times with distilled water, and dried to constant weight at 80 ◦C. The dull red MRP powder sample was then obtained.

8. (222)Preparation and characterization of poly(urea-formaldehyde) microcapsules filled with epoxy resins

Preparation of microcapsules

PUF microcapsules were prepared by the following two-step process:

(1) At room temperature (20–25 C), U, F and deionized water were mixed in a 250 ml three-neck round- bottomed flask connected to a reflux condenser and equipped with a mechanical stirrer. After the urea

dissolved, the pH of solution was adjusted to 8–9 with TEA and temperature was kept at 60–70 C for 1 h, then the U–F pre-polymer solution was obtained. Fig. 2(a) shows the reaction scheme of the formation of U–F in alkaline media.

(2) Under agitation, 100 ml of 2 wt% aqueous solution of SDBS was added to the as prepared pre-polymer solution, and then a slow stream of a prepared mixture of DGEBPA and BGE (weight ratio of BGE to

DGEBPA: 0.2) was added to form an oil in water (O/W) emulsion. After stirred for 20–30 min, the pH of the emulsion was adjusted slowly

3. （1.pdf）Effects of polystyrene-encapsulated magnesium hydroxide

Styrene, azobisisobutyronitrile(AIBN), toluene, and hydrochloric acid were purchased from Shanghai Chemical Reagents Company and used without further treatment, except styrene which was distilled before use. 2.2. The preparation of PS-encapsulated Mg(OH)2

PS-encapsulated Mg(OH)2 was prepared as the method developed in our laboratory [23,24]. Magnesium hydroxide (Mg(OH)2) powder was dried at 120 _C for 6 h, and then was put into high-speed mixer by heating to 70

_C with a rotation speed of 1200 rpm. Then acetone solution of 3-(methacryloxy) propyltrimethoxy silane (MPS)

with water and acetic acid was added under stirring for 20 min. The modified powder was dried at 80 _C for 12 h. Finally, modified powder, monomer (styrene), additional initiator (AIBN) were placed into the mixer with agitation fixed at 1200 rpm and heated in an oil bath at 80 _C for 45 min. The scheme of the polymer covering on the solid surface is shown in Fig. 1.

2.4. Preparation of polymer-encapsulated Mg(OH)2 composites

氢氧化镁表面的羟基和硅烷MPS中的烷氧基反应接上到硅烷的主练，其中硅烷的主链上面含有不饱和双键，当再次加入苯乙烯单体和引发剂后苯乙烯单体被引发到硅烷的主链上面，变成硅烷和聚苯乙烯的主链其中的末端带上氢氧化镁分子。整个原位反应是在高速混合机中进行的。

END-04-Synthesis of a novel intumescent flame retardant and its flame retardancy in

polypropylene

poly(ethylene glycol) (PEG) Preparation of GMFAPP

Synthesis of prepolymer: PEG (6, 9, 12, 15 or 18 g), 4 g melamine and 200 ml distilled water were put into a three neck bottle with a stir. The mixture was adjusted to pH 4–5 with acetic acid, heated to about 90 °C and kept at that temperature for 1.5 h. Then the pH was adjusted by 10% Na2CO3 solution to 8–9, 4 g melamine and 10 ml 37% formaldehyde solution were added into the system. The temperate was kept at 90 °C for 1 h. The prepolymer solution was prepared and ready for use of the microencapsulation.

Preparation of GMFAPP: 40 g APP was first dispersed in 100 ml ethanol. The prepolymer solution obtained from above step was added into the mixture, and the pH of the mixture was adjusted to 4–5 with sulfuric acid. The resulting mixture was heated at 80 °C for 2 h. After that, the mixture was cooled to room temperature, filtered, washed with distilled water to the neutrality, and dried at 105 °C, and the GMFAPP powder was finally obtained. The proposed reaction scheme of formation of GMF resin is presented in Scheme 1.

