WO2019137303A1 - 一种高结晶速率聚酰胺及其制备方法和应用 - Google Patents
一种高结晶速率聚酰胺及其制备方法和应用 Download PDFInfo
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- WO2019137303A1 WO2019137303A1 PCT/CN2019/070355 CN2019070355W WO2019137303A1 WO 2019137303 A1 WO2019137303 A1 WO 2019137303A1 CN 2019070355 W CN2019070355 W CN 2019070355W WO 2019137303 A1 WO2019137303 A1 WO 2019137303A1
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
Definitions
- the invention relates to the field of polymer technology, in particular to a high crystallization rate polyamide and a preparation method and application thereof.
- Polyamide is widely used in the fields of electrical and electronic, automotive, home appliances, sporting goods, etc. due to its excellent mechanical properties, heat resistance, abrasion resistance, chemical resistance and self-lubricating properties.
- Engineering plastics High temperature resistant polyamides based on semi-aromatic polyamides have broad application prospects in the electrical and electronic industries due to their higher heat resistance temperature and dimensional stability.
- the development trend of miniaturization of electrical equipment requires high-temperature polyamides to have a high crystallization rate in order to shorten the molding cycle and reduce molding defects.
- prepolymerization + solid phase thickening is the mainstream method for preparing polyamides.
- the prepolymerized product is usually subjected to a granulation treatment, followed by a solid phase viscosity increasing reaction.
- the particle morphology of the polyamide prepolymer has an important influence on the structure of the product of the solid phase thickening reaction.
- Japanese Patent No. JP2000044677, JP2008239908 indicates that the excessively large polymer particles cause a large difference in the degree of surface and internal polymerization, an uneven molecular weight distribution, and a gel generated on the surface of the particles.
- the uneven structure of the polyamide molecular chain causes the crystallization rate to be slow, which affects the injection molding process.
- the nucleating agent In order to increase the crystallization rate of the polyamide, it is common practice to add 0.1%-5% of the nucleating agent during the blending and extrusion process. However, if the nucleating agent is added in an amount exceeding 0.2%, the mechanical properties and the yellowing resistance of the material may be poor. The effect, and the nucleating agent has limited help in the material crystallization rate increase, can not fundamentally solve the problem of slow material crystallization rate.
- Another object of the present invention is to overcome the above drawbacks and to provide a polyamide having a high crystallization rate. Another object of the present invention is to provide a process for the preparation of the polyamide.
- the high crystallization rate polyamide has a nucleating agent content of zero.
- the nucleating agent is a substance capable of increasing the crystallization rate of the polyamide, wherein the nucleating agent may be an inorganic nucleating agent and an organic nucleating agent.
- the inorganic nucleating agent is kaolin, talc, montmorillonite, graphite, glass fiber, magnesium oxide, aluminum oxide, zinc oxide, silicon dioxide, titanium dioxide, zirconium dioxide, antimony trioxide, calcium carbonate, At least one of calcium fluoride and magnesium sulfate.
- the organic nucleating agent is at least one of an adipamide dimer, a polyaryl ether sulfone, a polyphenylene sulfide, a phthalocyanine blue, a phenyl hypophosphite, an acetate, and a carbon fiber.
- the high crystallization rate polyamide does not contain any additives such as a nucleating agent capable of increasing the crystallization rate of the polyamide.
- the high crystallization rate polyamide constitutes a repeating unit from a dicarboxylic acid and a diamine.
- the dicarboxylic acid is at least one selected from the group consisting of an aromatic diacid or an aliphatic diacid; and the diamine is at least one selected from the group consisting of aliphatic diamines having 2 to 13 carbon atoms. .
- the high crystallization rate polyamide consists of repeating units derived from:
- the aromatic diacid accounts for 70-100 mol% of (a)
- the 1,10-decanediamine accounts for 70-100 mol% of (b).
- the aliphatic diacid is selected from the group consisting of oxalic acid, malonic acid, 1,4-succinic acid, 1,5-glutaric acid, 1,6-hexanedioic acid, 1,7-pimelic acid, 1 , 8-octanedioic acid, 2-methyl suberic acid, 1,9-sebacic acid, 1,10-sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid At least one of 1,13-tridecanedioic acid and 1,14-tetradecanedioic acid; preferably at least one of 1,6-hexanedioic acid and 1,10-sebacic acid.
