CN1037900A - 主链上有异氰酸官能团的缩醛共聚物 - Google Patents
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Abstract
合成了用碘异氰基、碘脲和唑改性的1，3-二
氧杂环庚-5-烯环状单体，并用于同三烷进行共聚
反应，从而制得主链上有官能团的缩醛共聚物。本发
明还涉及从主链上带双键的缩醛共聚物制备含碘脲
和唑官能团的缩醛共聚物的方法。
Description
聚缩醛共聚物是具有工业价值的大分子，它们在很多实际应用中可以同金属、陶瓷和尼龙相竞争。按照现在的工艺方法，它们是采用三噁烷与一种共聚用单体诸如环氧乙烷、二氧戊环、或丁二醇缩甲醛经共聚制得。这种共聚物的每个分子最多带有二个官能团，如羟基端基。对于诸如制备接枝共聚物和带有化学键合的稳定剂的聚合物来说，最好是合成出官能团含量较高的聚缩醛类。本发明的一个目的便是制备三噁烷的聚缩醛类共聚物，其稳定性要相当于或高于常用的树脂，同时还具有可用于进一步改性或连结添加剂的官能团。
从常用的缩醛类树脂产物中，诸如脒热稳定剂之类的添加剂往往会存在于聚合物的无定形区。由于这种非结晶区在空间的分布是无规的，就宏观性质而论，添加剂的这种分布常常不是最适宜的。如果能够把官能团的部分设置在有规则或半有规则的间隔（例如无规共聚物），这就可以使稳定剂或冲击改性剂连结在树脂中预定的空间位置，从而得到优良而更加均匀的性质。由于聚缩醛的晶体结构使添加剂可以在空间阻断结晶区，这种方法尤其优越。因此，最理想的是提供聚合物主链部份，它们可以按可控制的方式阻断聚合物的晶体结构，并为连结添加剂提供空间位置。
具有这种主链官能团的聚缩醛共聚物在很多重要的实际应用场合中会是有用的，诸如：a）制备带有化学键合稳定剂的三噁烷共聚物;b）制备带有化学键合冲击改性剂的三噁烷共聚物;c）制备三噁烷的接枝共聚物，用作与已有市售的缩醛类共聚物共混体的相容剂，或用作与别的聚合物材料（如玻璃或矿物）的相容剂;d）制备适合于表面改性的共聚物;e）制备交联的共聚物。
本发明涉及5-碘-6-异氰基-1，3-二氧杂环庚烷、5-碘-6-脲-1，3-二氧杂环烷以及5，6-噁唑-1，3-二氧杂环庚烷的制备，并涉及用这些共聚用单体同三噁烷聚合，以制取主链上有官能团的缩醛类共聚物。
本发明还涉及由三噁烷和1，3-二氧杂环庚-5-烯共聚制得的TX-DXPE缩醛共聚物制取带有碘脲和噁唑官能团的缩醛共聚物的方法。对TX-DXPE共聚物主链上双键的改性可在乙腈溶剂体系中有效地完成。
实施例1
单体的合成：
1，3-二氧杂环庚-5-烯，DXPE
将176克（2摩尔）顺式-2-丁烯-1，4-二醇，60克（2摩尔）多聚甲醛，25毫升苯和0.25克对甲苯磺酸的混合物借助一个迪安-斯达克（Dean-Stark）分水器进行回流，至水完全除掉。反应混合物脱萃后蒸馏得到172克1，3-二氧杂环庚-5-烯（沸点120～126℃）的粗产品。粗产品尚含有少量水和甲醛，将它用固体氢氧化钾中再蒸馏一次加以纯制，得到160克1，3-二氧杂环庚-5-烯（沸点＝130℃）的纯产品。
实施例2
