CN115353759B - 缓解聚合物粘釜的涂层材料及其在聚合反应器中的应用 - Google Patents
缓解聚合物粘釜的涂层材料及其在聚合反应器中的应用 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
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- C08F120/10—Esters
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C09D133/04—Homopolymers or copolymers of esters
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- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
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Abstract
本发明公开了一种缓解聚合物粘釜的涂层材料及其在聚合反应器中的应用。所述涂层材料包括底漆和面漆;所述底漆中各组分质量份为:硅溶胶50‑60份,改性硅氧烷30‑50份,无机填料5‑15份,催化剂1‑10份;所述面漆中各组分质量份为:硅溶胶40‑55份,改性硅氧烷35‑55份,羟基硅油5‑15份,催化剂5‑10份。本发明提供的涂层材料可以避免或缓解烯烃聚合反应中聚合物粘釜的问题,从而显著延长装置运行周期,并降低聚合物结垢清理的难度。
Description
技术领域
本发明涉及一种涂层材料,尤其涉及一种缓解聚合物粘釜的涂层材料及其在聚合反应器中的应用。
背景技术
聚烯烃弹性体(POE)是由茂金属催化乙烯和α-烯烃反应制得的无规共聚物,具有优异的耐候性和耐化学药品性,同时兼具有橡胶的高弹性和塑料的易加工性,近年来生产需求逐渐增加。作为POE重要原料的α-烯烃由乙烯齐聚制得,其生产技术是制约POE产业化的关键因素。
实验过程中发现,乙烯齐聚除了生成线性α-烯烃外,也会生成少量聚合物,而聚合物的物性与小分子化合物不同,其自身具有粘性,从而在生产过程中容易粘附在聚合反应器的内壁上影响反应的连续进行,甚至形成难以清除的结垢,这导致操作速率降低或产品成本增加。不可避免地,POE生产过程中也存在聚合物在反应器内容易挂壁粘附的问题,长时间不清理会堵塞管线进而导致装置停车。
因此,如何缓解或避免聚合物在反应器壁上的粘附,延长清理周期是亟需解决的问题。
专利CN112759963B公开了一种炊具用不粘陶瓷涂料,其采用三层硅油结构,两种分子量不同的硅油可位于涂层的不同位置,形成表面-中部-底部的硅油梯度,提高涂层的不粘持久性。但由于聚合物和小分子存在物性上的显著区别,解决聚合物防粘釜问题的难度更大,针对小分子物质作为防粘对象的涂层方案一般不适用于聚合反应器。
专利US4970278A通过将醌-胺化合物的涂料组合物涂覆反应器的内表面,改善聚合反应器壁表面的粘附性,防止聚合物垢沉积。但该方法仅使用于极性聚丙烯酸酯的生产聚合体系,对于非极性的烯烃聚合物在反应釜中的粘附问题不具有通用性;此外,该方法中采用的二胺是烯烃聚合中助催化剂的淬灭剂,会导致整个反应体系失活。
