CN1172813A - 从悬浮法制备丙烯酸类聚合物的方法 - Google Patents

从悬浮法制备丙烯酸类聚合物的方法 Download PDF

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CN1172813A
CN1172813A CN96123344A CN96123344A CN1172813A CN 1172813 A CN1172813 A CN 1172813A CN 96123344 A CN96123344 A CN 96123344A CN 96123344 A CN96123344 A CN 96123344A CN 1172813 A CN1172813 A CN 1172813A
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P·雷维尼
F·吉伯蒂
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Abstract

本发明涉及在含水悬浮液中聚合丙烯酸类单体的方法,其中至少有一种共聚用单体在水中的溶解度为每100克水不小于5克,从而在可溶于单体的自由基引发剂和聚合的悬浮剂的存在下得到含可溶于水的共聚用单体的重量百分含量达60%的共聚物,所述聚合的悬浮剂选自其式中R1、R2、R3、A和M的定义如说明书中所述的上式化合物的均聚物。

Description

从悬浮法制备丙烯酸类聚合物的方法
本发明涉及丙烯酸类(共)聚合物珠粒的制造方法，具体地说涉及含有以下定义的可溶于水的丙烯酸类共聚用单体的丙烯酸类共聚物。
在悬浮液中聚合丙烯酸类单体是已知的，该方法按以下方式执行，其中，丙烯酸类单体通常以小液滴状悬浮于连续相中，由可溶于该单体的自由基型引发剂引发反应。连续相通常是水，连续相(水)与非连续相(单体)的比例一般为1∶1-3∶1。最终产物由直径为0.1-1mm的聚合物颗粒(珠粒)的悬浮液构成，该颗粒很容易通过离心作用与水分离。
在这类方法的实际操作过程中，必须使用悬浮稳定剂来防止进一步聚合反应中单体小液滴聚结。
使用的悬浮稳定剂是对单体分子具有亲合力的可溶于水的大分子，所以其在有机相和水相之间的界面形成一层保护膜，阻止颗粒附聚。在聚合结束时，悬浮剂可以用水洗而从聚合物颗粒表面除去。
无论对于最终产品的质量，还是生产成本，如原材料具体消耗、生产效率等，悬浮剂的特征都决定着整个方法的特性，因此悬浮剂是一个关键性因素。
丙烯酸类单体在水悬浮液中的各种聚合方法通常是已知的。欧洲专利申请457,356号公开了其中的一种方法：以选自下式化合物的均聚物的特定聚合物作为含水悬浮液的悬浮剂和稳定剂：
Figure A9612334400041
这里R1=H，CH3；R2和R3相同或不同，为H，C1-C8的直链或支链烷基；M为碱金属、碱土金属，或丙烯酸类单体与上述化合物的共聚物。
上述申请的实验表明：使用水/单体的比为1∶1-3∶1的上述欧洲专利申请的分散剂进行悬浮聚合，不可能得到本发明的共聚物本身。
上述申请的实验还证明：当可溶于水的单体参加共聚时，悬浮液的稳定性受损，出现附聚现象。在剧烈的情况下，整个聚合物结成块，妨碍搅拌。不严重的情况下，在聚合反应器的内壁上生成硬皮壳结构和聚合物块。总之，这些情况使得该方法不能工业化应用，除非降低反应的临界状态，比如采用高的水/单体比和/或相当慢的聚合反应动力学。而在任何情况下，上述改变都会损害生产效率。
本领域内已知的还有其他有机或无机悬浮剂，比如聚乙烯醇，羟烷基纤维素等；无机类的如磷酸三钙和所谓的增充剂(表面活性剂)结合使用。
但是，使用这些悬浮剂的弊端在于：所得到聚合物的光学性能不适合应用于丙烯酸类产品的典型应用领域，比如照明设备、汽车灯、标示牌等。
在非水介质(溶剂)悬浮液中进行聚合也是已知的，但其弊端是溶剂和聚合物回收需要更高的成本，同时溶剂本身易燃易爆带来安全问题。
本领域所知采用溶液聚合方法也可以生产本发明的共聚物：丙烯酸类单体溶于适宜的溶剂中，自由基方式聚合。采用该方法可以制成本发明的共聚物，但该方法的缺点是溶剂不易从上述聚合物中分离。
