WO2011097832A1

WO2011097832A1 - Long carbon-chain semi-aromatic high temperature resistant polyamide homopolymer and copolymer and synthesis method thereof

Info

Publication number: WO2011097832A1
Application number: PCT/CN2010/070714
Authority: WO
Inventors: 谷勤翠; 张怀忠; 杨桂生
Original assignee: 上海杰事杰新材料(集团)股份有限公司
Priority date: 2010-02-11
Filing date: 2010-02-23
Publication date: 2011-08-18
Also published as: CN102153741A; CN102153741B

Abstract

A synthesis method of long carbon-chain semi-aromatic high temperature resistant polyamide homopolymer and copolymer and the polymerization product obtained are disclosed. The synthesis method comprises the following steps: (a) pre-polymerizing terephthalic acid with 1,10-diaminodecane at a molar ratio of 1:1.00-1.02, and optionally with other copolymerizable components, to obtain the prepolymer which has an intrinsic viscosity of 0.4-1.1dl/g, (b) solid-phase polymerizing the prepolymer obtained from step (a), controlling the intrinsic viscosity to 1.2-2.6dl/g,to obtain the long carbon-chain semi-aromatic high temperature resistant polyamide PA10T or its copolymer.

Description

Homopolymer and copolymer of long carbon chain semi-aromatic high temperature resistant polyamide and synthesis method thereof

The present invention relates to a polyamide material, in particular to a long carbon chain semi-aromatic high temperature resistant polyamide

PA10T and its synthesis method. Background technique

High temperature resistant polyamide is a member of the polyamide family. It has high temperature resistance due to its structure containing a benzene ring or other aromatic ring structure. It is usually composed of aliphatic or alicyclic diacids or diamines and aromatics. The diamine or diacid is obtained by polycondensation, and may also be obtained by copolycondensation of three or more diacid/diamine monomers according to performance requirements. Semi-aromatic polyamides are the main products of high temperature resistant nylon because of their superior physical and mechanical properties than aliphatic polyamides and unparalleled processing properties of aromatic polyamides. Representative products include DuPont's HTN series (PA6T/66, etc.) ), Kuraray's PA9T, Mitsubishi Gas's MXD6, DSM's PA46 and PA4T, EMS's PA6T, etc., and the patent reports on such products are too numerous to mention.

Most of the prior art patents are related to PA6T. These polyamides have higher melting points, generally above 300 °C, and have excellent thermal deformation properties and physical and mechanical properties. However, the disadvantages of the material are not negligible. Aspects: First, the rigidity is so strong that its tensile elongation at break is generally below 5%, which severely limits the application of such materials in the field of pipes; second, the water absorption of such materials is higher than that of PA66 and PA6. It is much lower, but dimensional stability and performance retention in wet conditions are still unsatisfactory.

One of the effective methods for solving the above problems is to increase the ratio of the flexible chain in the molecular structure design to improve the toughness of the product, and at the same time reduce the relative content of the amide group and thereby reduce the water absorption rate of the material. The introduction of the flexible chain can be carried out by substituting hexamethylenediamine, decylamine, dodecanediamine, tridecanediamine or the like in place of hexamethylenediamine to prepare semi-aromatic polyamides such as PA9T, PA10T, PA12T, PA13T and the like. PA10T is the best in terms of raw material source, cost and comprehensive performance index. It is a new type of semi-aromatic nylon made from terephthalic acid and decane diamine. In addition to petroleum, it can also be derived from natural castor oil. Therefore, PA10T is a bio-based material and has important environmental significance. The presence of a benzene ring on the main chain gives PA10T good physical and mechanical properties and heat resistance, while long chain methylene groups increase the toughness of the material and reduce its water absorption, which can be made by injection molding and extrusion processing. Products are used in automotive parts, gears, bearings and more. PA10T's comprehensive performance index exceeds semi-aromatic polyamides such as PA6T, and it is a promising high-performance high-temperature engineering plastic. PA10T also has incomparable advantages such as PA6T in the polymerization process. For example, an important issue to be aware of when preparing semi-aromatic polyamides is the possibility of polymerization. The high melting point, ie the high molecular weight component, will be formed. The ratio of such high molecular weight components should not be too high, otherwise the material will not be processed properly. Generally speaking, the content of the high molecular weight component in the first tank polymerization process is not very obvious, but if the thorough cleaning operation of the polymerization tank is not carried out, the phenomenon becomes more and more serious as the number of polymerization increases, especially in the preparation. PA6T series semi-aromatic polyamide. In comparison, the PA10T does not need to worry too much about this problem. The required process conditions are much looser than the PA6T series, making it easier to industrialize.

