CN102990901B - 聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机 - Google Patents
聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机 Download PDFInfo
- Publication number
- CN102990901B CN102990901B CN201210594319.2A CN201210594319A CN102990901B CN 102990901 B CN102990901 B CN 102990901B CN 201210594319 A CN201210594319 A CN 201210594319A CN 102990901 B CN102990901 B CN 102990901B
- Authority
- CN
- China
- Prior art keywords
- screw extruder
- double screw
- ppd
- phenylenediamine
- order double
- 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 - Fee Related
Links
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 title claims abstract description 18
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 title claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000005855 radiation Effects 0.000 abstract description 3
- 238000010008 shearing Methods 0.000 abstract description 3
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 238000011105 stabilization Methods 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920006253 high performance fiber Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
- B29C48/39—Plasticisers, homogenisers or feeders comprising two or more stages a first extruder feeding the melt into an intermediate location of a second extruder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
- B29C48/385—Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in separate barrels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Polyamides (AREA)
Abstract
本发明涉及一种聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机，由两阶双螺杆T型组合而成；其中，一阶双螺杆挤出机的螺纹结构为异向啮合，二阶双螺杆挤出机的螺纹结构为同向啮合。本发明可以预缩聚时提高混合效果减少剪切，使分子量分布均匀；反应过程中脱挥段设计，聚合后端加大剪切，控制相转变；实现了粉料连续稳定聚合；本发明可以实现更好的散热，得到聚合物的分子量高，而且分布窄，能够得到稳定聚合物。
Description
技术领域
本发明属于聚对苯甲酰聚对苯二胺树脂化工设备领域，特别涉及一种聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机。
背景技术
芳纶纤维具有超高强度、高模量、耐高温、耐酸碱、质量轻等优良性能，其中比强度是刚的5~6倍，模量是钢丝和玻璃纤维的2~3倍，韧性是钢丝的2倍，而质量仅为钢丝的1/5左右。芳纶是综合性能优良、产量最大、应用最广的高性能纤维，在高性能纤维中占有重要的地位，在国防，航空航天，汽车减重节能减排，新能源开发和经济建设等方面具有不可替代的作用。
USP5726257公开了一种间歇式制备聚对苯二甲酰对苯二胺树脂的方法，该方法是对苯二胺和对苯二甲酰氯在N-甲基吡咯烷酮溶剂体系中，分批聚合制备树脂，反应首先在一根同时具有搅拌和造粒作用的聚合齿轮的圆柱形反应容器中进行，当对苯二甲酰氯加入时，反应体系受到漩涡搅拌，生成聚合物被粉碎，聚合反应和聚合物的粉碎在同一容器中进行。漩涡状的搅拌方式能够保证反应体系充分混合，反应迅速进行，得到较高粘度的聚合物。这种方法制备的对苯二甲酰对苯二胺树脂只能分批进行，效率比较低且难得到性能稳定的树脂聚合物。