4. 四川大学刘渊，（2.pdf）Melamine cyanurate-microencapsulated rp flame retardant

2.1. Materials

RP was provided by Tianjin Chemical Reagent Company,China; PA66 pellet (EPR27N) was purchased from ShenmaCo., China; melamine and cyanurate powder products were purchased

from Sichuan Chemical Company Limited Co., China;conventional melamine formaldehyde resin modified RP wasprovided by Changzheng Chemical Reagent Co., China. 2.2. Preparation of MERP

A calculated amount of fine RP powder was pre-dispersed in water, and melamine, cyanurate and catalyst with a set weight ratio (126/129/2) were added to conduct the self-assembly reaction for 1-1.5 h at 80-90 _C. With the increase of the system viscosity, original suspending solution was changed into viscous paste, which was dried and pulverized to MERP powder.

ＭＣＡ是由三聚氰胺和三聚氰酸在水中合成的三聚氰胺-三聚氰酸盐,是一种靠氢键结合的加合物。利用三聚氰胺氰尿酸盐、三聚氰胺和氰尿酸在溶剂中溶解度的差异将三聚氰胺、氰尿酸从MC产品中除去, 得到纯净的三聚氰胺氰尿酸盐, 然后根据溶剂处理前后MC 产品的质量变化得到产品中准确的三聚氰胺氰尿酸盐含量。 相关文献：必须参考

[1] 张宏宇,杜长海. 阻燃润滑剂氰尿酸三聚氰胺盐的一步法合成研究[J]化工新型材料, 2006,(11) . 【2】阻燃润滑剂三聚氰胺氰尿酸盐的合成，河北省科学院学报

[2] 姚峰. 改性MCA的制备及其阻燃尼龙6性能研究[D]湖南工业大学, 2009 .

刘渊. 通过分子复合改性三聚氰胺氰尿酸盐及对PA6阻燃性能的研究[D]四川大学, 2004 .

2.3. Preparation of flame retarded PA66

A calculated MERP with PA66 (and GF) was pre-mixed in a mixer, and the mixture was extruded and injection molded into standard bars by a twin-screw extruder (F: 30 mm, L/D: 32, SLJ-30 Longchang Chemical Engineering Equipment Co., China) and injector (K-TEC 40 Ferromatik Milacron Corporation, Germany), respectively.

物质 燃点 吸湿% 颜色

Melamine formaldehyde(resin/RP weight ratio: 1/4) 290 1.82 Shallow red microencapsulated RPMERP (MCA/RPweight ratio: 1/4) 298 1.35 Shallow red Pure RP 251 4.21 Reddish-brown

研究反应时间和MCA粘度的关系曲线 微胶囊红磷的SEM，TEM照片

微胶囊红磷中MCA含量对燃点，吸湿率，颜色 MCA含量对LOI影响，阻燃剂含量对LOI影响 燃烧残炭树脂表面形貌

阻燃PA66力学（拉伸，冲击）垂直燃烧等级性能

与传统微胶囊阻燃剂添加量进行对比（氧指数、力学性能）

5. 四川大学刘渊，(3.pdf) Preparation of Microencapsulated Red Phosphorus

Granulated RP were first wet-ground into a fine powder with average size 2 μm, which was evenly

predispersed in water, then a calculated melamine, cyanurate, and a amount of catalyst were added to conduct the self-assembly reaction for 1.5 h of heating, and the paste product were finally dried and pulverized to a fine powder.

Preparation of Flame Retarded PA6

A weighed amount of microencapsulated RP and PA6 pellet were premixed in a high-speed mixer, then the mixture was extruded by a twin-screw extruder (_: 30 mm, L/D: 32, model: SLJ-30 Longchang Chemical Engineering Equipment Co., China). Finally, the bars for testing were prepared by injection molding (injector: K-TEC 40 Terromatik Milacron Corporation, Germany). 研究了TEM微胶囊的形态 燃点和MCA胶囊含量的曲线 吸湿率和MCA胶囊含量的曲线

氧指数与和MCA胶囊含量的曲线（分别填充7%和10%阻燃PA6）

热失重分析讨论不同PA/微胶囊MCA含量的红磷 剩余残炭的表面SEM图片

与传统的微胶囊红磷对比，氧指数，垂直燃烧，还有拉伸冲击弯曲强度比较

6. APP/MCA复合阻燃增强聚丙烯的研究-中国塑料， 1.1 主要原料

PP,700-501 30B,中国石油化工股份有限公司;APP,聚合度>1000,山东世安化工有限公司;

