Preparation method and application of permanent polymer antistatic agent

Abstract

The present invention provides a preparation method and application of a permanent polymer antistatic agent, wherein a diacid monomer, a diol monomer, and a catalyst are mixed and esterified in a specific ratio to obtain a polyester prepolymer; the polyester prepolymer and an epoxy compound are vacuum copolymerized in a ratio to obtain a permanent polymer antistatic agent. The present invention prepares a polyester prepolymer first, and then copolymerizes it with an epoxy compound, and the functional polyether structure is connected to the polyester molecular chain in the form of a covalent bond to form a structurally integrated permanent polymer antistatic agent. When the permanent polymer antistatic agent of the present invention is used, it is not easily affected by temperature and humidity due to its large molecular weight, long molecular chain, and stable molecular structure, and has the characteristics of permanent antistatic. It can be widely used in the fields where dust and gas explosions need to be prevented, and precision electronic instruments are manufactured and used; and the preparation method of the present invention is simple and easy to implement, and has good prospects for industrial application.

Description

Technical Field

[0001] The invention relates to the technical field of antistatic polymer materials, and in particular to a preparation method and application of a permanent polymer antistatic agent. Background Art

[0002] In recent years, accidents such as fires, explosions, and electric shocks caused by static electricity in polymer materials such as plastics and rubber have occurred from time to time. During the use of general polymer materials, static electricity can easily accumulate on the surface due to friction, leading to static electricity accidents. The fundamental reason why polymer materials are prone to static electricity is that these polymer materials are composed of organic compounds, and there are covalent bonds in the molecules. They will not ionize, nor can they transfer electrons or ions, so they have very high volume resistance and surface resistance. When they rub against each other, they will generate a large static charge. Adding antistatic agents will cause polymer materials to discharge quickly, which can effectively prevent static electricity accumulation. There are many types of antistatic agents on the market.

[0003] In the prior art, antistatic polymer materials are mostly composite materials with a surface composite conductive layer or filled with conductive fillers. The raw materials of the conductive layer or the conductive fillers include anionic and cationic organic salts, non-ionic polyols, metal and carbon black fillers, etc. These materials have antistatic properties through physical compounding, but the antistatic properties are prone to attenuation.

[0004] The invention patent (application number is CN 202111136856.8) discloses an antistatic elastic anti-slip tape and a preparation method thereof, including a base film, an anti-slip layer, an elastic foam layer, a primer layer, a pressure-sensitive adhesive layer and a release layer, the elastic foam layer including: polytetramethylene ether glycol propylene oxide-ethylene oxide copolyether triol, polyethylene adipate glycol butylene glycol ester, 1,4-bis(isocyanate methyl)cyclohexane, diethylene glycol, HDI trimer, catalyst, foaming agent and flame retardant; although the method obtains a tape with both antistatic and anti-slip properties, the electrostatic function of the antistatic elastic anti-slip adhesive is the result of physical compounding of multiple antistatic polymer materials. When used, it produces an antistatic effect through the migration of electrostatic molecules. There is a problem that the antistatic function is easy to decay and gradually decreases with the passage of time, and it is not suitable for long-term use.

[0005] In view of this, it is necessary to design an improved preparation method and application of a permanent polymer antistatic agent to solve the above problems. Summary of the invention

[0006] The purpose of the present invention is to provide a preparation method and application of a permanent polymer antistatic agent. A polyester prepolymer is first prepared and then copolymerized with an epoxy compound to obtain a polymer antistatic agent. The polymer antistatic agent has a high molecular weight and a strong polyether structure molecular chain mobility. It can conduct and release static charges through ion conduction, has strong anti-interference ability, and has permanent antistatic properties.