CN101265326公开了一种对苯二甲酰对苯二胺树脂的制备方法以及设备，即先将对苯二胺溶解后，用三轴自清洁型预反应器，然后将对苯二甲酰氯按一定比例加入到预反应器中，并加入吡啶类酸吸收剂进行反应，反应完全后挤出，然后在静置、洗涤、脱水、干燥后得到聚对苯二酰对苯二胺树脂，并公开了一种三轴自清洁预反应设备，制的了较高分子量的树脂，但是此反应是间歇式反应。
目前，对苯二甲酰对苯二铵树脂的合成工业上主要是通过在双螺杆挤出机中进行低温缩聚反应合成的。在聚合过程单体的纯度及分数以及加入的助溶剂和产生的小分子的脱除对反应都有很大的影响。且随着聚合反应的进行，体系粘度增加，产生凝胶现象，聚合物由于端基包埋无法进一步反应，致使生成的聚合物的分子量较小，且分布比较宽。
发明内容
本发明所要解决的技术问题是提供一种聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机，该组合式双螺杆挤出机预缩聚时提高混合效果减少剪切，使分子量分布均匀；反应过程中脱挥段设计，聚合后端加大剪切，控制相转变；实现了粉料连续稳定聚合；可以实现更好的散热，得到聚合物的分子量高，而且分布窄，能够得到稳定聚合物。
本发明的一种聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机，由两阶双螺杆T型组合而成如图所示；其中，一阶双螺杆挤出机的螺纹结构为异向啮合，二阶双螺杆挤出机的螺纹结构为同向啮合。
所述一阶双螺杆挤出机的螺杆直径为100~130mm，长径比为12~16，转速为200~400rpm，物料停留时间为10~30s。
所述二阶双螺杆挤出机的螺杆直径为100~150mm，长径比为40~60，转速为40~300rpm，物料停留时间为3~15min。
所述一(Ⅰ)阶双螺杆挤出机的冷却温度为-15~15℃。
所述二(Ⅱ)阶双螺杆挤出机分三个温度区，温度设定为-5~5℃，0~20℃，30~50℃。
所述一阶双螺杆挤出机后段开孔，通过抽真空脱除聚合物中产生的副产物氯化氢小分子。
本发明一阶双螺杆挤出机为预缩聚反应器，用来将对苯二胺溶解和部分对苯二甲酰氯预缩聚；合成一定粘度的预聚物，然后将预聚物和剩余的对苯二甲酰加入第二阶双螺杆中进一步反应。第二阶双螺杆挤出机是主缩聚反应器，并在其后段开孔抽真空脱除反应产生的副产物氯化氢小分子，且具有三段不同的螺纹段组成，具有最佳混合、输送、脱挥的效果。
有益效果
本发明可以预缩聚时提高混合效果减少剪切，使分子量分布均匀；反应过程中脱挥段设计，聚合后端加大剪切，控制相转变；实现了粉料连续稳定聚合；本发明可以实现更好的散热，得到聚合物的分子量高，而且分布窄，能够得到稳定聚合物。
附图说明
图1为本发明组合式双螺杆挤出机示意图；
图2a为I阶螺杆螺纹结构示意图；图2b为Ⅱ阶螺杆螺纹结构示意图。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
本实施例提供的一种聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机，由两阶双螺杆T型组合而成；其中，一阶双螺杆挤出机的螺纹结构为异向啮合，二阶双螺杆挤出机的螺纹结构为同向啮合。一阶双螺杆挤出机后段开孔，通过抽真空脱除聚合物中产生的副产物氯化氢小分子。
在50L带夹套的不锈钢反应釜中加入15Kg无水N-甲基吡咯烷酮，加入1Kg经高温活化的无水氯化钙，完成溶解后，通过液体计量加料系统将预制成的溶剂加入到第一台双螺杆中，冷却至15℃，加入0.65kg对苯二胺粉末加入到直径120mm,长径比14，转速300rpm第一阶双螺杆反应器中至溶解，然后将冷却到-10℃，加入对苯二甲酰氯0.325Kg进行预聚，停留30s，将低聚物和吡啶分别以290g/min，7g/min的流量以计量泵同时加入直径为100mm,长径比48，转速为150rpm的双螺杆挤出机中，控制双螺杆三段温度分别为-5℃，5℃，40℃。12min可以挤出淡黄色面包屑状的聚合体，通过多次水洗除去溶剂后真空干燥得到对苯二甲酰对苯二胺粉末，测得其比浓对数粘度为6.5dl/g。
对比例
在50L带夹套的不锈钢反应釜中加入15Kg无水N-甲基吡咯烷酮，加入1Kg经高温活化的无水氯化钙，加入0.65kg对苯二胺粉末搅拌溶解，然后将冷却到-10℃，加入对苯二甲酰氯0.325Kg进行预聚，然后低聚物和剩余的0.905kg对苯二甲酰氯一起加入到入直径为100mm,长径比48，转速为150转的双螺杆挤出机中，控制双螺杆三段温度分别为-5℃，5℃，40℃。约12min中可以挤出淡黄色面包屑状的聚合体，通过多次水洗除去溶剂后真空干燥得到对苯二甲酰对苯二胺粉末，测得其比浓对数粘度为6.0dl/g。
Claims (3)
1.一种聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机，其特征在于：由两阶双螺杆T型组合而成；其中，一阶双螺杆挤出机的螺纹结构为异向啮合，二阶双螺杆挤出机的螺纹结构为同向啮合；二阶双螺杆挤出机分三个温度区，温度设定为-5～5℃，0～20℃，30～50℃；一阶双螺杆挤出机的螺杆直径为100～130mm，长径比为12～16，转速为200～400rpm，物料停留时间为10～30s；二阶双螺杆挤出机的螺杆直径为100～150mm，长径比为40～60，转速为40～300rpm，物料停留时间为3～15min。
2.根据权利要求1所述的一种聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机，其特征在于：所述一阶双螺杆挤出机的冷却温度为-15～15℃。
