醇溶性酚醛树脂设计说明书
酚醛树脂产品技术说明书
引燃温度(℃)： 420(粉云)爆炸上限%(V/V)： 无资料
爆炸下限%(V/V)：无资料
别 名
----
危规编号
32197
分 子 式
----
危险性类别
第3.2类中闪点易燃液体
危险特性
易燃，遇明火、高热能燃烧。受高热分解放出有毒的气体。粉体与空气可形成爆炸性混合物,当达到一定浓度时,遇火星会发生爆炸
急性毒性
LD50：无资料
LC50：无资料
禁 忌
强氧化剂
有害燃烧产物
一氧化碳、二氧化碳
泄漏应急处理
迅速撤离泄漏污染区人员至安全区，并进行隔离，严格限制出入。切断火源。建议应急处理人员戴自给正压式呼吸器，穿防静电工作服。若是液体。尽可能切断泄漏源。防止流入下水道、排洪沟等限制性空间。小量泄漏：用干燥的砂土或类似物质吸收。大量泄漏：构筑围堤或挖坑收容。用泡沫覆盖，降低蒸气灾害。用防爆泵转移至槽车或专用收集器内，回收或运至废物处理场所处置。若是固体，收集于干燥、洁净、有盖的容器中。然后在专用废弃场所深层掩埋。若大量泄漏，收集回收或运至废物处理场所处置
健康危害
接触加工或使用本品过程中所形成的粉尘，可引起头痛、嗜睡、周身无力、呼吸道粘膜刺激症状、喘息性支气管炎和皮肤病，还可发生肾脏损害。空气环境分析发现苯酚、甲醛和氨。在缩聚过程中，可发生甲醛、酚、一氧化碳中毒
灭火方法
喷水冷却容器，可能的话将容器从火场移至空旷处。灭火剂：雾状水、泡沫、二氧化碳、干粉、砂土
酚醛树脂产品技术说明书
理 化
指 标
外观与性状： 根据化学结构和分子量大小的不同, 有液体或固体之分。
熔点(℃)： 无资料沸点(℃)： 无资料
第三章酚醛树脂
其催化性质温和，用量一般为0.5％一3％左右，也可制得热
固性树脂。可在树脂脱水过程中除去，故树脂的电性能较好。
氢氧化钡：
用量一般为1％一1.5％，反应结束后通入CO2，使催化剂与 CO2反应生成BaCO3沉淀，过滤后可除去残留物，因此，也 可得电性能较好的树脂；
第 三
章 有机胺： 如三乙胺作催化剂的，所得树脂相对分子质量小且电性
树
速度快5倍以上，因此主要产物是二酚基甲烷：
脂
OH +C H 2O
OH H 2 OH C + H 2O
当甲醛和苯酚的摩尔数比为0.8比1时，所得酚醛树脂
大分子链中酚环大约有5个，数均相对分子质量 Mn＝500左右。
生成的二酚基甲烷与甲醛反应的速度大致与苯酚和甲醛的
第 三
反应速度相同，因此缩聚产物的分子链可进一步增长，并通过
酚 醛
可成为固体树脂。
树
脂
注意： 上述各种树脂的分子中都含有可以进一步缩聚的羟
甲基。因为加成反应速率比缩聚反应速率大得多， 所以只要控制好反应条件，就可得到低相对分子质量 的多元酚醇的缩聚物。
3. 强碱催化下的反应历程：
（推动力－酚负离子的亲核性）
第
三
1）甲醛在水溶液中的平衡反应
章
H2 O OH C C H 2 δ H + O δ + - H 2 O
脂
5.反应介质PH值的影响
有人认为反应介质的pH值对产品性质的影响比催化剂性质的
影响还大。研究指出：将37％甲醛水溶液与等量的苯酚混合反
应，当介质pH＝时，加热沸腾数日也无反应，若加入酸使PH＜
3.0或加入碱使pH＞3.1时，则缩聚反应就会立即发生，故称pH
酚醛树脂（MSDS）安全技术说明书
理
包装标志：易燃液体
UN 编号：1866
包装分类：Ⅱ
贮 包装方法：铁桶。
储运条件：储存于阴凉通风的仓间内。远离火种、热源，避免阳光直射。与氧化剂隔离储运。 运 搬运时要轻装轻卸，防止容器渗漏。储存期不宜过久，防止变质。
酚醛树脂
标 中文名：酚醛树脂 分子式：
识 危规号： 32197
英文名：Phenolic resin
分子量：
CAS 号：
理 性状： 红棕色透明液体。为热固性酚醛树脂，用醇类作溶剂。
溶解性：
化
熔点（℃）：
沸点（℃）：
相对密度（水＝1）：
性 临界温度（℃）：
临界压力（MPa）：
相对密度（空气＝1）：
质 燃烧热（KJ/mol）：
1211 灭火剂、砂土灭火。用水保持火场中容器冷却。
毒 接触限值：
性
对 人 体 危 害
急 应使吸入蒸气的患者脱离污染区，安置休息并保暖。眼睛受刺激用水冲洗，对溅入眼内的严重
救 患者须就医诊治。皮肤接触用溶剂擦清，再用肥皂彻底洗涤。误服立即漱口，送医院救治。
防
护
泄 首先切断一切火源，戴好防毒面具与手套。用砂土混合油灰刀刮起，倒至空旷地方掩埋或焚烧 漏 炉中烧掉。 处
最小点火能（mJ）：
饱和蒸汽（KPa）：
燃烧性： 易燃
燃烧分解产物：
燃 闪点（℃）： ≤23℃
烧 爆炸下限（％）：
爆 炸
爆炸上限（％）：
危 引燃温度（℃）：
聚合危害： 稳定性： 最大爆炸压力（MPa）： 禁忌物：
险 危险特性：遇高热、明火、氧化剂有引燃危险。高浓度时有麻醉作用。
性 灭火方法：消防人员必须穿戴防毒面具与全身防护服。用抗溶性泡沫、雾状水、二氧化碳、干粉
【酚醛树脂】MSDS安全技术说明书(精编版)
酚醛树脂安全技术说明书标识中文名：酚醛树脂英文名：Phenolicresin分子式：分子量：CAS号：9003-35-4 危规号：32197理化性质性状：红棕色透明液体。
为热固性酚醛树脂，用醇类作溶剂。
溶解性：熔点（℃）：无资料沸点（℃）：无资料相对密度（水＝1）：无资料临界温度（℃）：无资料临界压力（MPa）：无资料相对密度（空气＝1）：无资料燃烧热（KJ/mol）：无资料最小点火能（mJ）：无资料饱和蒸汽压（KPa）：无资料燃烧爆炸危险性燃烧性：易燃燃烧分解产物：一氧化碳、二氧化碳。
闪点（℃）：无资料聚合危害：不能出现爆炸下限（％）：无资料稳定性：稳定爆炸上限（％）：无资料最大爆炸压力（MPa）：引燃温度（℃）：禁忌物：强氧化剂。
危险特性：易燃，遇明火、高热能燃烧。
受高热分解放出有毒的气体。
粉体与空气可形成爆炸性混合物,当达到一定浓度时,遇火星会发生爆炸。
灭火方法：喷水冷却容器，可能的话将容器从火场移至空旷处。
灭火剂：雾状水、泡沫、二氧化碳、干粉、砂土。
毒性接触限值：中国MAC(mg/m3)：6(酚基塑料),0.1(按苯酚计),0.05(按甲醛计) 前苏联MAC(mg/m3)：0.1(按苯酚计),0.05(按甲醛计)急性毒性：LD50：无资料 LC50：无资料健康危害侵入途径：吸入食入健康危害：接触加工或使用本品过程中所形成的粉尘，可引起头痛、嗜睡、周身无力、呼吸道粘膜刺激症状、喘息性支气管炎和皮肤病，还可发生肾脏损害。
空气环境分析发现苯酚、甲醛和氨。
在缩聚过程中，可发生甲醛、酚、一氧化碳中毒。
急救皮肤接触：脱去污染的衣着，用肥皂水和清水彻底冲洗皮肤。
眼睛接触：提起眼睑，用流动清水或生理盐水冲洗。
就医。
吸入：迅速脱离现场至空气新鲜处。
保持呼吸道通畅。
如呼吸困难，给输氧。
如呼吸停止，立即进行人工呼吸。
就医。
食入：饮足量温水，催吐。
就医。
防护工程控制：密闭操作。
提供良好的自然通风条件。
个体防护：一般不需要特殊防护，高浓度接触时可佩戴自吸过滤式防尘口罩；必要时，戴化学安全防护眼镜；穿防静电工作服；戴一般作业防护手套；工作现场严禁吸烟。
醇溶性酚醛树脂工艺设计
8 举例——醇溶性酚醛树脂工艺设计1．题目：醇溶性酚醛树脂工艺设计2．生产要求：1000t/a 每年工作300天，每天工作8小时。
3．原料：表8-1 生产醇溶性酚醛树脂的原料名称含量苯酚98%(质量分数，含杂质)甲醛37%(质量分数)氨水〔催化剂〕20%(质量分数)乙醇95%(V/V)4．配料比：苯酚∶甲醛〔37%〕=1∶1.2〔摩尔比〕5．产品质量：固含量：60%水：﹤8%游离苯酚：﹤5%〔存于树脂中〕氨水的用量：5%〔为纯苯酚质量的5%〕生产流程或生产方案1．生产流程方案，使其在碱性环境下缩合成树脂，经真空脱水后制得成品。
本工艺利用真空吸入原料苯酚,室内供热系统提供水蒸汽作为热源。
其他原料来自高位槽并可参加适量乙醇用以调节粘度防止结垢。
2．生产流程简述苯酚先在镀锌铁桶内加热熔化，升温至60℃，用真空将苯酚吸入反响釜内，通入蒸汽保温；将37%的甲醛水溶液以苯酚∶甲醛=1∶1.2〔mol〕的比例缓慢参加反响釜内，开启电动搅拌系统开始搅拌，再参加浓度为20%的氨水催化剂，加热升温至70℃,由于反响放热，温度会自动上升。
当温度升至78℃时，即用循环冷却水调节，使反响温度缓缓上升并保温在85℃～95℃间〔不超过95℃〕。
使反响釜保温反响1小时后，终止反响。
用循环冷却水调节到75℃，进行真空脱水2.5～3小时，再冷却到50℃参加乙醇调稀，最后自然冷却到40℃出料，即为产品。
3．工艺流程简图和参数流程简图如图图8-1所示：工艺参数如表8-2所示：表8-2 醇溶性酚醛树脂的生产工艺参数合成阶段脱水阶段调稀阶段原料20℃-70℃75℃〔2.5～3h〕冷却到50℃冷却水—20℃升到30℃—水蒸汽—75℃降到40℃—整个生产周期如图8-2所示：图8-2醇溶性酚醛树脂的生产周期物料衡算苯酚的官能度f=3，甲醛的官能度f=2，苯酚和甲醛以摩尔比为1∶1.2的比例混合反响，那么苯酚过量。
两基团数不相等，那么平均官能度〔以甲醛的量来计算〕：2 1.222.1821 1.2f -⨯⨯==+故反响程度：2121(1)(1)0.840(12)2.1821222,0.9172.182n nn p x f x x f-----=-=⨯-==→∞===c 取当时临界反应程度p即有 p < p c因参加的原料苯酚和甲醛都在产品所测的固含量内，那么有 m 苯酚+m 甲醛=m 树脂+m 游离酚+m 缩合水 即有 m 苯酚+m 甲醛-m 缩合水＝m 树脂+m 游离氛以1mol 苯酚和1.2mol 甲醛反响为基准，苯酚上有两个氢原子参加反响那么生成1个水分子，故固化时生成的缩合水的量为：1.220.9171.10042⨯⨯=mol 那么有 94130 1.2 1.100418110.1928g ⨯+⨯-⨯= 因为产品的固含量为60％，所以所得产品的质量为：0110.1928183.65560%m g ==由任务书有每小时的产品质量为：10001000416.6673008m kg ⨯==⨯产并以此作为计算基准。
MSDS危险化学品安全技术说明书——32197--酚醛树脂
危险特性：易燃，遇明火、高热能燃烧。受高热分解放出有毒的气体。粉体与空气可 形成爆炸性混合物, 当达到一定浓度时, 遇火星会发生爆炸。
有害燃烧产物：一氧化碳。 灭火方法：用雾状水、泡沫、二氧化碳、干粉、砂土灭火。 灭火注意事项及措施：消防人员必须佩戴空气呼吸器、穿全身防火防毒服，在上风
向灭火。喷水冷却容器，可能的话将容器从火场移至空旷处。处在火场中 的容器若已变色或从安全泄压装置中产生声音，必须马上撤离。
第六部分 泄漏应急处理