[0007] To achieve the above-mentioned object of the invention, the present invention provides a method for preparing a permanent polymer antistatic agent, comprising the following steps:

[0008] S1, mixing and esterifying the diacid monomer, the diol monomer and the catalyst in a specific ratio, wherein the esterification temperature is 230-260° C. and the esterification time is 120-300 min to obtain a polyester prepolymer;

[0009] S2. The polyester prepolymer obtained in step S1 is subjected to vacuum copolymerization with an epoxy compound in a certain proportion, wherein the copolymerization temperature is 265-275° C., the time is 150-200 min, and the vacuum degree is less than 100 Pa, to obtain a permanent polymer antistatic agent.

[0010] As a further improvement of the present invention, the specific ratio is that the molar ratio of the diacid monomer, the diol monomer, and the catalyst is 1:(0.9-1.5):(0.02-0.05); in step S2, the molar ratio of the polyester prepolymer to the alkylene oxide monomer is 1:(0.02-0.2).

[0011] As a further improvement of the present invention, in step S1, the diacid monomer includes one of terephthalic acid, adipic acid, maleic acid, glutaric acid, and succinic acid.

[0012] As a further improvement of the present invention, in step S1, the diol monomer includes one of ethylene glycol, 1,3-propylene glycol, and 2,3-butanediol.

[0013] As a further improvement of the present invention, in step S2, the epoxy compound includes one of ethylene oxide, propylene oxide and butylene oxide.

[0014] As a further improvement of the present invention, the catalyst includes one of antimony glycolate, antimony trioxide, antimony acetate, tetraisopropyl titanate, tetraisobutyl titanate, titanium glycolate, stannous oxalate, and stannous octoate.

[0015] A permanent polymer antistatic agent prepared by any of the preparation methods described above, wherein the molecular chain of the permanent polymer antistatic agent is composed of polyether and polyester, and the polyether is connected to the molecular chain of the polyester in the form of a covalent bond.

[0016] As a further improvement of the present invention, the number average molecular weight of the permanent polymer antistatic agent is 20,000 to 100,000, and the surface resistivity of the permanent polymer antistatic agent is 10 6 ~10 8 Ω.

[0017] An application of a permanent polymer antistatic agent prepared by any of the preparation methods described above or described in any of the above items, wherein the permanent polymer antistatic agent is mixed with a polyester material or a polyolefin material according to a set ratio, dried, and a permanent antistatic polyester material or a permanent antistatic polyolefin material is obtained after blending and modification.

[0018] As a further improvement of the present invention, in the permanent antistatic polyester material, the mass percentage of the permanent polymer antistatic agent and the polyester material is (60% to 95%):(5% to 40%); the permanent antistatic polyolefin material also includes a compatibilizer, and the mass percentage of the permanent polymer antistatic agent, the polyolefin material and the compatibilizer is (50% to 85%):(5% to 40%):10%, and the compatibilizer is a copolymer of polyester and polyolefin.

[0019] The beneficial effects of the present invention are:

[0020] 1. The present invention provides a preparation method and application of a permanent polymer antistatic agent, wherein a diacid monomer, a diol monomer, and a catalyst are mixed and esterified in a specific ratio to obtain a polyester prepolymer; the polyester prepolymer and an epoxy compound are vacuum copolymerized in proportion to obtain a permanent polymer antistatic agent. The present invention prepares a polyester prepolymer first, and then copolymerizes it with an epoxy compound to obtain a polymer antistatic agent; the polymer antistatic agent has a high molecular weight, a large number of active hydrophilic groups on the surface of the material, and a strong mobility of the polyether structure molecular chain, and can conduct and release static charges through ion conduction, has strong anti-interference, does not completely rely on surface water absorption, is less affected by the temperature and humidity of the environment, has the characteristics of permanent antistatic, and can be widely used in the fields of preventing dust and gas explosions, manufacturing and using precision electronic instruments.

