CN102190794A - Method for synthesizing rigid chain polyamide and synthetic product thereof - Google Patents

Method for synthesizing rigid chain polyamide and synthetic product thereof Download PDF

Info

Publication number
CN102190794A
CN102190794A CN 201110049270 CN201110049270A CN102190794A CN 102190794 A CN102190794 A CN 102190794A CN 201110049270 CN201110049270 CN 201110049270 CN 201110049270 A CN201110049270 A CN 201110049270A CN 102190794 A CN102190794 A CN 102190794A
Authority
CN
Grant status
Application
Patent type
Prior art keywords
rigid
chain
polyamide
structure
polymerization
Prior art date
Application number
CN 201110049270
Other languages
Chinese (zh)
Inventor
戴礼兴
方乃照
李红尽
石帅
许广平
Original Assignee
骏马化纤股份有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date

Links

Abstract

The invention belongs to the field of polymerization of macromolecules, and relates to a method for combining melting polymerization and solid phase polymerization of rigid chain polyamide, and a synthetic product thereof. The method comprises the following steps of: putting 93.5 to 96.5 mass percent of compound with NH2 and COOH groups at both ends and a rigid structure in the middle and 3.5 to 6.5 mass percent of compound with NH2 and COOH groups at both ends and a flexible structure in the middle or a corresponding cyclic compound into a reaction kettle for melting polymerization to obtain an oligomer with the logarithmic viscosity number of 0.6 to 1.0, and performing solid phase polymerization of the oligomer under the vacuum condition and at high temperature to obtain rigid polymer with the logarithmic viscosity number of 1.8 to 2.5. The method has the advantages of no usage of solvents in the polymerization process, environmental friendliness, simple working procedure, low production cost and wide application prospect in the field of high-performance fibers.

Description

一种刚性链聚酰胺的合成方法及其合成产物 Synthesis of a rigid-chain polyamide and synthetic products

技术领域 FIELD

[0001] 本发明属于高分子聚合领域,涉及一种刚性链聚酰胺的熔融聚合和固相聚合相结合的方法。 [0001] The present invention belongs to the field of high polymer, the method relates to the combination of a rigid-chain polyamide melt polymerization and solid phase polymerization.

背景技术 Background technique

[0002] 主要的含刚性链结构的聚酰胺是聚对苯二甲酰对苯二胺(PPTA)、聚间苯二甲酰间苯二胺(PMIA)和聚对苯甲酰胺(PBA)等,其中PPTA是一种新型高科技材料,制成的纤维具有超高强度、高模量和耐高温、耐酸耐碱、重量轻等优良性能,其强度是钢丝的5〜6倍,模量为钢丝或玻璃纤维的2〜3倍,韧性是钢丝的2倍,而重量仅为钢丝的1/5左右,在560 度的温度下,不分解,不融化。 [0002] Polyamide rigid main chain structure containing a poly-p-phenyleneterephthalamide (PPTA), poly-m-phenylene isophthalamide (of PMIA) benzamide and poly (PBA) and the like wherein the PPTA is a new high-tech materials, fibers of high tensile strength, high modulus and high temperature resistance, acid and alkali resistance, light weight and excellent performance, which is 5 to 6 times the wire strength, modulus 2 to 3 times the wire or glass fiber, the toughness is 2 times the wire, and the wire weight is only about 1/5, at a temperature of 560 degrees, does not decompose without melting. 这些芳香族聚酰胺纤维都具有优异的化学稳定性、耐热性、阻燃性和其它特殊性能,它具有良好的绝缘性和抗老化性能,具有很长的生命周期。 These aromatic polyamide fibers have excellent chemical stability, heat resistance, flame retardancy and other specific properties, which has good insulating properties and aging resistance, has a long life cycle. 主要用于防弹材料,已作为一种高技术含量的材料被广泛应用于航天航空、机电、建筑、汽车、海洋水产、体育用品等国民经济各个方面。 Mainly used for bullet-proof material, has been widely used in aerospace, electronics, construction, automotive, marine fisheries, sporting goods and other economic aspects as a high-tech material is. 后者具有优异的化学稳定性、热稳定性、阻燃性等,主要用于防原子能辐射、高空高速飞行材料等方面。 The latter has excellent chemical stability, thermal stability, flame retardancy, is mainly used to prevent atomic radiation, high altitude flying material aspects.

