聚丙烯腈（PAN）碳纤维原丝用油剂和中间相沥青基碳纤维原丝用油剂是碳纤维生产中必不可少的关键助剂，能够阻燃、不融化，防止PAN单丝/中间相沥青基单丝在预氧化过程中发生单丝之间熔融粘结或并丝，不起毛丝和断裂。油剂直接影响到稳定化生产和PAN原丝/中间相沥青基原丝的质量，也对碳纤维质量及强度产生重大影响。油剂赋予PAN原丝/中间相沥青基原丝以柔软、抗静电，润滑作用，防止单丝表面之间摩擦与磨损，降低丝束与传动辊之间的摩擦，减少毛丝。

我国聚丙烯腈/中间相沥青基碳纤维原丝生产企业使用的含硅油剂依赖进口，属于我国“卡脖子”关键技术，从日本竹本和松本进口油剂价格高达40万元/吨，严重制约我国碳纤维品质提高和生产成本。国内院校企业通常采用逆向分析国际品牌油剂，模仿进口油剂产品组成，复配油剂主要成分包括氨基改性硅油、聚醚改性硅油和环氧改性硅油（如图1所示）。

氨基改性硅油在复配油剂乳液中容易同环氧改性硅油发生交联反应，导致复配油剂乳液中各种组成发生相分离和破乳现象，上油过程中吸附到PAN原丝表面油剂组成与上油槽中的组成发生变化，导致上油率，上油后PAN原丝表面油剂成分均匀性不一致，影响碳纤维质量稳定性。同时，上油后PAN原丝在高温干燥时氨基改性硅油同环氧改性硅油的交联反应迅速，导致复配硅油分子量急剧上升，产生黏辊现象。

吉林乾仁新材料-太阳√集团城官网1407有限公司（简称吉林乾仁）承担吉林省（市）碳纤维产业链中关键助剂“卡脖子”攻关任务，自主开发系列含硅油剂体系，产品技术创新性在于将氨基、环氧基、聚醚基等一体化设计，同时将环氧树脂嵌入分子链段中，大量降低油剂中含硅量（如图2所示）。吉林乾仁油剂一方面避免复配油剂组成在储存过程中和纺丝上油过程中发生交联反应，由此解决了我国油剂储存稳定性和热稳定性差、黏辊、上油后原丝毛羽量高、集束性差等技术难点，另一方面，油剂在碳化过程中因含硅量低，对碳纤维及碳化设备污染低，同时，吉林乾仁油剂通过多组分一体化设计保证聚丙烯腈碳纤维原丝连续化生产过程中油槽及上油在碳纤维原丝表面的油剂组成稳定。

吉林乾仁新材料-太阳√集团城官网1407有限公司设计生产的油剂对标竹本油剂，适合PAN原丝湿纺工艺；松本油剂，适合PAN原丝干喷湿纺工艺；和第三类油剂，适合中间相沥青基原丝生产。吉林乾仁油剂有利于上油后PAN原丝/中间相沥青基原丝的预氧化，由于上油后PAN原丝表面的疏水性脂肪链容易在较低温度下引发预氧化反应，由此导致空气容易渗透扩散到PAN原丝内部，因此，PAN原丝预氧化速度较日本竹本油剂上油后PAN原丝预氧化速度快（如图3-5 所示），PAN原丝和碳化后碳纤维性能达到或超过使用国际同类油剂生产的同类产品（如表1-3所示）。

JLQR OIL AGENT

Date:2022.01.18

The oil agent or spinning finish for polyacrylonitrile (PAN) carbon fiber precursor is an essential key additive in the production of carbon fiber. The oil agent should be flame retardant and prevent its coated PAN monofilament from melting, bonding or merging in the pre-oxidation process, without fluffing and yarn breakage. The oil agent not only directly affects the stable production and the quality of PAN carbon fiber precursor, but also has a significant impact on the quality of the carbon fiber subsequently carbonized from PAN carbon fiber precursor. The oil agent endows PAN carbon fiber precursor with softness, antistatic and lubrication, prevents friction and wear between monofilament surfaces, reduces the friction between fiber tow and drive roller, and reduces fluffing.

The oil agent contained silicone used by China's PAN carbon fiber precursor production enterprises depends on imports, which belongs to China's "stuck neck" key technology. The price of the oil agent imported from Japan is as high as 400000 yuan / ton, which seriously restricts the improvement of carbon fiber quality and production cost in China.  Domestic universities and enterprises usually utilize the reverse analysis of international brand oil agents to imitate the composition of imported oil agents. The main components of compound oil agents generally consist of amino modified silicone oil, polyether modified silicone oil and epoxy modified silicone oil (as shown in Figure 1).