[0021] 2. In the preparation method of the permanent polymer antistatic agent of the present invention, the esterification process of the diacid monomer and the diol monomer is controlled by controlling the temperature and time of preparing the polyester prepolymer to prevent them from continuing to undergo polycondensation or copolymerization to form a polyester prepolymer; the polyester prepolymer is further copolymerized with the epoxy compound, and the obtained functional polyether structure is connected to the polyester molecular chain in the form of a covalent bond to form a permanent polymer antistatic agent with an integrated structure. When the permanent polymer antistatic agent of the present invention is used, it is not easy to migrate out of the polymer due to its large molecular weight, long molecular chain and stable molecular structure, so it is not easy to be affected by temperature and humidity. Therefore, it is not easy to attenuate the electrostatic effect, and the prepared antistatic material has good performance and a long service life.

[0022] 3. The permanent polymer antistatic agent of the present invention is a polymer material itself, and has good compatibility with polyester materials, so that the obtained antistatic material has a stable, lasting effect and good antistatic performance. In addition, the preparation method of the present invention is simple and easy to implement. By selecting specific raw material components and contents, and limiting process parameters, so that it cooperates with the raw materials, the preparation of the permanent polymer antistatic agent can be achieved, and it has good industrial application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is the structural formula of the permanent polymer antistatic agent prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0025] It should also be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and / or processing steps closely related to the scheme of the present invention are shown in the drawings, while other details that are not closely related to the present invention are omitted.

[0026] In addition, it should be noted that the terms "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or apparatus.

[0027] A method for preparing a permanent polymer antistatic agent comprises the following steps:

[0028] S1, esterifying the diacid monomer, diol monomer and catalyst in a specific ratio at a temperature of 230 to 260° C. for a time of 120 to 300 min to obtain a polyester prepolymer;

[0029] S2. The polyester prepolymer obtained in step S1 is subjected to vacuum copolymerization with an epoxy compound in a certain proportion, the copolymerization temperature is 265-275° C., the time is 150-200 min, and the vacuum degree is less than 100 Pa, to obtain a permanent polymer antistatic agent.

[0030] In particular, the specific ratio is that the molar ratio of the diacid monomer, the diol monomer, and the catalyst is 1: (0.9-1.5): (0.02-0.05); in step S2, the molar ratio of the polyester prepolymer to the alkylene oxide monomer is 1: (0.02-0.2). The present invention controls the esterification process of the diacid monomer and the diol monomer by controlling the temperature and time of preparing the polyester prepolymer, and matching the raw material components and content, so as to avoid their continued polycondensation or copolymerization to form a polyester prepolymer; the polyester prepolymer is further copolymerized with the epoxy compound, and the obtained polyether structure will be connected to the polyester molecular chain in the form of a covalent bond to form a permanent polymer antistatic agent with an integrated structure. The preparation method of the present invention is simple and easy to implement. By selecting specific raw material components and contents, and limiting the process parameters, so that it cooperates with the raw materials, the preparation of a permanent polymer antistatic agent can be achieved, and it has good prospects for industrial application.

[0031] Specifically, in step S1, the diacid monomer includes one of terephthalic acid, adipic acid, maleic acid, glutaric acid, and succinic acid. The diol monomer includes one of ethylene glycol, 1,3-propylene glycol, and 2,3-butanediol. The catalyst includes one of ethylene glycol antimony, antimony trioxide, antimony acetate, tetraisopropyl titanate, tetraisobutyl titanate, ethylene glycol titanium, stannous oxalate, and stannous octoate. In step S2, the epoxy compound includes one of ethylene oxide, propylene oxide, and butylene oxide.

[0032] A permanent polymer antistatic agent, the molecular chain of which is composed of polyether and polyester, and the polyether is connected to the molecular chain of polyester by covalent bonds. The molecular weight of the permanent polymer antistatic agent is 20,000 to 100,000, and the surface resistivity of the permanent polymer antistatic agent is 10 6 ~10 8 Ω.

[0033] Compared with the high molecular antistatic agent in the prior art which is formed by physically mixing several polymers, the present invention combines polyether and polyester into one in the form of covalent bonds, realizes the integration of various molecular chain structures, and makes the prepared permanent high molecular antistatic agent have long molecular chain, large molecular weight and stable molecular structure; it is not easy for the antistatic polymer to migrate out of the polymer and the antistatic performance to weaken during use; the prepared antistatic material has good performance and long service life.