[0003] 在已有技术中,芳香族聚酰胺都是用溶液法聚合得到,如中国发明专利“一种聚对苯二甲酰对苯二胺聚合物的合成方法”(专利号:200410017670),将对苯二胺及添加剂溶于溶剂中配制成一定浓度,然后向溶液中分批添加对苯二甲酰氯进行缩聚反应,合成反应结束,得到聚对苯二甲酰对苯二胺聚合物溶液。 [0003] In the prior art, the aromatic polyamide is obtained by a solution polymerization method, such as China patent "a poly p-phenylene terephthalamide polymer synthesis Phenylenediamine" (patent number: 200410017670) , p-phenylenediamine is dissolved in a solvent and additives formulated in a certain concentration, and then add portionwise a polycondensation of terephthaloyl chloride to the reaction solution, the end of the synthesis reaction, to obtain poly-p-phenylene terephthalamide polymer solution. 中国发明专利“聚芳酰胺的聚合方法”(专利号:87100176)叙述了在一种聚合溶剂系统中制备聚对苯二甲酰对苯二胺的方法,这种溶剂系统包括一种N-烷基取代酰胺和一种季铵氯化物。 Chinese patent "polymerization process polyarylene amide" (patent number: 87100176) describes the preparation of a polymeric solvent system polyparaphenylene terephthalamide benzene diamine, N- such a solvent system comprising one alkyl substituted amide and a quaternary ammonium chloride. 据US Pat. 3,600, 350和US Pat. 3,225,011报道,聚对苯甲酰胺都是在低温溶液聚合下得到。 According to US Pat. 3,600, 350 and US Pat. 3,225,011 reported that of polyethylene is obtained at low temperatures benzamide solution polymerization. 聚对苯甲酰胺合成常以对氨基苯甲酸为单元、N-甲基吡咯烷酮为溶剂,在催化剂、助催化剂存在和80〜90°C的条件下,反应3小时。 Benzamide Synthesis of poly para-aminobenzoic acid is often means, N- methylpyrrolidone as a solvent, at catalyst, a cocatalyst and the presence of 80~90 ° C, for 3 hours. 然后,将物料沉析到酒精中,用水洗涤树脂,干燥,即可得到纺丝用树脂。 Then, the material to alcohol precipitation, the resin was washed with water, and dried, to obtain a spinning resin. 树脂的特性粘度控制在1.8〜2. 2范围内。 Viscosity control characteristics of the resin in the range of 1.8~2. 2. 还有采用双螺杆挤出机为主反应器,以二甲基乙酰胺(DMAc)为溶剂体系制备了较高相对分子质量的聚间苯二甲酰间苯二胺(PMIA) (合成纤维工业,2005,28 (1),44-45)。 There are mainly using a twin screw extruder reactor to dimethylacetamide (DMAc) as a solvent system of high molecular weight poly-prepared phenylenediamine isophthalamide (of PMIA) (Synthetic Fiber Industry , 2005, 28 (1), 44-45).

[0004] 因为一般刚性链结构聚酰胺的合成的一个明显特点都需要在特殊溶剂中进行,所以技术复杂,成本高,实施困难,对环境有害。 [0004] Since the general structure of a rigid-chain synthetic polyamide distinct features need to be a special solvent, it is technically complex, costly, difficult to implement, harmful to the environment.

发明内容 SUMMARY

[0005] 本发明的目的是提供一种刚性链聚酰胺的熔融合成方法及其合成产物,特别是提供一种采用熔融聚合方法先得到较低粘度的聚合物、再经过固相聚合得到合乎要求粘度的聚合物的刚性链聚酰胺的熔融合成方法及其合成产物,避免使用溶剂,简化工序,降低成本,保护环境。 [0005] The object of the present invention is to provide a chain of rigid polyamide molten synthetic methods and synthesis product, particularly to provide a method by melt polymerization to obtain a polymer of lower viscosity, and then through solid-phase polymerization to obtain a desirable the method of rigid-chain polyamide molten synthetic polymer and the viscosity of the synthesized product, avoiding the use of solvents, simplifying the process, reducing costs and protect the environment.

[0006] 本发明的一种刚性链聚酰胺的合成方法,主要包括如下步骤: [0006] The method of synthesis of a rigid-chain polyamide of the present invention, including the steps of:

[0007] a、熔体聚合[0008] (1)配料: [0007] a, melt polymerization [0008] (1) Ingredients:

[0009] 将质量分数93. 5-96. 5 %的两端有NH2和COOH基团、中间含刚性结构的化合物和质量分数3. 5-6. 5%的两端有NH2和COOH基团、中间含柔性结构的化合物或对应的环状化合物加入到反应釜内,用氮气充压排除空气,加热至釜内物料全部融化; [0009] A 93. 5-96. 5% by mass fraction of the two ends of NH2 and COOH groups, and the mass fraction of the compound containing the intermediate ends 3. 5-6. 5% of the rigid structure are NH2 and COOH groups , flexible structure containing the intermediate compound, or the corresponding cyclic compound was added to the reaction vessel and pressurized with nitrogen to exclude air, and heated to melt the entire contents of the autoclave;

[0010] (2)聚合反应: [0010] (2) Polymerization:

[0011] 保持釜内温度为200〜230°C,压力0. 3-0. 5MPa,保持3_5个小时后,缓慢卸除釜压后,抽真空至釜内真空度为-0. 5〜-0. 9MPa,进行真空聚合反应; [0011] maintained at an inner temperature of 200~230 ° C, pressure of 0. 3-0. 5MPa, after holding 3_5 hours, the autoclave was slowly removed, the autoclave was evacuated to a vacuum degree of -0. 5~- 0. 9MPa, the polymerization reaction is carried out in vacuo;

[0012] (3)聚合物粘度控制: [0012] (3) polymeric viscosity control:

[0013] 反应时间3-5个小时,得到一种比浓对数粘度为0. 6〜1. 0的刚性链聚酰胺;在反应过程中每隔半小时取样测比浓对数粘度,得到搅拌棒功率与物料粘度的对应关系,以搅拌棒功率推知物料粘度,当达到所要求的粘度时反应结束,搅拌棒功率与粘度的关系对于特定聚合釜、特定的物料量和特定反应条件可以找到较好的对应关系。 [0013] The reaction time of 3-5 hours, to obtain a logarithmic viscosity of rigid-chain polyamide 0. 0. 6~1;. Every half hour samples measured inherent viscosity ratio during the reaction, to give stirring correspondence relationship rod power and material viscosity, the stirring rod power inferred viscosity of the material, upon reaching the desired viscosity the reaction was stirred relationship rod power and viscosity can be found for a particular polymerization vessel, a specific amount of material and the particular reaction conditions good correspondence.