在溶液聚合中可供选择的方法是本体聚合，即溶剂就取单体本身。
从工业的观点看，溶液聚合和本体聚合这两种方法通常都是连续化生产，如果使用同样体积的设备，比半连续生产有更高的效率，但其缺点是产品缺少工业上的柔韧性。
一般而言，水溶性共聚单体的共聚物的生产容积目前还不适宜于连续化生产的设备。一个连续生产方法需要对未反应单体和一系列转变过程中生成的聚合物的回收进行一系列的处理。
本发明的共聚物也可以通过乳液聚合得到，但乳液的分离对设备要求更高，成本也更高。另外，由于表面活性剂和/或凝结剂的加入导致所得共聚物的光学纯度降低。
人们希望通过某种处理找到一种工业化生产含有水溶性共聚单体共聚物的方法，其应生产量大，产品具备高质量丙烯酸类产品所具有的良好机械、光学性能，而且采用多用途(不连续)装置也能生产。
现在，我们有一个意想不到的、令人吃惊的发现，就是通过下面描述的方法可使人们上述愿望成为可能。
本发明的目的是找到丙烯酸类单体在水悬浮液中聚合的方法，其中至少一种共聚单体在水中溶解度为每100克水至少5g，从而在可溶于单体的自由基引发剂以及聚合悬浮剂的存在下，得到含可溶于水共聚单体达60％，更好为0.5-40％，最好为2-20％重量的共聚物，所述聚合悬浮剂选自：
(a)下式表示的化合物的均聚物：
Figure A9612334400061
这里R1＝H或CH3；R2和R3相同或不同，是H或C1-C8的烷基，任选地为支链烷基；M是碱金属、碱土金属或铵；A是NH、O或NCH3，
(b)不超过40wt％的丙烯酸类单体与(I)式化合物的共聚物，该方法的特征在于，该聚合反应中的水相全部或部分来源于丙烯酸类单体聚合所得到的母液，甚至不同于将要制造的聚合物所使用的液相，也不含有水可溶性共聚用单体，珠状产物分离后，上述母液有一个由悬浮剂和聚合生成的其他产物构成的有机相，可选择地进一步向母液中加入上述分散剂，以便得到一种水相，该水相中含有0.01-1％重量的悬浮剂和0.05-5％、优选0.05-1.5％重量的上述聚合生成的产物。
悬浮剂的较佳浓度是0.03-0.3％。
本发明方法可以使用悬浮聚合通常的方式进行，即水相与单体比一般为1∶1-3∶1，较好为1.5∶1-2.5∶1，采用可溶于单体的分子量调节剂和自由基聚合引发剂。
反应温度是引发剂分解的温度，通常是50-120℃
假如考虑上述悬浮剂和聚合中得到的“其他产物”的最低浓度，则水相中应有10-100％，较好为30-100％重量是从先前聚合得到的母液而来。
母液不一定必须由与上述发明目标单体相为同一组成的单体聚合而得到。
将丙烯酸类聚合物通过如离心或过滤分离后所得到的这种母液，根据反应条件不同，一般含有0.3-3％重量份的有机相(上述的“其他产物”)，这是在160℃为干残渣时测定。上述母液的10-100％可以循环使用，如果必要可以任选地补充一定量的含有新鲜悬浮剂的水。
根据本发明方法，可以聚合的单体混合物构成如下：a1)一种或多种丙烯酸或甲基丙烯酸的C1-C8烷基酯，直链或支链，如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸异丙酯、丙烯酸丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯；b1)一种或多种可溶于水的单体，其23℃时在水中的溶解度为每100克水不小于5克，且其含量一般不超过60％重量，较好为50％重量，如丙烯酸、甲基丙烯酸、丙烯酰胺、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯；c1)任意另一种单体，其含量不超过50％重量，比如，苯乙烯、α-甲基苯乙烯、(甲基)丙烯腈，正烷基或芳基-马来酰亚胺(其中烷基有1-10个碳原子，芳基有6-12个碳原子)，丁二烯、磺化苯乙烯，N-乙烯基吡咯烷酮。
自由基引发剂为过氧化物，如叔丁基过氧化-2-乙基己酸酯，过氧化二苯甲酰，叔丁基过氧化二乙基乙酸酯或为不稳定的偶氮化合物，如偶氮二异丁腈。