应急行动：消除所有点火源。根据液体流动和蒸气扩散的影响区域划定警戒区，无关 人员从侧风、上风向撤离至安全区。建议应急处理人员戴正压自给式呼吸 器，穿一般作业工作服。穿上适当的防护服前严禁接触破裂的容器和泄漏 物。尽可能切断泄漏源。用塑料布覆盖泄漏物，减少飞散。勿使水进入包 装容器内。用洁净的铲子收集泄漏物，置于干净、干燥、盖子较松的容器 中，将容器移离泄漏区。
酚醛树脂
第2
页
储存注意事项：储存于阴凉、通风的库房。库温不宜超过 37℃，远离火种、热源。 保持容器密封。应与氧化剂分开存放，切忌混储。配备相应品种和数量的 消防器材。储区应备有泄漏应急处理设备和合适的收容材料。
第八部分 接触控制/个体防护
接触限值：
MAC(mg/m3): PC-STEL（mg/m3）: 10[总尘] TLV-TWA(mg/m3):
PC-TWA（mg/m3）: 6[总尘] TLV-C(mg/m3): 未制定标准 TLV-STEL(mg/m3):
监测方法：无资料。
工程控制：密闭操作。提供良好的自然通风条件。
呼吸系统防护：一般不需要特殊防护，高浓度接触时可佩戴过滤式防尘呼吸器。
眼睛防护：必要时，戴化学安全防护眼镜。
酚醛树脂(phenolic resin)
酚醛树脂（phenolic resin）1. introduction:Phenolic resin is the world's first found and thermosetting synthetic resin industry, as raw materials, synthesis process and convenient, has the mechanical strength and good heat resistance, has excellent mechanical properties and electrical properties, has the characteristics of high temperature creep resistance heat resistance, flame retardant, it is still widely used in plastics, friction material, adhesive, coating, casting resin, foam and other fields. However, with the rapid development of industrial economy, more and more requirements for the properties of phenolic resin have been put forward. The reaction mechanism, structure and properties of phenolic resin are still deeply studied. Many achievements have been made in toughening, reinforcing and modifying of phenolic resin. A variety of phenolic composite materials have also been listed as human engineering plastics series. Phenolic hydroxyl groups and methylene groups in phenolic resin structure are easily oxidized, so that their heat resistance is affected, and phenolic resin is brittle after curing. Therefore, until now, how to improve phenolic resin and apply it to industry is still an important topic.2. technology development:The development of bakelite, after all to the modification of phenolic resin modified phenolic resin, now mainly in the following aspects: 1. using natural plant oil modified phenolic resin; 2. using thermal plastic resin modified phenolic resin;3. low molecular chemical modified phenolic resin; modifiedphenolic resin 4. thermosetting resin; 5. rubber modified phenolic resin; 6. nano material toughened phenolic resin; 7. thermotropic liquid crystal toughened phenolic resin.2.1 natural vegetable oil modified phenolic resinThe natural plant oil modified phenolic resin is chemically modified, flexible long chain molecular structure in vegetable oil containing double bond or conjugated triple bond, by double or triple bond phenolic resin synthesized in the reaction process, the flexible long chain into rigid phenolic molecule chain, play in the role of toughening, thereby improving the phenolic resin brittle.2.1.1 cashew nut shell oil modified phenolic resinCashew nut shell oil is a by-product of cashew processing, and it is a very rich biological resource. Compared with phenol, cashew nut shell oil is much cheaper. From the structure of main components can be seen, the characteristics of cashew oil both phenolic compounds, aliphatic compounds and flexible, with the modified phenolic resin, heat resistance and toughness were significantly improved and modified products used for friction materials, friction performance, flexible film formed on the surface of carbonization process of friction easy to fall off, the friction and heat state of the material surface evenly, ensure stable friction properties. A cashew oil modified phenolic resin was synthesized by Novalac Liu Xuemei, the middle shell oil content is continuous, notched impact strength and flexural strength of cashew oil modified phenolic resins and molding materials were increased by 10.7% and 14.8%. Thisis because the long alkane chain structure of cashew shell oil in existence, the equivalent in phenolic resin matrix are introduced in the flexible chain, to the toughening effect of phenolic resin, so as to increase the notched impact strength of molding materials prepared and bending strength.2.1.2 tung oil modified phenolic resinWhen tung oil reacted with phenol, tung oil became positive ion under the action of acid catalyst, and then reacted with phenol instead of phenol. When the ratio of phenol / tung oil is greater than 6, the interpenetrating network of phenolic resin modified by tung oil and tung oil is obtained, thus improving the toughness of phenolic resin. Shang Shibin with tung oil, bismaleimide maleic anhydride, reaction with phenolic resin, prepared Eleostearic Acid Anhydride imide phenolic resin by thermal analysis method of tung