3.根据权利要求1所述的一种聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机，其特征在于：所述一阶双螺杆挤出机后段开孔，通过抽真空脱除聚合物中产生的副产物氯化氢小分子。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210594319.2A CN102990901B (zh) | 2012-12-31 | 2012-12-31 | 聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210594319.2A CN102990901B (zh) | 2012-12-31 | 2012-12-31 | 聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102990901A CN102990901A (zh) | 2013-03-27 |
| CN102990901B true CN102990901B (zh) | 2016-04-06 |
Family
ID=47920263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210594319.2A Expired - Fee Related CN102990901B (zh) | 2012-12-31 | 2012-12-31 | 聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102990901B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108623803B (zh) * | 2018-06-22 | 2020-08-04 | 清华大学 | 聚对苯二甲酰对苯二胺高浓度连续稳定聚合方法及其系统 |
| CN109012528B (zh) * | 2018-08-14 | 2024-03-08 | 无锡创彩光学材料有限公司 | 一种管式反应器及用其制备单分散聚酰胺酸溶液的方法 |
| CN109295506B (zh) * | 2018-09-13 | 2020-07-28 | 清华大学 | 一种对位芳纶纺丝原液配制系统及其配制方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020737A (zh) * | 2007-03-01 | 2007-08-22 | 烟台万华新材料科技有限公司 | 一种热塑性聚氨酯弹性体tpu的连续生产方法 |
| CN101245143A (zh) * | 2008-03-21 | 2008-08-20 | 哈尔滨工业大学 | 一种制备聚对苯撑苯并二噁唑的连续聚合反应装置 |
| CN102529056A (zh) * | 2011-12-26 | 2012-07-04 | 北京工商大学 | 一种高熔体强度聚乳酸的制备方法及挤出机 |
-
2012
- 2012-12-31 CN CN201210594319.2A patent/CN102990901B/zh not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020737A (zh) * | 2007-03-01 | 2007-08-22 | 烟台万华新材料科技有限公司 | 一种热塑性聚氨酯弹性体tpu的连续生产方法 |
| CN101245143A (zh) * | 2008-03-21 | 2008-08-20 | 哈尔滨工业大学 | 一种制备聚对苯撑苯并二噁唑的连续聚合反应装置 |
| CN102529056A (zh) * | 2011-12-26 | 2012-07-04 | 北京工商大学 | 一种高熔体强度聚乳酸的制备方法及挤出机 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102990901A (zh) | 2013-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102838744B (zh) | 一种聚对苯二甲酰对苯二胺树脂的连续生产装置 | |
| CN101220148B (zh) | 聚对苯二甲酰对苯二胺树脂的制造方法 | |
| Cao et al. | Room temperature ionic liquids (RTILs): A new and versatile platform for cellulose processing and derivatization | |
| CN102206339B (zh) | 一种连续制备聚对苯二甲酰对苯二胺聚合体的装置和它的制备方法 | |
| CN102990901B (zh) | 聚对苯甲酰聚对苯二胺树脂聚合用组合式双螺杆挤出机 | |
| CN101798385B (zh) | 一种聚对苯二甲酰对苯二胺树脂的生产工艺 | |
| CN102558548B (zh) | 一种聚对苯二甲酰对苯二胺树脂的制备方法 | |
| CN104479089A (zh) | 一种高热稳定性封端含联苯结构聚芳醚酮树脂的工业化合成方法 | |
| CN202849301U (zh) | 一种聚对苯二甲酰对苯二胺树脂的连续生产装置 | |
