CN109627435B - Method for preparing permanent antistatic branched polyamide elastomer, elastomer prepared by method and application thereof - Google Patents
Method for preparing permanent antistatic branched polyamide elastomer, elastomer prepared by method and application thereof Download PDFInfo
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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
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
Abstract
The invention discloses a method for preparing a permanent antistatic polyamide elastomer, the permanent antistatic polyamide elastomer prepared by the method and application thereof. The preparation method of the permanent antistatic branched polyamide elastomer comprises the following steps: adding a polyamide hard-segment polymer unit, a hydrophilic group-containing soft-segment polymer unit, a molecular weight regulator, distilled water, a catalyst and a branching modifier into a high-pressure kettle, then carrying out salt forming reaction, ring-opening polymerization, continuous polymerization, vacuumizing, filling nitrogen for balancing pressure, adding an auxiliary agent, and then casting a belt, drawing a strip, granulating and drying to obtain the permanent antistatic branching polyamide elastomer. The permanent antistatic polyamide elastomer has excellent natural color appearance, high flowability and good compatibility with engineering plastics, and can well maintain various mechanical properties of high polymer materials in a wide range of high and low temperatures.
Description
Technical Field
The invention belongs to the field of new polymer material preparation, and particularly relates to a method for preparing a permanent antistatic branched polyamide elastomer, the permanent antistatic branched polyamide elastomer prepared by the method and application of the permanent antistatic branched polyamide elastomer.
Background
The polyamide elastomer is a novel thermoplastic elastomer which is developed and applied in recent years, has the elasticity of rubber, the processability of plastics, good chemical properties and high and low temperature use resistance, but has electrical insulation property like most macromolecules, and the surface resistance is usually 1014-1017Omega, static problem is easy to generate in the using process, dust influences surface cleanness when the static problem is light, and spark and short circuit are easy to cause by static discharge when the static problem is heavy, so that the popularization and the use of the polyamide elastomer in specific fields of electronic appliances and chemical energy are limited, and the polyamide elastomer with permanent antistatic property needs to be developed.
The antistatic properties of polymers are currently mainly improved by the following methods: 1) the resin prepared by mixing a small amount of micromolecular antistatic agent in the macromolecule can maintain the effect by micromolecular migration, but can not maintain the antistatic effect for a long time. 2) The conductive filler is kneaded in the polymer to have a permanent antistatic effect, but the conductive filler has large addition amount, poor compatibility, difficult processing, great influence on mechanical properties and excessively dark color appearance. 3) The polymer type permanent antistatic agent is blended and added into the macromolecule, the migration and the washing resistance are avoided, the antistatic property is permanent, but the method has the compatibility problem when the blending and the addition are large, and the heat resistance and the mechanical strength are lost when the addition is large. 4) Polymeric antistatic resins, polymeric resins of blocks of hydrophobic polymeric units and hydrophilic polymeric units, impart permanent antistatic properties. But lack fluidity in certain use environments.
Patent application CN 1302318A describes the use of a mixture of alkali metal alkylsulfonates and polyglycols to obtain an antistatic agent which can be added to other molten resins to obtain masterbatch. However, the antistatic agent is not high temperature resistant and easy to discolor, and the prepared composition has complex processability.
Patent application CN 1284976 a describes an antistatic composition based on polyamide, comprising: at least one polyamide, a sufficient amount of carbon black, using a co-mixer type extruder to obtain the antistatic composition. However, the composition in this report is too black in color, and has a problem of compatibility because the addition ratio of carbon black is high for good antistatic property.
Patent application CN 105801913 a describes that expanded graphite with surface modified by polyethylene glycol type antistatic agent and polyamide are mixed uniformly in a high speed mixer to obtain antistatic polyamide composition. The composition has permanent antistatic property, and the addition amount of graphite is reduced. However, in this report, polyamide mixed with a graphite-based antistatic agent has a problem that dispersibility is not uniform during use, and the color does not reach a white natural color appearance, thereby limiting the field of application.