oil anhydride imide resin at 170 degrees bake for 4 h, the measured temperature index of up to 165.8 DEG C, indicating a good heat-resistant resin. Li Chao of tung oil / phenolic resin and nano SiO2 / 2 phenolic / tung oil modified phenolic resin were studied. The results show that the decomposition temperature in 420 degrees Celsius above their initial heat, nano SiO2 / tung oil / phenolaldehyde system heat resistance is better than that of phenolic / tung oil, and 600 C, the former than the latter in each a focus on the loss of heat temperature has increased by 30 to 50 DEG C. A friction material made of this tung oil modified phenolic resin,Not only the friction coefficient of low temperature (100~200 DEG C) remains at 0.45 ~ 0.51, but also the friction coefficient at high temperature (200~300 DEG C) is up to 0.38 ~ 0.51, andthe friction factor recovery performance is good, and can be maintained at more than 0.40.2.1.3 Catalpol modified phenolic resinThe phenolic resin modified by catalpa oil is a kind of resin which reacts the excess phenol with vegetable oil under acidic conditions, and then reacts with formaldehyde under alkaline condition to produce the resin. The principle is similar to that of Tung oil. It was found that the toughness and heat resistance of phenolic resin modified by catalpa oil were improved.2.1.4 linseed oil modified phenolic resinLinseed oil is eighteen carbon three acid esters of glycerol, 3 non conjugated double bonds in the molecule, in the presence of acid and linseed oil non conjugated three ene of nuclear phenol alkylation reaction, obtained linseed oil modified phenolic resin, improve the toughness of resin. Study on phenolic resin modified by linseed oil on Yuan Xinhua's show in 320 ~ 600 DEG C linseed oil modified phenolic resin was 53.11%, while the ordinary phenolic resin 73.51% weight loss; the peak temperature of thermal decomposition, common phenolic resin 400 ~ 425 and 540 ~ 600 DEG C, and linseed oil modified is 440 ~ 470 C and 600 to 660 DEG C. Linseed oil modified phenolic resin for testing wear properties and mechanical properties of friction material showed that the modified resin adhesion and toughness are improved, the friction coefficient of the material is large and stable, low wear rate, impact strength, hardness, can be used as matrix resin for high performance friction materials.2.2 thermoplastic resin modified phenolic resinThe blending of thermoplastic resin with phenolic resin is a simple and easy way to strengthen and toughen. Thermoplastic resins for strengthening and toughening include polyether, polyamide, polyvinyl alcohol and polyvinyl acetals.2.2.1 polyether modified phenolic resinGe Dongbiao et al modified phenolic resins with a series of different molecular weight polyethylene glycol (PEG) and active polyethers. The tensile strength and elongation at break of PEG modified phenolic resin begin to increase with the increase of molecular weight of PEG. When the molecular weight is 1000, the peak value is reached, and then decreases with the increase of molecular weight of PEG. For the same molecular weight PEG and active polyether, the tensile strength and elongation at break of the modified polyether are better than those of the corresponding PEG modification. Among them, the tensile strength and elongation of PEG1000 modified phenolic resin 11.546MPa and 2.358% respectively; the tensile strength and elongation of 1000 active polyether modified phenolic resin 19.032MPa and 3.779% respectively. In addition, the effect of toughening modification of active polyether is better than that of carboxyl terminated nitrile rubber. This is mainly because the hydroxyl of -NCO based active polyether resin reaction more easily and makes the introduction of flexible ether phenolic resin chain network system, and the reaction probability of hydroxy carboxyl and hydroxyl of PEG1000 resin and carboxyl terminated nitrile rubber in the very small, tend to be morephysical modification.2.2.2 polyamide modified phenolic resinPolyamide has good toughness and mechanical properties. It can be co cured with phenolic resin or form a partially interpenetrating network structure to improve mechanical properties of the resin. Gao Yuejing, with three yuan of nylon modified phenolic resin was found in modified phenolic resin system, nylon as dispersed phase, phenolic resin as continuous phase copolymerization of dispersion phase particle size distribution was narrow, the mechanical properties of plastic is much