链转移剂可以使用直链或支链的C3-C20，最好C4-C12的烷基硫醇。比如正丁硫醇、正辛硫醇、正十二硫醇、叔一十二硫醇、环己硫醇、蒎烷硫醇。
参考欧洲专利457,356号，本发明方法所使用的稳定剂是在水溶液中由式(I)的化合物均聚合或其与丙烯酸类单体共聚合而制备。
特别地，式(I)的化合物可以是：2-丙烯酰氨基-2-甲基丙磺酸钠，2-甲基丙烯酰氨基-2-甲基丙磺酸钠、2-丙烯酰氨基丙磺酸钠，2-丙烯酰氨基-2-乙磺酸钠。
式(I)的化合物中R2和R3优选是C1-C8的烷基，也可以是支链烷基。
能够与(I)式化合物共聚的丙烯酸类单体是：(甲基)丙烯酰胺，(甲基)丙烯酸的碱金属或碱土金属盐，(甲基)丙烯酸与C1-C4脂肪醇的酯，丙烯腈。
采用本发明的方法，可以工业制造上述组成的珠粒，即该珠粒含可溶于水单体达60％，优选为丙烯酸类单体，其操作条件水/单体比例接近1，聚合动力学大约2个小时，并且具备以下优点：
- 浮液有最理想的稳定性。因此没有出现聚合物附聚或粘污反应器内壁的不愿见到的现象。
-需要除去的生产用水明显减少。
-悬浮剂的消耗量明显减少，但没有影响所得聚合物良好的机械和光学性能。
下面给出本发明的实施例，但不限于这些实施例。实施例1
               悬浮剂的制备
将120份40％(重量)的NaOH溶液，630份去离子水装入反应器。缓慢加入250份2-丙烯酰氨基-2-甲基丙磺酸(AMPS)，然后用少量苏打或AMPS调节溶液pH值在7-8之间。向溶液中通N2气以除去O2气，并加热到50℃，然后加入0.075份过硫酸钾和0.025份焦亚硫酸钠。聚合反应大约60分钟，然后加入4000份去离子水稀释，得到一种含有5.5％(重量)干残渣(160℃时)的溶液，其在25℃时布氏粘度为4Pa·s。实施例2(对比)
          甲基丙烯酸以及甲基丙烯酸甲酯共聚物的制备
甲基丙烯酸甲酯以及甲基丙烯酸进行悬浮聚合，采用实施例1中所得到的2-丙烯酰氨基-2-甲基丙磺酸的钠盐的均聚物作为悬浮剂。
将193份去离子水和7份实施例1中所得的溶液(相应于0.385份干残渣产物)加入一带搅拌、有套层、耐压的反应器中，通入N2除去O2，把溶液加热至80℃。加入100份去氧的混合物，该混合物组成为：甲基丙烯酸甲酯90份，甲基丙烯酸8份，丙烯酸甲酯2份，叔丁基过氧化-2-乙基己酸酯0.25份，正丁硫醇0.19份。反应器密封，压力为100KPa，连续搅拌，在120分钟内将混合液逐渐加热至110℃。这样就制得了一种不稳定的悬浮液，反应器局部阻塞，该制得的聚合物不能应用。
反应器需要机械方式除去凝块，然后用溶剂清洗。实施例3(对比)
                  母液的制备
甲基丙烯酸甲酯以及丙烯酸乙酯进行悬浮聚合，采用实施例1中所得的2-丙烯酰氨基-2-甲基丙磺酸的钠盐的均聚物作悬浮剂。
将193份去离子水和7份实施例1中所得溶液(相应于0.385份干残渣产物)放入一带搅拌、有套层、耐压的反应器中，通入N2排除O2，并把溶液加热到80℃。然后加入：甲基丙烯酸甲酯98份，丙烯酸甲酯2份，叔丁基过氧化-2-乙基己酸酯0.25份，正丁硫醇0.19份。反应器密封，压力为100KPa，连续搅拌下在120分钟内将混合液加热到110℃。然后维持15分钟再冷却。得到的珠状聚合物产品通过离心作用与母液分离，用去离子水洗涤后于80℃炉中干燥。然后把聚合物放500μm的滤网上过筛，剩下部分低于0.5％。
珠状产品通过挤压成为细颗粒以便注模造型。所得到的细粒其性能见表2。母液中含有约0.62％重量的干残渣(160℃时)，其由一部分悬浮剂(0.2％重量)和聚合生成的少量其他产物构成。把母液收集起来在以后的聚合实验中可以重新利用。聚合反应器出料用水冲洗后，清洁干净，所以适合接着进行下一个聚合反应。实施例4
          甲基丙烯酸以及甲基丙烯酸甲酯共聚物的制备
使用实施例2中同样的反应器，采用上述实施例所述的操作方法，以实施例3聚合反应中得到的母液的一部分作为悬浮剂，由甲基丙烯酸甲酯以及甲基丙烯酸进行悬浮聚合反应。