[0014] 比浓对数粘度的测定:将0. 125g聚酰胺溶于98%浓硫酸中,用乌氏粘度计在30士0.2°C的恒温水浴中测定,Jlinh= ln(t/t0)/C [0014] Determination of inherent viscosity ratio of: 0. 125g of polyamide dissolved in 98% concentrated sulfuric acid, measured in a thermostatic water bath at 30 [deg.] C in Shi 0.2, Jlinh = ln (t / t0) using Ubbelohde viscometer / C

[0015] t_聚酰胺溶液流出时间(S) [0015] t_ polyamide solution flow time (S)

[0016] tQ-纯溶剂流出时间(S) [0016] tQ- flow time of pure solvent (S)

[0017] C-每分升聚酰胺的重量克数(g. dL) [0017] C- weight of polyamide per deciliter in grams (g. DL)

[0018] b、固相聚合 [0018] b, the solid phase polymerization

[0019] (1)投料:将前述刚性链聚酰胺切片加入到真空转鼓内; [0019] (1) feeding: the rigidity of the sections added to the polyamide chain vacuum drum;

[0020] (2)反应条件:真空转鼓内温度为190_250°C,真空度小于_0. 5MPa ; [0020] (2) Reaction conditions: temperature of the vacuum within the drum 190_250 ° C, vacuum is less than _0 5MPa;.

[0021] (3)出料:当比浓对数粘度达到1. 8-2. 5时,用惰性气体充压至常压,出料,得到刚性链聚酰胺。 [0021] (3) Discharge: 1. Upon reaching 8-25 inherent viscosity with inert gas is pressurized to atmospheric pressure, the material to obtain a rigid polyamide chain.

[0022] 作为优选的技术方案: [0022] As a preferred technical solution:

[0023] 如上所述的一种刚性链聚酰胺的合成方法,所述的两端有NH2和COOH基团、中间含刚性结构的化合物为NH2-R1-COOH, R1是含芳环或杂环的刚性结构。 [0023] The method of synthesis described above of a rigid polyamide chain, both ends of the NH2 and COOH groups, an intermediate compound having the rigid structure is NH2-R1-COOH, R1 is an aromatic or heterocyclic ring-containing the rigid structure.

[0024] 如上所述的一种刚性链聚酰胺的合成方法,所使用柔性结构的化合物为对应的环状化合物时,加入去离子水作为引发剂,加入量为该环状化合物量的1_2%。 When the [0024] synthesis described above of a rigid-chain polyamide, the flexible structure of the compound corresponding to the cyclic compound, deionized water was added as an initiator, an amount that an amount of cyclic compound 1_2% .

[0025] 如上所述的一种刚性链聚酰胺的合成方法,所述的两端有NH2和COOH基团、中间含柔性结构的化合物为NH2-R2-COOH或对应的环状化合物,R2是含3-8个亚甲基的结构。 [0025] The method of synthesis of a rigid polyamide chain as described above, there are two ends of the NH2 and COOH groups, an intermediate compound having the flexible structure is NH2-R2-COOH, or the corresponding cyclic compounds, R2 is 3-8 methylene-containing structure.

[0026] 本发明还提供了一种刚性链聚酰胺,所述的刚性链聚酰胺具有以下结构式 [0026] The present invention also provides a chain of rigid polyamide, said polyamide having the structure rigid chain of formula

[0027] ... ABAAABAABAAAA... [0027] ... ABAAABAABAAAA ...

[0028] A和B随机排列; [0028] A and B are randomly arranged;

[0029] 其中结构单元A为-NH-R1-CO-, R1是含芳环或杂环的刚性结构; [0029] wherein the structural unit A is -NH-R1-CO-, R1 is a rigid structure having an aromatic or heterocyclic ring;

[0030] 结构单元B为-NH-R2CO-, R2是含3_8个亚甲基的结构; [0030] The structural unit B is -NH-R2CO-, R2 is a methylene 3_8 containing structure;

[0031] A 的个数为100-200 ; Number [0031] A 100 to 200;

[0032] B 的个数为10-20。 The number of [0032] B 10-20.

[0033] 如上所述的一种刚性链聚酰胺,所述的刚性链结构含芳香环、萘环或咪唑结构。 [0033] A rigid polyamide chain as described above, the rigid chain structure containing an aromatic ring, a naphthalene ring or an imidazole structure.