better than that of blends of plastic material. The impact strength of modified nylon resin modified by unmodified resin, blending three yuan nylon and copolymerization three yuan is 57 KJ/m2, 47.1 KJ/m2 and 112 KJ/m2 respectively. The properties of copolymer modified resins are best due to the formation of graft phase copolymers during the synthesis and curing of modified resins. In addition, the phenolic resin toughened with nylon 3 has obtained good results. The nylon 3 molecule contains amide groups which react with hydroxymethyl groups in the phenolic resin, thereby improving the impact toughness and adhesion of the phenolic resin, and maintaining the advantages of the phenolic resin. The impact strength of the resin before and after modification is 3.5 to 4.5KJ/m2 and 5~12 KJ/m2 respectively, and the tensile strength is 7 to 11MPa and 15 to 20MPa respectively.2.2.3 polyvinyl alcohol modified phenolic resinIn the curing process of phenolic resin, if the PVA is added, the hydroxyl groups on the polyvinyl alcohol will react with the hydroxymethyl group of the phenolic polymer to form the graft copolymer. Jiang Detang in the development of a new HF- I modified epoxy resin, adding polyvinyl alcohol modifier. The results show that the addition of modifier to improve resin adhesion, improve the brittleness of phenolic resin, reduce the curing rate, thereby reducing the molding pressure, the toughening effect of phenolic resin on. However, the amount of use should not be too high, otherwise it will affect its strength.2.2.4 polyvinyl butyral modified phenolic resinThe phenolic resin modified with polyvinyl alcohol acetal is a modified phenolic resin which is applied earlier in industry. Under heating conditions, hydroxyl groups in polyvinyl acetals can undergo dehydration reactions with hydroxyl groups in phenolic resins to form graft or block copolymers. Polyvinyl alcohol acetal can improve the brittleness of phenolic resin, improve adhesion and mechanical properties, and reduce molding pressure. However, because of the introduction of longer fat chains in the structure of phenolic resins, heat resistance is affected. In order to improve the heat resistance, the polyvinyl alcohol acetal with higher heat resistance is often used, and a certain proportion of organosilicon monomer is added.2.3 low molecular chemical modified phenolic resin2.3.1 dicarboxylic acid modified phenolic resinThe molecular weight of the polymer molecules can also be used to improve the brittleness of resole resin (DA4), adipic acid, suberic acid (DA6), sebacic acid (DA8) and twelve alkyl acid (DA10) can be used to improve the brittleness of resole resin.A study found that the elasticity of dicarboxylic acid and resole resin in curing process in the reaction of ester bond formation, and also can be formed in the dibasic acid ester bond of carboxyl and hydroxyl methyl reaction into phenolic resin in brittle tensile strength of modified resin, toughness and fracture elongation increased with the increase of DA8 content, but the content in per gram of resin DA8 is over 0.014mol the performance decreased. Indicating the incorporation of flexible groups containing dibasic acid can improve the brittleness of resin. The performance of the modified resin decreased after the content of DA8 exceeded 0.014mol, indicating that more DA8 would lead to a decrease in the properties of the resin, or an unreacted DA8 would become defective in phase separation. When the phenolic resin was modified with DA6 with the best molecular chain length, the tensile strength of the resin increased by 54% and the toughness increased by 64%.2.3.2 halogenated phenolic resin modified by cyanogenLinear phenolic resins can react with cyanogen halides to form phenolic three - triazine resins. Novolac resin first with cyanogen bromide and three yuan amine reaction of Novolac Cyanate Ester and Novolac Cyanate Ester in the heat under the action of the cyclization reaction of three, eventually formingthree phenolic cyanate resin mesh structure. Phenol three Benzoxazine Resin has the following characteristics: the solubility of melt viscosity and gel time length, thermal oxidative stability, long-term in a low boiling solvent high low, under different curing conditions of Tg can reach 399 DEG C, polyimide system elongation and fracture mechanics with high performance, low toxicity, low the flame retardancy and smoke rate. At the same time, the network structure of phenolic three triazine contains tenacity ether bond, so