- the aliphatic diamine having 2-13 carbon atoms is selected from the group consisting of ethylenediamine, propylenediamine, carnitine, cadaverine, 2-methylpentanediamine, 1,6-hexanediamine, 1, 7-heptanediamine, 1,8-octanediamine, 2-methyloctanediamine, 2,4,4-trimethylhexamethylenediamine, 5-methyl-nonanediamine, 1,9 At least one of hydrazine diamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine; preferably 1,6-hexanediamine, 1 At least one of 8-octyldiamine, 1,12-dodecanediamine, and 1,13-tridecanediamine.
- the aromatic diacid is terephthalic acid.
- a method for preparing a high crystallization rate polyamide comprising the steps of:
- (A) prepolymerization step adding a dicarboxylic acid, a diamine, a reaction aid to the reaction vessel, heating the reaction vessel, and performing a prepolymerization reaction. After the reaction is completed, the prepolymer is pressurized by the pressure in the reaction vessel. Spraying out;
- the weight percentage of the substance is not less than 70%;
- (C) Tackifying reaction step The powdery granular prepolymer is subjected to a viscosity-increasing reaction to obtain a polyamide.
- the powdery granular prepolymer having a particle diameter of more than 500 ⁇ m accounts for not more than 5% by weight of the total powdery granular prepolymer.
- the dicarboxylic acid is at least one selected from the group consisting of an aromatic diacid or an aliphatic diacid; and the diamine is at least one selected from the group consisting of aliphatic diamines having 2 to 13 carbon atoms. .
- the high crystallization rate polyamide consists of repeating units derived from:
- the aromatic diacid accounts for 70-100 mol% of (a)
- the 1,10-decanediamine accounts for 70-100 mol% of (b).
- the aliphatic diacid is selected from the group consisting of oxalic acid, malonic acid, 1,4-succinic acid, 1,5-glutaric acid, 1,6-hexanedioic acid, 1,7-pimelic acid, 1 , 8-octanedioic acid, 2-methyl suberic acid, 1,9-sebacic acid, 1,10-sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid At least one of 1,13-tridecanedioic acid and 1,14-tetradecanedioic acid.
- the aliphatic diamine having 2-13 carbon atoms is selected from the group consisting of ethylenediamine, propylenediamine, carnitine, cadaverine, 2-methylpentanediamine, 1,6-hexanediamine, 1, 7-heptanediamine, 1,8-octanediamine, 2-methyloctanediamine, 2,2,4-trimethylhexamethylenediamine, 5-methyl-nonanediamine, 1,9 At least one of decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, and 1,13-tridecanediamine.
- the aromatic diacid is terephthalic acid.
- a nylon salt may be added before heating the reaction vessel;
- the nylon salt includes hexamethylenediamine adipate, hexamethylenediamine sebacate, hexamethylenediamine 12 At least one of an acid salt, hexamethylenediamine tridecanate, hexamethylenediamine tetradecanoate, and hexamethylenediamine hexadecandioate.
- the reaction auxiliary agent is at least one selected from the group consisting of a catalyst and a molecular weight modifier.
- the catalyst is added in an amount of 0.02-0.2 wt% based on the total weight of the added dicarboxylic acid, diamine, molecular weight regulator, nylon salt, catalyst; the catalyst is selected from the group consisting of phosphoric acid, phosphorous acid, and secondary Phosphoric acid, phenylphosphonic acid, phenylphosphinic acid, phosphate, phosphite, hypophosphite, phenylphosphonate, phenylphosphinate, triphenyl phosphate, triphenyl phosphite, phosphite At least one
- the molecular weight modifier is added in an amount of 0.5 to 2.5% by weight based on the total weight of the dicarboxylic acid, the diamine, the nylon salt, the molecular weight modifier, and the catalyst to be added; the molecular weight modifier is selected from the group consisting of monobasic acid At least one of or one of the monoamines.
- the monobasic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutylene.
- the monoamine is selected from the group consisting of methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, At least one of dicyclohexylamine, aniline, toluidine, diphenylamine, naphthylamine; preferably decylamine and/or benzylamine.
- the tackifying reaction is carried out under vacuum or nitrogen.
- the reaction temperature is 210-260 ° C, and the reaction time is 1-3 hours.
- the viscosity increasing reaction step the reaction temperature is 230-260 ° C, the reaction time is 6-16 hours, and the vacuum degree is 50-9000 Pa.
- the viscosity increasing reaction step comprises a reaction temperature of 245-255 ° C, a reaction time of 8-12 hours, and a vacuum degree of 100-1000 Pa.
- the high crystallization rate polyamide is used in the fields of electrical and electronic equipment, automobile parts, office supplies, household goods and the like.
- the polyamide of the present invention has the advantage of high crystallization rate, and the crystallization peak half-width ⁇ T 1/2 is 6-12 ° C without adding a nucleating agent or the like which accelerates the crystallization rate of the polyamide, which shortens the material injection molding. Molding cycle to improve production efficiency.