At present, the patent documents for PA10T are mostly reported as a form of composition, and reports on PA10T as a main product are rarely seen.

The singularity of the pre-polymer is 0. 3 dl / g or less, preferably 0. 08-0. 2dl/g. However, the choice of organic solvent will greatly increase the production cost and involve the problem of solvent recovery, which is very challenging for industrial production, and is also very unfavorable for environmental protection. If it is based on the same performance requirements, it is green. The method of producing PA10T is of more significance; in addition, the relatively low intrinsic viscosity of the prepolymer will impose a great burden on the later solid phase polymerization. The molecular weight distribution of the product after polymerization will be wider, and the required physics will be achieved. Mechanical properties require longer solid phase polymerization times. Although the solid phase polymerization temperature is relatively low, long-term reactions also cause hue problems, the so-called time-temperature equivalent.

Although Mitsui Chemicals Co., Ltd. described the synthesis of PA10T in JP2002-293926, most of its work is carried out on compositions and modified materials. The prepolymer obtained in this patent is also subjected to solid phase polymerization and melting. The polymerization process after two steps of polymerization is carried out to increase the molecular weight of PA10T. The entire process requires at least 70 h, the production cost is high, and the problem in WO 2009/079886 A1 also exists.

In summary, there is a lack of a simple, environmentally friendly, and excellent method for preparing a long carbon chain semi-aromatic high temperature resistant polyamide PA10T. Summary of the invention

A first object of the present invention is to provide a process for preparing a long carbon chain semi-aromatic high temperature resistant polyamide PA10T and a copolymer thereof which are simple, environmentally friendly and excellent in performance.

A second object of the present invention is to obtain a long carbon chain semi-aromatic high temperature resistant polyamide PA10T and a copolymer thereof which are simple, environmentally friendly and excellent in performance. In a first aspect of the invention, a long carbon chain semi-aromatic high temperature polyamide homopolymer PA10T is provided And a method for synthesizing the same, comprising the steps of:

(a) prepolymerizing terephthalic acid and 1,10-decanediamine in a molar ratio of 1: 1.00 to 1.02, and optionally other copolymerization components, to obtain an intrinsic viscosity number of 0. 4-1. a prepolymer of ldl/g;

(b) The prepolymer of the step (a) is subjected to solid phase polymerization to control the intrinsic viscosity to 1.2 to 2. 6 dl/g to obtain the long carbon chain semiaromatic high temperature resistant polyamide PA10T. 6-1. 0 dl/g。 In the step (a), the intrinsic viscosity is controlled at 0. 6-1. 0 dl / g.

In a preferred embodiment, the prepolymer is directly extruded into a strand granulation and used in step (b). In a specific embodiment of the present invention, in the step (a), the prepolymer having an intrinsic viscosity of 0.4 to 0.6 is uniformly stirred in a water bath with stirring, and the temperature of the water bath is controlled at 40- At 80 ° C, it is dried in vacuum and used in step (b). In a specific embodiment of the present invention, in the step (a), the composition of the copolymerization component is selected from the group consisting of PA66, PA610, PA10I, PA6T, PA6T/66, PA11, PA12, PA612, PA1010, PA1212; The copolymerization component is contained in an amount of not more than 50% by mole based on the total moles of terephthalic acid, 1, 10-decanediamine and the copolymerization component. That is, the composition of the copolymerization system is selected from the group consisting of PA10T/66, PA10T/610, PA10T/10I, PA10T/6T, PA10T/6T/66, PA10T/1 U PA10T/12, PA10T/612, PA10T/1010, PA10T/1212 And the content of the other copolymerization component in the copolymerization system is not more than 50% by mole based on the total moles of terephthalic acid, 1, 10-decanediamine and other copolymerization components.