专利KR101677735B1提出了一种包含酚醛树脂、二氧化硅、聚乙烯醇的有机-无机杂化组合物,以解决聚合垢在反应器中附着的问题,但该组合物涂层同样仅适用于具有双键单体的聚合过程,若应用于烯烃聚合中,则酚醛树脂中的游离羟基会与助催化剂反应,导致助催化剂吸附在涂层表面成为活性位点,加速聚合物在位点处的生成。
发明内容
为了解决以上技术问题,本发明提出一种缓解聚合物粘釜的涂层材料及其在聚合反应器中的应用。
本发明人在研究中意外地发现,烯烃聚合反应中,产品聚合物或副产聚合物不仅由于其粘合特性容易粘附于反应器内壁上,而且反应器内壁金属表面缺陷会促进催化剂或助催化剂的吸附和沉积,使得活性中心转移至内壁表面的受限空间,从而改变了活性中心的化学环境,导致聚合物在内壁表面的加速生长。
本发明首先提供一种低表面能、高机械硬度的涂层材料,具有避免或缓解烯烃聚合物粘釜的技术效果;同时,改性硅氧烷的引入可以使粘附于反应器内壁上的烯烃聚合催化剂失活,避免在反应器内壁上形成活性中心而加速聚合物的生长和沉积,不仅使生成的聚合物结垢更容易清除,而且可以起到显著延长装置运行周期的作用。
本发明还提供一种缓解聚合物粘釜的涂层材料在烯烃聚合反应器中的应用。该涂层材料针对烯烃聚合反应器存在的聚合物粘釜的问题而针对性开发,将其施工于烯烃聚合反应器的碳钢内壁后,可以避免反应器壁表面的聚合物生长和沉积,延长装置清理周期,降低工艺成本。
为实现上述目的,本发明所采用的技术方案如下:
一种缓解聚合物粘釜的涂层材料,包括底漆和面漆;
所述底漆中各组分质量份为:
所述面漆中各组分质量份为:
根据本发明提供的实施方案,所述改性硅氧烷具有如下分子结构表达式:
其中,R1、R3和R4选自C1-C15的直链或支链烷烃、氢,R2选自C1-C3烷烃、酯基、羰基,X为卤素,m取自1-3,n取自10-15,p取自1-3,q取自0-15。
在一些示例中,所述硅溶胶中SiO2的浓度为10-35%,硅溶胶粒子比表面积为50-400m2/g,粒径为5-100nm。
在一些示例中,所述无机填料为氧化铝、氧化锌、云母粉、滑石粉、高岭土、硅藻土、碳酸钙、碳酸钡、二氧化硅、膨润土、纤维素中的一种或多种。
在一些示例中,所述催化剂为有机酸,优选甲酸、乙酸、柠檬酸、苹果酸、酒石酸、丁二酸、草酸中的一种或多种。
在一些示例中,所述羟基硅油的粘度为15-30000cp,羟基含量为3.5-8%。
在一些示例中,所述改性硅氧烷的制备方法如下:
1)将式I所示反应物与式II所示反应物在溶剂中混合,加热至45-60℃回流反应20-30h,冷却、析出后洗涤干燥,得到式III所示中间产物;
其中,R1、R2、R3、R4、X的定义与权利要求2相同,p取自1-3,q取自0-15;
2)惰性氛围下,将式III所示中间产物与式IV所示反应物在溶剂中混合,添加引发剂,80-100℃加热回流12-20h,得到粗产品;将粗产品旋蒸除去溶剂,正己烷洗涤、干燥,得到所述改性硅氧烷;
其中,m取自1-3。
在一些示例中,步骤1)中,式I所示反应物与式II所示反应物的摩尔比为(1.2-1.5):1;
优选地,步骤2)中,式III所示中间产物与式IV所示反应物的摩尔比为1:(1.0-1.3);
优选地,步骤2)中,引发剂的用量以摩尔量计,为式III所示中间产物摩尔量的0.1-0.5倍。
在一些示例中,所述式I所示反应物选自甲基丙烯酸二甲氨基乙酯、甲基丙烯酸二乙基氨基乙酯、6-(二甲基氨基)-1-己烯-3-酮、N,N-二甲基-4-戊烯-1-胺中的一种或多种;
