CN113583439A - Permanent antistatic semi-aromatic polyamide material capable of being used under high-pressure condition - Google Patents
Permanent antistatic semi-aromatic polyamide material capable of being used under high-pressure condition Download PDFInfo
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- CN113583439A CN113583439A CN202110609755.1A CN202110609755A CN113583439A CN 113583439 A CN113583439 A CN 113583439A CN 202110609755 A CN202110609755 A CN 202110609755A CN 113583439 A CN113583439 A CN 113583439A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses a permanent antistatic semi-aromatic polyamide material used under high pressure condition, which comprises the following components in percentage by weight: nylon: 100 parts of (A); glass fiber: 100-110 parts; antioxidant: 0.2-0.5 part; lubricant: 0.2-0.5 part; coupling agent: 0.1-0.2 parts; and (3) combination 2: semi-aromatic polyimide: 100 parts of (A); permanent antistatic agent: 3-10 parts; antioxidant: 0.2-0.5 part; lubricant: 0.2-0.5 part; nucleating agent: 0.05 to 0.1 portion. The nylon has medium viscosity PA6 or PA66, wherein the content of terminal amine groups of the nylon is more than 84 percent. The product obtained by the invention has higher bending strength and bending modulus, and meanwhile, the prepared product has permanent antistatic performance and improved high pressure resistance.
Description
Technical Field
The invention relates to a permanent antistatic semi-aromatic polyamide material which can be used under high pressure conditions.
Background
The plastic is used for replacing steel, so that the material cost can be reduced, the product design can be diversified, the production efficiency is higher, but the performance of the plastic is different from that of a metal product, and the technical problem is solved, for example, some liquid conveying pipe fittings work at higher temperature and pressure for a long time and have excellent chemical resistance, thermal conductivity and antistatic effect.
The semi-aromatic polyamide PA6t/66, PA6T/6I, PA9T, PA10T and the like are semi-crystalline thermoplastic plastics, the long-term use temperature can reach 180 ℃, and the semi-aromatic polyamide PA has the characteristics of high strength, low water absorption, stable size and the like, but cannot meet the use environment requiring high pressure resistance and antistatic property.
Application No.: 201410789751.6 discloses a copolymer containing high temperature resistant polyamide block and polyether block and its preparation method; the copolymer is composed of one or more polyamide blocks of homo-or copolyamides having dicarboxylic chain ends and one or more polyether polyols having at least 2 hydroxyl chain ends; the method comprises the following steps: nylon salt and polyether polyol are taken to react for 2 to 12 hours in a high-pressure reaction kettle at the temperature of 220 ℃ and the pressure of 1.2 to 3.0MPa, and then polyamide-polyether block copolymer is polymerized; the polyamide blocks account for 51 to 99 wt% of the total weight of the copolymer, the polyamide blocks consist of units containing at least one semi-aromatic polyamide and at least one aliphatic polyamide or other polyamide, and the polyether blocks account for 1 to 49 wt% of the total weight of the copolymer; compared with the corresponding pure high-temperature resistant polyamide material, the copolymer has higher impact resistance, fluidity, barrier property and high-temperature resistance, and the melting point of the copolymer is 260-320 ℃. However, the invention is used in the fields of building material heat insulation strips, electronic and electrical components and the like, and has different required performances.
Disclosure of Invention
The main object of the present invention is to provide a permanently antistatic semi-aromatic polyamide material which can be used under high pressure conditions. The material can be used for liquid conveying pipe fittings, not only can work at higher temperature and pressure for a long time, but also has excellent chemical resistance, thermal conductivity and antistatic effect.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a permanently antistatic semi-aromatic polyamide material useful in high pressure conditions comprising:
combination 1: 100 portions of nylon
Glass fiber: 100 to 110 portions of
Antioxidant: 0.2 to 0.5 portion
Lubricant: 0.2 to 0.5 portion
Coupling agent: 0.1 to 0.2 portion
And (3) combination 2: semi-aromatic polyamide: 100 portions of
Permanent antistatic agent: 3-10 parts of
Antioxidant: 0.2 to 0.5 portion
Lubricant: 0.2 to 0.5 portion
Nucleating agent: 0.05 to 0.1 portion.