In a preferred embodiment, the aromatic diacid is selected from the group consisting of isophthalic acid and naphthalic acid; the alicyclic diacid is cyclohexanedioic acid; and the aliphatic diacid is a C6-C16 diacid such as Adipic acid, azelaic acid, suberic acid, etc.; the lactam such as caprolactam, laurolactam; the amino acid such as 11-aminoundecanoic acid, etc., the nylon salt such as PA66 salt, PA610 salt, PA6T salt One or more of PA612 salt, PA46 salt, PA1010 salt, and PA1212 salt. In a specific embodiment of the present invention, the 1, 10-decanediamine of the step (a) is derived from plant ramie. In a specific embodiment of the invention, the step (a) is free of an organic solvent. In the step (b), the intrinsic viscosity is controlled to be 1. 3 - 1. 8 dl / g. In a specific embodiment of the present invention, the prepolymer of the step (a) is precrystallized at 130-180 ° C for 1-8 h, and then heated to 200-260 ° C for solid phase polymerization of the step (b). . A second aspect of the invention provides a long carbon chain semi-aromatic, high temperature resistant polyamide PA10T homopolymer or copolymer prepared by the process. BEST MODE FOR CARRYING OUT THE INVENTION

6-1. ldl/g, preferably 0. 6-1. 6-1. ldl / g, preferably 0. 6-1. 6-1. ldl / g, preferably 0. 6-1. 6-1. ldl / g, preferably 0. 6-1. O dl / g; The intrinsic viscosity of the final product obtained by solid phase polymerization of the prepolymer is 1. 2 - 2. 6dl / g, preferably 1. 3 - 1. 8dl / g, obtained in addition to excellent physical In addition to its mechanical properties and processability, it also exhibits excellent high temperature resistance and low water absorption of PA10T materials, making it suitable for automotive, electronics, electrical and other related industries. The present invention has been completed on this basis. The technical idea of the present invention is as follows:

The invention provides a method for synthesizing a long-chain semi-aromatic polyamide and a copolymer thereof. The polyamide is mainly composed of terephthalic acid and 1,10-decanediamine, and may also contain one of aromatic, alicyclic or aliphatic other diacids, lactams, amino acids and nylon salts. Or several. The semi-aromatic polyamide obtained by the two-step polymerization method has a melting point of 270-32 CTC, which belongs to the category of high-temperature nylon. One of the characteristics of the semi-aromatic polyamide is that it has excellent physical and mechanical properties, thermal deformation and good processing properties and impact resistance of the wholly aromatic polyamide; the second characteristic is that its molecular structure The low low water absorption determined by the low amide group content is essential for maintaining the stability of the product during performance and dimensional stability; the third characteristic is that the bisdiamine which is one of the main raw materials for synthesizing the polyamide can be It is derived from plant ramie and is a bio-based material. Various aspects of the invention are described in detail below, and various materials of the invention may be obtained commercially, unless otherwise specified; or prepared according to conventional methods in the art. Unless otherwise defined or stated, All of the professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described can be applied to the method of the invention: Prepolymerization

The method for synthesizing the long carbon chain semi-aromatic high temperature resistant polyamide PA10T of the present invention comprises the following prepolymerization step: (a) terephthalic acid and 1, 10-anthracene having a molar ratio of 1: 1.00 - 1. 02 4-1. ldl / g of prepolymer. The prepolymer of the intrinsic viscosity is controlled at 0. 4-1. ldl / g. 6-1. 0 dl/g。 Preferably, in the step (a), the intrinsic viscosity is controlled at 0. 6-1. 0 dl / g.

Preferably, said step (a) is an aqueous phase reaction. More preferably, said step (a) is free of organic solvents. In a preferred embodiment, the prepolymer is directly extruded into a strand and granulated for use in the subsequent step (b). In a preferred embodiment, in the step (a), the prepolymer having an intrinsic viscosity of 0.4 to 0.6 is placed in a water bath with stirring, and the temperature of the water bath is controlled at 40-80 ° C. After vacuum drying, it is used in step (b). In a preferred embodiment, in the step (a), the copolymer component is an aromatic, alicyclic or aliphatic other diacid, lactam, amino acid. And one or more of nylon salts and the like.

The copolymer system used may be PA10T/66, PA10T/610, PA10T/10I, PA10T/6T, PA10T/6T/66, PA10T/1 U PA10T/12, PA10T/612, PAlOT/1010, PA10T/1212, etc. . And the content of the copolymerization component is not more than 50% by mole based on the total weight of the copolymerization system.

Typically, the 1, 10-decanediamine of step (a) is derived from plant ramie. It is also possible to use 1, 10-decanediamine obtained by the petroleum method as a raw material.

Preferably, the prepolymer of the step (a) is precrystallized at 130-180 ° C for 1-8 h, and then heated to 200-260 ° C for the subsequent step (b).