[0034] The permanent polymer antistatic agent of the present invention has a high molecular weight, is rich in a large number of active hydrophilic groups on the surface of the material, has a strong polyether structure molecular chain mobility, can conduct and release static charges through ion conduction, has strong anti-interference ability, does not completely rely on surface water absorption, is less affected by the temperature and humidity of the environment, has permanent antistatic properties, and can be widely used in fields where dust and gas explosions need to be prevented and precision electronic instruments are manufactured and used.

[0035] The application of a permanent polymer antistatic agent is to mix and dry the permanent polymer antistatic agent with a polyester material or a polyolefin material according to a set ratio, and obtain a permanent antistatic polyester material or a permanent antistatic polyolefin material after blending and modification. The permanent polymer antistatic agent itself is a polymer material and has good compatibility with the polyester material, so that the obtained antistatic material has a stable and lasting effect and good antistatic performance.

[0036] Specifically, in the permanent antistatic polyester material, the mass percentage of the permanent high molecular antistatic agent and the polyester material is (60% to 95%): (5% to 40%). In the permanent antistatic polyolefin material, a compatibilizer is also included, and the mass percentage of the permanent high molecular antistatic agent, the polyolefin material and the compatibilizer is (50% to 85%): (5% to 40%): 10%, and the compatibilizer is a copolymer of polyester and polyolefin. According to the feasibility of the polyester material or the polyolefin material, it can be used for spinning, spunbonding, casting, meltblowing and other molding processes.

[0037] In some specific embodiments, the polyester is one of PET (polyethylene terephthalate), PLA (polylactic acid), and PBAT (polybutylene terephthalate-adipate); the polyolefin is one of PP (polypropylene) and PE (polyethylene). The compatibilizer is one of POE-g-GMA (polyolefin graft copolymer glycidyl methacrylate) and PP-g-MAH (polypropylene graft maleic anhydride).

[0038] Example 1

[0039] This embodiment provides a preparation method and application of a permanent polymer antistatic agent, comprising the following steps:

[0040] S1, terephthalic acid, ethylene glycol, and ethylene glycol antimony are mixed and esterified in a specific ratio, the esterification temperature is 250° C., and the esterification time is 200 min to obtain a polyester prepolymer; the molar ratio of terephthalic acid, ethylene glycol, and ethylene glycol antimony is 1:1.2:0.03;

[0041] S2, vacuum copolymerizing the polyester prepolymer obtained in step S1 with ethylene oxide at a molar ratio of 1:0.1, with a copolymerization temperature of 270° C., a time of 180 min, and a vacuum degree of less than 100 Pa, to obtain a permanent polymer antistatic agent; the number average molecular weight of the permanent polymer antistatic agent is 20,000;

[0042] S3, mixing the permanent high molecular antistatic agent and the polyester material PET in a mass percentage of 80%:20%, drying, and obtaining a permanent antistatic polyester material after blending and modification.

[0043] See also Figure 1 As shown, Figure 1 is the structural formula of the permanent polymer antistatic agent prepared in this embodiment. It can be seen from the structural formula that the polyether structure is connected to the polyester molecular chain in the form of a covalent bond to form a permanent polymer antistatic agent with an integrated structure; the permanent polymer antistatic agent has a large molecular weight, a long molecular chain, and a stable molecular structure. It is not easily affected by temperature and humidity and migrates out of the polymer, so it is not easy for the electrostatic effect to decay. The prepared antistatic material has good performance and a long service life.

[0044] Example 2

[0045] The present embodiment provides a preparation method and application of a permanent polymer antistatic agent. Compared with Example 1, the difference is that in step S3, the present embodiment mixes and dries the permanent polymer antistatic agent with a polyolefin material PP and a compatibilizer POE-g-GMA in a mass percentage of 70%:20%:10%, and obtains a permanent antistatic polyolefin material after blending and modification; the rest is substantially the same as Example 1 and will not be described again herein.

