CN1039600A - 主链上有溴官能团的缩醛类共聚物 - Google Patents
主链上有溴官能团的缩醛类共聚物 Download PDFInfo
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- CN1039600A CN1039600A CN89102216A CN89102216A CN1039600A CN 1039600 A CN1039600 A CN 1039600A CN 89102216 A CN89102216 A CN 89102216A CN 89102216 A CN89102216 A CN 89102216A CN 1039600 A CN1039600 A CN 1039600A
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- main chain
- bromo
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- halogen
- trioxane
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/02—Seven-membered rings
- C07D321/04—Seven-membered rings not condensed with other rings
- C07D321/06—1,3-Dioxepines; Hydrogenated 1,3-dioxepines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G4/00—Condensation polymers of aldehydes or ketones with polyalcohols; Addition polymers of heterocyclic oxygen compounds containing in the ring at least once the grouping —O—C—O—
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- Polymers & Plastics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
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Abstract
本发明涉及一种制造主链上有溴官能团的缩醛共聚物的方法,它包括将三烷与5,6-二溴-1,3-二氧杂环庚烷进行共聚合。本发明还涉及将含有溴官能团的缩醛类共聚物加以改性的方法以及用本发明方法制得的共聚物。
Description
聚缩醛类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两个官能团,如端羟基。对诸如制备接枝共聚物和带化学结合稳定剂的聚合物说来,最好是合成出官能团含量较高的聚缩醛类。本发明的目的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,同时又具有可用来进一步改性或连结添加剂的官能团。
在通常的缩醛树脂产物中,诸如脒热稳定剂之类的添加剂往往会存在在聚合物的无定形区。由于这种非结晶区在空间的分布是无规的从宏观性质看来,这种添加剂的分布常常不是最适宜的。如果官能团的部分能够按有规则的或半有规则的间距设置(如无规共聚物),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,这样便能获得优良而更为均匀的性质。由于聚缩醛的晶体结构使添加剂可以从空间阻断结晶区,这种方法尤其有效。因此,最理想的是,构成聚合物主链的部份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类共聚物在很多重要的实际应用中会是有用的,诸如:a)制备含化学键合稳定剂的三噁烷共聚物;
b)制备含化学结合的冲击改性剂的三噁烷共聚物;c)制备三噁烷的接枝共聚物,用作与已有的市售缩醛共聚物共混体的相容剂,或与别的聚合物材料诸如玻璃或矿物的相容剂;d)制备可接受表面改性的共聚物;e)制备交联的共聚物。
本发明涉及一种制备主链上含卤素官能团的缩醛共聚物的方法。某个优选的实施例涉及一种制备含溴官能团的共聚物的方法,这种方法包括用三噁烷与5,6-二溴-1,3-二氧杂环庚烯进行共聚。
本发明还涉及用这种新的方法制得的缩醛类共聚物以及这些共聚物的进一步改性。
实施例1
a)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)分水器回流直至水完全除掉。反应混合物经脱苯后蒸馏得到172克1,3-二氧戊-5-烯(沸点120~126℃)粗产物。这种含有少量水和甲醛的粗产物通过从固体氢氧化钾中再蒸馏一次加以精制。得到160克1,3-二氧戊-5-烯(沸点=130℃)的纯产品。
实施例2
5,6-二溴-1,3-二氧杂环庚烷
将15.2克(0.15摩尔)1,3-二氧杂环庚-5-烯在20毫升四氯化碳中的溶液置于冰浴中冷却。然后在搅拌下逐滴加入24克(0.15摩尔)溴在20毫升四氯化碳中的溶液。接着用蒸馏除去溶剂,残留物用乙醇重结晶,制得8.1克5,6-二溴-1,3-二氧杂环庚烷,熔点为37℃。
实施例3
三烷与5,6-二溴-1,3-二氧戊烷的共聚合
在干燥的烧瓶(Kjeldahl,100毫升)中放入10克三噁烷和2.5克5,6-二溴-1,3-二氧杂环庚烷。瓶子用橡皮塞盖住。在真空下脱除掉反应混合物中的空气和溶解的气体之后,用氮气冲洗烧瓶。将瓶子置于油浴(60~65℃)中用磁搅拌器将瓶中的东西熔融并混合在一起。接着通过橡皮塞往瓶内注射进0.2微升的三氟化硼醚合物。溶液从棕色变成白色。该溶液于大约30分钟之内由于聚合物生长遍及整个烧瓶变成不流动了。使反应在60℃进行20小时。聚合结束即移出聚合物并研成小块。9.5克粗产物先用含2%三乙醇胺的10毫升甲醇溶液洗涤,再用甲醇洗涤三次。在40℃真空干燥得到9克共聚物。
这种共聚物在紫外光照射下很易产生游离基。它由电子自旋共振吸收所显示共聚物具有的感光性可用于聚合物的光化学改性,如表面接枝。本发明还试图制备用别的卤素诸如氯改性的共聚用单体。按照本发明的方法也可以制备主链上有卤素官能团诸如氯的三噁烷的缩醛类共聚物。溴原子和氯原子对紫外光和高能辐照的光敏性加上缩醛共聚物本身具有的拉链式(unzipping)特性,使本发明的卤素改性的共聚物可用作制造集成电路用的光致抗蚀剂。
Claims (8)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US181,237 | 1988-04-13 | ||
US07/181,237 US4906728A (en) | 1988-04-13 | 1988-04-13 | Acetal copolymers with backbone bromo functional groups |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1039600A true CN1039600A (zh) | 1990-02-14 |
Family
ID=22663444
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN89102216A Pending CN1039600A (zh) | 1988-04-13 | 1989-04-12 | 主链上有溴官能团的缩醛类共聚物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US4906728A (zh) |
EP (1) | EP0337754A3 (zh) |
JP (1) | JPH0211629A (zh) |
KR (1) | KR890016037A (zh) |
CN (1) | CN1039600A (zh) |
BR (1) | BR8901747A (zh) |
Families Citing this family (3)
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 |
JPH0761337A (ja) * | 1993-08-26 | 1995-03-07 | Aisin Seiki Co Ltd | 車輪ブレーキのリトラクト機構付きブレーキ装置 |
US20020037472A1 (en) * | 2000-09-08 | 2002-03-28 | Shipley Company, L.L.C. | Novel polymers and photoresist compositions comprising labile polymer backbones for short wave imaging |
Family Cites Families (8)
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 | |||
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 |
US4399272A (en) * | 1979-11-15 | 1983-08-16 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing polyacetal copolymers |
US4751272A (en) * | 1986-05-01 | 1988-06-14 | Toray Industries, Inc. | Process for producing oxymethylene copolymer and resinous composition |
-
1988
- 1988-04-13 US US07/181,237 patent/US4906728A/en not_active Expired - Lifetime
-
1989
- 1989-04-12 EP EP89303605A patent/EP0337754A3/en not_active Ceased
- 1989-04-12 KR KR1019890004831A patent/KR890016037A/ko not_active Application Discontinuation
- 1989-04-12 CN CN89102216A patent/CN1039600A/zh active Pending
- 1989-04-12 BR BR898901747A patent/BR8901747A/pt not_active Application Discontinuation
- 1989-04-12 JP JP1092775A patent/JPH0211629A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
JPH0211629A (ja) | 1990-01-16 |
BR8901747A (pt) | 1989-11-28 |
EP0337754A3 (en) | 1990-03-14 |
US4906728A (en) | 1990-03-06 |
KR890016037A (ko) | 1989-11-28 |
EP0337754A2 (en) | 1989-10-18 |
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