三聚氰胺,分析纯,北京化学试剂公司;氰尿酸,分析纯,北京化学试剂公司;偶联剂(KH-560),分析纯,北京化学试剂公司。 1.2 主要设备及仪器

双辊开炼机,LRM-S-150/3E,瑞典Labtech Engi-neering公司;破碎机,HP-150,北京环亚天元机械技术有限公司;注塑机,XTF80X1,宁波海天塑料机械有限公司;电子万能试验机,CMT6104,深圳新三思材料检测有限公司;极限氧指数仪,FTT0077,英国FTT公司;扫描电子显微镜(SEM),TESCAN VEGAⅡ,捷克TESCAN公司;热失重分析仪(TGA),Q5000IR,美国TA公司。 1.3 样品制备

MCA的合成:将三聚氰胺81.17 g,氰尿酸79.25 g,盐酸20.9 mL在水浴80℃下,搅拌条件下依 次加入,搅拌速度为270 r/min,反应150 min后,用布氏漏斗过滤沉淀,并水洗至中性,在120℃下干燥12 h,产物为白色粉末,产率96.6 %;

APP/MCA阻燃PP复合材料的制备:按APP/MCA分别为10/0,9/1,8/2,7/3,6/4,5/5,0/10(质量 比,下同)的比例进行混合,制备阻燃剂APP/MCA,将25份APP/MCA加入PP中,加入二者总质量的 0.5 %的偶联剂KH-560,混合均匀。经双辊开炼机在200℃下开炼,经破碎机破碎造粒,经注塑机注射成型样条。

耿妍，南京航空航天大学硕士论文 (1)分散包裹法

该法是先将阻燃剂磨碎、分散，然后用天然或合成高分子化合物或低分子有机物、无机物进行包裹而形成微胶囊。这种方法比较简单，应用最广。具体是将一种或几种单体在引发剂、乳化剂(有时亦可不用)存在的条件下发生共聚或缩聚反应，在阻燃剂周围包覆上一层高分子膜。其中，包裹剂本身的可燃性要小，若采用酚醛树脂、脲醛树脂或三聚氰胺-甲醛树脂则比较理想；其溶解度参数要与被阻燃的高聚物相近，以保证两者有良好的相容性；另外，包裹阻燃剂微粒的高分子膜必须能承受一定温度和压力而不致破裂。当制品一旦遇火受热时，又要求这层高分子膜立即熔融破裂，释放阻燃剂，以发挥阻燃功效。

用于包裹的成膜物质可分为两大类，一类是无机物如水玻璃(硅胶)、无机盐水溶液、氢氧化铝以及Si、Ti、Mg、Fe、Zr的氧化物等。另一类是有机高分子物，它又分天然的和合成的。前者有动物胶、阿拉伯树胶、各种蛋白质、淀粉及纤维素的衍生物(如乙基纤维素)；后者有聚乙烯醇、聚乙烯缩醛、聚氯乙稀、聚苯乙烯、聚酰胺、酚醛树脂、水溶性脲醛树脂、三聚氰胺-甲醛树脂、环氧树脂等。 3.2.1三聚氰胺-甲醛树脂(预聚体)的合成机理

三聚氰胺-甲醛树脂的结构直接影响其自身的性质和使用性能。三聚氰胺-甲醛树脂的合成大致可以分为两步[55]：第一步是由三聚氰胺和甲醛在一定反应下经羟甲基化反应得到，这是一种加成反应。但这种加成反应最后得到的往往并不是单一的加成产物的混合物。第二步是在加成后进一步发生缩聚反应，形成大分子树脂。在三聚氰胺的分子上有三个氨基(-NH2)，因此对于甲醛来说共有六个官能团。在酸或碱的催化下，每摩尔三聚氰胺可以和1~6个摩尔的甲醛反应生成相应的羟甲基三聚氰胺[56~58]。其反应速度与反应体系的pH值、温度、反应物的比例以及反应时间有关。三聚氰胺与甲醛在中性或弱