[0046] Comparative Example 1

[0047] Comparative Example 1 provides a polymer antistatic material commonly used in the prior art, which is physically mixed with polyethylene terephthalate, polyethylene oxide and polylactic acid.

[0048] The surface resistivity of the antistatic materials of Examples 1 to 2 and Comparative Example 1 and the surface resistivity after 30 days and 180 days were tested. Meanwhile, conventional polyester material PET and polyolefin material PP were used as control groups, respectively. The results are shown in the following table.

[0049] Table 1 Material performance test results of Examples 1-2, Comparative Example 1 and Control Group

[0050]

[0051]

[0052] As shown in Table 1, the antistatic polyester / polyolefin materials prepared in Examples 1 and 2 have lower surface resistivity and better conductive effect than conventional polyester or polyolefin materials, indicating that they have better antistatic effect. From the surface resistivity of the materials in Comparative Example 1 and Example 1 at 30 days and 180 days, it can be seen that the existing polymer antistatic materials have the problem that the antistatic function is easy to decay and gradually decreases with the passage of time, while the antistatic material prepared by the permanent polymer antistatic agent of the present invention has good antistatic effect, stable performance and good practicality.

[0053] Comparative Examples 2-3

[0054] Comparative Examples 2 to 3 provide a preparation method and application of a permanent polymer antistatic agent. Compared with Example 1, the difference is that the copolymerization parameters are set as shown in the following table, and the rest are roughly the same as Example 1 and will not be repeated here.

[0055] Table 2 Parameter settings for esterification and copolymerization of Comparative Examples 2 to 3

[0056] Copolymerization temperature Copolymerization time / min Comparative Example 2 250 180 Comparative Example 3 270 120

[0057] The surface resistivity of the antistatic materials of Comparative Examples 2 to 3 and the surface resistivity after 30 days and 180 days were tested, and the results are shown in the following table.

[0058] Table 3 Material performance test results of comparative examples 2 to 3

[0059] Surface resistivity(Ω) Surface resistivity after 30 days (Ω) Surface resistivity after 180 days (Ω) Comparative Example 2 <![CDATA[8.15*10 8 ]]> <![CDATA[8.19*10 8 ]]> <![CDATA[8.63*10 8 ]]> Comparative Example 3 <![CDATA[6.09*10 8 ]]> <![CDATA[6.23*10 8 ]]> <![CDATA[6.46*10 8 ]]>

[0060] As can be seen from Table 3, from the test results of Comparative Examples 2 to 3, when the copolymerization temperature is insufficient, it will affect the process of the polyether structure being connected to the polyester molecular chain with a covalent bond, thereby affecting the antistatic performance and durability of the antistatic material. The polyether structure not connected to the polyester molecular chain will migrate out of the polymer after the antistatic material is used for a long time, causing the antistatic performance to decay; as the copolymerization time increases, the antistatic performance of the polyester is better, which is mainly because as time increases, the polymerization efficiency of the antistatic small molecules is higher, the degree of connection to the polyester molecular chain is higher, and the antistatic performance and durability of the polyester are better; but when the reaction occurs more thoroughly, the effect of time on the copolymerization is small, so from an economic point of view, the preferred copolymerization time range is 150 to 200 minutes.

