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CN110183583B - Preparation method of colloidal electrolyte for hydrazine gas detection - Google Patents

Preparation method of colloidal electrolyte for hydrazine gas detection Download PDF

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CN110183583B
CN110183583B CN201910358651.0A CN201910358651A CN110183583B CN 110183583 B CN110183583 B CN 110183583B CN 201910358651 A CN201910358651 A CN 201910358651A CN 110183583 B CN110183583 B CN 110183583B
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electrolyte
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thermal initiator
prepolymer
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CN110183583A (en
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方涛
徐光�
赵全
郑雪玲
李弥异
吕立强
郝龙
刘岩
金朝旭
李瑶
张瑜
许宏
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Beijing Institute of Aerospace Testing Technology
Shijiazhuang University
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Shijiazhuang University
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    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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Abstract

本发明属于电化学传感器的技术领域，具体地说，涉及一种用于肼气体检测的胶体电解质的制备方法，该制备方法将高分子单体、电解质、添加剂、热引发剂加入到有机溶剂中，进行热聚合反应，得到所述的胶体电解质。本发明所述的制备方法采用简化的工艺获得了性能优异的、适于电流型肼气体传感器的胶体电解质。The invention belongs to the technical field of electrochemical sensors, and in particular relates to a preparation method of a colloidal electrolyte for hydrazine gas detection. The preparation method adds a polymer monomer, an electrolyte, an additive and a thermal initiator into an organic solvent , and thermal polymerization is carried out to obtain the colloidal electrolyte. The preparation method of the present invention adopts a simplified process to obtain a colloidal electrolyte with excellent performance and suitable for a current-type hydrazine gas sensor.