Patent application CN 102634191A introduces a permanent antistatic nylon elastomer material, which is prepared by uniformly mixing 50-90 parts of nylon elastomer, 10-30 parts of polymer permanent antistatic agent and 0.3-2 parts of processing aid in a high-speed mixer, and then extruding and granulating the mixture to obtain the antistatic nylon elastomer with excellent impact property. But when the surface resistivity requirement is very low, the gain effect cannot be ensured by blending and extruding preparation, and the extrusion is unstable when the addition amount is large.
Patent application CN 101358126 a describes a method for preparing a permanent antistatic agent, which is to synthesize aromatic ester having benzene ring and polyether structure by heating aromatic diester or diacid and anhydride compound thereof and ether alcohol compound according to molar ratio in solvent. The solvent is separated and then compounded with alkali metal to form the antistatic agent. However, a large amount of solvent is used in the synthesis process, separation is needed in the later period, the preparation is complex, and a large amount of waste liquid is generated.
Patent application CN 102959035A describes an antistatic agent and an antistatic resin composition. A block polymer synthesized from a hydrophobic polymer unit and a hydrophilic polymer unit and an organofluorine-modified polyolefin are blended with a Henschel mixer to prepare an antistatic agent. However, these antistatic agents lack sufficient flowability and are not satisfactory for all elastomer processing and applications.
Patent application CN 1273256 a describes an antistatic polymer composition comprising a thermoplastic polymer and a copolymer combination of polyetheramine and polyether blocks, having the characteristic of permanent antistatic properties independent of ambient humidity. However, this composition lacks sufficient fluidity and cannot fully satisfy the requirements in terms of processing.
In order to obtain more excellent application effects, the development of a permanent antistatic polyamide elastomer with excellent natural color appearance and high fluidity is still needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a permanent antistatic polyamide elastomer, and a preparation method and application thereof.
In one aspect, the present invention provides a process for the preparation of a permanently antistatic branched polyamide elastomer, said process comprising the steps of:
1) adding a polyamide hard block polymer unit, a soft block polymer unit containing a hydrophilic group, a molecular weight regulator, distilled water, a catalyst and a branching modifier into an autoclave;
2) after air is replaced by high-purity nitrogen, heating to 85-95 ℃ under the protection of the high-purity nitrogen gas to carry out salt forming reaction, and mechanically stirring for 1-4 hours;
3) heating to 140 ℃ and 210 ℃ for ring-opening polymerization, and mechanically stirring for reaction for 1-3 hours;
4) heating to 240 ℃ and 280 ℃ for continuous polymerization, and mechanically stirring for reaction for 1-4 hours;
5) vacuumizing to 20-1000Pa, continuously mechanically stirring, and reacting for 1-3 hours; and
6) and filling nitrogen to balance pressure, casting a belt, drawing a strip, granulating and drying to obtain the permanent antistatic branched polyamide elastomer.
The permanently antistatic branched polyamide elastomer obtained is a copolymer polymer branched by a branching modifier and comprising polyamide hard block polymer units and soft block polymer units containing a hygrophilic group.
In a specific embodiment, in the above preparation method, the polyamide hard segment polymer unit may be selected from monomers that undergo ring-opening polymerization or polycondensation reaction, and the monomers may use one or more of lactam, aminocarboxylic acid, diamine, dicarboxylic acid, diisocyanate-modified polyamide monomers. The content of the polyamide hard segment polymer unit is 20 to 95 parts by weight, preferably 40 to 85 parts by weight, based on 100 parts by weight of the polyamide hard segment polymer unit and the hydrophilic group-containing soft segment polymer unit.
In a specific embodiment, in the above preparation method, as the lactam, there can be used C2-C12 lactams, preferably, but not limited to, valerolactam, caprolactam, caprylolactam, laurolactam; as the aminocarboxylic acid, C2-C12 aminocarboxylic acids can be used, and ω -aminocaproic acid, ω -aminoheptanoic acid, ω -aminocaprylic acid, ω -aminosebacic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferable, but not limited thereto. In a specific embodiment, in the above-mentioned preparation method, as the diamine, aliphatic diamine and aromatic diamine of C2-C20, preferably hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, isophoronediamine, p-xylylenediamine, m-xylylenediamine, 1, 3-cyclohexyldimethylamine, 4-diaminodicyclohexylmethane, 3-dimethyl-4, 4-diaminodicyclohexylmethane can be used, but not limited thereto. As the dicarboxylic acid, aliphatic dicarboxylic acids and aromatic dicarboxylic acids of C2 to C20 can be used, and adipic acid, sebacic acid, suberic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid are preferable, but not limited thereto.