[0061] In summary, the present invention provides a method for preparing and applying a permanent polymer antistatic agent, wherein a diacid monomer, a diol monomer, and a catalyst are mixed and esterified in a specific ratio to obtain a polyester prepolymer; the polyester prepolymer and an epoxy compound are vacuum copolymerized in a certain ratio to obtain a permanent polymer antistatic agent. The present invention prepares a polyester prepolymer first, and then copolymerizes it with an epoxy compound. The obtained functional polyether structure is connected to the polyester molecular chain in the form of a covalent bond to form a permanent polymer antistatic agent with an integrated structure. When the permanent polymer antistatic agent of the present invention is used, it is not easy to migrate out of the polymer due to its large molecular weight, long molecular chain and stable molecular structure, so it is not easy to be affected by temperature and humidity, so the attenuation of electrostatic effect is not easy to occur; and the polymer antistatic agent has a high molecular weight, the material surface is rich in a large number of active hydrophilic groups, the polyether structure molecular chain has strong mobility, can conduct and release static charges through ion conduction, has strong anti-interference ability, does not completely rely on surface water absorption, is less affected by environmental temperature and humidity, has permanent antistatic characteristics, and can be widely used in the fields of preventing dust and gas explosions and manufacturing and using precision electronic instruments.

[0062] The above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solution of the present invention.

Claims

1. A method for preparing a permanent polymer antistatic agent, characterized in that: The following steps are involved: S1. Mixing and esterifying a diacid monomer, a diol monomer and a catalyst in a specific ratio, wherein the esterification temperature is 230-260° C. and the esterification time is 120-300 min to obtain a polyester prepolymer; wherein the specific ratio is a molar ratio of the diacid monomer, the diol monomer and the catalyst of 1:(0.9-1.5):(0.02-0.05); S2. The polyester prepolymer obtained in step S1 is subjected to vacuum copolymerization with an epoxy compound in proportion, the copolymerization temperature is 265-275° C., the time is 150-200 min, and the vacuum degree is less than 100 Pa, to obtain a permanent polymer antistatic agent; the molar ratio of the polyester prepolymer to the alkylene oxide monomer is 1:(0.02-0.2).

2. The method for preparing a permanent polymer antistatic agent according to claim 1, characterized in that: In step S1, the diacid monomer includes one of terephthalic acid, adipic acid, maleic acid, glutaric acid, and succinic acid.

3. The method for preparing a permanent polymer antistatic agent according to claim 1, characterized in that: In step S1, the diol monomer includes one of ethylene glycol, 1,3-propylene glycol, and 2,3-butanediol.

4. The method for preparing a permanent polymer antistatic agent according to claim 1, characterized in that: In step S2, the epoxy compound includes one of ethylene oxide, propylene oxide and butylene oxide.

5. The method for preparing a permanent polymer antistatic agent according to claim 1, characterized in that: In step S1, the catalyst includes one of antimony glycolate, antimony trioxide, antimony acetate, tetraisopropyl titanate, tetraisobutyl titanate, titanium glycolate, stannous oxalate, and stannous octoate.

6. A permanent polymer antistatic agent prepared by the preparation method according to any one of claims 1 to 5, characterized in that: The molecular chain of the permanent high molecular antistatic agent is composed of polyether and polyester, and the polyether is connected to the molecular chain of the polyester in the form of a covalent bond.

7. The permanent polymer antistatic agent according to claim 6, characterized in that: The number average molecular weight of the permanent polymer antistatic agent is 20,000 to 100,000, and the surface resistivity of the permanent polymer antistatic agent is 10 6 ~10 8 Ω.

8. Use of a permanent polymer antistatic agent prepared by the preparation method according to any one of claims 1 to 5 or according to any one of claims 6 to 7, characterized in that: The permanent high molecular antistatic agent is mixed with the polyester material or the polyolefin material according to a set ratio, dried, and after blending and modification, a permanent antistatic polyester material or a permanent antistatic polyolefin material is obtained.

9. The use of the permanent polymer antistatic agent according to claim 8, characterized in that: In the permanent antistatic polyester material, the mass percentage of the permanent polymer antistatic agent and the polyester material is (60%~95%):(5%~40%); the permanent antistatic polyolefin material also includes a compatibilizer, and the mass percentage of the permanent polymer antistatic agent, the polyolefin material and the compatibilizer is (50%~85%):(5%~40%):10%, and the compatibilizer is a copolymer of polyester and polyolefin.

Images