Description

Preparation method of colloidal electrolyte for hydrazine gas detection
Technical Field
The invention belongs to the technical field of electrochemical sensors, and particularly relates to a preparation method of a colloidal electrolyte for hydrazine gas detection.
Background
The gas sensor has the advantages of high reaction speed and low manufacturing cost, is rapidly developed in recent decades, and is widely applied to the fields of chemistry, biology, environment, medicine and the like. In addition, in the field of aerospace science and technology, the gas sensor also shows unique characteristics in the aspect of hydrazine rocket propellant detection. The current type gas sensor in the gas sensor mainly adopts water system electrolyte, and because the water saturation vapor pressure is very big, the water in the sensor volatilizes fast, therefore, the sensor adopting water system electrolyte usually has a short service life, and the similar hydrogel electrolyte is difficult to overcome the defect that the water volatilizes fast. In order to solve the technical defect, the people in the day of the year have proposed an organic system using N-methyl-2 pyrrolidone as a solvent and tetraethylammonium tetrafluoroborate as an electrolyte, and relatively speaking, the organic solvent with low saturated vapor pressure relieves the solvent volatilization to some extent, but has a new problem that the sensitivity and detection limit are not as good as those of a water system.
Therefore, there is a need for a new electrolyte system for hydrazine gas detection that solves the above-mentioned drawbacks of the prior art, extends the lifetime of the gas sensor and at the same time improves the detection sensitivity.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a colloidal electrolyte for hydrazine gas detection.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of a colloidal electrolyte for hydrazine gas detection comprises the following steps: adding a high molecular monomer, an electrolyte, an additive and a thermal initiator into an organic solvent, and carrying out thermal polymerization reaction to obtain the colloidal electrolyte.
The production method according to an embodiment includes the steps of:
s1, taking a high molecular monomer with the weight of W1, adding a thermal initiator with the weight of W2, heating, and carrying out prepolymerization reaction to obtain a prepolymer;
s2, adding the prepolymer into an organic solvent, adding an additive, a high-molecular monomer with the weight of W3, a thermal initiator with the weight of W4 and an electrolyte, and carrying out heating polymerization reaction for a certain time to obtain the colloidal electrolyte.
The preparation method of the invention firstly takes part of the high molecular monomer to prepare the high molecular prepolymer, then mixes the high molecular prepolymer with the additive, the high molecular monomer, the thermal initiator and the electrolyte to carry out the on-site thermal initiation polymerization reaction, and adopts the simplified process to obtain the colloidal electrolyte which has excellent performance and is suitable for the current type hydrazine gas sensor. The preparation method improves the polymerization degree of the high polymer, obtains the high polymer capable of firmly locking the electrolyte in the high polymer, reduces the loss rate of the electrolyte and prolongs the service life of the colloidal electrolyte. In addition, the electrolyte is added finally, which is helpful for improving the ionic conductivity of the colloidal electrolyte and improving the electrical property.
As an embodiment, the preparation method comprises the following steps:
s1, adding a thermal initiator with the weight of W2 into a high-molecular monomer with the weight of W1, uniformly mixing, heating at the temperature of 60-80 ℃ for 1-3 hours until the viscosity is increased to 50 m-200 Pa.s, rapidly cooling to room temperature, and terminating the polymerization reaction to obtain a prepolymer;
s2, adding the prepolymer into an organic solvent, sequentially adding an additive, a high-molecular monomer with the weight of W3 and a thermal initiator with the weight of W4, uniformly mixing, finally adding an electrolyte, and carrying out heating polymerization reaction for a certain time to obtain the colloidal electrolyte.
In the step S1, the temperature and the heating time are adopted to obtain the prepolymer with the viscosity of 50 m-200 Pa · S, and the prepolymer is convenient to be rapidly and fully polymerized with the residual amount of the high molecular monomer under the action of the thermal initiator and the additive to obtain the target high molecular polymer with specific performance, and the prepolymer has good compatibility with the electrolyte, so that the electrolyte loss rate of the colloidal electrolyte is further reduced, the stability is improved, and the service life is prolonged.
Preferably, the average molecular weight of the high molecular prepolymer is 500-3000.
In one embodiment, the temperature of the heating polymerization reaction in step S2 is 40 to 100 ℃.
As an embodiment, step S2 is:
and adding the prepolymer into an organic solvent, sequentially adding an additive, a high-molecular monomer W3 and a thermal initiator W4, uniformly mixing, finally adding an electrolyte, stirring until the mixture is completely dissolved, heating in a water bath at the temperature of 60-80 ℃ for 2-24 hours until the system is condensed to form an elastomer, and thus obtaining the colloidal electrolyte.
The elastic body has certain elastic restoring force, has proper rigidity and flexibility, is convenient to be installed and matched with electrodes of electrical elements and the like, and is convenient to use.
The charging sequence, temperature control and heating time of the step S2 can further improve the locking effect of the electrolyte, reduce the loss rate, and obtain the colloidal electrolyte in an elastomer state, which maintains an elastic solid state in a certain temperature range and has better elastic recovery capability, so that the colloidal electrolyte is convenient to match and mount with the electrode of the electrical element.
As an embodiment, W1: w3 is 20-7: 1, preferably W1: w3 is 10-8: 1.
The addition of the high molecular monomer in batches according to the addition ratio is helpful for further promoting the polymerization degree of the high molecular monomer, so as to obtain the high molecular polymer capable of firmly locking the electrolyte in the interior and reduce the loss rate of the electrolyte.