it has better toughness after modification.2.3.3 molybdenum modified phenolic resinMolybdenum phenolic resin (Mo2PF) is a modified phenolic resin in which the metal element molybdenum is chemically bonded to the main molecular chain of the phenolic resin by chemical reaction. Is the reaction by molybdate and phenol in the presence of catalyst into molybdate benzene ester, phenyl ester and molybdate addition reaction and condensation reaction with formaldehyde, generation of phenolic resin, after cooling is a green solid, with the increase of molybdenum content in the resin resin, the initial decomposition temperature rise. Liu Xiaohong et al made aluminum phenolic resin with aluminum modifier, phenol and formaldehyde as main raw materials. The metal molybdenum could enter the molecular chain of phenolic resin, and the great bonding O - MO - O bond could connect the benzene ring to improve the heat resistance. The thermal decomposition temperature of modified phenolic resin prepared by this method can reach 522 DEG C, and the weight loss is only 17.5% at 600 centigrade,Other properties are comparable to that of ordinary phenolic resins. In addition, the in situ polymerization method was used to improve the heat resistance, impact properties and tensile properties of the molybdenum phenolic resin /TiO2 nanocomposite by filling and modifying the surface treated nano TiO2. Zhang Shuangqing with phenol and formaldehyde in the first synthesis of hydroxymethyl phenol, and molybdic acid and hydroxymethyl by esterification reaction to obtain a new thermosetting phenolic resin and its carbon residue rate was 56.31%, the rate of 13 percentage points higher than the average carbon residue of thermosetting phenolic resin.2.3.4 boron modified phenolic resinThe modification of phenolic resin with boron compounds, the change of its structure, the formation of B - O bond with higher bond energy and the formation of boron - containing three - direction crosslink structure are one of the effective methods to improve its heat resistance. Che Jianfei by in situ synthesis method with TiO2 nanoparticles added to the boron phenolic resin, can significantly improve the heat resistance and toughness, when 5% TiO2 was added, the initial decomposition temperature is increased by about 150 degrees, the impact strength increased 231%. In addition, the processing technology of modified phenolic resin was also improved obviously. The introduction of boron is also beneficial to improve the flame retardancy of phenolic resin. Modified phenolic resin with boric acid and Aman Chang [16], the product still has a solid residue 75.3% in 700.8 DEG, 900 DEG C without decomposition residue is still above 64%, far higher than similar foreign products (700 C solid residue 63%). Theflexural strength, flexural modulus and impact strength of the composites obtained by Qiu Jun and other carbon fiber composite boron phenolic resins have been greatly improved. Tung oil, high performance double boron modified phenolic resin was synthesized by two steps such as Wang Manli, used it as a non asbestos braided brake belt has good friction performance of matrix resin, reached the level of similar foreign products.2.3.5 amine modified phenolic resinIs the main aromatic amine compounds and total phenol and formaldehyde condensation reaction in the presence of catalyst, introducing aromatic amine unit structure and good heat resistance in the structure of the phenolic resin, aromatic amines are commonly used melamine and melamine methylol compound and aniline. Amine modified phenolic resin, the heat resistance is improved, thermogravimetric analysis results show that aniline modified phenolic resin thermal decomposition temperature is 410 DEG C, melamine modified resin is 438 DEG, 380 DEG C than the pure phenolic resin to improve its heat resistance is high, reason is the introduction of a more stable heterocyclic the construction and curing resin crosslinking density increased. The prepared friction material has good friction property at high temperature, and it is a common modification method.2.3.6 silicone modified phenolic resinSilicone modified phenolic resin has high heat resistance, thermal stability, toughness and other excellent properties, the modified method is: the phenolic resin is reacted withorganosilicon compounds containing alkoxy groups, forming a three-dimensional network structure containing silicon oxygen bond, there is a competitive reaction from poly phenolic reaction process, so