优选地,所述式II所示反应物选自溴代十二烷、氯代十二烷、溴代十六烷、氯代十六烷中的一种或多种;
优选地,式IV所示反应物选自2-巯基乙基三甲基硅烷、3-巯丙基三甲氧基硅烷中的一种或两种;
优选地,引发剂选自偶氮二异丁腈、异丙苯过氧化氢、偶氮二异庚腈、过氧化二碳酸二异丙酯、过氧化苯甲酰中的一种或多种。
本发明还提供一种如前文所述的缓解聚合物粘釜的涂层材料在聚烯烃聚合反应器中的应用。
本发明中缓解聚合物粘釜的涂层材料的制备工艺,包括以下步骤:
(1)底漆的制备:
将硅溶胶、改性硅氧烷和催化剂按比例在40-50℃下搅拌混合20-30min,随后加入无机填料混匀后研磨至细度≤20μm,得到底漆;
(2)面漆的制备
将硅溶胶、改性硅氧烷、羟基硅油和催化剂按比例在40-50℃下搅拌混合20-30min,得到面漆。
经反应器应用现场测试,以上工艺制备的底漆涂料喷涂完流平干燥约5-10min(干膜厚10-20μm)后,即可喷涂面漆(干膜厚20-30μm),总的干膜厚30-50μm,流平5-15min,然后在200-300℃下烘烤120-240min进行熟化,其漆膜硬度≥8H,附着力≤1级,光泽≥40GU。
与现有技术相比,本发明提供的涂层材料,将低表面能、高机械强度的底漆与可交联的面漆相结合,在满足工程机械涂装领域中的漆膜外观、硬度、附着力等要求的同时,还可以避免或缓解烯烃聚合反应中聚合物粘釜的问题,从而显著延长装置运行周期,并降低聚合物结垢清理的难度。
说明书附图
图1为准备实施例1制得的改性硅氧烷的核磁共振氢谱谱图。
图2为实施例1制备涂层材料对应的聚合反应器在连续生产150h之后的内壁结垢示意图。
图3为对比例1制备涂层材料对应的聚合反应器在连续生产150h之后的内壁结垢示意图。
图4为对比例2制备涂层材料对应的聚合反应器在连续生产150h之后的内壁结垢示意图。
具体实施方式
下面通过具体实施例对本发明做进一步说明,本发明所述实施例只是作为对本发明的说明,不限制本发明的范围。
本发明以下实施例主要涉及的原料信息如下:
硅溶胶:型号1030CS,粒度10-15nm,30wt%,pH值=9-10,阿克苏诺贝尔有限公司;
甲酸:>96%,上海阿拉丁生化科技股份有限公司;
乙酸:99.8%,上海阿拉丁生化科技股份有限公司;
草酸:98.0%,上海阿拉丁生化科技股份有限公司;
柠檬酸:99.5%,上海阿拉丁生化科技股份有限公司;
二氧化硅:型号QS-10,平均粒径15nm,德山(化工)浙江有限公司;
氧化铝:型号VK-L05C,平均粒径15nm,宣城晶瑞新材料科技有限公司;
滑石粉:Finntalc M04SLC,星贝达(上海)化工材料有限公司;
羟基硅油:羟基含量3.5%,粘度30000cp,浙江环新氟材料股份有限公司;
甲基丙烯酸二甲氨基乙酯:99.0%,上海阿拉丁生化科技股份有限公司;
甲基丙烯酸二乙基氨基乙酯:99.0%,上海麦克林生化科技有限公司;
6-(二甲基氨基)-1-己烯-3-酮:97.0%,上海麦克林生化科技有限公司;
N,N-二甲基-4-戊烯-1-胺:96.0%,上海麦克林生化科技有限公司;
溴代十二烷:98.0%,上海麦克林生化科技有限公司;
溴代十六烷:98.0%,上海麦克林生化科技有限公司;
氯代十二烷:98.0%,上海麦克林生化科技有限公司;