In a specific embodiment, in the above preparation method, the soft segment polymer unit containing a hydrophilic group is selected from one or more of polyether diol, polyether diamine, and diisocyanate-modified polyether diol. The content of the hydrophilic group-containing soft segment polymer unit is 5 to 80 parts by weight, preferably 15 to 60 parts by weight, based on 100 parts by weight of the polyamide hard segment polymer unit and the hydrophilic group-containing soft segment polymer unit.
In a specific embodiment, in the above preparation method, the polyether glycol is preferably Polytetrahydrofuran (PTMEG), polyethylene glycol (PEG), polypropylene glycol (PPG), but is not limited thereto. The polyether diamine is preferably, but not limited to, an amino-terminated polyoxypropylene ether or an amino-terminated polyoxyethylene ether. The number average molecular weight of the polyether diol or polyether diamine is 300-8000, preferably 600-4000.
In a specific embodiment, in the above preparation method, the molecular weight modifier may be selected from dicarboxylic acids, and C2-C20 aliphatic dicarboxylic acids and aromatic dicarboxylic acids, preferably adipic acid, sebacic acid, suberic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, may be used, but is not limited thereto. And the content of the molecular weight modifier is 0.3 to 8.5 parts by weight, preferably 1 to 7 parts by weight, based on 100 parts by weight of the polyamide hard segment polymer unit and the hydrophilic group-containing soft segment polymer unit.
In a specific embodiment, in the above preparation method, the catalyst may be selected from one or more of phosphoric acid, sulfuric acid, aminocaproic acid, sodium hypophosphite, metaphosphoric acid, oxalic acid, but is not limited thereto. The catalyst is used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the polyamide hard segment polymer unit.
In a specific embodiment, in the above production method, the distilled water is used in an amount of 0.5 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyamide hard segment polymer unit.
In a specific embodiment, in the above preparation method, the branching modifier is one or more selected from cyclotriphosphazene, trimesic acid, biphenyltetracarboxylic acid, ethylenediaminetetraacetic acid, azobenzenetetracarboxylic acid, but is not limited thereto. The branching modifier is used in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the polyamide hard segment polymer units and the hydrophilic group-containing soft segment polymer units.
In a specific embodiment, in steps 2) -5) of the above preparation method, the rotation speed of the mechanical stirring may be 60-500 rpm.
In another aspect, the present invention provides a permanently antistatic branched polyamide elastomer prepared according to the above process.
In a particular embodiment, the permanently antistatic branched polyamide elastomer has a hardness ranging from 20 to 65D, preferably from 30 to 60D; the glass transition temperature is-70 to-55 ℃; the tensile strength is in the range of 7-60MPa, preferably in the range of 12-50 MPa; elongation at break greater than 200%, preferably greater than 350%; the relative viscosity is in the range of 1.7 to 3.0, preferably 1.9 to 2.4.
The invention also provides the use of the permanently antistatic branched polyamide elastomer described above as a permanent antistatic.
In addition, the invention also provides a permanent antistatic composition which comprises the permanent antistatic branched polyamide elastomer and other high molecular polymers.
In a particular embodiment, the permanent antistatic composition comprises 5 to 25 parts by weight of the above-mentioned permanent antistatic branched polyamide elastomer and 70 to 93 parts by weight of the other high molecular polymer.
In a specific embodiment, the other high molecular polymer may be one or more selected from acrylonitrile-butadiene-styrene terpolymer (ABS), polycarbonate/acrylonitrile-butadiene-styrene terpolymer (PC/ABS), nylon (PA), Polyester (PBT), polyvinyl chloride (PVC), Polyoxymethylene (POM), Polystyrene (PS), polypropylene (PP), Polyethylene (PE).