If the copolymerization of PA10T is prepared, the reaction system may contain isophthalic acid, naphthalic acid, caprolactam, laurolactam, 11-amino-acid, PA66 salt, PA610 salt, PA6T salt, PA612 salt, PA46 salt, PA1010 salt. One or more of the PA1212 salts, the present invention does not exclude the addition of antioxidants, flame retardants, defoamers, heat stabilizers, toners, dyes, fillers, impact modifiers, Plasticizers, nucleating agents, mold release agents, antistatic agents, brighteners, etc. Most of the inorganic fillers commonly used in engineering plastics are also suitable for use in the present invention, such as glass fibers, carbon fibers, glass beads, kaolin, montmorillonite, talc, calcium carbonate, mica, and the like.

Among them, 1, 10-decanediamine and terephthalic acid (PTA) can be made into nylon 10T salt for use first. By means of direct feeding, the former amine/acid equivalent ratio is relatively easy to control, while the latter saves time and effort. The invention adopts 1,10-diamine and terephthalic acid (PTA) from nature as main raw materials to prepare PA10T homopolymer and copolymer by two-step polymerization method, and does not exclude 1, 10 obtained by petroleum method. - Hydrazine diamine as raw material, the raw materials which may be used in the preparation of PA10T copolymer include other diacids such as aromatic isophthalic acid, naphthalic acid, alicyclic cyclohexanedioic acid, aliphatic adipic acid, hydrazine Diacids, suberic acid, lactams such as caprolactam, laurolactam, amino acids such as 11-aminoundecanoic acid, etc., may also contain nylon salts such as PA66 salt, PA610 salt, PA6T salt, PA612 salt, PA46 salt, PA1010 salt Or one or more of the PA1212 salts, the preferred amount of terephthalic acid in the copolymerization system is 40-90%, more preferably 50-80% and most preferably 60-75% (molar content), according to Heat resistance requires adjustment of the ratio of the copolymerization system. The melting point range of the polymer is controlled at 270-320 ° C, most preferably 280-310 ° C. The reason for selecting the melting point range is that the melting point is too low to meet the requirements of high temperature resistance, and the melting point is too high to be thermally degraded during processing. It causes foaming, extrusion swell and increases energy consumption during production. The blocking agent is a monocarboxylic acid such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, benzoic acid or the like, preferably benzoic acid or acetic acid. The amount of the blocking agent is determined by the molecular weight of the polymer, the reactivity of the blocking agent, the boiling point of the blocking agent, etc., and is usually in an amount of from 0.01 to 10% by mole based on the total amount of the diacid/diamine. The catalyst used to prepare the prepolymer of the present invention includes phosphoric acid, phosphate or ester, phosphorous acid, phosphite or ester, hypophosphorous acid, hypophosphite or the like, and the present invention employs sodium hypophosphite. The invention does not exclude the addition of an antioxidant, a flame retardant, an antifoaming agent, a heat stabilizer, a toner, a dye, a filler, an impact modifier, a plasticizer, a nucleating agent, a mold release agent to a polymerization reaction system. , antistatic agents, brighteners, etc. Most of the inorganic fillers commonly used in engineering plastics are also suitable for use in the present invention, such as glass fibers, carbon fibers, glass beads, kaolin, montmorillonite, talc, calcium carbonate, mica, and the like.

In a specific embodiment, terephthalic acid (PTA) and 1,10-decanediamine, a catalyst, a blocking agent, and a deionization are mixed in a closed polymerization vessel at a molar ratio of 1:1.00 to 1.02. Water, wherein 1, 10-decanediamine and terephthalic acid (PTA) can be first prepared into a nylon 10T salt, or a method in which a salt is first polymerized in a polymerization vessel. The polymerization process firstly replaces the air in the kettle with nitrogen or carbon dioxide for 2-5 times. For the direct input of terephthalic acid (PTA) and 1,10-diamine, the temperature is raised to 100-200 °C for neutralization reaction. 1-5. 5MPa, By using a nylon 10T salt, the neutralization reaction step is omitted; the temperature is increased to 0. 5 - 5. 0MPa, preferably 1. 5 - 3. 5MPa, by removing the system The water pressure is maintained to maintain a constant pressure in the reaction vessel. The pressure is reduced to 280-320 ° C in the period of 1-3 hours. The pressure relief time is 0-180 min, and the pressure relief pressure is 0-2. 5 MPa. A vacuum operation is performed to increase the molecular weight of the prepolymer. The prepolymer having a viscosity of 0. 4-0. 6 dl/g is placed with stirring In the water bath, the temperature of the water bath is controlled at 40-80 ° C, and the particle size is relatively uniform after stirring, which is helpful for the later solid phase polymerization; the prepolymer having a viscosity of 0.6 dl/g or more is It can be directly extruded and granulated.