[0034] 如上所述的一种刚性链聚酰胺,所述的刚性链聚酰胺中,短的柔性链段随机分散分子链中,提高柔韧性和易加工性。 [0034] A rigid polyamide chain as described above, the rigidity of the polyamide chain, a short soft segment molecular chain randomly dispersed, improve flexibility and processability. [0035] 有益效果 [0035] beneficial effects

[0036] 本发明的一种刚性链聚酰胺的合成方法,聚合过程避免了使用溶剂,保护环境,工序简单,生产成本低具有良好的市场前景。 [0036] The method of synthesis of a rigid-chain polyamide of the present invention, the polymerization process avoids the use of solvents, environmental protection, simple process, low production cost has a good market prospect.

[0037] 本发明的一种刚性链聚酰胺,利用其刚性、韧性、低密度性能,用其复合材料作雷达罩及天线骨架。 [0037] The present invention is a rigid-chain polyamide, with its rigidity, toughness, low density property, with which the composite material for radomes and antenna skeleton.

具体实施方式 detailed description

[0038] 下面结合具体实施方式,进一步阐述本发明。 [0038] Next, with reference to specific embodiments, further illustrate the present invention. 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。 It should be understood that these embodiments are illustrative only and the present invention is not intended to limit the scope of the invention. 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。 Furthermore, it should be understood that, after reading the teachings of the present invention, those skilled in the art that various changes or modifications may be made to the present invention, and these equivalents also fall within the scope of the appended claims of the present application as defined.

[0039] 本发明的一种刚性链聚酰胺的合成方法,主要包括如下步骤: [0039] The synthesis method of the present invention the rigidity of the polyamide chain, including the steps of:

[0040] a、熔体聚合 [0040] a, melt polymerization

[0041] (1)配料: [0041] (1) Ingredients:

[0042] 将质量分数93. 5-96. 5 %的两端有NH2和COOH基团、中间含刚性结构的化合物和质量分数3. 5-6. 5%的两端有NH2和COOH基团、中间含柔性结构的化合物或对应的环状化合物加入到反应釜内,用氮气充压排除空气,加热至釜内物料全部融化; [0042] A 93. 5-96. 5% by mass fraction of the two ends of NH2 and COOH groups, and the mass fraction of the compound containing the intermediate ends 3. 5-6. 5% of the rigid structure are NH2 and COOH groups , flexible structure containing the intermediate compound, or the corresponding cyclic compound was added to the reaction vessel and pressurized with nitrogen to exclude air, and heated to melt the entire contents of the autoclave;

[0043] (2)聚合反应: [0043] (2) Polymerization:

[0044] 保持釜内温度为220〜230°C,压力0. 3-0. 5MPa,保持3_5个小时后,缓慢卸除釜压后,抽真空至釜内真空度为-0. 5〜-0. 9MPa,进行真空聚合反应; [0044] maintaining the autoclave temperature 220~230 ° C, pressure of 0. 3-0. 5MPa, after holding 3_5 hours, the autoclave was slowly removed, the autoclave was evacuated to a vacuum degree of -0. 5~- 0. 9MPa, the polymerization reaction is carried out in vacuo;

[0045] (3)聚合物粘度控制: [0045] (3) polymeric viscosity control:

[0046] 反应时间3-5个小时,得到一种比浓对数粘度为0. 6〜1. 0的刚性链聚酰胺;在反应过程中每隔半小时取样测比浓对数粘度,得到搅拌棒功率与物料粘度的对应关系,以搅拌棒功率推知物料粘度,当达到所要求的粘度时反应结束,搅拌棒功率与粘度的关系对于特定聚合釜、特定的物料量和特定反应条件可以找到较好的对应关系。 [0046] The reaction time of 3-5 hours, to obtain a logarithmic viscosity of rigid-chain polyamide 0. 0. 6~1;. Every half hour samples measured inherent viscosity ratio during the reaction, to give stirring correspondence relationship rod power and material viscosity, the stirring rod power inferred viscosity of the material, upon reaching the desired viscosity the reaction was stirred relationship rod power and viscosity can be found for a particular polymerization vessel, a specific amount of material and the particular reaction conditions good correspondence.

[0047] 比浓对数粘度的测定:将0. 125g聚酰胺溶于98%浓硫酸中,用乌氏粘度计在30士0.2°C的恒温水浴中测定,Jlinh= ln(t/t0)/C [0047] Determination of inherent viscosity ratio of: 0. 125g of polyamide dissolved in 98% concentrated sulfuric acid, measured in a thermostatic water bath at 30 [deg.] C in Shi 0.2, Jlinh = ln (t / t0) using Ubbelohde viscometer / C

[0048] t-聚酰胺溶液流出时间(S) [0048] t- polyamide solution flow time (S)

[0049] tQ-纯溶剂流出时间(S) [0049] tQ- flow time of pure solvent (S)

[0050] C-每分升聚酰胺的重量克数(g. dL) [0050] C- weight of polyamide per deciliter in grams (g. DL)

[0051] b、固相聚合 [0051] b, the solid phase polymerization

[0052] (1)投料:将前述刚性链聚酰胺切片加入到真空转鼓内; [0052] (1) feeding: the rigidity of the sections added to the polyamide chain vacuum drum;

[0053] (2)反应条件:真空转鼓内温度为190_250°C,真空度小于_0. 5MPa ; [0053] (2) Reaction conditions: temperature of the vacuum within the drum 190_250 ° C, vacuum is less than _0 5MPa;.