氯代十六烷:98.0%,上海麦克林生化科技有限公司;
2-巯基乙基三甲基硅烷:99.0%,上海麦克林生化科技有限公司;
3-巯丙基三甲氧基硅烷:99.0%,上海麦克林生化科技有限公司;
乙腈:99.0%,上海麦克林生化科技有限公司;
乙酸乙酯:99.0%,上海麦克林生化科技有限公司;
偶氮二异丁腈(AIBN):98.0%,上海麦克林生化科技有限公司;
乙酰丙酮铬:98.0%,上海麦克林生化科技有限公司;
改性甲基铝氧烷(MMAO-3a):7wt%Al,正庚烷溶液,Nouryon;
甲基环己烷:99.0%,上海麦克林生化科技有限公司;
甲基三乙氧基硅烷:工业级,杭州桂宝化工集团有限公司;
iPr-PNP配体:根据文献Journal of the American Chemical Society(2004),126(45),14712-14713合成。
本发明以下实施例主要涉及的测试方法如下:
<1>气相色谱
气相色谱的分析条件:进样品温度:250℃;柱箱温度:35℃;
升温程序:先在35℃下保持10分钟,然后以10℃/min的速率升至250℃,接着在250℃下保持10min,然后开始降温,直至室温;
检测器温度:250℃;载体:1.0Mpa;空气:0.03Mpa;氢气:0.03Mpa;
产物的表征以壬烷作为内标物,进行表征,计算的方法如下:
式中的m1代表了某一种物质的质量,m为壬烷的质量,a1为这种物质在GC中测量出的峰面积,a为壬烷在GC中测量出的峰面积。k为校正系数。
<2>漆膜光泽:参考GB/T9754-2007中方法;
<3>漆膜硬度:参考GB/T6739-2006中方法;
<4>漆膜附着力:参考GB1720-1979中方法。
通过以下准备实施例1-5制备改性硅氧烷:
【准备实施例1】
反应表达式如下:
其中,m=3,n=10,p=2,q=11。
(1)将10g甲基丙烯酸二甲氨基乙酯和13.3g溴代十二烷(摩尔比1.2:1)溶于20ml乙腈中,45℃加热回流20h,反应结束后冷却至-5℃以下,析出固体,用无水乙醚洗涤数次,抽滤,真空干燥,得到中间产物;
(2)氮气氛围下,将5g 3-巯丙基三甲氧基硅烷与10.4g制得的中间产物(摩尔比1.0:1)溶于23ml乙酸乙酯中,随后加入0.4g引发剂AIBN(摩尔比0.1:1),80℃加热回流12h,得到粗产品;将粗产品旋蒸除去溶剂,加入正己烷洗涤、沉淀,抽滤,真空干燥,得到改性硅氧烷A。
对产物进行1H-NMR测试,以氘代二甲基基亚砜为溶剂(浓度为5wt%),其核磁共振氢谱谱图如图1所示。其中,化学位移在3.29ppm处的峰对应的是中-O-CH3-上氢原子的吸收峰,化学位移在1.21ppm和2.99ppm处的峰分别对应中-(CH2)q-氢原子吸收峰和连接在N原子上的-CH3氢原子吸收峰。
【准备实施例2】
其中,m=3,n=14,p=2,q=11。
(1)将10g甲基丙烯酸二乙基氨基乙酯和3.7g氯代十二烷(摩尔比1.5:1)溶于18ml乙腈中,60℃加热回流30h,反应结束后冷却至-10℃以下,析出固体,用无水乙醚洗涤数次,抽滤,真空干燥,得到中间产物;
(2)氮气氛围下,将5g 3-巯丙基三甲氧基硅烷与7.6g中间产物(摩尔比1.3:1)溶于24ml乙酸乙酯中,随后加入1.6g引发剂AIBN(摩尔比0.5:1),100℃加热回流20h,得到粗产品;将粗产品旋蒸除去溶剂,加入正己烷洗涤、沉淀,抽滤,真空干燥,得到改性硅氧烷B。