More specifically, the terephthalic acid and 1,10-nonanediamine, the catalyst, the terminal blocking agent, the deionized water and the above-mentioned additive can be mixed in a closed polymerization vessel at a molar ratio of 1:1.00-1.02. Agents and fillers, wherein 1, 10-decanediamine and terephthalic acid (PTA) can be first made into nylon 10T salt, or can be directly fed. The copolymerization system may also be added with other diacids such as aromatic isophthalic acid, naphthalenedicarboxylic acid, alicyclic cyclohexanedioic acid, aliphatic adipic acid, sebacic acid, suberic acid, lactam such as Caprolactam, laurolactam, amino acids such as 11-amino-monoacid, etc., may also be added to one or more of nylon salts such as PA66 salt, PA610 salt, PA6T salt, PA612 salt, PA46 salt, PA1010 salt, PA1212 salt. To prepare copolymerized PA10T. First, purge the air in the kettle 2-5 times with nitrogen or carbon dioxide. The stirring speed is

10-50r/min, for the direct polymerization of terephthalic acid and 1,10-denanediamine, the temperature of the kettle should be raised to 100-200 ° C for salt formation, preferably 110-140 ° C. More preferably, it is 120-130 ° C, and the salt formation reaction time is preferably 2-10 h; for the case where the nylon 10T salt is used as the raw material, the 10T salt is first prepared. In both cases, the pressure of the system is raised to 0. 5 - 5. OMPa, preferably 1. 5 - 3. 5MPa, the pressure in the kettle is maintained by removing the moisture in the system, and the constant pressure reaction is to be carried out. When the temperature of the system rises to 280-320 °C, it is discharged to normal pressure, the pressure relief time is 0-180min, and the pressure relief pressure is 0-2. 5MPa. It is also possible to determine whether to carry out vacuum operation to increase the molecular weight of the prepolymer. If necessary, use nitrogen to pressurize the discharge. The prepolymer of the viscosity of 0. 4-0. 6dl / g shall be placed in a water bath with a stirring device, the temperature of the water bath is controlled between 40-80 ° C, and the particle size is relatively uniform after stirring; The prepolymer at a level of 0.6 dl/g or more can be directly extruded into a granulation. Solid phase polymerization

The method of the present invention further comprises a solid phase polymerization step: (b) solid phase polymerization of the prepolymer of step (a), controlling the intrinsic viscosity to 1.2 - 2. 6 dl / g, to obtain the long carbon chain Semi-aromatic high temperature resistant polyamide PA10T. The long carbon chain is a conventional term in the art, and usually the polymerized monomer has a carbon number of not less than 10.

In a preferred embodiment, in the step (b), the intrinsic viscosity is controlled at 1.3 to 1.8 dl/g.

In a specific embodiment, the prepolymer is completely dried and then enters a solid phase polymerization process, and the solid phase polymerization is carried out in a vacuum drum or a fixed bed reactor, first pre-crystallization at 130-180 ° C for 1-8 h, pre- On the one hand, crystallization contributes to the improvement of the crystallinity of the material, thereby effectively avoiding agglomeration of the raw material during solid phase polymerization, and on the other hand, it also plays an important role in improving the material properties. After the pre-crystallization is completed, the temperature of the system is rapidly increased to 200. Solid phase polymerization was carried out at 260 °C. The vacuum of the vacuum drum should be kept below 150 Pa. The flow rate of the fixed-bed reactor is hot nitrogen, the flow rate of nitrogen is 0. 5-10 L / min, and the polymerization time is controlled at 1 to 15 h according to the polymerization degree.