将200份实施例3中所得母液加入反应器中，加热至80℃，然后加入甲基丙烯酸甲酯90份，甲基丙烯酸8份，丙烯酸甲酯2份，叔丁基过氧化-2-乙基己酸酯0.25份，正丁硫醇0.19份。根据实施例2所述的方法进行聚合反应。聚合结束后反应器维持在110℃ 15分钟，然后冷却。珠状聚合物通过离心过程与母液分离，用去离子水洗涤并放于80℃炉中干燥。然后放于500微米滤网上过筛，留下部分不到0.5％。
珠状产品挤压成细颗粒以便注模成型。所得细颗粒的性质列于表2中。聚合反应器出料用水冲洗后，干净清洁，所以适合以后的聚合反应。实施例5-11
以下的实施例5-11，其操作方式与实施例4同，使用同一反应器，同样组成的水相进行反应。
表1中列出了单体相的组成，所得聚合物的性质列于表2中。
聚合反应器每次试验出料用水冲洗后都是清洁的，因此适宜于进行下一次聚合反应。
表1
 实施例号  水相  甲基丙烯酸甲酯(MMA)  甲基丙烯酸  苯乙烯 丙烯酸 丙烯酰胺   引发剂(*)   调节剂(**)
 (份)     (份)   (份)   (份)   (份)   (份)    (份)   (份)
    5  200     60    40     -     -     -     0.25     0.19
    6  200     80    20     -     -     -     0.25     0.19
    7  200     84    8     8     -     -     0.25     0.23
    8  200     72    8     20     -     -     0.25     0.19
    9  200     52    8     40     -     -     0.25     0.19
    10  200     90     -     -     10     -     0.25     0.19
    11  200     90     -     -     -     10     0.25     0.19
(*)叔丁基过氧化-2-乙基己酸酯
(**)正丁硫醇
表2
实施例号  黄度指数(*)   霾系数(**)  透光率(***)    特性粘度(****)     MFR(□)   维卡49N(□*)
    ％     ％     cc/g      g     ℃
    2     -    (□**)    (□**)    (□**)    (□**)    (□**)
    3     2.1     0.50     92     48     3.0     108
    4     3.2     0.50     92     50     1.1     117
    5     6.0     0.50     92     60     0.2     145
    6     4.3     0.50     92     55     0.6     135
    7     3.7     0.53     92     40     3.9     119
    8     4.2     0.60     91     50     1.7     117
    9     6.1     0.70     91     62     3.5     111
    10     4.0     0.50     92     50     3.0     116
    11     4.5     0.55     92     50     3.0     110
(*)美国材料试验学会(ASTM)D1925-70标准(**)试样厚度3mm，ASTM D1003-61标准(***)(400-900nm)，试样厚3mm，ASTM D1003-61标准(****)ISO 1628-116标准(□)230℃，3.8kg，ISO 1133标准(□*)ISO 306标准(□**)没有得到珠状产物(反应器阻塞)