The nylon is high-end amino nylon, wherein the content of the end amino group of the nylon is more than 84%;
the mass ratio of the combination 1 to the combination 2 is 1: 2-4; the raw materials are uniformly mixed according to the formula proportion, a single-screw extruder is adopted in the combination 1, wherein the first side feeding of the glass fiber is added, other materials are added from the main feeding, a double-screw extruder is adopted in the combination 2, the permanent antistatic agent is added from the side feeding, the combination 2 is uniformly mixed by the double-screw extruder, then the mixture is directly added from a die of the extruder, and then the mixture is uniformly mixed with the combination 1 by the single-screw extruder, and then the mixture is extruded, drawn and granulated.
In a preferred embodiment, the content of the terminal amine groups of the nylon is more than 85%.
In a preferred embodiment, the glass fiber is alkali-free chopped fiber, and the chopped length of the glass fiber is 5-12 mm; the diameter is 11-13 μm.
In a preferred embodiment, the antioxidant is one or a combination of sterically hindered phenols, sterically hindered amines, phosphates, thioesters.
In a preferred embodiment, the lubricant is one or a combination of E wax, EBS, sodium montanate and hyperbranched polymer
In a preferred embodiment, the coupling agent is one or a combination of a silane coupling agent and a titanate coupling agent.
In a preferred embodiment, the permanent antistatic agent is one or a combination of nano carbon black, graphite, carbon nano tubes and carbon fibers.
In a preferred embodiment, the carbon nanotubes of the permanent antistatic agent can be first made into corresponding master batches. The nano carbon black and graphite can be made into corresponding master batches but are not required, and the carbon fiber is not made into corresponding master batches.
In a preferred embodiment, the nucleating agent is one or a combination of calcium carboxylate, calcium aryl sulfonate and composite nucleus p22 which mainly comprises long carbon chain components.
Another object of the present invention is to provide a method for preparing a permanently antistatic semi-aromatic polyamide material which can be used under high pressure conditions, comprising the steps of:
the raw materials are uniformly mixed according to a formula ratio, a single-screw extruder is adopted in a combination 1, wherein the first side feeding of glass fiber is added, other materials are added from a main feeding, a double-screw extruder is adopted in a combination 2, a permanent antistatic agent is added from the side feeding, the combination 2 is uniformly mixed by the double-screw extruder, then the mixture is discharged from a die of the extruder, then the mixture is directly added from a second side feeding port of the single screw, and the mixture is uniformly mixed with the combination 1 by the single-screw extruder, and then the mixture is extruded, drawn and granulated to obtain the product.
The combination 1 of the invention adopts a nylon material with high-end amino group content, which can improve the bonding performance of nylon and glass fiber, and then the combination is matched with a coupling agent, which can obviously improve the bonding force of the nylon material and the glass fiber, meanwhile, a single-screw extruder is adopted, the shearing force is lower, the glass fiber form can be better kept, the combination 2 can lead the permanent antistatic agent to achieve better dispersion and distribution in the semi-aromatic polyimide through a double-screw extruder, after the combination 1 and the combination 2 are extruded and mixed uniformly through a single screw, the obtained product has higher bending strength and bending modulus, and simultaneously, the prepared product has permanent antistatic performance and improved high pressure resistance.
Detailed Description
The present invention will be further illustrated by the following examples
The product model of the medium-viscosity nylon is U3602; american soda-water weda;
high-end amido nylon, the model is EP158-NH, Zhejiang Huafeng
The glass fiber 568, Chinese boulder
Antioxidant SEED, Kelaien
Lubricant AC540A, HONEYWELL
Nucleating agent P22, Bluggeman
Example 1
The mass ratio of combination 1 to combination 2 was 1: 3. The following "parts" in combination 1 and "parts" in combination 2 are used only for describing the mass ratio of combination 1 or combination 2 itself, and the "parts" of both are not equivalent masses.
The combination 1 comprises the following components in percentage by mass: 100 parts of high-end amino nylon (85%); 110 parts of glass fiber;
0.3 part of antioxidant; 0.3 part of a lubricant; 0.1 part of a coupling agent;
the combination 2 comprises the following components in percentage by mass: 1100 parts of semi-aromatic polyamide; 18 parts of permanent antistatic agent;
0.3 part of antioxidant; 0.3 part of a lubricant; 0.1 part of nucleating agent.