In addition, the invention also provides a preparation method of the permanent antistatic composition, which comprises the following steps:
and uniformly mixing the permanent antistatic branched polyamide elastomer and other high molecular polymers at a high speed through a mixer, then blending and melting at the temperature of 150-270 ℃ through a screw extruder, and extruding, bracing and granulating.
Advantageous effects
The permanent antistatic branched polyamide elastomer is a branched polyamide elastomer with multiple side chains, and is obtained by block copolymerization or random copolymerization under the action of a branching modifier. On one hand, more polar groups are enriched on branched side chains of the elastomer, and the branched side chains are more easily and uniformly distributed on the surface of the resin in a layered structure or a filiform form, so that a conductive 'conduction network' is formed on the surface of the resin, a stronger moisture absorption capacity is provided for the surface of the resin, and a better permanent antistatic effect is obtained. On the other hand, the branched elastomer has good melt flowability and wide adjustable range of processing while basically maintaining the mechanical properties.
The permanent antistatic branched polyamide elastomer has white natural color appearance, no migration, washing resistance, no influence of environmental humidity, excellent permanent antistatic effect, high flowability and excellent processing performance. In addition, the permanent antistatic branched polyamide elastomer has good compatibility with various engineering plastics, and can well maintain various mechanical properties of high polymer materials in a wide range of high and low temperatures. Due to the properties, the permanent antistatic branched polyamide elastomer can be suitable for various processing forms of thin-wall products, complex precision parts and the like, can also be directly melt spun, can be used as antistatic fiber, is applied to the fields of spinning, carpets, brush wires and dust prevention, and can also be used as a permanent antistatic agent for high polymer materials such as ABS, PC/ABS, nylon, polyester, PVC, POM, PS, PP, PE and the like.
Detailed Description
The present invention is explained below by way of specific embodiments, but the scope of the present invention is not limited to these embodiments, but is defined by the claims of the present invention and may include various reasonable variations within the scope understood by those skilled in the art.
Example (b):
example 1:
3400g of caprolactam, 110g of distilled water, 600g of polyoxypropylene glycol (Mn ═ 2000), 69g of dodecanedioic acid, 70g of phosphoric acid and 20g of cyclotriphosphazene are added into a 10L polymerization kettle, and the mixture is heated to 90 ℃ under the protection of nitrogen and reacted for 1 hour under the mechanical stirring of 100 rpm; then heating to 180 ℃, and reacting for 3 hours under mechanical stirring at 300 rpm; then reacting for 4 hours at 240 ℃ under mechanical stirring at 300 rpm; the reaction was continued for 3 hours at 260 ℃ under vacuum to 100Pa with mechanical stirring at 200rpm, followed by casting, drawing, granulating, and drying.
Example 2:
2800g of 11-aminoundecanoic acid, 600g of amino-terminated polyoxyethylene ether (Mn 2000), 600g of amino-terminated polyoxypropylene ether (Mn 2000), 87g of sebacic acid, 50g of distilled water, 26g of metaphosphoric acid and 25g of biphenyltetracarboxylic acid were put into a 10L polymerization kettle, and the mixture was heated to 90 ℃ under the protection of nitrogen, and reacted for 1 hour under mechanical stirring at 100 rpm; then heating to 170 ℃, and reacting for 2 hours under mechanical stirring at 300 rpm; then reacting for 4 hours at 220 ℃ under mechanical stirring at 300 rpm; vacuumizing to 200Pa at 240 ℃, continuously reacting for 1 hour under the mechanical stirring of 200rpm, finally adding 20g of sodium polystyrene sulfonate, and then carrying out casting, drawing into strips, granulating and drying.
Example 3:
707g of hexamethylenediamine, 1705g of dodecanedioic acid, 1600g of polyethylene oxide (Mn ═ 800), 500g of distilled water, 60g of sodium hypophosphite and 32g of cyclotriphosphazene are added into a 10L polymerization kettle, the temperature is raised to 90 ℃ under the protection of nitrogen, and the reaction is carried out for 2 hours under the mechanical stirring of 100 rpm; then heating to 170 ℃, and reacting for 2 hours under mechanical stirring at 300 rpm; then reacting for 3 hours at 210 ℃ under mechanical stirring at 300 rpm; vacuumizing to 20Pa at 230 ℃, continuously reacting for 3 hours under the mechanical stirring of 200rpm, finally adding 30g of sodium polystyrene sulfonate, and then carrying out casting, drawing into strips, granulating and drying.