two kinds of reactivity is the key to the success of the modified. Allyl phenolic resin reacted with organosilicon compound to form organosilicon modified phenolic resin with excellent heat resistance. The tribological properties of the friction material modified with silicone resin are stable and the wear rate is low. The friction coefficient varies little (=0.136 ~ 0.140) at the temperature range of 100 ~ 350 DEG CPhenolic resin modified by 2.3.7 aromaticsThe modified aromatic hydrocarbons are toluene, xylene, substituted benzene, naphthalene and so on. The modified principle is introduced so that the stability of the aromatic molecules increased, increased rigidity, thereby improving the heat resistance modification methods were as follows: the main aromatic hydrocarbons (Ar) reacts with formaldehyde to produce aromatic alcohols, and then generate the phenol and formaldehyde resin. Aromatic hydrocarbon, phenol and formaldehyde react simultaneously to form resin. The heat resistance of the modifier depends on the structure of the aromatic compound. The 53 Research Institute of ordnance industry has achieved satisfactory results by using the tower substrate (aromatic compound) extracted from xylene to modify phenolic resin. The modified route using first methods, modified phenolic thermal decomposition temperature above 450 degrees, thanThe phenolic resin is higher than 50 DEG C, and the weight loss rate at high temperature increases slowly,Suitable for high temperature use, the friction material produced has good friction performance, high temperature coefficient of friction is high and stable, low wear rate.2.4 thermosetting resin modified phenolic resin2.4.1 polyimide modified phenolic resinPolyimide is composed of two aromatic amines and two anhydrides. It has excellent heat resistance and flame retardancy, and can remarkably improve the heat resistance of phenolic resin. Yan Yehai and so on were synthesized bismaleimide modified phenolic resin I, the cured resin has outstanding heat resistance, the thermal deformation temperature (HDT) is 273 DEG C, and the glass temperature is 288 DEG C. The structure content of high phenyl ring and high cross linking density are the structural basis for the excellent heat resistance of cured resins. Phenolic resin II was obtained by blending resin I with appropriate high temperature curing agent. Resin II with deformation temperature and glass transition temperature of the bending performance of more excellent and more heat than resin I, use this source in high temperature curing agent to improve the crosslinking density of the cured resin, so as to ensure the heat resistance of the cured resin. Resin I and II with glass cloth composite materials with excellent mechanical properties and heat resistance based at 300 DEG C based on the flexural strength and modulus of I resin composite material retention rate is respectively 65% and 78%, the II phenolicresin composites flexural strength and modulus retention rate of up to 73% and 83% respectively.2.4.2 polysulfone modified phenolic resinPolysulfone has excellent heat resistance, outstanding creep resistance and dimensional stability, excellent electrical insulation and other characteristics. It has become a comprehensive engineering plastics, and occupies an important position in plastic varieties. Dong Ruiling, Qi Shuhua and others found that polysulfone modified phenolic resin, polysulfone in the form of grafting and blending exist simultaneously. The modified phenolic resin glass fiber reinforced plastic toughness is improved, the impact strength increased from 200KJ/m2 to 283KJ/m2, the tensile strength of 960MPa, the dielectric strength reached 20KV/mm, Martin heat resistance temperature more than 310 DEG C. The glass fiber reinforced mould plastics made of this kind of polysulfone modified phenolic resin have been successfully applied to aerospace products.Phenolic resin modified with 2.4.3 maleimide polymerIn order to improve the toughness and heat resistance of phenolic resin, maleimide resin was used as modifier. The modified resin had high toughness and heat resistance, and the modification effect was obvious. Novolac resin with maleimide groups (PMF) is composed of phenol and N- mixture and 4 hydroxy phenol formaldehyde polyimide under acid catalysis reaction and its curing, mainly through maleimide group addition polymerization. This system greatly improved the heatresistance of phenolic resin and improved the thermal stability of the resin