- the polyamide of the present invention does not contain any additives such as an nucleating agent for increasing the crystallization rate of the polyamide, and does not have any influence on the basic properties of the polyamide.
- the preparation method of the polyamide of the invention is such that the granular prepolymer having a particle diameter of less than 80 ⁇ m accounts for not less than 70% by weight of the particulate prepolymer, so that the heat transfer during the thickening process is more rapid, and the particle surface The heat can quickly diffuse into the interior of the particles, promoting the near-surface polymerization of the particles and inhibiting gel formation on the surface of the particles.
- the method is simple in operation, cheap and easy to obtain raw materials, and is suitable for mass production.
- the raw materials used in the invention are all derived from commercially available products
- Pre-polymerization step According to the ratio of Table 1, a weighed dicarboxylic acid, a diamine, a nylon salt is added to an autoclave equipped with a magnetic coupling stirring, a condenser tube, a gas phase port, a feed port, and a pressure explosion port. , benzoic acid, sodium hypophosphite, after vacuuming, filling N 2 to normal pressure, repeating vacuuming, filling N 2 process three times, and finally raising the N 2 pressure to 0.3 MPa. The temperature was raised to 220 ° C over 2 hours with stirring, and the reaction mixture was stirred at 220 ° C for 1 hour, and then the temperature of the reactant was raised to 230 ° C with stirring.
- the reaction was continued at a constant temperature of 230 ° C and a constant pressure of 2.2 MPa for 2 hours.
- the pressure was kept constant by removing the formed water, and after the completion of the reaction, it was discharged in a spray state, and the prepolymer was vacuum dried at 80 ° C for 24 hours. .
- Prepolymer pulverization step The prepolymer was placed in a YK-160 type rocking granulator. The screen and drum speed are adjusted to control the particle size of the prepolymer. Thereafter, the prepolymer particles were quickly transferred to a GFG high-efficiency boiling dryer, and the drying temperature was set to 90 ° C and dried for 10 minutes to obtain a particulate prepolymer.
- the particle size distribution of the powdery particulate prepolymer is shown in Table 1.
- the YK-160 type swinging granulator and the GFG high-efficiency boiling dryer are all manufactured by Changzhou Rongsheng Drying Equipment Co., Ltd.
- the viscosity-increasing reaction step the pre-pulverized prepolymer is heated to 150 ° C at a heating rate of 50 ° C / hour; the temperature is raised to 200 ° C at a heating rate of 30 ° C / hour; and the temperature is raised to 230 at a heating rate of 10 ° C / hour. °C; Finally, the temperature was raised to 250 ° C at a heating rate of 5 ° C / hour, the temperature was maintained at a vacuum of 100 Pa, and the obtained polyamide was tested for relative viscosity, melting point and crystallization peak half-width. The results are shown in the table. 1 in.
- Pre-polymerization step According to the ratio of Table 1, a weighed dicarboxylic acid, a diamine, a nylon salt is added to an autoclave equipped with a magnetic coupling stirring, a condenser tube, a gas phase port, a feed port, and a pressure explosion port. , benzoic acid, sodium hypophosphite, after vacuuming, filling N 2 to normal pressure, repeating vacuuming, filling N 2 process three times, and finally raising the N 2 pressure to 0.3 MPa. The temperature was raised to 220 ° C over 2 hours with stirring, and the reaction mixture was stirred at 220 ° C for 1 hour, and then the temperature of the reactant was raised to 230 ° C with stirring.
- the reaction was continued at a constant temperature of 230 ° C and a constant pressure of 2.2 MPa for 2 hours. The pressure was kept constant by removing the formed water. After the completion of the reaction, the prepolymer was vacuum dried at 80 ° C for 24 hours to obtain a preheat. Polymer.
- Prepolymer granulation step 600 g of water was added to 3000 g of prepolymer and mixed well. After discharging, it was placed in a YK-160 type rocking granulator. The particle size of the prepolymer is controlled by adjusting the speed of the screen and the drum. Thereafter, the prepolymer particles were quickly transferred to a GFG high-efficiency boiling dryer, and the drying temperature was set to 90 ° C, and dried for 10 minutes to obtain a particulate prepolymer. The particle size distribution of the particulate prepolymer is shown in Table 1.