[0054] (3)出料:当比浓对数粘度达到1. 8-2. 5时,用惰性气体充压至常压,出料,得到刚性链聚酰胺。 [0054] (3) Discharge: 1. Upon reaching 8-25 inherent viscosity with inert gas is pressurized to atmospheric pressure, the material to obtain a rigid polyamide chain.

[0055] 作为优选的技术方案: [0055] As a preferred technical solution:

[0056] 如上所述的一种刚性链聚酰胺的熔融合成方法,所述的两端有NH2和COOH基团、 中间含刚性结构的化合物为NH2-R1-COOH, R1是含芳环或杂环的刚性结构。 [0056] The molten synthetic method of a rigid polyamide chain as described above, both ends of the NH2 and COOH groups, an intermediate compound having the rigid structure is NH2-R1-COOH, R1 is an aryl or heteroaryl containing a rigid ring structure.

[0057] 如上所述的一种刚性链聚酰胺的熔融合成方法,所使用柔性结构的化合物为对应的环状化合物时,加入去离子水作为引发剂,加入量为该环状化合物量的1_2%。 [0057] The molten synthetic method of a rigid polyamide chain as described above, the compounds used in the flexible structure when the corresponding cyclic compound, deionized water was added as an initiator, an amount that the amount of cyclic compound 1_2 %.

[0058] 如上所述的一种刚性链聚酰胺的熔融合成方法,所述的两端有NH2和COOH基团、 中间含柔性结构的化合物为NH2-R2-COOH或对应的环状化合物,R2是含3-8个亚甲基的结构。 [0058] The molten synthetic method of a rigid polyamide chain as described above, both ends of the NH2 and COOH groups, an intermediate compound having the flexible structure is NH2-R2-COOH, or the corresponding cyclic compounds, R2 structure containing 3-8 methylene groups.

[0059] 本发明还提供了一种刚性链聚酰胺,所述的刚性链聚酰胺具有以下结构式 [0059] The present invention also provides a chain of rigid polyamide, said polyamide having the structure rigid chain of formula

[0060] ... ABAAABAABAAAA... [0060] ... ABAAABAABAAAA ...

[0061] A和B随机排列; [0061] A and B are randomly arranged;

[0062] 其中结构单元A为-NH-R1-CO-, R1是含芳环或杂环的刚性结构; [0062] wherein the structural unit A is -NH-R1-CO-, R1 is a rigid structure having an aromatic or heterocyclic ring;

[0063] 结构单元B为-NH-R2-CO-, R2是含3_8个亚甲基的结构; [0063] The structural unit B is -NH-R2-CO-, R2 is a structure having 3_8 methylene;

[0064] A 的个数为100-200 ; Number [0064] A 100 to 200;

[0065] B 的个数为10-20。 The number of [0065] B 10-20.

[0066] 如上所述的一种刚性链聚酰胺,所述的刚性链结构含芳香环、萘环或咪唑结构。 [0066] A rigid polyamide chain as described above, the rigid chain structure containing an aromatic ring, a naphthalene ring or an imidazole structure.

[0067] 如上所述的一种刚性链聚酰胺,所述的刚性链聚酰胺中,短的柔性链段随机分散分子链中,提高易加工性。 [0067] A rigid polyamide chain as described above, the rigidity of the polyamide chain, a short soft segment molecular chain randomly dispersed, to improve the ease of processing.

[0068] 实施例1 [0068] Example 1

[0069] 将96. 5%的对氨基苯甲酸和3. 5%的的ω -氨基己酸加入到反应釜内,用氮气充压排除空气,加热至釜内物料全部融化;保持釜内温度为220°C,压力0. 3MPa,保持3小时后,缓慢卸除釜压后,抽真空至釜内真空度为-0. 5MPa,进行真空聚合反应;反应结束时,停止搅拌,用氮气充压至常压,出料。 [0069] The 96.5% of ω p-aminobenzoic acid and 3.5% of - aminocaproic acid was added to the reaction vessel and pressurized with nitrogen to exclude air, and heated to melt the entire contents of the autoclave; maintaining an inner temperature to 220 ° C, pressure 0. 3MPa, after 3 hours, the autoclave was slowly removed, the autoclave was evacuated to a vacuum degree of -0 5MPa, the polymerization reaction is carried out in vacuo; At the end of the reaction, stirring was stopped, filled with nitrogen pressure to atmospheric pressure, the material. 在反应过程中每隔半小时取样测比浓对数粘度,得到搅拌棒功率与物料粘度的对应关系,以搅拌棒功率推知物料粘度,当达到所要求的粘度时反应结束,反应时间3小时。 Half hour samples measured inherent viscosity, to give the corresponding relationship stir bar power and material viscosity, the stirring rod power inferred viscosity of the material, upon reaching the desired viscosity the reaction was completed, the reaction time of 3 hours intervals during the reaction. 聚合结束得到一种比浓对数粘度为0. 6的刚性链聚酰胺预聚物。 End of the polymerization to obtain a logarithmic viscosity of rigid-chain polyamide prepolymer is 0.6. 将前述刚性链聚酰胺切片加入到真空转鼓内固相聚合,真空转鼓内温度为190°C,真空度-0. 5MPa ;用惰性气体充压至常压,出料,得到比浓对数粘度达到1. 8刚性链聚酰胺。 The rigidity of the chain sections is added to the polyamide solid-phase polymerization in a vacuum drum, the vacuum drum temperature of 190 ° C, vacuum degree -0 5MPa;. With an inert gas pressurized to atmospheric pressure, the material, the ratio of concentrated to give viscosity reaches 1.8 rigid polyamide chain.