More specifically, the prepolymer is vacuum dried at 80 ° C for 24 h and then placed in a vacuum drum or fixed bed reactor for solid phase polymerization. When the vacuum drum is used, the drum is first filled with nitrogen twice for gas replacement. The drum speed is 20-40r/min. The pre-crystallization is carried out at 130-180 ° C, preferably 140-160 ° C, and the pre-crystallization time is 1-8 h. At this time, the degree of vacuum in the system is 50-150 Pa, and then the temperature of the system is rapidly raised to 200-260 °. C begins the solid phase polymerization process, the vacuum is constant at 10-60 Pa, and the solid phase polymerization time is l-15 h, depending on the degree of polymerization and the viscosity of the prepolymer. The process of solid phase polymerization using a fixed bed reactor is the same as that of a vacuum drum. It is also pre-crystallized at 130-180 ° C, preferably 140-160 ° C for 1-8 h and then started solid phase polymerization at 200-260 ° C. 5-10L/min。 The flow rate of the nitrogen is 0. 5-10L / min, the flow rate of the nitrogen is 0. 5-10L / min. The advantages of the invention are:

1. One of the raw materials of PA10T, the diamine is mainly derived from natural ramie other than petroleum, so PA10T prepared by the invention belongs to bio-based high-temperature nylon;

6-1. l dl / g, a relatively high intrinsic viscosity number. The solid phase polymerization time can be greatly shortened, and the prepolymer is in the form of particles or can be extruded and granulated, which greatly improves the dust pollution caused by the low viscosity prepolymer, and is important for industrial production. Meaning

3. Prepolymerization directly uses aqueous phase polymerization to avoid the inconvenience caused by the use of organic solvents;

4. Pre-crystallization process is carried out in the early stage of solid phase polymerization, which contributes to the improvement of crystallinity of the material and effectively avoids agglomeration of raw materials during solid phase polymerization. On the other hand, it also plays an important role in improving the material properties;

5. The PA10T homopolymer and copolymer prepared by the invention have good color tone and high crystallinity, the melting point of the homopolymer is about 310 ° C, the processing window is wide, and there is no phenomenon such as extrusion swelling and broken strips. Processability and physical and mechanical properties are greatly improved;

6. The PA10T prepared by the invention has high temperature resistance performance, and the heat distortion temperature (HDT, 1.82 MPa) of the homopolymerized PA10T is close to 120 °C, and the HDT after the glass fiber reinforced modification can reach above 290 °C.

Other aspects of the invention will be apparent to those skilled in the art from this disclosure. The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are merely illustrative of the invention and are not intended to limit the scope of the invention. The experimental methods in the following examples which do not specify the specific conditions are usually determined in accordance with national standards. If there is no corresponding national standard, it is carried out in accordance with general international standards, general conditions, or in accordance with the conditions recommended by the manufacturer. Unless otherwise stated, all parts are by weight, all percentages are by weight, and the molecular weight of the polymer is number average molecular weight.

All professional and scientific terms used herein have the same meaning as those skilled in the art, unless otherwise defined or indicated. Furthermore, any methods and materials similar or equivalent to those described may be employed in the methods of the invention.

test methods

Method for determining intrinsic viscosity

The inherent viscosity ri _inh of the PA10T homopolymer or copolymer having a concentration of 0.05, 0.1, 0.2, 0.5, and lg/dl was measured in concentrated sulfuric acid at 25 °C. The intrinsic viscosity number [η] is obtained by extrapolating the inherent viscosity ri _inh to a concentration of zero.

Determination of mechanical properties

Example 1 PA10T homopolymer

2500g of terephthalic acid, 2600g of 1,10-decanediamine, 5g of sodium hypophosphite, 40g of benzoic acid and 3000g of deionized water were mixed in a 25L closed polymerization vessel, and the air in the kettle was replaced twice with nitrogen. The temperature is 20r/min, and the temperature is raised to 130 °C for salt formation reaction, the reaction time is 3h, then the temperature is raised and 2小时, the system pressure is raised to 2. 5-2. 7MPa, constant pressure reaction and rapid temperature rise to 300 ° C when the pressure relief begins, 30 minutes to the normal pressure, atmospheric pressure reaction 15min, then nitrogen pressure pressure discharge, pre- The polymer is extruded through a die of the discharge port to granulate, and the surface of the material is air-cooled to maintain a good color of the material.

The prepolymer was dried at 80 ° C for 24 h and then put into a vacuum drum. The drum was first filled with nitrogen twice for gas replacement, and the vacuum was started. After reaching a certain degree of vacuum at normal temperature, the hot oil was started, and the rotation speed of the drum was 20r/min. First, it was pre-crystallized at 160 ° C for about 3 hours under vacuum of about 100 Pa, and then rapidly heated to 240 ° C to start solid phase polymerization for 6 h. The solid phase polymerization vacuum was constant at 30 Pa. The prepolymer and the solid phase polymerized final polymer were dried and then injection molded to prepare a sample for performance testing. The properties of the prepolymer are shown in Table 1. The properties of the prepolymer and the final polymer are shown in Table 2.