Claims (5)

1 一种丙烯酸类单体悬浮聚合的方法，其中至少有一种共聚单体在水中的溶解度为每100克水不小于5克，从而在可溶于单体的自由基引发剂和聚合悬浮剂的存在下，获得含可溶于水共聚单体达60wt％的共聚物，聚合悬浮剂选自：a)下式化合物的均聚物
Figure A9612334400021
这里R1＝H或CH3；R2和R3相同或不同，是H或C1-C8的烷基，任选地是支链烷基；M是碱金属、碱土金属或铵；A是NH、O或NCH3，b)不超过40wt％的丙烯酸类单体与(I)式化合物的共聚物，其特征在于：聚合反应中的水相全部或部分来源于丙烯酸类单体聚合得到的母液，甚至不同于将要制造的聚合物所使用的液相，也不含有可溶于水的共聚单体，珠状产物分离后，上述母液有一个由悬浮剂和聚合生成的其他产物构成的有机相，可以任选地加入一定量的上述悬浮剂，以便得到含0.01-1％重量的悬浮剂，上述聚合生成的产物含量为0.05-5％重量的水相。
2 根据权利要求1所述的丙烯酸类单体的悬浮聚合方法，其中至少一种共聚单体可溶于水，其特征在于：聚合反应的水相中，上述提到的聚合中得到的“其他产物”含量为0.05-1.5％重量，悬浮剂的浓度为0.03-0.3％重量。
3 根据权利要求1和权利要求2所述的丙烯酸类单体的悬浮聚合方法，其中至少一种共聚单体可溶于水，其特征在于：水和单体的比例为1.5∶1-2.5∶1。
4 根据权利要求1-3所述的丙烯酸类单体的悬浮聚合方法，其中至少一种共聚单体可溶于水，其特征在于：单体混合物由以下构成：a1)一种或多种丙烯酸或甲基丙烯酸的C1-C8烷基酯，烷基是直链或支链，如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸异丙酯、丙烯酸丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯；b1)一种或多种可溶水的单体，其23℃时在水中的溶解度为每100克水不小于5克，其含量不超过60％重量，较好为50％重量，如丙烯酸、甲基丙烯酸、丙烯酰胺、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯；c1)任选地另一种单体，其含量不超过的50％重量，比如苯乙烯、α-甲基苯乙烯、(甲基)丙烯腈、C1-C10正烷基或C6-C12芳基-马来酰亚胺、丁二烯、磺化苯乙烯、N-乙烯基吡咯烷酮。
5 根据权利要求1-4所述的丙烯酸类单体的悬浮聚合方法，其中至少一种共聚单体可溶于水，其特征在于：(I)式所示的悬浮剂从以下化合物选取：2-丙烯酰氨基-2-甲基丙磺酸钠、2-甲基丙烯酰氨基-2-甲基丙磺酸钠、2-丙烯酰氨基丙磺酸钠、2-丙烯酰氨基-2-乙磺酸钠。
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CN100378135C (zh) * 2001-01-18 2008-04-02 克拉通聚合物研究有限公司 苯乙烯嵌段共聚物在印刷板中的用途
CN110914318A (zh) * 2017-07-31 2020-03-24 阿科玛法国公司 包含含有甲基丙烯酸甲酯、(甲基)丙烯酸和苯乙烯单体的共聚物的组合物

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IT1282651B1 (it) * 1996-02-19 1998-03-31 Atohaas Holding Cv Processo per la preparazione di perle di polimeri a base acrilica
US7067188B1 (en) 1999-01-21 2006-06-27 Arkema Polymeric articles having a textured surface and frosted appearance
IT1317864B1 (it) * 2000-02-01 2003-07-15 Elf Atochem S A Ora Atofina Composizioni di polimeri acrilici.
US6878436B2 (en) 2002-05-23 2005-04-12 Atofina Light emitting diode signs and translucent plastic sheets used therein
FR3045056B1 (fr) 2015-12-09 2019-08-02 Arkema France Methode de preparation d'une composition comprenant un copolymere comprenant des monomeres de methacrylate de methyle et d'acide methacrylique

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CN100378135C (zh) * 2001-01-18 2008-04-02 克拉通聚合物研究有限公司 苯乙烯嵌段共聚物在印刷板中的用途
CN110914318A (zh) * 2017-07-31 2020-03-24 阿科玛法国公司 包含含有甲基丙烯酸甲酯、(甲基)丙烯酸和苯乙烯单体的共聚物的组合物

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