【准备实施例3】
其中,m=3,n=12,p=2,q=15。
(1)将10g 6-(二甲基氨基)-1-己烯-3-酮和16.6g溴代十六烷(摩尔比1.3:1)溶于44ml乙腈中,50℃加热回流24h,反应结束后冷却至0℃以下,析出固体,用无水乙醚洗涤数次,抽滤,真空干燥,得到中间产物;
(2)氮气氛围下,将5g 3-巯丙基三甲氧基硅烷与9.5g中间产物(摩尔比1.2:1)溶于25ml乙酸乙酯中,随后加入1.0g引发剂AIBN(摩尔比0.3:1),90℃加热回流15h,得到粗产品;将粗产品旋蒸除去溶剂,加入正己烷洗涤、沉淀,抽滤,真空干燥,得到改性硅氧烷C。
【准备实施例4】
其中,m=3,n=13,p=2,q=15。
(1)将10g N,N-二甲基-4-戊烯-1-胺和14.6g氯代十六烷(摩尔比1.4:1)溶于48ml乙腈中,55℃加热回流28h,反应结束后冷却至0℃以下,析出固体,用无水乙醚洗涤数次,抽滤,真空干燥,得到中间产物;
(2)氮气氛围下,将5g 3-巯丙基三甲氧基硅烷与8.9g中间产物(摩尔比1.1:1)溶于27ml乙酸乙酯中,随后加入1.5g引发剂AIBN(摩尔比0.4:1),95℃加热回流18h,得到粗产品;将粗产品旋蒸除去溶剂,加入正己烷洗涤、沉淀,抽滤,真空干燥,得到改性硅氧烷D。
【准备实施例5】
其中,m=2,n=11,p=2,q=11。
(1)将10g甲基丙烯酸二甲氨基乙酯和13.3g溴代十二烷(摩尔比1.2:1)溶于36ml乙腈中,45℃加热回流20h,反应结束后冷却至0℃以下,析出固体,用无水乙醚洗涤数次,抽滤,真空干燥,得到中间产物;
(2)氮气氛围下,将5g 2-巯基乙基三甲基硅烷与11.2g中间产物(摩尔比1.0:1)溶于30ml乙酸乙酯中,随后加入0.6g引发剂AIBN(摩尔比0.1:1),80℃加热回流12h,得到粗产品;将粗产品旋蒸除去溶剂,加入正己烷洗涤、沉淀,抽滤,真空干燥,得到改性硅氧烷E。
以下实施例1-5用于制备不同的涂层材料:
【实施例1】
(1)底漆的制备:
将55g硅溶胶、30g改性硅氧烷A和7g乙酸在40-50℃下搅拌混合20-30min,随后加入8g二氧化硅混匀后研磨至细度≤20μm,得到底漆;
(2)面漆的制备
将50g硅溶胶、35g改性硅氧烷A、5g羟基硅油和10g乙酸在40-50℃下搅拌混合20-30min,得到面漆。
【实施例2】
(1)底漆的制备:
将55g硅溶胶、35g改性硅氧烷B和5g草酸在40-50℃下搅拌混合20-30min,随后加入10g二氧化硅混匀后研磨至细度≤20μm,得到底漆;
(2)面漆的制备
将40g硅溶胶、40g改性硅氧烷B、10g羟基硅油和6g草酸在40-50℃下搅拌混合20-30min,得到面漆。
【实施例3】
(1)底漆的制备:
将50g硅溶胶、40g改性硅氧烷C和10g柠檬酸在40-50℃下搅拌混合20-30min,随后加入15g氧化铝混匀后研磨至细度≤20μm,得到底漆;
(2)面漆的制备
将45g硅溶胶、45g改性硅氧烷C、15g羟基硅油和8g柠檬酸在40-50℃下搅拌混合20-30min,得到面漆。。
【实施例4】
(1)底漆的制备:
将52g硅溶胶、50g改性硅氧烷D和9g乙酸在40-50℃下搅拌混合20-30min,随后加入13g滑石粉混匀后研磨至细度≤20μm,得到底漆;
(2)面漆的制备