[0070] 实施例2 [0070] Example 2

[0071] 将重量百分数93. 5%的对氨基苯甲酸和6. 5%的©-氨基己酸加入到反应釜内, 用氮气充压排除空气,加热至釜内物料全部融化;保持釜内温度为220°C,压力0. 5MPa,保持5个小时后,缓慢卸除釜压后,抽真空至釜内真空度为-0. 9MPa,进行真空聚合反应;反应结束时,停止搅拌,用氮气充压至常压,出料。 [0071] The weight percentage of 93.5% of p-aminobenzoic acid and 6.5% of © - aminocaproic acid was added to the reaction vessel and pressurized with nitrogen to exclude air, the autoclave was heated to melt all the material; holding tank temperature of 220 ° C, pressure 0. 5MPa, after keeping it for five hours, the autoclave was slowly removed, the autoclave was evacuated to a vacuum degree of -0 9MPa, the polymerization reaction is carried out in vacuo; At the end of the reaction, stirring was stopped, with pressurized to atmospheric pressure with nitrogen, the feed. 在反应过程中每隔半小时取样测比浓对数粘度,得到搅拌棒功率与物料粘度的对应关系,以搅拌棒功率推知物料粘度,当达到所要求的粘度时反应结束,反应时间5个小时。 Half hour samples measured inherent viscosity, to give the corresponding relationship stir bar power and material viscosity, the stirring rod power inferred viscosity of the material, upon reaching the desired viscosity the reaction was completed at intervals during the reaction, the reaction time of 5 hours . 聚合结束得到一种比浓对数粘度为1. 0的刚性链聚酰胺预聚物。 End of the polymerization to obtain a logarithmic viscosity of rigid-chain polyamide prepolymer is 1.0. 将前述刚性链聚酰胺切片加入到真空转鼓内固相聚合,真空转鼓内温度为250°C,真空度-0. SMPa ;用惰性气体充压至常压,出料,得到比浓对数粘度达到2. 2刚性链聚酰胺。 The rigidity of the chain sections is added to the polyamide solid-phase polymerization in a vacuum drum, the vacuum drum temperature of 250 ° C, vacuum degree -0 SMPa;. With an inert gas pressurized to atmospheric pressure, the material, the ratio of concentrated to give viscosity reaches 2.2 rigid polyamide chain.

[0072] 实施例3 [0072] Example 3

[0073] 将96. 5 %氨基咪唑-2-羧酸和3. 5 %的辛内酰胺加入到反应釜内,用氮气充压排除空气,加热至釜内物料全部融化;保持釜内温度为220°C,压力0. 4MPa,保持4个小时后,缓慢卸除釜压后,抽真空至釜内真空度为-0. 8MPa,进行真空聚合反应;反应结束时,停止搅拌,用氮气充压至常压,出料。 [0073] The aminoimidazole 96.5% and 3.5% 2-carboxylic acid in octanamide added to the reactor, filled with nitrogen to exclude air pressure within the autoclave was heated to melt all the material; inner temperature was kept 220 ° C, pressure 0. 4MPa, held 4 hours after, the autoclave was slowly removed, the autoclave was evacuated to a vacuum degree of -0 8MPa, the polymerization reaction is carried out in vacuo; At the end of the reaction, stirring was stopped, filled with nitrogen pressure to atmospheric pressure, the material. 在反应过程中每隔半小时取样测比浓对数粘度,得到搅拌棒功率与物料粘度的对应关系,以搅拌棒功率推知物料粘度,当达到所要求的粘度时反 Half hour samples measured inherent viscosity, to obtain the corresponding relationship between power and material viscosity stir bar to stir rod material viscosity extrapolated power in every reaction process, when the anti-viscosity reached the desired

6应结束,反应时间4个小时。 6 should be ended, the reaction time of 4 hours. 聚合结束得到一种比浓对数粘度为0. 8的刚性链聚酰胺预聚物。 End of the polymerization to obtain a logarithmic viscosity of rigid-chain polyamide prepolymer is 0.8. 将前述刚性链聚酰胺切片加入到真空转鼓内固相聚合,真空转鼓内温度为230°C,真空度-0. 7MPa ;用惰性气体充压至常压,出料,得到比浓对数粘度达到2. 0刚性链聚酰胺。 The rigidity of the chain sections is added to the polyamide solid-phase polymerization in a vacuum drum, the vacuum drum temperature of 230 ° C, vacuum degree -0 7MPa;. With an inert gas pressurized to atmospheric pressure, the material, the ratio of concentrated to give viscosity reaches 2.0 rigid polyamide chain.