异氰酸酯官能团的引入
改性的环状单体
将2克（0.02摩尔）DXPE与5克（0.02摩尔）碘和过量的氰酸银（6克，0.04摩尔）反应，制取改性的环状单体。反应产物然后用过量的无水氨反应。用两种不同的溶剂，乙醚和乙睛对该反应进行试验。结果发现，在乙醚中进行反应，混合物于5小时后仍然保持棕色，这表明所有的碘尚未反应。过滤混合物以除去无机盐，将无水氨鼓泡通入滤液，导致生成一种黄色的固体。然后过滤该混合物并分离出若干产物。在放置后发现形成了棕色粘性的液体。
推荐的产物结构为：
如果反应是在乙睛中进行，几分钟后便可发现混合物的棕色消失。产量要比在醚中反应要高。产物的碳-13核磁共振波谱与用醚作反应溶剂得到的产物的波谱相同。用乙睛作溶剂制得的产物的红外光谱是用Beckman 4260红外光谱仪测得。在3450，3350，3250以及1560出现的峰表明产物中有酰胺，在1650出现的峰表明产物中有羰基。还观察到在2900，1440以及1360（CH）和1070-1150（C-O-C）出现有峰。
这种5-碘-6-脲-1，3-二氧杂环庚烷单体再通过加热改性制成具有下面推荐的结构式的5，6-噁唑-1，3-二氧杂环庚烷单体：
本发明如上所述合成的这种脲和噁唑改性的共聚用单体可用于共聚反应，以制取主链上分别含有脲和噁唑官能团的缩醛共聚物。
实施例3
共聚物双键通过形成异氰酸酯改性
三噁烷与1，3-二氧杂环庚-5-烯的共聚合
在干燥的烧瓶（Kjeldahl，100毫升）中放入28.5克三噁烷和1.5克1，3-二氧杂环庚-5-烯。将烧瓶盖上橡胶塞子。用真空脱除反应混合物中的空气和溶解的气体后，用氮气吹洗烧瓶。将烧瓶置于油浴中加热到60～65℃并用磁搅拌器搅拌，使瓶内物熔融混合。然后通过置于60℃油浴中的烧瓶的橡皮塞往瓶内注射进2微升三氟化硼醚合物。溶液的颜色立即变成深棕色。在约几分钟之内，溶液由于聚合物生长遍及整个烧瓶变成不流动了。使该聚合反应在60℃进行20小时。聚合结束，移出聚合物，并研成碎块。用60毫升含2%三乙醇胺的甲醇溶液洗涤聚合物粗产物，然后过滤收集。产物约24克。按下面的步骤用碱水解除去不稳定的端基。
把一个500毫升二颈圆底烧瓶配以空气冷却的直管形冷凝器，温度计和磁搅拌器，往瓶中放入24克聚合物粗产品，120毫升二甲基甲酰胺，120毫升苯甲醇，以及占溶液总体积1%的三乙醇胺。将混合物在160～170℃加热搅拌，使固体溶解。并使瓶内物保护在回流条件下直到看见其中的甲醛放出为止。将聚合物溶液冷却，使固体物质沉淀出来。移出固体，用丙酮洗涤三次。过滤出聚合物，在40℃真空干燥。产量约为18克。
这种共聚物的碳-碳双键可以提供为进一步改性的良好部位从而起到使聚合物稳定的作用。这种改性之一是碘异氰酸酯的加成。首先在醚溶剂中试验碘异氰酸酯与双键的加成。在乙醚中进行的反应产物的红外光谱和碳-13核磁共振波谱表明，没有改性成功的迹象。将共聚物与醚溶剂中无机盐分离是十分困难的。
在乙睛中进行上述反应则可避免这个问题。由于碘与氰酸银在乙睛中反应很快，可将共聚物加入到一种预制的碘异氰酸酯溶液。使混合物反应20小时。然后过滤出共聚物，用乙睛洗涤四次。然后，这样改性的产物可同无水氨进一步反应，从而生成具有下面结构的单元：