Example 4:
779g of hexamethylene diamine, 1233g of adipic acid, 2000g of amino-terminated polyoxyethylene ether (Mn ═ 1200), 400g of distilled water, 50g of sodium hypophosphite and 32g of biphenyl tetracarboxylic acid are added into a 10L polymerization kettle, the temperature is raised to 90 ℃ under the protection of nitrogen, and the mixture reacts for 2 hours under the mechanical stirring of 100 rpm; then heating to 190 ℃, and reacting for 3 hours under mechanical stirring at 300 rpm; then reacting for 3 hours at 250 ℃ under mechanical stirring of 300 rpm; vacuumizing to 100Pa at 270 ℃, continuously reacting for 1 hour under the mechanical stirring of 200rpm, finally adding 30g of sodium dodecyl sulfate, and then carrying out casting, drawing into strips, granulating and drying.
Example 5:
1600g of laurolactam, 1200g of amino-terminated polyoxyethylene ether (Mn 1200), 1200g of polyoxyethylene (Mn 1200), 292g of adipic acid, 200g of distilled water, 100g of sulfuric acid and 40g of trimesic acid are added into a 10L polymerization kettle, and the mixture is heated to 90 ℃ under the protection of nitrogen and reacted for 1 hour under the mechanical stirring of 100 rpm; then heating to 180 ℃, and reacting for 3 hours under mechanical stirring at 300 rpm; then reacting for 3 hours at 260 ℃ under mechanical stirring at 300 rpm; vacuumizing to 100Pa at 240 ℃, continuously reacting for 3 hours under the mechanical stirring of 200rpm, finally adding 20g of sodium dodecyl sulfate, and then carrying out casting, drawing into strips, granulating and drying.
Comparative example 1:
adding 3000g of caprolactam, 146g of adipic acid, 100g of distilled water, 1000g of amino-terminated polyoxyethylene ether (Mn 1000) and 80g of phosphoric acid into a 10L polymerization kettle, heating to 170 ℃ under the protection of nitrogen, and reacting for 3 hours under mechanical stirring at 300 rpm; then reacting for 3 hours at 240 ℃ under mechanical stirring at 300 rpm; the reaction was continued for 1 hour at 260 ℃ under vacuum to 100Pa with mechanical stirring at 200rpm, followed by casting, drawing, granulating, and drying.
Comparative example 2:
a commercially available polyamide antistatic elastomer Pebax MH1657 (Arkema, france) was chosen.
Comparative example 3:
779g of hexamethylene diamine, 1223g of adipic acid, 2000g of amino-terminated polyoxyethylene ether (Mn ═ 1200), 400g of distilled water and 50g of sodium hypophosphite are added into a 10L polymerization kettle, the temperature is raised to 190 ℃ under the protection of nitrogen, and the mixture reacts for 3 hours under the mechanical stirring of 300 rpm; then reacting for 3 hours at 250 ℃ under mechanical stirring of 300 rpm; vacuumizing to 100Pa at 270 ℃, continuously reacting for 2 hours under the mechanical stirring of 200rpm, finally adding 30g of sodium dodecyl sulfate, and then carrying out casting, drawing into strips, granulating and drying.
The elastomer prepared in the above examples was injection molded into standard sample bars for testing in standard dimensions, and the physical properties were tested according to the national standard of China, with the results shown in Table 1 and the specific test methods for the physical properties shown in Table 2. The physical properties include the following:
melting point, density, hardness, surface resistance, mechanical properties (tensile strength, elongation at break, tensile modulus, notched impact strength).