将55g硅溶胶、50g改性硅氧烷D、8g羟基硅油和10g乙酸在40-50℃下搅拌混合20-30min,得到面漆。
【实施例5】
(1)底漆的制备:
将60g硅溶胶、43g改性硅氧烷E和4g乙酸在40-50℃下搅拌混合20-30min,随后加入6g二氧化硅混匀后研磨至细度≤20μm,得到底漆;
(2)面漆的制备
将40g硅溶胶、55g改性硅氧烷E、12g羟基硅油和5g乙酸在40-50℃下搅拌混合20-30min,得到面漆。
【对比例1】
按照与实施例1基本相同的配方和方法提供涂层材料,区别仅在于,将底漆和面漆中的改性硅氧烷替换为甲基三乙氧基硅烷。
【对比例2】
参照专利CN112759963B实施例5中方案制备陶瓷涂料。
对各实施例、对比例制备得到的涂层材料进行表1所示的性能测试,测试结果如下:
表1、各涂层材料的性能测试结果
光泽/GU | 硬度 | 附着力 | |
实施例1 | 90 | 9H | 0级 |
实施例2 | 89 | 8H | 1级 |
实施例3 | 92 | 8H | 0级 |
实施例4 | 93 | 8H | 0级 |
实施例5 | 91 | 9H | 0级 |
对比例1 | 85 | 8H | 1级 |
对比例2 | 84 | 8H | 1级 |
说明:光泽测试的是60°镜面光泽。
按照以下方法,将各实施例、对比例制备得到的涂层材料分别施工到相同规格的不同聚合反应器中,得到涂覆有涂层的相应聚合反应器:
经反应器应用现场测试,以上工艺制备的底漆(干膜厚20μm)涂料喷涂完流平干燥约5min后,再喷涂面漆(干膜厚20μm),总的干膜厚为40μm,流平10min,然后在260℃下烘烤150min进行熟化。其中对比例2中涂料配方既作为底漆又作为面漆。
按照以下聚合方法,分别在各实施例、对比例中涂层材料应用的聚合反应器中进行乙烯齐聚反应:
将iPr-PNP配体和乙酰丙酮铬溶解于甲基环己烷溶液中,配置成铬浓度为0.5μmol/ml的催化剂。
向容积500ml反应器中分别进料,其中溶剂甲基环己烷进料量为270g/h,催化剂进料量为8.4g/h,MMAO-3a进料量为1.0g/h,乙烯进料量为100g/h,停留时间1h。
在各聚合反应器连续运行150h之后,实时分析并记录反应转化率、选择性以及反应活性,同时拆釜观察聚合物粘釜情况,各测试结果如表2所示:
表2、乙烯齐聚反应结果
说明:①聚合物可去除性根据聚合物结垢的清理难度从易到难分为1、2、3档,其中,1表示聚合物结垢沟通过抹布轻轻擦拭即可清除;2表示聚合物结垢沟通过抹布擦除较为费力,但仍可擦拭除去;3表示聚合物结垢较为致密,只能通过钢丝球摩擦除去。②聚合物结垢量通过拆釜后收集聚合物,再真空干燥称量干重获得。
此外,对实施例1、对比例1、对比例2制备涂层材料对应的聚合反应器在连续生产150h之后的内壁表面进行拍照观察(分别如图2-4所示),可以看出,实施例1对应的聚合反应器内聚合物结垢较少,对比例1中有所增多,而对比例2中最多,由此表明,本发明提供的涂层材料对缓解聚合物粘釜的问题具有重要作用。
以上所述仅是本发明的优选实施方式,应当指出,对于本领域技术的普通技术人员,在不脱离本发明方法的前提下,还可以做出若干改进和补充,这些改进和补充也应视为本发明的保护范围。
Claims (15)
1.一种缓解聚合物粘釜的涂层材料,其特征在于,包括底漆和面漆;