in the higher temperature region, but the toughness was not improved. Someone uses a new addition curing system to improve the toughness of resin system, this system is composed of PMF resin and novolac resin containing allyl group (PAF) according to the different ratio of mixed into, in the reaction with allyl blends.With the increase of the content of propyl phenol, the crosslinking density of the cured matrix decreases, the toughness increases, and the mechanical properties increase. Under the curing conditions, the optimum performance is obtained when the equivalence ratio of allyl and maleimide is 1 to 3.2.4.4 epoxy modified phenolic resinPhenolic hydroxyl groups and hydroxymethyl groups on phenolic resins can react with epoxy groups and hydroxyl groups in epoxy resins to form an cross-linked structure, which reduces the crosslinking density of the cured products and increases the flexibility of the molecules. The study of Jiang Detang and others showed that the brittleness of phenolic resin was improved and the mechanical properties were obviously improved after adding epoxy resin. When the equivalence ratio between epoxy and phenolic resin was 1 to 3, two diglycidyl ether bisphenol A epoxy modified phenolic resin was obtained with the largest KIC (0.85MPa, m1/2). The properties of the composites are also considerably improved than those of DDS curable materials. When the content of novolac resin in thecross-linked network structure increases, the Tg of themodified resin decreases and the toughness increases. In addition, with the increase of linear phenolic resin content, the flame retardancy of the modified resin will increase significantly. Therefore,We can obtain a dense system with excellent mechanical properties and flame retardancy by controlling the content of novolac resin.2.5 rubber modified phenolic resinMany large molecules such as Ding Jing, styrene butadiene rubber and natural rubber were used to toughen phenolic resin. The rubber toughened phenolic resin is a kind of physical mixing modification, but there are different degrees of graft or block copolymerization in the course of curing. Li Xinming et al [17 study found that without nitrile rubber, the impact strength of pure phenolic resin was 5.43 KJ/m2, adding 1% nitrile rubber, the impact strength reached 8.60KJ/m2, an increase of about 58.4%; nitrile rubber with 2%, the impact strength of phenolic resin reached 11.49 KJ /m2, increased by about 116%, improve the the amplitude is the other modification methods can not be compared. With the increase of NBR dosage, the impact strength of phenolic resin is further improved, but the amplitude increases. In addition to the nitrile rubber, rubber containing active functional groups such as epoxy based liquid butadiene rubber, acrylic acid carboxylated nitrile rubber and epoxy adduct can also toughened phenolic resin, and the toughening effect, improved heat resistance. Especially in the liquid rubber toughening system, because the liquid rubber is easy to form the island structure, the form structure which improvedthe impact strength of the composite hardness, heat resistance and little influence on the materials, is an ideal toughening system.Phenolic resin toughened with 2.6 nanometer materialThere are two main methods: 1 nanoparticles toughened polymer nanoparticles and polymer blends; using nano material intercalation method, namely the first polymer monomer is dispersed into layered silicate layers, then in situ polymerization. The polymerization of the released heat can be put into the stripping layer structure of silicate structure unit thickness 1nm width and length of about 10nm, which are uniformly dispersed in the phenolic resin, composite resin and stripping unit structure on the nanometer scale. The toughened phenolic resin has better toughness and thermal stability than the conventional toughened phenolic resin.2.7 thermotropic liquid crystal toughened phenolic resinToughening of thermosetting resins with thermotropic liquid crystals improves toughness and toughness while maintaining heat resistance and stiffness of the resin. Liquid crystalline macromolecules contain a large number of rigid mesogenic units and a certain amount of flexible spacers, and their structural characteristics determine their excellent properties. The presence of a small amount of thermotropic liquid crystalline polymer fibrils can prevent cracks and improve the toughness of the brittle matrix without decreasing the heat resistance and