- the viscosity increasing reaction step the granulated prepolymer is heated to 150 ° C at a heating rate of 50 ° C / hour; the temperature is raised to 200 ° C at a heating rate of 30 ° C / hour; and then raised to a temperature rising rate of 10 ° C / hour to 230 ° C; Finally, the temperature was raised to 250 ° C at a heating rate of 5 ° C / hour, the temperature was constant, the vacuum was 100 Pa, the viscosity-increasing reaction was carried out, and the obtained polyamide was tested for relative viscosity, melting point and crystallization peak half-width, and the results are listed in in FIG. 1.
- Relative viscosity ( ⁇ r ) test Refer to the People's Republic of China standard GB12006.1-89, the polyamide viscosity number measurement method for testing. The specific test method is to measure the relative viscosity ⁇ r of the polyamide with a concentration of 0.25 g/dl in 98 wt% concentrated sulfuric acid at 25 ⁇ 0.01 ° C, using the NCY-2 automatic viscometer manufactured by Shanghai Silda Scientific Instrument Co., Ltd. measuring.
- T m Melting point test: The test was carried out in accordance with ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry. The specific test method is to test the melting point of the sample by using a Perkin Elmer Dimond DSC analyzer; the nitrogen atmosphere has a flow rate of 40 mL/min; the temperature is first raised to 350 ° C at 10 ° C / min, maintained at 350 ° C for 5 min, and then at 10 ° C / The temperature was cooled to 50 ° C, and the temperature was raised to 350 ° C at 10 ° C / min, and the endothermic peak temperature at this time was taken as the melting point Tm.
- the polyamide of the present invention has a crystal half-width ⁇ T 1/2 of 6-12 ° C and an excellent crystallization rate.
- the polyamide of Comparative Example 1-10 had a crystal half-width ⁇ T 1/2 12.5-23.5 ° C and a slow crystallization rate.