碱性介质中发生加成反应，生成结构不同但比较稳定的羟甲基三聚氰胺：

在三聚氰胺-甲醛树脂合成反应中，根据三聚氰胺与甲醛摩尔比的不同，可以分别得到三羟甲基三聚氰胺、四羟甲基三聚氰胺、五羟甲基三聚氰胺和六羟甲基三聚氰胺[59]。

低级三聚氰胺-甲醛树脂相应的性能主要取决于树脂中各类缩合产物之间的比例以及合成树脂过程中所采用的反应条件和工艺过程。如果有酸性催化剂存在，低级三聚氰胺-甲醛树脂生成以后，各羟甲基之间或羟甲基与其它氨基上的氢原子之间可进一步发生缩合反应，在各分子链内或链间由次甲基键或部分醚键放出小分子的水或甲醛，最终固化生成网状结构的体型三聚氰胺-甲醛树脂大分子。

3.1.2三聚氰胺-甲醛树脂包覆APP的反应机理

当三聚氰胺与甲醛通过缩聚反应生成羟甲基三聚氰胺即预聚体后，将APP均匀混合在其中，在酸性介质中经过加热，羟甲基三聚氰胺中的羟甲基进一步与氨基(-NH2)或羟基(-OH)发生缩合反应，生成线型或支链型结构的低级三聚氰胺甲醛树脂。在酸性条件催化下，各羟甲基之间或羟甲基与其它氨基上的氢原子可以进一步发生缩合反应，在各分子链内或链间有次甲基键或部分醚键放出小分子的水或甲醛，最终固化生成体型网状结构，将APP包裹在其中，形成核壳结构。羟甲基三聚氰胺之间的缩聚反应可按下式进行[60,61]：

3.3.2试验步骤

3.3.2.1预聚体的制备

将一定量的三聚氰胺与质量百分比浓度为37%的甲醛溶液按照摩尔比1：3混合，加入适量蒸馏水，

置于80C水浴锅中机械搅拌1小时，搅拌速度约为450r/min，并用20%的NaOH溶液调节pH值至8.5～9.0，得到三聚氰胺-甲醛树脂预聚体，固含量约为20%。 3.3.2.2 APP微胶囊化

方法一：将APP与适量蒸馏水混合，并在其中加入预聚体溶液，用10%的HCl溶液调节pH值至5.5左右，在80C水浴锅中机械搅拌2小时，搅拌速度约为400r/min；通过抽滤、烘干、研磨得到粉末。

方法二：将APP与适量甲醇和蒸馏水混合(甲醇：蒸馏水＝3：1)，并在其中加入预聚体溶液，用10%的HCl溶液调节pH值至5.5左右，在80C水浴锅中机械搅拌2小时，搅拌速度约为400r/min；通过抽滤、烘干、研磨得到粉末。

红磷经微胶囊化处理后,一是可克服红磷性能上的上述缺点,消除红磷在贮运、材料加工过程中的隐患;二是白度化,淡化红磷的颜色,拓宽红磷的应用范围;三是可改善与基材的相容性,减小对基材力学性能的影响;四是可通过对囊材的选择,实现多种阻燃剂的复配,提高阻燃抑烟效能。 包覆技术目前对微胶囊红磷的包覆技术有一定的初步研究,但尚不够系统和深入,因此,需要对包覆囊材的选择和改性、囊心处理、包覆方法、包覆方式、包覆条件、包覆工艺、包覆结果和效果(如膜层结构、膜层厚度、粒度大小与粒径分布、白度、团聚性、与基材的相容性)等进行更系统和深入的研究,以获得更优的阻燃性能。