其中，脲的部份可以用作甲醛的受体。将过量的无水氨鼓泡通过洗过的共聚物与乙睛的混合物，便可进行上述反应。然后过滤出共聚物，再用乙睛洗涤四次。
改性后的共聚物的红外光谱显示出特征的缩醛峰（2900，1460，1360，1240，1100和900厘米-1）以及1740的羰基（C＝0）峰和1700的酰胺峰，表明产物已经实现了所要求的改性。产物的氢核核磁共振波谱在8.1ppm（NH）位置显示一个峰，而未改性的共聚物则没有此峰。产物的碳-13核磁共振波谱在169ppm（C＝0）显示出一个明显的峰。未改性的共聚物在该区域没有峰。68ppm（CH2-CH＝CH-CH2）的双峰在改性的共聚物波谱中仍然可以看到，而且发现其强度与未改性的共聚物的峰强度几乎相同。相反，在128ppm（CH2CH＝CH-CH2）的峰的强度看来要比未改性的共聚物的小些，表明至少有部份双键已经被改性。还可以进一步使这种碘和脲取代的单元改性，生成具有下式结构的聚合物：
碘和脲结构改性成噁唑结构可通过加热来实现。将共聚物的链终止单元转化成噁唑结构，以除掉会造成聚合物降解的碘，这会是有益的。从另一方面来说，碘当然也可用来连结另外的官能团。
Claims (12)
1、5-碘-6-异氰基-1，3-二氧杂环庚烷；
2、5-碘-6-脲-1，3-二氧杂环庚烷;
3、5，6-噁唑-1，3-二氧杂环庚烷;
4、一种制备5-碘-6-异氰酸酯-1，3-二氧杂环庚烷的方法，它包括将1，3-二氧杂环庚-5-烯、碘和氰酸银在乙睛溶剂中进行反应。
5、一种制备5-碘-6-脲-1，3-二氧杂环庚烷的方法，它包括先将1，3-二氧杂环庚-5-烯，碘和氰酸银在乙睛溶剂中进行反应，然后加入过量的无水氨。
6、一种制备5，6-噁唑-1，3-二氧杂环庚烷的方法，它包括将5-碘-6-脲-1，3-二氧戊烷的乙睛溶液进行加热。
7、一种制备主链上有脲基的缩醛共聚物的方法，它包括将三噁烷与5-碘-6-脲-1，3-二氧杂环庚烷进行共聚。
8、一种制备主链上有噁唑基的缩醛共聚物的方法，它包括将三噁烷与5，6-噁唑-1，3-二氧杂环庚进行共聚。
9、一种制备主链上有碘和脲基的缩醛共聚物的方法，它包括：
a）用三噁烷同1，3-二氧杂环庚-5-烯共聚，以制取一种缩醛共聚物;
b）用上面制得的共聚物同乙睛制成第一混合物;
c）在第一混合物里加入碘和氰酸银，并使其反应合适的一段时间;
d）过滤出共聚物;
e）制备该共聚物同乙睛的第二混合物;
f）往第二混合物里加入过量的无水氨，并使其反应一个合适的时间。
10、根据权利要求9的方法制得的缩醛共聚物。
11、一种制备主链上有噁唑基的缩醛共聚物的方法，它包括：
a）用三噁烷同1，3-二氧杂环庚-5-烯共聚，以制取一种缩醛共聚物;
b）用上面制得的共聚物同乙睛制成第一混合物;
c）在第一混合物里加入碘和氰酸银，并使其反应一个合适的时期;
d）过滤出共聚物;
e）制备该共聚物同乙睛的第二混合物;
f）往第二混合物里加入过量的无水氨，并使其反应一个合适的时间;
g）过滤出该共聚物，用乙睛洗涤共聚物;
h）制备经洗涤的共聚物同乙睛的第三混合?