Amino modified silicone oil is easy to react with epoxy modified silicone oil in the compounding oil agent emulsion, resulting in the phase separation and demulsification of various components in oil agent emulsion. Because the components of compound oil agent have different affinity or adhesion to PAN carbon fiber precursor, the composition of the oil agent adsorbed and coated onto the surface of PAN precursor fiber and that of remained composition of the oil agent in oil tank keep changing during the process of oil agent coating on PAN carbon fiber precursor fiber, leading to the discontinuous and unstable rate of oil agent coating on the surface of PAN carbon fiber precursor. The homogeneity of the oil agent composition coated on the PAN carbon fiber precursor was not consistent, which further affect the continuous stability of carbon fiber produced from subsequently carbonization of PAN carbon fiber precursor.  At the same time, when PAN carbon fiber precursor coated by oil agent is drying at high temperature, the cross-linking reaction between amino modified silicone oil and epoxy modified silicone oil in the compound oil agent is rapid, resulting in a sharp increase in the molecular weight of the compound oil agent and roll sticking.

Jilin Qianren Innovative Material Co., Ltd. (hereinafter referred to as JLQR) undertakes the task of tackling the " stuck neck " technology of key additives applied in the carbon fiber industry chain from Jilin Province (city), and independently develops a series of oil agents containing silicone. The product technology innovation from JLQR lies in the integrated self-assembly and self-emulsification design of amino, epoxy and polyether silicone oil, without external emulsifiers, defoamers, antistatic agents and other additives.  At the same time, the epoxy resin is embedded in the molecular chain segment of the oil agent to greatly reduce its silicon content (as shown in Fig. 2). On the one hand, the oil agent of JLQR avoids phase separation and cross-linking reaction in the storage process and spinning oiling process, thus leading to solves the technical difficulties such as poor storage stability, low thermal stability, roll sticking of the oil agent ， fluffing and poor bundling of PAN carbon fiber precursor coated from oil agent. On the other hand, in the carbonization process, the oil agent has low pollution to carbon fiber and carbonization equipment because of low silicon content in the oil agent of JLQR.  At the same time, the oil agents of JLQR ensures its stable composition both in oil tank and on the surface of carbon fiber precursor during the continuous spinning production of PAN carbon fiber precursor through multi-component integrated, self-assembly and self-emulsification design of its oil agent.

The oil agent designed and produced by JLQR is conducive to the pre oxidation of PAN carbon fiber precursor coated by its oil agent.  Because the hydrophobic fat chain of oil agent coated on the surface of PAN carbon fiber precursor is easy to trigger the pre-oxidation reaction at a lower temperature to generate porous surface, and air is easy to penetrate and diffuse into PAN carbon fiber precursor through porous oil agent’s coating to trigger oxidative reaction. Therefore, the pre-oxidation speed of PAN carbon fiber precursor coated with oil agent of JLQR is faster than that of PAN carbon fiber precursor coated with Japanese Takemoto Co., Ltd. (as shown in Figure 3-5).  The properties of PAN carbon fiber precursor produced from the oil agent of JLQR and subsequently carbonized carbon fiber meet or exceed those of similar products produced with the oil agents of the international enterprise (as shown in table 1-3).

图1 文献专利上PAN原丝用复配油剂分子结构

图 2 吉林乾仁新材料-太阳√集团城官网1407有限公司自乳化含硅油剂一体化设计

图3 吉林乾仁新材料-太阳√集团城官网1407有限公司油剂在PAN原丝预氧化过程中加速作用

图4吉林乾仁新材料-太阳√集团城官网1407有限公司生产的含硅油剂乳液粒径及其分布测试结果

图5 使用吉林乾仁新材料-太阳√集团城官网1407有限公司油剂生产的PAN 原丝（***左边一束）对比使用日本竹本油剂生产的PAN原丝在吉林国兴碳纤维生产线上进行预氧化和碳化过程

表1吉林乾仁新材料-太阳√集团城官网1407有限公司生产的油剂产品特性

表2 吉林乾仁新材料-太阳√集团城官网1407有限公司油剂同国际油剂上油后PAN 碳纤维原丝性能对比

表3 PAN碳纤维原丝（吉林乾仁新材料-太阳√集团城官网1407有限公司油剂同国际油剂）碳化后碳纤维性能对比