Claims (7)

  1. 1. 一种刚性链聚酰胺的合成方法,其特征是主要包括如下步骤:a、熔体聚合(1)配料:将质量分数93. 5-96. 5%的两端有NH2和COOH基团、中间含刚性结构的化合物和质量分数3. 5-6. 5%的两端有NH2和COOH基团、中间含柔性结构的化合物或对应的环状化合物加入到反应釜内,用氮气充压排除空气,加热至釜内物料全部融化;(2)聚合反应:保持釜内温度为200〜230°C,压力0. 3-0. 5MPa,保持3_5个小时后,缓慢卸除釜压后, 抽真空至釜内真空度为-0. 5〜-0. 9MPa,进行真空聚合反应;反应结束时,停止搅拌,用氮气充压至常压,出料;(3)聚合物粘度控制:反应时间3-5个小时,得到一种比浓对数粘度为0. 6〜1. 0的刚性链聚酰胺;在反应过程中每隔半小时取样测比浓对数粘度,得到搅拌棒功率与物料粘度的对应关系,以搅拌棒功率推知物料粘度,当达到所要求的粘度时反应结束 A method for synthesis of a rigid polyamide chain, characterized in that the steps include: a, melt polymerization (1) Ingredients: 93. The two ends of 5-965% by mass fraction of NH2 and COOH groups have , and the intermediate compound containing a mass fraction ends 3. 5-6. 5% of the rigid structure are NH2 and COOH groups, or the intermediate compound containing the corresponding cyclic compound was added to the flexible structure of the reactor, filled with nitrogen pressure exclusion of air heated to melt the entire contents of the autoclave; (2) polymerization: maintaining an inner temperature of 200~230 ° C, pressure of 0. 3-0 5MPa, after holding 3_5 hours, the autoclave was slowly removed. the autoclave was evacuated to a vacuum degree of -0 5~-0 9MPa, the polymerization reaction is carried out in vacuo; end of the reaction, stirring was stopped, pressurized to atmospheric pressure with nitrogen, the feed; (3) polymeric viscosity control: reaction time of 3-5 hours, to obtain a logarithmic viscosity of rigid-chain polyamide 0. 0. 6~1;. every half hour samples measured inherent viscosity ratio during the reaction, and stirred to obtain a power bar corresponding relationship between the viscosity of the material, in order to infer power stir bar material viscosity, when the viscosity reaches the desired end of the reaction 搅拌棒功率与粘度的关系对于特定聚合釜、特定的物料量和特定反应条件可以找到较好的对应关系;b、固相聚合(1)投料:将前述刚性链聚酰胺切片加入到真空转鼓内;(2)反应条件:真空转鼓内温度为190-250°C,真空度小于-0. 5MPa ;(3)出料:当比浓对数粘度达到1. 8-2. 5时,用惰性气体充压至常压,出料,得到刚性链聚酰胺。 Relationship between viscosity and stirring rod power can be found for a particular corresponding well polymerizer, specific amount of material and the particular reaction conditions; B, solid-phase polymerization (1) feeding: the rigidity of the sections added to the polyamide chain vacuum drum inside; (2) reaction conditions: temperature of the drum in vacuo 190-250 ° C, vacuum is less than -0 5MPa; (3) discharge: when the inherent viscosity is 1. 8-25. with an inert gas pressurized to atmospheric pressure, the material to obtain a rigid polyamide chain.
  2. 2.根据权利要求1所述的一种刚性链聚酰胺的合成方法,其特征在于,所述的两端有NH2和COOH基团、中间含刚性结构的化合物为NH2-R1-COOHA1是含芳环或杂环的刚性结构。 The synthesis method of a rigid-chain polyamide claim, wherein both ends of the NH2 and COOH groups, the rigid structure of the intermediate compound containing NH2-R1-COOHA1 containing aromatic heterocyclic ring or a rigid structure.
  3. 3.根据权利要求1所述的一种刚性链聚酰胺的合成方法,其特征在于,所使用柔性结构的化合物为对应的环状化合物时,加入去离子水作为引发剂,加入量为该环状化合物量的1-2%。 The synthesis method of rigid-chain polyamide according to claim 1, wherein the flexible structure of the compound is used when the corresponding cyclic compound, deionized water was added as an initiator, an amount for the ring compound 1-2% volume.
  4. 4.根据权利要求1所述的一种刚性链聚酰胺的合成方法,其特征在于,所述的两端有NH2和COOH基团、中间含柔性结构的化合物为NH2-Ii2-COOH或对应的环状化合物,&是含3_8 个亚甲基的结构。 The synthesis method of a rigid-chain polyamide claim, wherein both ends of the NH2 and COOH groups, a compound containing the intermediate structure is flexible NH2-Ii2-COOH, or the corresponding cyclic compound, having the structure & 3_8 methylene.
  5. 5. 一种刚性链聚酰胺,其特征是:所述的刚性链聚酰胺具有以下结构式...ABAAABAABAAAA...A和B随机排列;其中结构单元A为-NH-R1-CO-, R1是含芳环或杂环的刚性结构;结构单元B为-NH-R2-CO-, R2是含3-8个亚甲基的结构;A的个数为100-200 ;B的个数为10-20。 A rigid polyamide chain, characterized in that: said rigid chain polyamides having the structural formula ... ABAAABAABAAAA ... A and B are randomly arranged; wherein the structural unit A is -NH-R1-CO-, R1 a rigid structure having an aromatic or heterocyclic ring; structural unit B is -NH-R2-CO-, R2 is a structure containing 3-8 methylene groups; a is the number of 100-200; number of B 10-20.
  6. 6.根据权利要求5所述的一种刚性链聚酰胺,其特征在于,所述的刚性链结构含芳香环、萘环或咪唑结构。 A rigid-chain polyamide according to claim 5, characterized in that said rigid chain structure containing an aromatic ring, a naphthalene ring or an imidazole structure.
  7. 7.根据权利要求5所述的一种刚性链聚酰胺,其特征在于,所述的刚性链聚酰胺中,短的柔性链段随机分散分子链中。 A rigid-chain polyamide according to claim 5, wherein the rigid-chain polyamide, a short soft segment molecular chain randomly dispersed.
CN 201110049270 2011-03-02 2011-03-02 Method for synthesizing rigid chain polyamide and synthetic product thereof CN102190794A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201110049270 CN102190794A (en) 2011-03-02 2011-03-02 Method for synthesizing rigid chain polyamide and synthetic product thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201110049270 CN102190794A (en) 2011-03-02 2011-03-02 Method for synthesizing rigid chain polyamide and synthetic product thereof

