CN1013662B - 在双(二氯磷酰基)酰亚胺存在下制备聚氯磷腈的方法 - Google Patents
在双(二氯磷酰基)酰亚胺存在下制备聚氯磷腈的方法Info
- Publication number
- CN1013662B CN1013662B CN88101229A CN88101229A CN1013662B CN 1013662 B CN1013662 B CN 1013662B CN 88101229 A CN88101229 A CN 88101229A CN 88101229 A CN88101229 A CN 88101229A CN 1013662 B CN1013662 B CN 1013662B
- Authority
- CN
- China
- Prior art keywords
- dichlor
- polycondensation
- phosphoryl base
- polychlorophosphnitrile
- phosphoryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/097—Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/097—Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms
- C01B21/098—Phosphonitrilic dihalides; Polymers thereof
- C01B21/0986—Phosphonitrilic dichlorides; Polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/10—Halides or oxyhalides of phosphorus
-
- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Catalysts (AREA)
Abstract
本发明涉及制备聚氯磷腈的方法。
在双(二氯磷酰基)酰亚胺存在下,通过N-(二氯磷酰基)三氯磷腈缩聚而得到该聚合物。
双(二氯磷酰基)酰亚胺的存在特别加速了缩聚反应的速度。
Description
本发明的目的是制备聚氯磷腈的方法。
在欧洲专利(公布号0026685)中叙述了按照下式通过N-(二氯磷酰基)三氯磷腈缩聚制备线型聚氯磷腈的一种方法:
与以前在美国专利3,370,020中所叙述的方法(它用六氯环三磷腈作为原料)相比,上述欧洲专利中叙述的方法能制得高分子量的非网构聚合物,分子量能控制在预计的数量而且使用的单体容易得到。
在此欧洲专利中叙述的方法一般是在温度240~350℃下进行,反应时间8至几十个小时,这要由所要求的分子量的数量而定。
本发明提出了一个使前述欧洲专利的方法更完善的方法。更准确说,本发明涉及一种通过N-(二氯磷酰基)三氯磷腈缩聚制备线型聚氯磷腈的方法,以及能显然加速该缩聚反应的方法。
该方法的特征在于,N-(二氯磷酰基)三氯磷腈的全部或部分
的缩聚反应是在双(二氯磷酰基)酰亚胺的存在下进行的,该化合物的结构式为:
式(3)的双(二氯磷酰基)酰亚胺本身是已知的,不属于本发明的目的。例如,L.Riesel,H.H.Patzmann,H.P.Bartich等人在Z.Anorg.Allg.Chem.t.404.219页(1974)中就对它进行了叙述,而且可以由式(1)的N-(二氯磷酰基)三氯磷腈通过一步水解的方法制得。因此,该产物作为缩聚催化剂的效能是惊人的,只要这种缩聚反应是在绝对没有水分的存在下进行,因为水分会导致聚氯磷腈网构化。
既然式(3)的双(二氯磷酰基)酰亚胺能很好地催化式(1)的单体缩聚成为基本为线型的聚氯磷腈,所以就部分或全部不会形成不溶而且通常也没有用的网构凝胶当式(1)的单体在缩聚前或缩聚过程中和水分相接触时就会得到这种网构物。
可以在缩聚开始、或中间、或逐次加入缩聚反应器中的式(3)的双(二氯磷酰基)酰亚胺的数量一般超过参加缩聚反应单体的0.05%(摩尔)。酰亚胺的最高量取决于各种因素,特别是预期的分子量、单体(1)的固有活性、为进行缩聚反应所选择的温度。一般说来,最好不超过式(1)单体的1.5%(摩尔),应承认这适于专门技术人员,在推荐的极限数量之内选择酰亚胺的准确数量使能得到预期的分子量,而又不发生网构化。
对于加入双(二氯磷酰基)酰亚胺,以及对于实际的缩聚反应,
适合本发明的该方法能够在溶液中进行,比如说在氯代单或多环芳烃,如三氯苯或三氯联苯中进行。
至于操作条件,能根据在欧洲专利0026685中叙述的一般说明和推荐条件,其内容列入本案作为参考。特别可以根据该文献中有关反应时间、温度、压力、在不同温度和/或不同压力逐次进行反应的可能性的说明。还可以参照该文献中关于缩聚的控制和制得的聚氯磷腈的提纯处理等内容。关于缩聚的进展,人们知道,该反应伴随着放出POCl3;因此,POCl3的放出速度与大分子链的生长速度成正比。适合本发明方法的优点可通过以下事实说明,即测量在使用和不使用双(二氯乙酰基)酰亚胺时,得到80%(重量)的理论POCl3需要的时间(t80-100%的时间即相当于放出全部POCl3和得到具有预期分子量的式(2)的聚合物的时间,该优点也可从后面诸实例中看出,这些实例仅用来说明本发明,在任何情况下不会限制本发明。
实例1至3
1.双(二氯磷酰基)酰亚胺的合成
按照前引的由Riesel等人叙述的操作方法,用甲酸和N-(二氯磷酰基)三氯磷腈反应实现其制备过程。
然后用三氯联苯稀释双(二氯磷酰基)酰亚胺,得到每100克溶液中含有4.994克(0.0199摩尔酰亚胺)的溶液(S)。