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Abstract
本发明提供一种高结晶速率聚酰胺,其结晶峰半峰宽ΔT1/2为6-12℃。所述的高结晶速率聚酰胺由二元羧酸和二元胺构成重复单元。其由衍生自以下的重复单元构成:(a)芳香族二酸和脂肪族二酸;(b)1,10-癸二胺和除1,10-癸二胺之外的碳原子个数为2-13的脂肪族二胺;其中,芳香族二酸占(a)的70-100mol%,1,10-癸二胺占(b)的70-100mol%。本发明的高结晶速率聚酰胺,其结晶速率高,缩短了材料注塑成型周期,提高生产效率。本发明还提供一种上述聚酰胺的制备方法,该方法操作简单、原料廉价易得,适合大规模生产;不添加成核剂等提高聚酰胺结晶速率的添加剂,对聚酰胺基本性质的影响小。
Description
本发明涉及高分子技术领域,特别是涉及一种高结晶速率聚酰胺及其制备方法和应用。
聚酰胺因其优良的力学性能、耐热性、耐磨损性、耐化学药品性和自润滑性等特点,广泛应用于电子电气、汽车、家电、体育用品等领域,是目前使用量最大的工程塑料。以半芳香聚酰胺为主的耐高温聚酰胺,因其耐热温度及尺寸稳定性更高,在电气及电子工业领域具有广阔的应用前景。电气设备微型化的发展趋势,要求耐高温聚酰胺具有较高的结晶速率,以达到缩短成型周期,减少成型缺陷的目的。
目前,“预聚合+固相增粘”是制备聚酰胺的主流方法。在现有技术中,通常对预聚产物进行造粒处理,然后进行固相增粘反应。聚酰胺预聚物的颗粒形态对固相增粘反应的产物的结构有重要影响。例如日本专利JP2000044677、JP2008239908指出,聚合物颗粒过大导致表面和内部聚合程度差别很大,分子量分布不均,并且有凝胶在粒子表面产生。聚酰胺分子链结构不均致使结晶速率变慢,影响注塑成型过程。为了提高聚酰胺结晶速率,通常做法在共混挤出过程中添加0.1%-5%的成核剂,然而成核剂添加量超过0.2%就会对材料的力学性能和耐黄变性能造成不良影响,并且成核剂对材料结晶速率提高的帮助有限,不能从根本上解决材料结晶速率慢的问题。
发明内容
本发明的目的在于克服以上缺陷,提供一种具有高结晶速率的聚酰胺。本发明的另一目的在于提供该聚酰胺的制备方法。
本发明是通过以下技术方案实现的:
一种高结晶速率聚酰胺,其结晶峰半峰宽ΔT
1/2为6-12℃。
所述的高结晶速率聚酰胺中成核剂含量为0。
所述的成核剂为能够提高聚酰胺的结晶速率的物质,其中,这些成核剂可以是无机类成核剂和有机类成核剂。
所述的无机类成核剂为高岭土、滑石粉、蒙脱土、石墨、玻璃纤维、氧化镁、氧化铝、氧化锌、二氧化硅、二氧化钛、二氧化锆、三氧化二钕、碳酸钙、氟化钙、硫酸镁中的至少一种。
所述的有机类成核剂为己二酰胺二聚体、聚芳醚砜、聚苯硫醚、酞菁蓝、苯基次磷酸盐、乙酸盐、碳纤维中的至少一种。
所述的高结晶速率聚酰胺中,不含有任何能够提高聚酰胺结晶速率的成核剂等添加剂。所述的高结晶速率聚酰胺由二元羧酸和二元胺构成重复单元。
所述的二元羧酸选自芳香族二酸或脂肪族二酸中的至少一种;所述的二元胺选自碳原子个数为2-13的脂肪族二胺中的至少一种。
所述的高结晶速率聚酰胺,其由衍生自以下的重复单元构成:
(a)芳香族二酸和脂肪族二酸;
(b)1,10-癸二胺和除1,10-癸二胺之外的碳原子个数为2-13的脂肪族二胺;
其中,芳香族二酸占(a)的70-100mol%,1,10-癸二胺占(b)的70-100mol%。
所述的脂肪族二酸选自乙二酸、丙二酸、1,4-丁二酸、1,5-戊二酸、1,6-己二酸、1,7-庚二酸、1,8-辛二酸、2-甲基辛二酸、1,9-壬二酸、1,10-癸二酸、1,11-十一烷二酸、1,12-十二烷二酸、1,13-十三烷二酸、1,14-十四烷二酸中的至少一种;优选1,6-己二酸、1,10-癸二酸中的至少一种。
所述的碳原子个数为2-13的脂肪族二胺选自乙二胺、丙二胺、腐肉胺、尸胺、2-甲基戊二胺、1,6-己二胺、1,7-庚二胺、1,8-辛二胺、2-甲基辛二胺、2,4,4-三甲基六亚甲基二胺、5-甲基-壬二胺、1,9-壬二胺、1,11-十一烷二胺、1,12-十二烷二胺、1,13-十三烷二胺中的至少一种;优选1,6-己二胺、1,8-辛二胺、1,12-十二烷二胺、1,13-十三烷二胺中的至少一种。
所述的芳香族二酸为对苯二甲酸。
一种高结晶速率聚酰胺的制备方法,包括以下步骤:
(A)预聚合步骤:将二元羧酸、二元胺、反应助剂加入到反应釜中,加热反应釜,进行预聚合反应,反应完成后,利用反应釜内的压力将预聚物以喷雾状态排出;