5.蒋文俊， 微胶囊红磷的制备及在PP中的阻燃应用

微胶囊化被认为是稳定超细红磷的一种有效技术,其中,聚合物包覆RP的效果最为显著。但是聚合物包覆并不是指聚合物熔融后直接包覆,因为那样可能会引起红磷着火或包覆不完全,因此,一般都是通过原位聚合的方法实现对红磷的有效包覆。已经出现的聚合物包覆材料有脲醛树脂、环氧树脂、糠醇树脂、酚醛树脂、三聚氰胺甲醛树脂(MF)及三聚氰胺氰尿酸酯等等,相比之下, MF因其具有耐热性好、固化速度快、包覆膜的拉伸强度高以及白度化效果突出等优异性能而倍受研究工作者和商家的推崇。 3·1 RP的预处理及微胶囊化

RP的预处理: RP粉末经无锡鑫光达粉体制造有限公司采用湿法研磨技术超细粉碎,在80℃的5%硫酸溶液中浸泡5 h,过滤,水洗5次,接着用80℃的5%的氢氧化钠溶液浸泡3 h,过滤,水洗5次,以除去加工过程中可能带进的微量铁、硅等杂质, 80℃真空烘12 h,冷却储存于密封干燥广口瓶中。

RP的微胶囊化: (1) MFP的制备:称取质量比为25∶100∶1∶5的三聚氰胺、甲醛、三乙醇胺及甲醇,混合并加入适量的水,控制反应温度在80℃左右, pH值在8~8·5,反应约25 min,保存。(2)称取250 g超细RP粉末,加入到已装有500 mL水与少量分散剂OP-10的三口烧瓶中,搅拌均匀,接着将一定量的过硫酸钾KPS以及MFP先后加入到该混合溶液中,温度控制在65℃左右。KPS的用量、pH值与反应时间见表1。所得产物经去离子水洗涤5次, 80℃下干燥12 h,

过筛后装瓶。此外,样品5的制备条件与样品4类似,不同在于未加入超细RP粉末,只是MF制备。

结 论

(1)以三聚氰胺与甲醛为原料,甲醇为阻聚剂,三乙醇胺为pH值调节剂,合成出MFP。以KPS为催化剂,采用原位聚合法制备了MRP。运用DSC, SEM, FTIR及XPS等手段研究了RP微胶囊化效果。结果表明, KPS的加入有助于提高MFP的反应活性,使三聚氰胺甲醛树脂有效地包覆在红磷颗粒表面,缩短了反应时间;且此时制备的MRP包覆效果最佳,其氧化反应峰温为480℃,较红磷原料要高出很多,可使用范围变宽。 (2)采用熔融挤出法制备了多组不同配方的PP复合材料。通过LOI, UL-94, FTIR及Raman等测试手段对复合材料进行了研究。当PP∶MRP∶MH=100(phr)∶15(phr)∶50(phr)时最好。

6. 陈美琴，微胶囊红磷膨胀型阻燃剂的制备及应用

预聚物制备：向三口烧瓶中依次加入一定量甲醛、三聚氰胺及蒸馏水，搅拌分散10min后，调节pH值至8.0。加热至55~60℃，至反应液透明时，即得三聚氰胺-甲醛预聚物。

红磷的包覆：将研磨好的红磷加入三口烧瓶中，并加入适量蒸馏水，搅拌10min，加入分散剂、一定量预聚物。加热升温至50℃左右，调节pH值至5.0，继续升温至60℃，保温搅拌2h，停止搅拌，调节pH值至7.0，将产物洗净过滤后，在103℃下干燥2 h。

IFR制备：称取一定量的季戊四醇、三聚氰胺以及包覆好的红磷，在玛瑙研钵中研磨混合均匀。

具体步骤是:先往反应釜中加入水,再加入三聚氰胺和氰尿酸,同时搅拌加入剩余的水,然后闭釜搅拌反应。反应结束后,将产品反复洗涤,抽滤,直到产品的pH值小于7为止。 1.4 分析测试

(1)转化率的测定 用分析天平称取2g MCA(精确到0.0002g),加入一定量的二甲基甲酰胺中,使样品中的氰尿酸充分溶解。然后抽滤,将滤饼烘干,称所得滤饼的重量。即可计算出产品的转化率。