i）将第三混合物加热一个合适的时期。
12、根据权利要求11的方法制得的缩醛共聚物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/181,236 US5071952A (en) | 1988-04-13 | 1988-04-13 | (iodo-urea and iodo-isocyano) dioxepane trioxane copolymers |
| US181,236 | 1988-04-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1037900A true CN1037900A (zh) | 1989-12-13 |
Family
ID=22663439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89102214A Granted CN1037900A (zh) | 1988-04-13 | 1989-04-12 | 主链上有异氰酸官能团的缩醛共聚物 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5071952A (zh) |
| EP (1) | EP0340926A3 (zh) |
| JP (1) | JP2722648B2 (zh) |
| KR (1) | KR890016038A (zh) |
| CN (1) | CN1037900A (zh) |
| BR (1) | BR8901748A (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851744A (zh) * | 2021-01-22 | 2021-05-28 | 南京师范大学 | 一种28-高芸苔素内酯的合成方法 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5206308A (en) * | 1989-05-12 | 1993-04-27 | Hoechst Celanese Corporation | Grafting of amine functional polymers onto functionalized oxymethylene polymers and the resulting graft polymers thereof |
| KR100207294B1 (ko) * | 1991-05-23 | 1999-07-15 | 미리암 디. 메코너헤이 | 폴리아세탈 수지 조성물 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA720516A (en) * | 1965-10-26 | Farbwerke Hoechst Aktiengesellschaft Vormals Meister Lucius And Bruning | Trioxane-1,3-dioxepane copolymers | |
| US3337587A (en) * | 1960-03-21 | 1967-08-22 | Union Carbide Corp | 2-hydrocarbon-5, 6-epoxy-1, 3-dioxepanes |
| NL271273A (zh) * | 1960-11-15 | |||
| BE631682A (zh) * | 1962-04-28 | |||
| GB1062920A (en) * | 1963-12-28 | 1967-03-22 | Asahi Chemical Ind | A process for preparing polyoxymethylene copolymers |
| US3385832A (en) * | 1964-09-28 | 1968-05-28 | Ici Ltd | Oxymethylene polymers having olefinic double bonds in the polymer chain |
| DE2062958A1 (de) * | 1970-01-23 | 1971-07-29 | Perstorp Ab | Verfahren zur Herstellung von stabilen Trioxan Copolymeren |
| BE787798A (fr) * | 1971-08-19 | 1973-02-21 | Hoechst Ag | Procede de preparation d'homopolymeres et de copolymeres d'acetals cycliques |
| US4389526A (en) * | 1981-08-03 | 1983-06-21 | The Regents Of The University Of California | Intermediates and synthesis of 2-amino-2-deoxytetritols |
| US4751272A (en) * | 1986-05-01 | 1988-06-14 | Toray Industries, Inc. | Process for producing oxymethylene copolymer and resinous composition |
-
1988
- 1988-04-13 US US07/181,236 patent/US5071952A/en not_active Expired - Fee Related
-
1989
- 1989-04-12 JP JP1092776A patent/JP2722648B2/ja not_active Expired - Fee Related
- 1989-04-12 KR KR1019890004832A patent/KR890016038A/ko not_active Application Discontinuation
- 1989-04-12 CN CN89102214A patent/CN1037900A/zh active Granted
- 1989-04-12 BR BR898901748A patent/BR8901748A/pt not_active Application Discontinuation
- 1989-04-12 EP EP89303608A patent/EP0340926A3/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851744A (zh) * | 2021-01-22 | 2021-05-28 | 南京师范大学 | 一种28-高芸苔素内酯的合成方法 |
| CN112851744B (zh) * | 2021-01-22 | 2022-10-14 | 南京师范大学 | 一种28-高芸苔素内酯的合成方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2722648B2 (ja) | 1998-03-04 |
| EP0340926A2 (en) | 1989-11-08 |
| BR8901748A (pt) | 1989-11-28 |
| EP0340926A3 (en) | 1990-08-01 |
| JPH0272172A (ja) | 1990-03-12 |
| US5071952A (en) | 1991-12-10 |
| KR890016038A (ko) | 1989-11-28 |
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