(B)预聚物粉碎步骤:将冷却后的预聚物粉碎,粉碎后的预聚物为粉末颗粒状预聚物,粒径小于80μm的粉末颗粒状预聚物占全部粉末颗粒状预聚物的重量百分数不低于70%;
(C)增粘反应步骤:将粉末颗粒状预聚物进行增粘反应,得到聚酰胺。
优选的,所述的预聚物粉碎步骤中,粒径大于500μm的粉末颗粒状预聚物占全部粉末颗粒状预聚物的重量百分数不超过5%。
所述的二元羧酸选自芳香族二酸或脂肪族二酸中的至少一种;所述的二元胺选自碳原子个数为2-13的脂肪族二胺中的至少一种。
所述的高结晶速率聚酰胺,其由衍生自以下的重复单元构成:
(a)芳香族二酸和脂肪族二酸;
(b)1,10-癸二胺和除1,10-癸二胺之外的碳原子个数为2-13的脂肪族二胺;
其中,芳香族二酸占(a)的70-100mol%,1,10-癸二胺占(b)的70-100mol%。
所述的脂肪族二酸选自乙二酸、丙二酸、1,4-丁二酸、1,5-戊二酸、1,6-己二酸、1,7-庚二酸、1,8-辛二酸、2-甲基辛二酸、1,9-壬二酸、1,10-癸二酸、1,11-十一烷二酸、1,12-十二烷二酸、1,13-十三烷二酸、1,14-十四烷二酸中的至少一种。
所述的碳原子个数为2-13的脂肪族二胺选自乙二胺、丙二胺、腐肉胺、尸胺、2-甲基戊二胺、1,6-己二胺、1,7-庚二胺、1,8-辛二胺、2-甲基辛二胺、2,2,4-三甲基六亚甲基二胺、5-甲基-壬二胺、1,9-壬二胺、1,11-十一烷二胺、1,12-十二烷二胺、1,13-十三烷二胺中的至少一种。
所述的芳香族二酸为对苯二甲酸。
优选的,在所述的预聚合步骤中,加热反应釜之前还可以加入尼龙盐;所述的尼龙盐包括己二胺己二酸盐、己二胺癸二酸盐、己二胺十二二酸盐、己二胺十三二酸盐、己二胺十四二酸盐以及己二胺十六二酸盐中的至少一种。
所述的反应助剂选自催化剂、分子量调节剂中的至少一种。
以加入的二元羧酸、二元胺、分子量调节剂、尼龙盐、催化剂的总重量计,所述催化剂的加入量为0.02-0.2wt%;所述的催化剂选自磷酸、亚磷酸、次磷酸、苯膦酸、苯次膦酸、磷酸盐、亚磷酸盐、次磷酸盐、苯膦酸盐、苯次膦酸盐、磷酸三苯酯、亚磷酸三苯酯、亚磷酸三酯中的至少一种;
以加入的二元羧酸、二元胺、尼龙盐、分子量调节剂、催化剂的总重量计,所述分子量调节剂的加入量为0.5-2.5wt%;所述的分子量调节剂选自一元酸中的至少一种或者一元胺中的至少一种。
所述的一元酸选自甲酸、乙酸、丙酸、丁酸、戊酸、己酸、辛酸、月桂酸、十三烷酸、肉豆蔻酸、棕榈酸、硬脂酸、特戊酸、异丁酸、环己烷羧酸、苯甲酸、、α-萘羧酸、β-萘羧酸、甲基萘羧酸、苯基乙酸中的至少一种;优选为甲酸、乙酸、苯甲酸中的至少一种。
所述的一元胺选自甲胺、乙胺、丙胺、丁胺、己胺、辛胺、癸胺、硬脂胺、二甲胺、二乙胺、二丙胺、二丁胺、环己胺、二环己胺、苯胺、甲苯胺、二苯基胺、萘胺中的至少一种;优选为癸胺和/或苯甲胺。
优选的,预聚合步骤中反应釜内有搅拌。
优选的,所述的增黏反应在真空或者氮气条件下进行。
优选的,所述的预聚合步骤中,反应温度为210-260℃,反应时间1-3小时。
所述的增粘反应步骤,反应温度230-260℃,反应时间6-16小时,真空度50-9000Pa。
优选的,所述的增粘反应步骤,反应温度245-255℃,反应时间8-12小时,真空度100-1000Pa。
所述的高结晶速率聚酰胺的制备方法制得的高结晶速率聚酰胺;
所述的高结晶速率聚酰胺应用于电气电子器材、汽车部件、办公用品、居家用品等领域。
本发明具有如下有益效果:
本发明的聚酰胺具有高结晶速率的优点,在不添加成核剂等加速聚酰胺结晶速率的添加剂的情况下,其结晶峰半峰宽ΔT
1/2为6-12℃,缩短了材料注塑成型周期,提高生产效率。本发明的聚酰胺中不含有加成核剂等其他为了提高聚酰胺结晶速率的添加剂,对聚酰胺的基本性质无任何影响。本发明的聚酰胺的制备方法,使得粉末颗粒粒径小于80μm的颗粒状预聚物占颗粒状预聚物的重量分数不低于70%,使得增粘过程中传热更为迅速,颗粒表面热量能够快速扩散至颗粒内部,促使颗粒表面和内部聚合度接近,抑制颗粒表面凝胶产生。该方法操作简单、原料廉价易得,适合大规模生产。
下面通过具体实施方式来进一步说明本发明,以下实施例为本发明较佳的实施方式,但本发明的实施方式并不受下述实施例的限制。
本发明所采用的原料均来源于市购产品;
实施例1-10高结晶速率聚酰胺的制备方法:
预聚合步骤:根据表1的配比,在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的压力釜中加入称量好的二元羧酸、二元胺、尼龙盐、苯甲酸、次磷酸钠,抽真空后充N
2至常压,重复抽真空后充N
2过程三次,最后将N
2压力升至0.3MPa。在搅拌下2个小时内升温到220℃,将反应混合物在220℃搅拌1小时,然后在搅拌下使反应物的温度升高到230℃。反应在230℃的恒温和2.2MPa的恒压下继续进行2小时,通过移去所形成的水而保持压力恒定,反应完成后以喷雾状态排出,后预聚物于80℃下真空干燥24小时。
预聚物粉碎步骤:将预聚物其置于YK-160型摇摆颗粒机中。调整筛网与滚筒转速,从而控制预聚物粒径。之后迅速将预聚物颗粒转移至GFG高效沸腾干燥机内,设置干燥温 度为90℃,干燥10min,得到颗粒状预聚物,粉末颗粒状预聚物的粒径分布列于表1中。其中,所述YK-160型摇摆颗粒机及GFG高效沸腾干燥机均为常州市荣臻干燥设备有限公司制造。
增粘反应步骤:粉碎后的预聚物以50℃/小时的升温速率升温至150℃后;以30℃/小时的升温速率升温至200℃;再以10℃/小时的升温速率升温至230℃;最后以5℃/小时的升温速率升温至250℃后恒温,真空度为100Pa条件下进行增粘反应,制得的聚酰胺测试相对粘度、熔点和结晶峰半峰宽,结果列于表1中。
对比例1-10聚酰胺的制备方法:
预聚合步骤:根据表1的配比,在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的压力釜中加入称量好的二元羧酸、二元胺、尼龙盐、苯甲酸、次磷酸钠,抽真空后充N
2至常压,重复抽真空后充N
2过程三次,最后将N
2压力升至0.3MPa。在搅拌下2个小时内升温到220℃,将反应混合物在220℃搅拌1小时,然后在搅拌下使反应物的温度升高到230℃。反应在230℃的恒温和2.2MPa的恒压下继续进行2小时,通过移去所形成的水而保持压力恒定,反应完成后出料,预聚物于80℃下真空干燥24小时,得到预聚物。
预聚物造粒步骤:将600g水加入3000g预聚物中,混合均匀。出料后,将其置于YK-160型摇摆颗粒机中。通过调整筛网与滚筒转速,从而控制预聚物粒径。之后迅速将预聚物颗粒转移至GFG高效沸腾干燥机内,设置干燥温度为90℃,干燥10min,得到颗粒状预聚物,颗粒状预聚物的粒径分布列于表1中。
增粘反应步骤:造粒后的预聚物以50℃/小时的升温速率升温至150℃后;以30℃/小时的升温速率升温至200℃;再以10℃/小时的升温速率升温至230℃;最后以5℃/小时的升温速率升温至250℃后恒温,真空度为100Pa条件下进行增粘反应,制得的聚酰胺测试相对粘度、熔点和结晶峰半峰宽,结果列于表1中。
测试标准:
(1)相对粘度(η
r)测试:参照中华人民共和国家标准GB12006.1-89,聚酰胺粘数测定方法进行测试。具体的测试方法为在25±0.01℃的98wt%的浓硫酸中测量浓度为0.25g/dl的聚酰胺的相对粘度η
r,采用上海思尔达科学仪器有限公司生产的NCY-2自动粘度计测量。
(2)熔点(T
m)测试:参照ASTM D3418-2003,Standard Test Method for Transition Temperatures of PolymersBy Differential Scanning Calorimetry进行测试。具体的测试方法为采用Perkin Elmer Dimond DSC分析仪测试样品的熔点;氮气气氛,流速为40mL/min;测试时先以10℃/min升温至350℃,在350℃保持5min,然后以10℃/min冷却到50℃,再 以10℃/min升温至350℃,将此时的吸热峰温度设为熔点Tm。
(3)结晶峰半峰宽(ΔT
1/2):参照ASTM D3418-2003,Standard Test Method for Transition Temperatures of PolymersBy Differential Scanning Calorimetry进行测试。具体的测试方法为采用Perkin Elmer Dimond DSC分析仪测试样品的熔点;氮气气氛,流速为40mL/min;测试时先以10℃/min升温至350℃,在350℃保持5min,然后以10℃/min冷却到50℃,将放热峰起始温度设为熔点T1,放热峰终点温度设为熔点T2,ΔT
1/2=(T1-T2)/2。