stiffness of the material. Compared with thermoplastics, the same toughening effect can be obtained by using only 25%- 30% of thermoplastic3. conclusionAt present, the toughening modification of phenolic resin on maturity, there have been many modified phenolic resin with high performance, such as excellent mechanical properties, high temperature resistance, electrical insulation, flame retardant, low smoke and low toxicity and mechanical processing of new phenolic resin. It can be predicted that with the continuous development of aviation, aerospace, automobile and electronics industry, study on modified phenolic resin constantly, will make "phenolic resin old" further development, play a greater role in more and more fields.Reference[1]., Min, Ho, Choi, Ho, Yun, Byun, In, Jae, Chung., Theeffect, of, chain, length, of, flexible, diacid, on, Morphologyand, mechanical, property, of,, modified, phenolicresin.Polymer, 2002,43 (): 4437 ~[2]. He J, Raghavan D, Hoffman D, Hunston D. Theinfluence of elastomer concentration on toughness in dispersions containing preformed acrylic elastomeric particles in an epoxy matrix?.Polymer1999,40 (8): 1923 ~ 1933.[3]., Reghunadhan, N, C, P., Advances, in, cure, phenolic, resins., Progress, addition-, in, Polymer, Science.2004,29 (5): 401 ~。
酚醛树脂的制备
酚醛树脂的制备
酚醛树脂的制备主要通过酚和醛在催化剂的作用下进行缩聚反应。
具体步骤如下：
1.原料准备：通常使用的原料包括苯酚、甲醛、催化剂（如盐酸、
磷酸、草酸或氢氧化铵）等。
2.缩聚反应：在催化剂的催化下，苯酚和甲醛进行缩聚反应，生成
线型或体型的高分子树脂。
反应过程中，酚与醛的摩尔比会影响产物的类型和性能。
当摩尔比大于或等于1时，生成线型树脂；
小于1时，生成多羟甲基酚衍生物。
3.反应条件：反应通常在70-100℃的温度下进行，反应时间一般为
2-6小时。
催化剂的加入方式会影响反应的速率和产物的性质。
例如，使用盐酸、磷酸、草酸作催化剂时，反应介质pH为0.5～1.5，有利于线型树脂的生成。
4.脱水过程：反应完成后，需要进行脱水处理。
脱水可以在常压或
减压下进行，最终脱水温度为140～160℃，树脂分子量为500～900。
5.醇溶性酚醛树脂的制备：在特定的配方和工艺条件下，苯酚与甲
醛反应生成醇溶性酚醛树脂。
例如，将熔化的苯酚加入反应釜中，加入甲醛溶液和催化剂，然后在特定的温度下进行反应，最终得到醇溶性酚醛树脂。
6.其他改性酚醛树脂：除了醇溶性酚醛树脂，还有聚乙烯醇改性酚
醛树脂、三聚氰胺改性酚醛树脂等，这些改性树脂具有不同的性能和用途。
7.需要注意的是，实验过程中使用的苯酚和甲醛的量应严格控制，
以避免反应过度或不足。
此外，实验结束后，反应容器需要清洗，以去除残留的化学物质。
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醇溶性酚醛树脂工艺设计
一、引言
酚醛树脂也叫电木，又称电木粉，英文名称phenolic resin,简称PF，比重1.25~1.30，是酚与醛经聚合制得的合成树脂统称, 原为无色或黄褐色透明物，，因含有游离分子而呈微红色，市场销售往往加着色剂而呈红、黄、黑、绿、棕、蓝等颜色，有颗粒、粉末状。
耐弱酸和弱碱，遇强酸发生分解，遇强碱发生腐蚀。
不溶于水，溶于丙酮、酒精等有机溶剂中。
对水、弱酸、弱碱溶液稳定。
由苯酚和甲醛在催化剂条件下缩聚、经中和、水洗而制成的树脂。
因选用催化剂的不同，可分为热固性和热塑性两类。
主要包括：线型酚醛树脂、热固性酚醛树脂和油溶性酚醛树脂。
其中以苯酚-甲醛树脂最重要。
酚醛树脂有热塑性和热固性两类。
热塑性酚醛树脂（或称两步法酚醛树脂），为浅色至暗褐色脆性固体，溶于乙醇、丙酮等溶剂中，长期具有可溶可熔性，仅在六亚甲基四胺或聚甲醛等交联剂存在下，才固化(加热时可快速固化)。
主要用于制造压塑粉，也用于制造层压塑料、清漆和胶粘剂。
热固性酚醛树脂（或称一步法酚醛树脂），可根据需要制成固体、液体和乳液，都可在热或（和）酸作用下不用交联剂即可交联固化。
为指导树脂合成和成型加工，常将其固化过程分为A、B、C三个阶段。
具有可溶可熔性的预聚体称作A阶酚醛树脂;交联固化为不溶不熔的最终状态称C阶酚醛树脂；在溶剂中溶胀但又不完全溶解，受热软化但不熔化的中间状态称B阶酚醛树脂,热固性酚醛树脂存放过程中粘度逐渐增大，最后可变成不溶不熔的C阶树脂。
因此,其存放期一般不超过3～6个月。
热固性酚醛树脂可用于制造各种层压塑料、压塑粉、层压塑料；制造清漆或绝缘、耐腐蚀涂料；制造日用品、装饰品；制造隔音、隔热材料等。
常见的高压电插座、胶粘剂和改性其他高聚物。
酚醛树脂具有良好的耐酸性能、力学性能、耐热性能，广泛应用于防腐蚀工程、胶粘剂、阻燃材料、砂轮片制造等行业。
二、酚醛树脂各项性质介绍
1、酚醛树脂的密度和比重
酚醛树脂的密度？酚醛树脂的比重？它的密度在1.0到1.7之间，具体由实际生产商决定。
比重是以前常用的概念，现在基本已经被淘汰了。
密度很简单，就是质量与体积的比。
比重，是相同体积的某物质与4摄氏度下的水的重量之比，所以称为“比重”。
由于4摄氏度下的水的密度是1g/ml所以比重与密度在数值上是相等的。
2、酚醛树脂溶解性
酚醛树脂溶解性：根据溶剂的不同，分为醇溶和水溶。
能溶解在水里而不溶于醇的为水溶醇不溶酚醛树脂；能溶解在醇里而不溶于水的为醇溶水不溶酚醛树脂；两者都能溶解的为醇溶水溶酚醛树脂。
3、酚醛树脂分子量
酚醛树脂属于高分子化合物，分子量有几百到几千甚至上万不等，根据树脂的类型有所分别。
4、酚醛树脂的重要性能
高温性能
酚醛树脂最重要的特征就是耐高温性，即使在非常高的温度下，也能保持其结构的整体性和尺寸的稳定性。
正因为这个原因，酚醛树脂才被应用于一些高温领域，例如耐火材料，摩擦材料，粘结剂和铸造行业。
粘结强度
酚醛树脂一个重要的应用就是作为粘结剂。
酚醛树脂是一种多功能，与各种各样的有机和无机填料都能相容的物质。
设计正确的酚醛树脂，润湿速度特别快。
并且在交联后可以为磨具、耐火材料，摩擦材料以及电木粉提供所需要的机械强度，耐热性能和电性能。
水溶性酚醛树脂或醇溶性酚醛树脂被用来浸渍纸、棉布、玻璃、石棉和其它类似的物质为它们提供机械强度，电性能等。
典型的例子包括电绝缘和机械层压制造，离合器片和汽车滤清器用滤纸。
高残碳率
在温度大约为1000℃的惰性气体条件下，酚醛树脂会产生很高的残碳，这有利于维持酚醛树脂的结构稳定性。
酚醛树脂的这种特性，也是它能用于耐火材料领域的一个重要原因。
低烟低毒
与其他树脂系统相比，酚醛树脂系统具有低烟低毒的优势。
在燃烧的情况下，用科学配方生产出的酚醛树脂系统，将会缓慢分解产生氢气、碳氢化合物、水蒸气和碳氧化物。
分解过程中所产生的烟相对少，毒性也相对低。
这些特点使酚醛树脂适用于公共运输和安全要求非常严格的领域，如矿山，防护栏和建筑业等。
抗化学性
交联后的酚醛树脂可以抵制任何化学物质的分解。
例如汽油，石油，醇，乙二醇和各种碳氢化合物。
三、醇溶性酚醛树脂工艺设计
1．原料：
生产醇溶性酚醛树脂的原料
名称含量
苯酚98%(质量分数，含杂质)
甲醛37%(质量分数)
氨水（催化剂）20%(质量分数)
乙醇95%(V/V)
2．配料比：苯酚∶甲醛（37%）=1∶1.2（摩尔比）
3．产品质量：
固含量：60%
水：﹤8%
游离苯酚：﹤5%（存于树脂中）
氨水的用量：5%（为纯苯酚质量的5%）
四、生产流程或生产方案
1．生产流程方案
用苯酚、甲醛为原料，控制摩尔比在1∶1.2，使其在碱性环境下缩合成树脂，经真空脱水后制得成品。
本工艺利用真空吸入原料苯酚,室内供热系统提供水蒸汽作为热源。
其他原料来自高位槽并可加入适量乙醇用以调节粘度避免结垢。
2．生产流程简述
苯酚先在镀锌铁桶内加热熔化，升温至60℃，用真空将苯酚吸入反应釜内，通入蒸汽保温；将37%的甲醛水溶液以苯酚∶甲醛=1∶1.2（mol）的比例缓慢加入反应釜内，开启电动搅拌系统开始搅拌，再加入浓度为20%的氨水催化剂，加热升温至70℃,由于反应放热，温度会自动上升。
当温度升至78℃时，即用循环冷却水调节，使反应温度缓缓上升并保温在85℃～95℃间（不超过95℃）。
使反应釜保温反应1小时后，终止反应。
用循环冷却水调节到75℃，进行真空脱水2.5～3小时，再冷却到50℃加入乙醇调稀，最后自然冷却到40℃出料，即为产品。
3．工艺流程简图和参数
流程简图如图图所示：
工艺参数如表所示：
醇溶性酚醛树脂的生产工艺参数
合成阶段脱水阶段调稀阶段原料20℃-70℃75℃（2.5～3h）冷却到50℃冷却水—20℃升到30℃—
水蒸汽—75℃降到40℃—
整个生产周期如图所示：
醇溶性酚醛树脂的生产周期
五、生产过程所需设备
1.溶液缩聚阶段：反应釜、冷却器、夹套、冷料槽
2.分离脱水阶段：真空系统、真空泵、反应釜
3熔融缩聚阶段：反应釜、真空系统
4．稀释阶段：稀释釜
六、生产工艺详图(另附CAD图纸)。