The processing method comprises the following steps: the raw materials are uniformly mixed according to the formula proportion, a single-screw extruder is adopted in the combination 1, wherein the first side feeding port for glass fiber is added, other materials are added from the main feeding port, a double-screw extruder is adopted in the combination 2, the permanent antistatic agent is added from the side feeding port, the combination 2 is uniformly mixed by the double-screw extruder, then the mixture is directly added from the second side feeding port of the single screw after coming out of the die of the extruder, and is uniformly mixed with the combination 1 by the single-screw extruder, and then the mixture is extruded, drawn and granulated. Hereinafter, this method will be referred to as "method (i)".
The formulations of examples 1-4 and comparative examples 1-6 are shown in Table 1 below
TABLE 1
Remarking: the processing method comprises the following steps: the method comprises the following steps of uniformly mixing the raw materials according to a formula ratio, adding the glass fiber from a side feeding port in a combination 1, adding other materials from a main feeding port in the combination 2, adding the permanent antistatic agent from a side feeding port in the combination 2, uniformly mixing the combination 2 through a double-screw extruder, directly adding the mixture from a die of the extruder, uniformly mixing the mixture with the combination 1 through a single-screw extruder, and extruding, drawing and granulating the mixture.
And secondly, uniformly mixing the raw materials of the combination 1 and the combination 2 according to the formula proportion, and then extruding and granulating by using a double-screw extruder, wherein the glass fiber and the permanent antistatic agent are added from a side feeding port.
Thirdly, uniformly mixing the raw materials of the combination 1 and the combination 2 according to the formula proportion, and then extruding and granulating by using a single-screw extruder, wherein the glass fiber and the permanent antistatic agent are added from a side feeding port.
The semi-aromatic nylon modified materials of examples 1 to 4 and comparative examples 1 to 5 were tested for their performance,
density: the test was carried out with reference to ISO 1183
Melting fingers: the test was carried out with reference to ISO1133, test conditions: 325 ℃ and 5KG
Tensile strength: testing with reference to ISO 527/2
Elongation at break: testing with reference to ISO 527/2
Bending strength: testing with reference to ISO 178
Flexural modulus: testing with reference to ISO 178
Impact strength of the simply supported beam notch: testing with reference to ISO 179/1
Volume resistivity: the test was carried out with reference to IEC62631-3-1
The method for testing the pressure resistance comprises the following steps: the marker post material is injected into a pipe fitting with the length of 10cm, the radius of 1.0cm and the threads at two ends, one end of the pipe fitting is sealed during testing, the other end of the pipe fitting is filled with water, the water inflow pressure is adjusted to a certain value, the time of cracking of the pipe fitting is recorded, and 5 tests are carried out to obtain an average value.
The results are shown in Table 2
The embodiment shows that the compression resistance and explosion resistance of the semi-aromatic polyamide can be improved, and the comparison 1 and 2 with the embodiment 1 and other comparison examples show that the comparison 1 without adding the high-end amino nylon has the worst compression resistance, so that the high-end amino nylon has good effect on improving the compression resistance and explosion resistance of the semi-aromatic polyamide, which is probably that the increase of the end amino causes the bonding effect between the glass fiber and the high-end amino nylon, and the bonding force between the glass fiber and the plastic is increased; from example 1 and comparative examples 5 and 6, it can be seen that the processing method is adopted: the processing method and the processing method are adopted to not only increase the contact area of the high-end amino nylon and the glass fiber, but also prevent the glass fiber from being excessively sheared and obtain the modified semi-aromatic polyamide with better performance.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. A permanent antistatic semi-aromatic polyamide material applicable to high pressure conditions is characterized by comprising the following raw materials:
combination 1: nylon: 100 portions of
Glass fiber: 100 to 110 portions of
Antioxidant: 0.2 to 0.5 portion
Lubricant: 0.2 to 0.5 portion
Coupling agent: 0.1 to 0.2 portion
And (3) combination 2: semi-aromatic polyamide: 100 portions of
Permanent antistatic agent: 3-10 parts of
Antioxidant: 0.2 to 0.5 portion
Lubricant: 0.2 to 0.5 portion
Nucleating agent: 0.05 to 0.1 portion.