2.缩聚
在装有收集POCl3的系统和用氮气充压系统的反应器中,在搅拌下加入a克N-(二氯磷酰基)三氯磷腈(P2NOCl5)、b克三氯联苯和c克上述1中的溶液(S),这使得催化剂/单体的摩尔比
为d。将混合物加热到g℃。作为时间的函数来测量POCl3的量,并注意回收80%理论POCl3时所必须的时间(t80),用小时表示。
在进行e次t80测定后停止实验。
在冷却之后,加入500毫升苯稀释生成的聚氯磷腈。
在装有1.18摩尔酚钠和150克二甘醇二甲醚的反应器中加入10%的这种新溶液。在蒸出苯以后,把混合物加热到120℃,共48小时。
加入350毫升的苯并用浓盐酸中和。聚合物和氯化钠被干燥并用苯洗涤。
得到的饼状物用其10倍体积的甲醇制成悬浮液,然后干燥。再用甲醇/水(80/20)混合物,以后再用80℃的水重复此操作。
将聚合物在一定温度(…℃)下溶于相当于其40倍体积的四氢呋喃(THF)中,然后过滤。将该溶液浓缩直至得到一种浆状物,然后慢慢倒入强烈搅拌下的1升水中。
在80℃和……毫米汞柱的低压下,将沉淀脱水并干燥。
这样得到的聚二苯氧基磷腈在30℃的THF中其特性粘度为f毫升/克。
在后面相当于用两批P2NOCl5进行的不同实验的表格中,对于适合本发明的三个实例(1、2和3)以及不用双(二氯磷酰基)酰亚胺,或是 (催化剂)/(单体) 摩尔比太高的三个对比例(C1、C2、C3)给出了不同的a、b、c、d、t80、e、f和g的值。
第1批单体
实施例 a b c d% t80e f g
1 124 122,8 2,638 0,114 1,93 20 32 260
2 144 142,6 10,653 0,397 1,60 20 32 160
C1133 131,7 - - 3,22 20 42 260
第2批单体
实施例 a b c d% t80e f g
3 160 158,45 32,39 1,1 0,9 20 31,5 270
C2138 136,66 - - 2,08 20 35,5 270
C3137 135,67 45,18 1,77 0,6 16,86 GEL 270
由实例1至3为一方,对比例C1至C3为一方,从叙述和比较可以得出结论,使用双(二氯磷酰基)酰亚胺能够减小t80的数值,在缩聚的所有阶段,t80都是表示反应活性的一个数值。此外,还能看出,双(二氯磷酰基)酰亚胺能强烈地催化缩聚反应,但在使用的双(二氯磷酰基)酰亚胺太多时,会导致生成不溶的凝胶(C3)。
Claims (2)
1、通过N-(二氯磷酰基)三氯磷腈缩聚制备线型聚氯磷腈的方法,其特征在于,该缩聚反应是全部或部分在下式的双(二氯磷酰基)酰亚胺的存在下进行的,其中,双(二氯磷酰基)酰亚胺/参加聚缩反应单体的摩尔比在0.05和1.5%之间。
2、按照权利要求1的方法,其特征在于,在缩聚开始或在缩聚中间或逐次地在缩聚介质中加入双(二氯磷酰基)酰亚胺。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8703250A FR2612170B1 (fr) | 1987-03-10 | 1987-03-10 | Procede de preparation de polychlorophosphazene en presence de bis(dichlorophosphoryl)imide |
FR8703250 | 1987-03-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN88101229A CN88101229A (zh) | 1988-10-05 |
CN1013662B true CN1013662B (zh) | 1991-08-28 |
Family
ID=9348798
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN88101229A Expired CN1013662B (zh) | 1987-03-10 | 1988-03-10 | 在双(二氯磷酰基)酰亚胺存在下制备聚氯磷腈的方法 |
Country Status (13)
Country | Link |
---|---|
US (1) | US4824648A (zh) |
EP (1) | EP0286465B1 (zh) |
JP (1) | JPS63236705A (zh) |
KR (1) | KR880011016A (zh) |
CN (1) | CN1013662B (zh) |
AT (1) | ATE67154T1 (zh) |
DE (1) | DE3864719D1 (zh) |
DK (1) | DK126088A (zh) |
ES (1) | ES2024652B3 (zh) |
FI (1) | FI84904C (zh) |
FR (1) | FR2612170B1 (zh) |
GR (1) | GR3003134T3 (zh) |
PT (1) | PT86929B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4221854A1 (de) * | 1992-07-03 | 1994-01-05 | Nuenchritz Chemie Gmbh | Phosphornitridchloride enthaltende Zusammensetzungen und Verfahren zu deren Herstellung |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2975028A (en) * | 1956-02-15 | 1961-03-14 | Pennsalt Chemicals Corp | Phosphorus compounds and process for making |