优级组合为A3B2C3,即温度115℃,反应体系pH值8.0~8.5,反应时间10h,该条件下获得的产品为无嗅、无味、有滑腻感的白色粉末

7. 李培培，微胶囊化改性氢氧化镁及其在低密度聚乙烯中的阻燃性能研究 三聚氰胺树脂包覆氢氧化镁

配制含氢氧化镁9%的浆料,搅拌加热至70℃, 按照甲醛和三聚氰胺物质的量比1∶2·5配制壁材。 将三聚氰胺一次性加入,再将甲醛溶液滴加至四口瓶中反应4h,将反应后的浆料经过滤、洗涤、干燥,得到微胶囊化氢氧化镁阻燃剂。分别改变温度和壁材含量重复以上实验,其中, 反应温度分别取60℃、70℃和80℃,壁材质量分数分别取10%、15%和20%。 1·3·2 脲醛树脂包覆氢氧化镁

配制含氢氧化镁9%的浆料,搅拌加热至70℃,按照甲醛和尿素物质的量比1∶1·6配制壁材。将甲醛溶液一次性加入,然后分3次加入尿素(按质量分数70%、25%和5%,分批加入),待物料在四口瓶中反应4h后经过滤、洗涤、干燥,得到微胶囊化氢氧化镁阻燃剂。

分别改变温度和壁材含量重复以上实验,其中,反应温度分别取60℃、70℃和80℃,壁材质量分数分别取10%、15%和20%。

8.郝冬梅，微胶囊化膨胀阻燃剂及膨胀阻燃聚丙烯性能的研究 微胶囊包覆APP

按配比向反应釜中投入APP和甲醛,搅拌,用碱液调节pH值至8~9,水浴加热升温,一次加入所需蜜胺,继续升温至一定温度,加入固化剂反应20~40 min,再醚化,加甲醛捕捉剂,继续搅拌30 min后出料,粗产品经过滤、干燥后,即得到IFR。 (2)PP/IFR试样制备

将PP、IFR阻燃剂和其它添加剂等混合均匀后,加入到双螺杆挤出机中进行混炼、造粒,然后依据测试内容不同制成PP/IFR质量比为90/10、80/20、75/25、70/30和65/35等各种标准要求的试样。

三聚氰胺-甲醛预聚物的制备

将40 g的三聚氰胺和80 mL甲醛（36%）及160g的去离子水依次加入装有回流冷凝管的圆底烧瓶中，加入一定量的去离子水后，用质量分数为20%NaOH溶液调整混合溶液的pH值至9.0左右，然后缓慢加热至80℃，至溶液变澄清后，继续保温15min，制得三聚氰胺-甲醛预聚物，在60℃保温待用。

三聚氰胺-甲醛预聚物的制备 将40 g三聚氰胺、100 g甲醛(36%)依次加入装有回流冷凝管的圆底烧瓶中,加入160 g去离子水后,用20% NaOH溶液调整溶液的pH至9.0左右,然后缓慢加热至80℃,至溶液变澄清后,继续保温15 min,制得三聚氰胺-甲醛预聚物。将其制成固含量分别为25%和17%的水溶液备用。

一种微胶囊化氮－磷膨胀型阻燃剂的生产方法

一种微胶囊化氮－磷膨胀型阻燃剂的生产方法，其特征在于： ①以氮－磷膨胀型阻燃剂、不饱和聚酯树脂、引发剂为原料，其中不饱和聚酯树脂的加入量为氮－磷膨胀型阻燃剂重量的１％～２０％，引发剂加入量为不饱和聚酯树脂重量的０．５％～５．０％； ②将氮－磷膨胀型阻燃剂粉碎至粒度大于４００目，并与不饱和聚酯树脂一起分散在惰性溶剂中，加入引发剂，缓慢升温至８０℃～１００℃，在此温度下保温０．５小时～５小时； ③然后降至室温，过滤，将滤饼置于烘箱内在１００℃～１１０℃下干燥２４小时，再粉碎，得微胶囊化氮－磷膨胀型阻燃剂（简称ＢＩＦＲ）。中国石化集团巴陵石油化工有限责任公司