TABLE 1
TABLE 2
| Physical Properties | Unit of | Test method |
| Density of | g/cm3 | GB/T 1033-2008 |
| Tensile strength | MPa | GB/T 1040-2006 |
| Elongation at break | ％ | GB/T 1040-2006 |
| Tensile modulus | MPa | GB/T 1040-2006 |
| Izod notched impact Strength | KJ·m-2 | GB/T 1843-2006 |
| Melting Point | ℃ | GB/T 19466-2004 |
| Shore hardness | D | GB/T 2411-2008 |
| Glass transition temperature | ℃ | GB/T 19466-2004 |
| Relative viscosity | GB/T 12006-2009 | |
| Melt index (250 ℃, 2.16kg) | g/10min | GB/T 3682-2000 |
| Surface resistance | Ω | GB/T 1410-2006 |
As can be seen from Table 1, the method of the present invention can prepare the permanent antistatic branched polyamide thermoplastic elastomer with excellent antistatic performance and high fluidity by the branching modification of the polyamide elastomer, the selection of the soft segment of the hydrophilic group and the application of the antistatic auxiliary agent.
The permanent antistatic branched polyamide elastomer can be used as a permanent antistatic agent for a high polymer material, and improves the antistatic property of the original material in practical application. As can be seen from table 3 below, the same antistatic effect was obtained with the addition of a relatively smaller amount of the elastomer of example 4 to the resin processed by blending modification of ABS, PC/ABS, PA, PBT, PP, PE, PS, PVC or POM, as compared with the case of adding the elastomer of comparative example 3, and thus, it was confirmed that the elastomer of the present application has an enhanced antistatic effect with respect to the unbranched elastomer. In addition, the permanent antistatic branched polyamide elastomer has high fluidity in the process of blending, extruding and injection molding with other macromolecules, so that the permanent antistatic branched polyamide elastomer is more easily dispersed on the surface of a macromolecular alloy, more polar groups are enriched, and the antistatic effect is further improved.
TABLE 3
Claims (16)
1. A process for preparing a permanently antistatic branched polyamide elastomer, comprising the steps of:
1) adding a polyamide hard block polymer unit, a soft block polymer unit containing a hydrophilic group, a molecular weight regulator, distilled water, a catalyst and a branching modifier into an autoclave;
2) heating to 85-95 ℃ under the protection of nitrogen to carry out salt forming reaction, and mechanically stirring for 1-4 hours;
3) heating to 140 ℃ and 210 ℃ for polymerization, and mechanically stirring for reaction for 1-3 hours;
4) heating to 240 ℃ and 280 ℃ for continuous polymerization, and mechanically stirring for reaction for 1-4 hours;
5) vacuumizing to 20-1000Pa, continuously mechanically stirring, and reacting for 1-3 hours; and
6) and casting a belt, drawing a strip, granulating and drying to obtain the permanent antistatic branched polyamide elastomer.
2. The method of claim 1, wherein the polyamide hard stage polymer units are selected from one or more of lactam, aminocarboxylic acid, diamine, dicarboxylic acid, diisocyanate-modified polyamide monomers, and/or
The polyamide hard segment polymer unit is contained in an amount of 20 to 95 parts by weight based on 100 parts by weight of the polyamide hard segment polymer unit and the hydrophilic group-containing soft segment polymer unit.
3. The method of claim 2, wherein the polyamide hard segment polymer unit is contained in an amount of 40 to 85 parts by weight, based on 100 parts by weight of the polyamide hard segment polymer unit and the hydrophilic group-containing soft segment polymer unit.
4. The method of claim 1, wherein the soft segment polymer units containing the hygrophilic groups are selected from one or more of polyether diols, polyether diamines, diisocyanate-modified polyether diols,
wherein the polyether glycol is selected from one or more of polytetrahydrofuran, polyethylene glycol and polypropylene glycol, and/or,
the polyether diamine is selected from amino-terminated polyoxypropylene ether or amino-terminated polyoxyethylene ether, and/or,
the number average molecular weight of the polyether diol or polyether diamine is 300-8000, and/or
The content of the hydrophilic group-containing soft segment polymer unit is 5 to 80 parts by weight based on 100 parts by weight of the polyamide hard segment polymer unit and the hydrophilic group-containing soft segment polymer unit.
5. The process as claimed in claim 4, wherein the polyether diol or diamine has a number average molecular weight of 600-4000, and/or
The content of the hydrophilic group-containing soft segment polymer unit is 15 to 60 parts by weight based on 100 parts by weight of the polyamide hard segment polymer unit and the hydrophilic group-containing soft segment polymer unit.