Example 2 PA10T homopolymer

The preliminary steps were the same as those in Example 1. After 15 minutes of atmospheric pressure reaction, the mixture was degassed under vacuum for 10 min, and nitrogen was pressurized to discharge. The prepolymer was extruded through a die of the discharge port to granulate, and the surface of the material was air-cooled to maintain the material. Good color. The properties of the prepolymer are shown in Table 1.

The solid phase polymerization conditions were the same as in Example 1. The properties of the prepolymer and the final polymer are shown in Table 2.

Example 3 PA10T homopolymer

The preliminary step is the same as in the first embodiment. After 15 minutes of atmospheric pressure reaction, the mixture is vacuum devolatilized for 20 minutes, and the nitrogen is pressurized and discharged. The prepolymer is extruded through the die of the discharge port to granulate the air to cool the surface of the material to maintain the material. Good color. The properties of the prepolymer are shown in Table 1.

Example 4 PA10T homopolymer

In the same period as in the first embodiment, after 15 minutes of atmospheric pressure reaction, the mixture was vacuum degassed for 30 minutes, and the nitrogen was pressurized to discharge. The prepolymer was granulated by the die strip of the discharge port, and the surface of the material was air-cooled to maintain the good color of the material. The properties of the prepolymer are shown in Table 1.

The solid phase polymerization conditions were the same as in Example 1.

Example 5 PA10T homopolymer

The preliminary step is the same as in the first embodiment. After 30 minutes of atmospheric pressure reaction, the mixture is vacuum degassed for 30 minutes, and the nitrogen is pressurized and discharged. The prepolymer is extruded through the die of the discharge port to form a pellet, and the surface of the material is air-cooled to maintain the material. Good color. Pre The properties of the polymer are shown in Table 1.

The solid phase polymerization conditions were the same as in Example 1.

Table 1. Performance of homopolymeric PA10T prepolymer in Examples 1-5

Examples 1-3 Performance comparison of homopolymerized PA10T prepolymer and final polymer

The properties of the PA10T prepolymer and the final polymer given in Table 2 can be seen to be greatly improved after the solid phase polymerization, as in Example 3, the tensile strength is increased from 46.3 MPa of the prepolymer to the final polymer. 90. 2 MPa, the elongation is increased from 5.9% to 12.6%, and the heat distortion temperature is also greatly increased, from 105.6 ° C of the prepolymer to 1 18 ° C of the final polymer. High temperature resistant nylon is especially important. 4%左右。 The moisture content of the homopolymer of the PA10T is about 0.4%. Example 6 PA10T/66 copolymer

2500 g of terephthalic acid, 2600 g of 1,10-decanediamine, 625 g of nylon 66 salt, 5 g of sodium hypophosphite, 50 g of benzoic acid and 4000 g of deionized water were mixed in a 25 L closed polymerization vessel. Example 1.

The solid phase polymerization process conditions were the same as in Example 1. The final polymer was dried and then subjected to injection proof for performance test. The results are shown in Table 3. It can be seen from Table 3 that the addition of 66 salt greatly reduces the heat resistance of the polymer, and its melting point and HDT are only 278 ° C and 87 ° C, respectively, which is nearly 20-fold lower than the HDT of the PA10T homopolymer in Examples 1-5. At 30 ° C, the toughness of the copolymer PA10T/66 was improved, and the notched impact strength (I Z0D) reached 16 KJ/m ² . Example 7 PA10T/6T Copolymer

2500g of terephthalic acid, 2600g of 1,10-decanediamine, 673g of nylon 6T salt, 5g of sodium hypophosphite, 50g of benzoic acid and 4000g of deionized water were mixed in a 25L closed polymerization vessel, and the air in the kettle was replaced by nitrogen. 2, stirring speed is 20r / min, and then the temperature is raised to 130 ° C for 3h, then the temperature is raised and the system pressure is raised to 2. 5MPa in two hours, the constant pressure reaction and accelerated temperature rise to 310 ° C when the pressure relief, After 30 minutes, it was discharged to normal pressure, and the atmospheric pressure reaction was carried out for 30 minutes under nitrogen pressure to discharge the material. The prepolymer was granulated by the die strip of the discharge port, and the surface of the air-cooled material was discolored.