Publications (1)

Publication Number Publication Date
CN102190794A true true CN102190794A (en) 2011-09-21

Family

ID=44599731

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201110049270 CN102190794A (en) 2011-03-02 2011-03-02 Method for synthesizing rigid chain polyamide and synthetic product thereof

Country Status (1)

Country Link
CN (1) CN102190794A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1198083A (en) * 1966-06-13 1970-07-08 Du Pont Co-Poly-p-Benzamides
US6048948A (en) * 1994-09-07 2000-04-11 Mazda Motor Corporation Method for producing a polymer composite material
CN1498912A (en) * 2002-11-07 2004-05-26 三菱瓦斯化学株式会社 Prepn. method of polyamide
CN1678660A (en) * 2002-08-30 2005-10-05 东洋纺织株式会社 Method for continuous production of polyamide
CN101492535A (en) * 2008-01-25 2009-07-29 东丽纤维研究所(中国)有限公司 Method for preparing block polyester-amide copolymer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1198083A (en) * 1966-06-13 1970-07-08 Du Pont Co-Poly-p-Benzamides
US6048948A (en) * 1994-09-07 2000-04-11 Mazda Motor Corporation Method for producing a polymer composite material
CN1678660A (en) * 2002-08-30 2005-10-05 东洋纺织株式会社 Method for continuous production of polyamide
CN1498912A (en) * 2002-11-07 2004-05-26 三菱瓦斯化学株式会社 Prepn. method of polyamide
CN101492535A (en) * 2008-01-25 2009-07-29 东丽纤维研究所(中国)有限公司 Method for preparing block polyester-amide copolymer

Similar Documents

Publication Publication Date Title
US3354127A (en) Aromatic copolyamides
US3294758A (en) Amorphous polyamides from a mixture of an alkyl substituted aliphatic diamine and unsubstituted aliphatic diamine
US3505288A (en) High melting polyamides containing ether groups
US4169932A (en) Method of producing poly-p-phenyleneterephthalamide or its copolymers
US3145193A (en) Polyamides from a mixture of isophthalic acid, terephthalic acid and branched chain aliphatic diamine
JPH0912868A (en) Polyamide composition
Shi et al. Packing mode and conformational transition of alkyl side chains in N-alkylated poly (p-benzamide) comb-like polymer
CN102286138A (en) A rapid temperature epoxy composition pultrusion
US4072665A (en) Polyamide from arylene diamine, isophthalic acid and alkylene dicarboxylic acid
JP2003055549A (en) Polyamide composition
JPH07300534A (en) Production of fiber or film using specific forming solution and fiber or film obtainable thereby
US4278786A (en) Aromatic polyamides containing ether linkages and process for producing same
Arnold et al. Rigid-rod polymers and molecular composites
US20090318660A1 (en) Crosslinkable aramid copolymers
Liou et al. Synthesis and properties of aromatic poly (ester amide) s with pendant phosphorus groups
JP2010515781A (en) Excellent polyarylene sulfide resin and a manufacturing method thereof brightness
WO2012093722A1 (en) Copolymer polyamide
JPH05170897A (en) Crystalline polyamide resin of high molecular weight
Dezern Synthesis and characterization of BTDA‐based polyamide‐imides
WO2011030911A1 (en) Flame-retardant polyamide resin composition
CN101456950A (en) Method for preparing high molecular weight poly(p-phenyleneterephthalamide) and products
Liou et al. Polyterephthalamides with naphthoxy‐pendent groups
CN104211954A (en) Preparation method of halogen-free flame retardant nylon 66 polymer
JP2000234021A (en) Solid-phase polymerization method for poly(meta- xylyleneadipamide)
Hsiao et al. Synthesis and properties of novel soluble polyamides having ether linkages and laterally attached p‐terphenyl units

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)