6. The process according to claim 1, wherein the catalyst is selected from one or more of phosphoric acid, sulfuric acid, aminocaproic acid, sodium hypophosphite, metaphosphoric acid, oxalic acid, and/or
The catalyst is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyamide hard segment polymer units, and/or
The distilled water is used in an amount of 0.5 to 50 parts by weight, based on 100 parts by weight of the polyamide hard segment polymer unit.
7. The process of claim 6, wherein the catalyst is used in an amount of 0.5 to 3 parts by weight, based on 100 parts by weight of the polyamide hard segment polymer units, and/or
The distilled water is used in an amount of 1 to 20 parts by weight, based on 100 parts by weight of the polyamide hard segment polymer unit.
8. The method of claim 1, wherein the branching modifier is one or more selected from cyclotriphosphazene, trimesic acid, biphenyltetracarboxylic acid, ethylenediaminetetraacetic acid, azobenzenetetracarboxylic acid, and/or
The branching modifier is used in an amount of 0.05 to 5 parts by weight, based on 100 parts by weight of the polyamide hard block polymer unit and the hydrophilic group-containing soft block polymer unit.
9. The method of claim 8, wherein the branching modifier is used in an amount of 0.1 to 3 parts by weight, based on 100 parts by weight of the polyamide hard block polymer units and the hydrophilic group-containing soft block polymer units.
10. The process according to claim 1, wherein the molecular weight regulator is selected from aliphatic and/or aromatic dicarboxylic acids of C2-C20, and/or
The content of the molecular weight modifier is 0.3 to 8.5 parts by weight based on 100 parts by weight of the polyamide hard segment polymer unit and the hydrophilic group-containing soft segment polymer unit.
11. The process of claim 10, wherein the molecular weight regulator is selected from one or more of adipic acid, sebacic acid, suberic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or 1, 4-cyclohexanedicarboxylic acid, and/or
The content of the molecular weight modifier is 1 to 7 parts by weight based on 100 parts by weight of the polyamide hard segment polymer unit and the hydrophilic group-containing soft segment polymer unit.
12. A permanently antistatic branched polyamide elastomer prepared according to the process of any one of claims 1 to 11.
13. Use of a permanently antistatic branched polyamide elastomer according to claim 12 as a permanent antistatic agent.
14. A permanent antistatic composition comprising a permanently antistatic branched polyamide elastomer according to claim 12 and a further high molecular polymer.
15. The permanent antistatic composition according to claim 14, comprising 5 to 25 parts by weight of the permanent antistatic branched polyamide elastomer and 70 to 93 parts by weight of the other high molecular polymer.
16. The permanent antistatic composition of claim 14 wherein the other high molecular polymer is one or more selected from acrylonitrile-butadiene-styrene terpolymer, polycarbonate/acrylonitrile-butadiene-styrene terpolymer, nylon, polyester, polyvinyl chloride, polyoxymethylene, polystyrene, polypropylene, polyethylene.
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| CN111234480A (en) * | 2020-03-23 | 2020-06-05 | 江苏科奕莱新材料科技有限公司 | Elastomeric foamed articles having permanent antistatic properties |
| CN112695403A (en) * | 2020-12-11 | 2021-04-23 | 杭州津源新材料有限公司 | Antistatic polyamide elastomer spinning and processing method thereof |
| CN113121950B (en) * | 2021-06-04 | 2023-01-20 | 兖矿鲁南化工有限公司 | High-conductivity polyformaldehyde and preparation method thereof |
| CN113665084A (en) * | 2021-08-16 | 2021-11-19 | 苏州艾力特塑胶有限公司 | Vacuum extrusion molding process for anti-static IC material tube |
| WO2023220625A1 (en) * | 2022-05-10 | 2023-11-16 | Ascend Performance Materials Operations Llc | Polyamide elastomers with high melting points |
| CN114940755B (en) * | 2022-07-04 | 2024-03-01 | 华润化学材料科技股份有限公司 | Polyamide elastomer and preparation method thereof |
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