(4)粒径分布比例测试:按照国家标准GB/T 20405.3-2006(失禁者用尿液吸收剂:聚合物基质吸液材料特性的测试方法——第3部分:筛分法对粒径分布的测定)进行测试。
表1:实施例与对比例配比及试样测试结果
续表1:
续表1:
从表1可以看出,本发明的聚酰胺,结晶半峰宽ΔT
1/2在6-12℃,具有优秀的结晶速率。而对比例1-10的聚酰胺,结晶半峰宽ΔT
1/212.5-23.5℃,结晶速率较慢。
Claims (14)
- 一种高结晶速率聚酰胺,其特征在于,其结晶峰半峰宽ΔT1/2为6-12℃。
- 根据权利要求1所述的高结晶速率聚酰胺,其特征在于,所述的高结晶速率聚酰胺中成核剂含量为0。
- 根据权利要求1所述的高结晶速率聚酰胺,其特征在于,所述的高结晶速率聚酰胺由二元羧酸和二元胺构成重复单元。
- 根据权利要求3所述的高结晶速率聚酰胺,其特征在于,所述的二元羧酸选自芳香族二酸或脂肪族二酸中的至少一种;所述的二元胺选自碳原子个数为2-13的脂肪族二胺中的至少一种。
- 根据权利要求4所述的高结晶速率聚酰胺,其特征在于,其由衍生自以下的重复单元构成:(a)芳香族二酸和脂肪族二酸;(b)1,10-癸二胺和除1,10-癸二胺之外的碳原子个数为2-13的脂肪族二胺;其中,芳香族二酸占(a)的70-100mol%,1,10-癸二胺占(b)的70-100mol%。
- 根据权利要求5所述的高结晶速率聚酰胺,其特征在于,所述的脂肪族二酸选自乙二酸、丙二酸、1,4-丁二酸、1,5-戊二酸、1,6-己二酸、1,7-庚二酸、1,8-辛二酸、2-甲基辛二酸、1,9-壬二酸、1,10-癸二酸、1,11-十一烷二酸、1,12-十二烷二酸、1,13-十三烷二酸、1,14-十四烷二酸中的至少一种;优选1,6-己二酸、1,10-癸二酸中的至少一种。
- 根据权利要求4所述的高结晶速率聚酰胺,其特征在于,所述的碳原子个数为2-13的脂肪族二胺选自乙二胺、丙二胺、腐肉胺、尸胺、2-甲基戊二胺、1,6-己二胺、1,7-庚二胺、1,8-辛二胺、2-甲基辛二胺、2,2,4-三甲基六亚甲基二胺、5-甲基-壬二胺、1,9-壬二胺、1,11-十一烷二胺、1,12-十二烷二胺、1,13-十三烷二胺中的至少一种;优选1,6-己二胺、1,8-辛二胺、1,12-十二烷二胺、1,13-十三烷二胺中的至少一种。
- 根据权利要求5所述的高结晶速率聚酰胺,其特征在于,所述的芳香族二酸为对苯二甲酸。
- 权利要求1-8任一项所述的一种高结晶速率聚酰胺的制备方法,其特征在于,包括以下步骤:(A)预聚合步骤:将二元羧酸、二元胺、反应助剂加入到反应釜中,加热反应釜,进行预聚合反应,反应完成后,利用反应釜内的压力将预聚物以喷雾状态排出;(B)预聚物粉碎步骤:将冷却后的预聚物粉碎,粉碎后的预聚物为粉末颗粒状预聚物,粒径小于80μm的粉末颗粒状预聚物占全部粉末颗粒状预聚物的重量百分数不低于70%;(C)增粘反应步骤:将粉末颗粒状预聚物进行增粘反应,得到聚酰胺。
- 根据权利要求9所述的高结晶速率聚酰胺的制备方法,其特征在于,所述的预聚物粉碎步骤中,粒径大于500μm的粉末颗粒状预聚物占全部粉末颗粒状预聚物的重量百分数不超过5%。
- 根据权利要求9或10所述的高结晶速率聚酰胺的制备方法,其特征在于,在所述的预聚合步骤中,加热反应釜之前还可以加入尼龙盐;所述的尼龙盐选自己二胺己二酸盐、己二胺癸二酸盐、己二胺十二二酸盐、己二胺十三二酸盐、己二胺十四二酸盐以及己二胺十六二酸盐中的至少一种。
- 根据权利要求9、10或11所述的高结晶速率聚酰胺的制备方法,其特征在于,所述的反应助剂选自催化剂、分子量调节剂中的至少一种。
- 根据权利要求12所述的高结晶速率聚酰胺的制备方法,其特征在于,以加入的二元羧酸、二元胺、分子量调节剂、尼龙盐、催化剂的总重量计,所述催化剂的加入量为0.02-0.2wt%,所述的催化剂选自磷酸、亚磷酸、次磷酸、苯膦酸、苯次膦酸、磷酸盐、亚磷酸盐、次磷酸盐、苯膦酸盐、苯次膦酸盐、磷酸三苯酯、亚磷酸三苯酯、亚磷酸三酯中的至少一种;以加入的二元羧酸、二元胺、尼龙盐、分子量调节剂、催化剂的总重量计,所述分子量调节剂的加入量为0.5-2.5wt%,所述的分子量调节剂选自一元酸中的至少一种或者一元胺中的至少一种。
- 权利要求9-13任一项所述的高结晶速率聚酰胺的制备方法制得的高结晶速率聚酰胺的应用,其特征在于,所述的高结晶速率聚酰胺应用于电气电子器材、汽车部件、办公用品、居家用品等领域。
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