聚丙烯腈（PAN）碳纖維原絲用油劑和中間相瀝青基碳纖維原絲用油劑是碳纖維生產(chǎn)中必不可少的關(guān)鍵助劑，能夠阻燃、不融化，防止PAN單絲/中間相瀝青基單絲在預(yù)氧化過(guò)程中發(fā)生單絲之間熔融粘結(jié)或并絲，不起毛絲和斷裂。油劑直接影響到穩(wěn)定化生產(chǎn)和PAN原絲/中間相瀝青基原絲的質(zhì)量，也對(duì)碳纖維質(zhì)量及強(qiáng)度產(chǎn)生重大影響。油劑賦予PAN原絲/中間相瀝青基原絲以柔軟、抗靜電，潤(rùn)滑作用，防止單絲表面之間摩擦與磨損，降低絲束與傳動(dòng)輥之間的摩擦，減少毛絲。

我國(guó)聚丙烯腈/中間相瀝青基碳纖維原絲生產(chǎn)企業(yè)使用的含硅油劑依賴進(jìn)口，屬于我國(guó)“卡脖子”關(guān)鍵技術(shù)，從日本竹本和松本進(jìn)口油劑價(jià)格高達(dá)40萬(wàn)元/噸，嚴(yán)重制約我國(guó)碳纖維品質(zhì)提高和生產(chǎn)成本。國(guó)內(nèi)院校企業(yè)通常采用逆向分析國(guó)際品牌油劑，模仿進(jìn)口油劑產(chǎn)品組成，復(fù)配油劑主要成分包括氨基改性硅油、聚醚改性硅油和環(huán)氧改性硅油（如圖1所示）。

氨基改性硅油在復(fù)配油劑乳液中容易同環(huán)氧改性硅油發(fā)生交聯(lián)反應(yīng)，導(dǎo)致復(fù)配油劑乳液中各種組成發(fā)生相分離和破乳現(xiàn)象，上油過(guò)程中吸附到PAN原絲表面油劑組成與上油槽中的組成發(fā)生變化，導(dǎo)致上油率，上油后PAN原絲表面油劑成分均勻性不一致，影響碳纖維質(zhì)量穩(wěn)定性。同時(shí)，上油后PAN原絲在高溫干燥時(shí)氨基改性硅油同環(huán)氧改性硅油的交聯(lián)反應(yīng)迅速，導(dǎo)致復(fù)配硅油分子量急劇上升，產(chǎn)生黏輥現(xiàn)象。

吉林乾仁新材料有限公司（簡(jiǎn)稱吉林乾仁）承擔(dān)吉林省（市）碳纖維產(chǎn)業(yè)鏈中關(guān)鍵助劑“卡脖子”攻關(guān)任務(wù)，自主開(kāi)發(fā)系列含硅油劑體系，產(chǎn)品技術(shù)創(chuàng)新性在于將氨基、環(huán)氧基、聚醚基等一體化設(shè)計(jì)，同時(shí)將環(huán)氧樹(shù)脂嵌入分子鏈段中，大量降低油劑中含硅量（如圖2所示）。吉林乾仁油劑一方面避免復(fù)配油劑組成在儲(chǔ)存過(guò)程中和紡絲上油過(guò)程中發(fā)生交聯(lián)反應(yīng)，由此解決了我國(guó)油劑儲(chǔ)存穩(wěn)定性和熱穩(wěn)定性差、黏輥、上油后原絲毛羽量高、集束性差等技術(shù)難點(diǎn)，另一方面，油劑在碳化過(guò)程中因含硅量低，對(duì)碳纖維及碳化設(shè)備污染低，同時(shí)，吉林乾仁油劑通過(guò)多組分一體化設(shè)計(jì)保證聚丙烯腈碳纖維原絲連續(xù)化生產(chǎn)過(guò)程中油槽及上油在碳纖維原絲表面的油劑組成穩(wěn)定。

吉林乾仁新材料有限公司設(shè)計(jì)生產(chǎn)的油劑對(duì)標(biāo)竹本油劑，適合PAN原絲濕紡工藝；松本油劑，適合PAN原絲干噴濕紡工藝；和第三類油劑，適合中間相瀝青基原絲生產(chǎn)。吉林乾仁油劑有利于上油后PAN原絲/中間相瀝青基原絲的預(yù)氧化，由于上油后PAN原絲表面的疏水性脂肪鏈容易在較低溫度下引發(fā)預(yù)氧化反應(yīng)，由此導(dǎo)致空氣容易滲透擴(kuò)散到PAN原絲內(nèi)部，因此，PAN原絲預(yù)氧化速度較日本竹本油劑上油后PAN原絲預(yù)氧化速度快（如圖3-5 所示），PAN原絲和碳化后碳纖維性能達(dá)到或超過(guò)使用國(guó)際同類油劑生產(chǎn)的同類產(chǎn)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).

圖1 文獻(xiàn)專利上PAN原絲用復(fù)配油劑分子結(jié)構(gòu)

圖 2 吉林乾仁新材料有限公司自乳化含硅油劑一體化設(shè)計(jì)

圖3 吉林乾仁新材料有限公司油劑在PAN原絲預(yù)氧化過(guò)程中加速作用

圖4吉林乾仁新材料有限公司生產(chǎn)的含硅油劑乳液粒徑及其分布測(cè)試結(jié)果

圖5 使用吉林乾仁新材料有限公司油劑生產(chǎn)的PAN 原絲（***左邊一束）對(duì)比使用日本竹本油劑生產(chǎn)的PAN原絲在吉林國(guó)興碳纖維生產(chǎn)線上進(jìn)行預(yù)氧化和碳化過(guò)程

表1吉林乾仁新材料有限公司生產(chǎn)的油劑產(chǎn)品特性

表2 吉林乾仁新材料有限公司油劑同國(guó)際油劑上油后PAN 碳纖維原絲性能對(duì)比

表3 PAN碳纖維原絲（吉林乾仁新材料有限公司油劑同國(guó)際油劑）碳化后碳纖維性能對(duì)比