US2925320A (en) * | 1956-02-16 | 1960-02-16 | Pennsalt Chemicals Corp | Compounds of the class p2x5no and process for producing same |
FR2466435A1 (fr) * | 1979-09-27 | 1981-04-10 | Inst Mondial Phosphate | Nouveaux polychlorophosphazenes et leur procede de preparation |
FR2571710B1 (fr) * | 1984-10-17 | 1986-12-26 | Elf Aquitaine | Procede de preparation de polychlorophosphazenes lineaires possedant un groupement terminal pxcl2, x designant o ou s, par polycondensation en solution des monomeres p2nxcl5 |
-
1987
- 1987-03-10 FR FR8703250A patent/FR2612170B1/fr not_active Expired
-
1988
- 1988-03-04 AT AT88400525T patent/ATE67154T1/de not_active IP Right Cessation
- 1988-03-04 DE DE8888400525T patent/DE3864719D1/de not_active Expired - Fee Related
- 1988-03-04 ES ES88400525T patent/ES2024652B3/es not_active Expired - Lifetime
- 1988-03-04 EP EP19880400525 patent/EP0286465B1/fr not_active Expired - Lifetime
- 1988-03-09 DK DK126088A patent/DK126088A/da not_active Application Discontinuation
- 1988-03-09 JP JP63055934A patent/JPS63236705A/ja active Granted
- 1988-03-09 FI FI881109A patent/FI84904C/fi not_active IP Right Cessation
- 1988-03-09 PT PT86929A patent/PT86929B/pt not_active IP Right Cessation
- 1988-03-10 KR KR1019880002458A patent/KR880011016A/ko not_active Application Discontinuation
- 1988-03-10 CN CN88101229A patent/CN1013662B/zh not_active Expired
- 1988-03-10 US US07/166,368 patent/US4824648A/en not_active Expired - Fee Related
-
1991
- 1991-11-14 GR GR91401745T patent/GR3003134T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
FR2612170A1 (fr) | 1988-09-16 |
JPS63236705A (ja) | 1988-10-03 |
KR880011016A (ko) | 1988-10-25 |
ATE67154T1 (de) | 1991-09-15 |
ES2024652B3 (es) | 1992-03-01 |
FI881109A (fi) | 1988-09-11 |
GR3003134T3 (en) | 1993-02-17 |
US4824648A (en) | 1989-04-25 |
PT86929A (pt) | 1988-04-01 |
FI84904B (fi) | 1991-10-31 |
PT86929B (pt) | 1992-05-29 |
CN88101229A (zh) | 1988-10-05 |
JPH0513087B2 (zh) | 1993-02-19 |
DK126088D0 (da) | 1988-03-09 |
EP0286465B1 (fr) | 1991-09-11 |
EP0286465A1 (fr) | 1988-10-12 |
FI84904C (fi) | 1992-02-10 |
FI881109A0 (fi) | 1988-03-09 |
DK126088A (da) | 1988-09-11 |
DE3864719D1 (de) | 1991-10-17 |
FR2612170B1 (fr) | 1989-06-16 |
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