| CN104530418A (zh) | 一种高热稳定性封端聚芳醚酮树脂的工业化合成方法 | |
| CN106750265B (zh) | 一种对位芳纶纳米纤维分散液的连续大批量制备方法 | |
| CN107474201A (zh) | 一种高热稳定性封端聚醚醚酮树脂的制备方法 | |
| CN101985497A (zh) | 一种半连续化制备含杂环的共聚芳香族聚酰胺溶液的方法 | |
| CN103467736A (zh) | 一种ppta合成过程中控制相转变的聚合方法 | |
| CN104072757B (zh) | 一种聚对苯二甲酰对苯二胺树脂的制备方法 | |
| CN105482050A (zh) | 聚醚醚酮树脂的制备方法 | |
| CN101328266B (zh) | 一种高粘度聚对苯二甲酰对苯二胺树脂的制备方法 | |
| WO2020140955A1 (zh) | 含芳香聚酰胺的三元合金及其制备方法 | |
| CN102757561A (zh) | 一种含酮基聚醚砜类树脂及其合成方法 | |
| CN1687186A (zh) | 一种连续化制备聚对苯二甲酰对苯二胺树脂的方法 | |
| CN104119526B (zh) | 连续化制备聚对苯二甲酰对苯二胺树脂的方法 | |
| CN113416305B (zh) | 长纤维增强聚芳醚酮复合材料及其制备方法 | |
| CN102558558A (zh) | 聚芳醚砜-腈树脂及其工业化合成方法 | |
| CN202030686U (zh) | 一种连续制备聚对苯二甲酰对苯二胺聚合体的装置 | |
| CN102977349B (zh) | 一种阻燃共聚物及其连续聚合方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: HEBEI SILICON VALLEY CHEMICAL CO., LTD. Effective date: 20130821 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Yu Muhuo Inventor after: Zhang Rui Inventor after: Liu Jing Inventor after: Zhong Hongpeng Inventor after: Li Shuangjiang Inventor after: Du Lingdong Inventor after: Shen Weibo Inventor after: Qiu Dalong Inventor after: Liu Xindong Inventor after: Kang Chunmao Inventor after: Li Xinxia Inventor after: Song Furu Inventor after: Xue Yuqing Inventor after: Kong Haijuan Inventor after: Ye Sheng Inventor after: Song Zhiqiang Inventor after: Song Juqiang Inventor after: Song Liqiang Inventor after: Han Keqing Inventor after: Teng Cuiqing Inventor before: Yu Muhuo Inventor before: Kong Haijuan Inventor before: Teng Cuiqing Inventor before: Zhang Rui |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: YU MUHUO KONG HAIJUAN TENG CUIQING ZHANG RUI TO: YU MUHUO SONG FURU KONG HAIJUAN YE SHENG SONG ZHIQIANG SONG JUQIANG SONG LIQIANG HAN KEQING TENG CUIQING ZHANG RUI LIU JING ZHONG HONGPENG LI SHUANGJIANG DU LINGDONG SHEN WEIBO QIU DALONG LIU XINDONG KANG CHUNMAO LI XINXIA XUE YUQING |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20130821 Address after: 201620 Shanghai Songjiang new town, North Renmin Road, No. 2999, No. Applicant after: Donghua University Applicant after: Hebei Silicon Valley chemical Co., Ltd. Address before: 201620 Shanghai Songjiang new town, North Renmin Road, No. 2999, No. Applicant before: Donghua University |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160406 Termination date: 20201231 |