The prepolymer is put into a vacuum drum, and the drum is first filled with nitrogen twice for gas replacement, and the vacuum is started. After reaching a certain degree of vacuum at normal temperature, the hot oil is started, and the rotating speed of the drum is 20 r/min, first at 160 Pre-crystallized for about 3 hours at °C and lOOPa, then rapidly heated to 240 °C for 6h solid phase polymerization, and the solid phase polymerization vacuum was constant at 30Pa. The solid phase polymerized final polymer was dried and subjected to injection proofing for performance testing. The test results are shown in Table 3. Table 3. Physical and mechanical properties of PA10T copolymer

Comparative Example PA6T/66 Copolymer

Mix 3000g of PA6T salt, 2000g of PA66 salt, 5g of hypophosphorous acid in a 25L closed polymerizer 5MPa, The constant pressure reaction starts when the temperature rises to 270 ° C, the sodium, 50 g of benzoic acid, and 3000 g of deionized water are used to displace the air in the autoclave twice with a stirring speed of 20 r / min. The pressure is released, and the pressure is discharged to the normal pressure within 15 minutes, and the nitrogen is pressurized to discharge the material. The prepolymer is cooled by water and dried under vacuum.

The dried prepolymer was placed in a vacuum drum, first filled with nitrogen twice, and the vacuum was started. After reaching a certain degree of vacuum at normal temperature, the hot oil was started, and the rotating speed of the drum was 20 r/min. First, it was pre-crystallized at 160 ° C and lOOPa for 3 h, then rapidly heated to 240 ° C to start solid phase polymerization for 10 h, and the solid phase polymerization vacuum was constant at 30 Pa. The solid phase polymerized final polymer was dried and subjected to injection proof for performance testing. Table 4 shows the physical and mechanical properties of the PA6T/66 copolymer. Table 4. Physical and mechanical properties of PA6T/66 copolymer

It can be seen from the comparative examples that the homopolymer and copolymer of PA10T have superior tensile strength, elongation at break, impact properties, heat distortion temperature and much lower moisture content than PA6T/66, and their comprehensive performance index exceeds Semi-aromatic polyamide of the PA6T type.

The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the technical scope of the present invention. The technical content of the present invention is broadly defined in the scope of the claims of the application, any technical entity completed by others. The method or method, if it is identical to the scope of the claims, or equivalents, is considered to be within the scope of the claims.

All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entireties in the the the the the the the the In addition, it should be understood that after reading the above contents of the present invention, the field A person skilled in the art can make various changes or modifications to the invention, and such equivalents are also within the scope defined by the appended claims.

Claims

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A method for synthesizing a homopolymer and a copolymer of a long carbon chain semi-aromatic high temperature resistant polyamide, characterized by comprising the steps of:

(4) The intrinsic viscosity is controlled at 0.44. The intrinsic viscosity is controlled at 0.4. -1. a prepolymer of ldl/g;

(b) The solid phase polymerization of the prepolymer of the step (a) is carried out, and the intrinsic viscosity is controlled to be 1.2 to 2. 6 dl/g to obtain the long carbon chain semiaromatic high temperature resistant polyamide PA10T or copolymerization thereof. Things.

2. The method of claim 1 wherein

6-1. 0 dl/g。 In the step (a), the intrinsic viscosity is controlled at 0. 6-1. 0 dl / g.

3. The method of claim 1 wherein:

In the step (a), the prepolymer having an intrinsic viscosity of 0. 4-0. 6 is uniformly stirred in a water bath with stirring, the temperature of the water bath is controlled at 40-80 ° C, and then dried by vacuum drying. In step (b).

4. The method of claim 1 wherein:

In the step (a), the composition of the copolymerization component is selected from the group consisting of PA66, PA610, PA10I, PA6T, PA6T/66, PA11, PA12, PA612, PA1010, PA1212; and the content of the copolymerization component is not higher than 50 mol%, based on the total moles of terephthalic acid, 1, 10-decanediamine and the copolymerization component.

5. The method of claim 1 wherein:

The 1, 10-decanediamine of the step (a) is derived from plant ramie.

6. The method of claim 1 wherein:

The step (a) does not contain an organic solvent.

7. The method of claim 1 wherein:

In the step (b), the intrinsic viscosity is controlled at 1.3 to 1.8 dl/g.

8. The method of claim 1 wherein:

The prepolymer of the step (a) is pre-crystallized at 130-180 ° C for 1-8 h, and then heated to 200-260 ° C. The solid phase polymerization of step (b) is carried out.

9. A long carbon chain semi-aromatic, high temperature resistant polyamide homopolymer or copolymer prepared by the process of claim 1.