The nylon is high-end amino nylon, wherein the content of the end amino group of the nylon is more than 84%;
the mass ratio of the combination 1 to the combination 2 is 1: 2-4; the raw materials are uniformly mixed according to the formula proportion, a single-screw extruder is adopted in the combination 1, wherein the first side feeding of the glass fiber is added, other materials are added from the main feeding, a double-screw extruder is adopted in the combination 2, the permanent antistatic agent is added from the side feeding, the combination 2 is uniformly mixed by the double-screw extruder, then the mixture is directly added from a die of the extruder, and then the mixture is uniformly mixed with the combination 1 by the single-screw extruder, and then the mixture is extruded, drawn and granulated.
2. The permanently antistatic semi-aromatic polyamide material usable in high pressure conditions, according to claim 1, characterized in that: the content of the nylon terminal amino groups is more than 85 percent.
3. The permanently antistatic semi-aromatic polyamide material usable in high pressure conditions, according to claim 1, characterized in that: the glass fiber is alkali-free chopped fiber, and the chopped length of the glass fiber is 5-12 mm; the diameter is 11-13 μm.
4. The permanently antistatic semi-aromatic polyamide material usable in high pressure conditions, according to claim 1, characterized in that: the antioxidant is one or a composition of sterically hindered phenols, sterically hindered amines, phosphates and thioesters.
5. The permanently antistatic semi-aromatic polyamide material usable in high pressure conditions, according to claim 1, characterized in that: the lubricant is one or a composition of E wax, EBS, sodium montanate and hyperbranched polymer.
6. The permanently antistatic semi-aromatic polyamide material usable in high pressure conditions, according to claim 1, characterized in that: the coupling agent is one or a composition of a silane coupling agent or a titanate coupling agent.
7. The permanently antistatic semi-aromatic polyamide material usable in high pressure conditions, according to claim 1, characterized in that: the permanent antistatic agent is one or a composition of nano carbon black, graphite, carbon nanotubes and carbon fibers.
8. The permanently antistatic semi-aromatic polyamide material usable in high pressure conditions, according to claim 7, characterized in that: in the permanent antistatic agent, the nano carbon black and the graphite are made into corresponding master batches, and the carbon fiber is not made into the corresponding master batches.
9. The permanently antistatic semi-aromatic polyamide material usable in high pressure conditions, according to claim 1, characterized in that: the nucleating agent is one or a combination of calcium carboxylate, calcium aryl sulfonate and composite p22 which mainly comprise long carbon chain components.
10. Process for the preparation of a permanently antistatic semi-aromatic polyamide material usable under high pressure conditions according to any one of claims 1 to 9, comprising the following steps:
the raw materials are uniformly mixed according to a formula ratio, a single-screw extruder is adopted in a combination 1, wherein the first side feeding of glass fiber is added, other materials are added from a main feeding, a double-screw extruder is adopted in a combination 2, a permanent antistatic agent is added from the side feeding, the combination 2 is uniformly mixed by the double-screw extruder, then the mixture is discharged from a die of the extruder, then the mixture is directly added from a second side feeding port of the single screw, and the mixture is uniformly mixed with the combination 1 by the single-screw extruder, and then the mixture is extruded, drawn and granulated to obtain the product.
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| CN109735101A (en) * | 2018-12-29 | 2019-05-10 | 上海普利特复合材料股份有限公司 | A kind of low water absorption, laser marking polyamide compoiste material and preparation method thereof |
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| US5252375A (en) * | 1990-03-22 | 1993-10-12 | Interface, Inc. | Permanent stain resistant treatment for polyamide fibers |
| US5500263A (en) * | 1993-04-02 | 1996-03-19 | Huels Aktiengesellschaft | Multilayer plastic pipe |
| EP1538161A2 (en) * | 1999-09-24 | 2005-06-08 | Human Genome Sciences, Inc. | 32 human secreted proteins |
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| CN103242649A (en) * | 2012-02-06 | 2013-08-14 | 金发科技股份有限公司 | Glass fiber reinforced nylon material used for extrusion molding, preparation method and application |
| CN104231617A (en) * | 2013-06-18 | 2014-12-24 | 上海杰事杰新材料(集团)股份有限公司 | Glass fiber reinforced semi-aromatic high-temperature-resistant nylon composite material and preparation method thereof |
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