所述底漆中各组分质量份为:
所述面漆中各组分质量份为:
所述改性硅氧烷具有如下分子结构表达式:
其中,R1、R3和R4选自C1-C15的直链或支链烷基、氢,R2选自C1-C3烷基、酯基、羰基,X为卤素,m取自1-3,n取自10-15,p取自1-3,q取自0-15。
2.根据权利要求1所述的缓解聚合物粘釜的涂层材料,其特征在于,所述硅溶胶中SiO2的浓度为10-35%,硅溶胶粒子比表面积为50-400m2/g,粒径为5-100nm。
3.根据权利要求1所述的缓解聚合物粘釜的涂层材料,其特征在于,所述无机填料为氧化铝、氧化锌、云母粉、滑石粉、高岭土、硅藻土、碳酸钙、碳酸钡、二氧化硅、膨润土、纤维素中的一种或多种。
4.根据权利要求1-3任一项所述的缓解聚合物粘釜的涂层材料,其特征在于,所述催化剂为有机酸。
5.根据权利要求4所述的缓解聚合物粘釜的涂层材料,其特征在于,所述催化剂为甲酸、乙酸、柠檬酸、苹果酸、酒石酸、丁二酸、草酸中的一种或多种。
6.根据权利要求1-3任一项所述的缓解聚合物粘釜的涂层材料,其特征在于,所述羟基硅油的粘度为15-30000cp,羟基含量为3.5-8%。
7.根据权利要求2所述的缓解聚合物粘釜的涂层材料,其特征在于,所述改性硅氧烷的制备方法如下:
1)将式I所示反应物与式II所示反应物在溶剂中混合,加热至45-60℃回流反应20-30h,冷却、析出后洗涤干燥,得到式III所示中间产物;
其中,R1、R3和R4选自C1-C15的直链或支链烷基、氢,R2选自C1-C3烷基、酯基、羰基,X为卤素,p取自1-3,q取自0-15;
2)惰性氛围下,将式III所示中间产物与式IV所示反应物在溶剂中混合,添加引发剂,80-100℃加热回流12-20h,得到粗产品;将粗产品旋蒸除去溶剂,正己烷洗涤、干燥,得到所述改性硅氧烷;
其中,m取自1-3。
8.根据权利要求7所述的缓解聚合物粘釜的涂层材料,其特征在于,步骤1)中,式I所示反应物与式II所示反应物的摩尔比为(1.2-1.5):1。
9.根据权利要求8所述的缓解聚合物粘釜的涂层材料,其特征在于,步骤2)中,式III所示中间产物与式IV所示反应物的摩尔比为1:(1.0-1.3)。
10.根据权利要求8所述的缓解聚合物粘釜的涂层材料,其特征在于,步骤2)中,引发剂的用量以摩尔量计,为式III所示中间产物摩尔量的0.1-0.5倍。
11.根据权利要求7-10任一项所述的缓解聚合物粘釜的涂层材料,其特征在于,所述式I所示反应物选自甲基丙烯酸二甲氨基乙酯、甲基丙烯酸二乙基氨基乙酯、6-(二甲基氨基)-1-己烯-3-酮、N,N-二甲基-4-戊烯-1-胺中的一种或多种。
12.根据权利要求11所述的缓解聚合物粘釜的涂层材料,其特征在于,所述式II所示反应物选自溴代十二烷、氯代十二烷、溴代十六烷、氯代十六烷中的一种或多种。
13.根据权利要求11所述的缓解聚合物粘釜的涂层材料,其特征在于,式IV所示反应物为3-巯丙基三甲氧基硅烷。
14.根据权利要求11所述的缓解聚合物粘釜的涂层材料,其特征在于,引发剂选自偶氮二异丁腈、异丙苯过氧化氢、偶氮二异庚腈、过氧化二碳酸二异丙酯、过氧化苯甲酰中的一种或多种。
15.一种如权利要求1-14任一项所述的缓解聚合物粘釜的涂层材料在聚烯烃聚合反应器中的应用。
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