As an embodiment, in the step S1, the addition amounts of the high molecular monomer and the thermal initiator satisfy W1: w2 is 1000: 1-500: 1.
In one embodiment, the weight ratio of the prepolymer to the organic solvent is 2:1 to 1: 4; the weight W3 of the high molecular monomer is 10-40% of the addition amount of the prepolymer; the addition amount of the thermal initiator or the additive is 0.1-2 per mill of the total amount of the high molecular monomer respectively; the adding amount of the electrolyte is 1 per mill-5 percent of the total weight of the raw materials.
The proportioning relation adopted by the substances can improve the ionic conductivity of the colloidal electrolyte, lock the fastness degree of the electrolyte, improve the polymerization degree of the high molecular monomer, enable the colloidal electrolyte to be in an elastomer state and have better elastic recovery capability.
In one embodiment, the polymer monomer is selected from one or a combination of methyl methacrylate, methyl acrylate, ethyl acrylate and butyl acrylate.
In one embodiment, the electrolyte is one or a combination of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate or tetraethylammonium tetrafluoroborate.
In one embodiment, the organic solvent is one or a combination of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, vinylene carbonate, N-dimethylformamide or N-methyl-2-pyrrolidone.
In one embodiment, the thermal initiator is dibenzoyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, 2' -azobis (2-methylpropionitrile), benzoyl peroxide/N, N-dimethylaniline or diisopropyl peroxydicarbonate;
the additive is one or a combination of more of dibutyl phthalate, dioctyl phthalate, tributyl phosphate, acetyl trioctyl citrate, triethyl citrate or tributyl citrate.
The preparation method of the invention is adopted to obtain the colloidal electrolyte for detecting hydrazine gas, the preparation raw materials comprise electrolyte, high molecular monomer, organic solvent and thermal initiator, and the preparation raw materials are mixed for thermal polymerization reaction to obtain the colloidal electrolyte.
In one embodiment, the colloidal electrolyte has an ionic conductivity of 1 × 10-6～2×10-3S·cm-1Preferably 1X 10-3～2×10-3S·cm-1。
As an embodiment, the working temperature of the colloidal electrolyte is-60 ℃ to 200 ℃, and preferably-40 ℃ to 120 ℃.
As an embodiment, the colloidal electrolyte has an average weight loss per year at room temperature of not more than 2%, preferably not more than 1%.
The colloidal electrolyte has high ionic conductivity and extremely low volatility, and can be used for preparing electrical devices with excellent electrical properties and good stability. In particular, the working temperature range of the colloidal electrolyte is wide, and the colloidal electrolyte can be suitable for working environments with lower temperature or higher temperature.
The colloidal electrolyte is directly prepared by a thermal initiation field polymerization process through a high-molecular prepolymer, a high-molecular monomer, an organic solvent and an electrolyte, and the performance of the colloidal electrolyte is particularly suitable for preparing a current type hydrazine gas sensor with good stability, high detection sensitivity and excellent detection limit, so that the service life of the current type hydrazine gas sensor is prolonged, and the colloidal electrolyte has a good application prospect.
In one embodiment, the polymer monomer is selected from one or a combination of methyl methacrylate, methyl acrylate, ethyl acrylate and butyl acrylate.
In one embodiment, the organic solvent is one or a combination of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, vinylene carbonate, N-dimethylformamide or N-methyl-2-pyrrolidone.
In one embodiment, the electrolyte is one or a combination of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate or tetraethylammonium tetrafluoroborate.
In one embodiment, the thermal initiator is dibenzoyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, 2' -azobis (2-methylpropionitrile), benzoyl peroxide/N, N-dimethylaniline, or diisopropyl peroxydicarbonate.
As an embodiment, the preparation raw material comprises an additive, and the additive is one or a combination of several of dibutyl phthalate, dioctyl phthalate, tributyl phosphate, acetyl trioctyl citrate, triethyl citrate or tributyl citrate.
In one embodiment, the weight ratio of the added polymeric monomer to the thermal initiator is 1000:1 to 500: 1.
The polymer obtained by adding the high molecular monomer and the thermal initiator according to the proportion can firmly lock the electrolyte, and the colloidal electrolyte is in an elastomer state, keeps an elastic solid state in a certain temperature range, and has better elastic recovery capability, so that the colloidal electrolyte is convenient to be matched and installed with the electrode of an electric appliance element.
In one embodiment, the thermal initiator is added in an amount of 0.1 to 2% by weight of the polymer monomer, and the additive is added in an amount of 0.1 to 2% by weight of the polymer monomer.
The high molecular monomer and the thermal initiator are added according to the proportion, the high molecular monomer is fully polymerized by adopting a lower additive amount, and the colloidal electrolyte in an elastomer state is obtained.
As an embodiment, the electrolyte is added in an amount of 1 per mill to 5 percent of the total weight of the raw materials for preparation.
The addition of the electrolyte is added according to the standard, so that the ionic conductivity of the colloidal electrolyte is improved, the compatibility of the electrolyte and a high molecular polymer is good, the loss rate of the electrolyte is reduced, and the stability is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention are described in detail and completely with reference to some examples, which are only used for illustrating the present invention and are not used for limiting the scope of the present invention.
Example 1
Putting 25g of freshly distilled methyl methacrylate monomer into a clean dry conical flask, adding 25mg of thermal initiator benzoyl peroxide, heating in a water bath at 60 ℃, intermittently oscillating the conical flask, and carrying out prepolymerization reaction for 1h to obtain a high-molecular prepolymer;
cooling the reaction system to room temperature, adding 75g of Propylene Carbonate (PC), 100mg of lithium perchlorate and 0.5g of dibutyl phthalate, adding 2.5g of freshly distilled methyl methacrylate monomer, stirring until the monomers are completely dissolved, adding 55mg of benzoyl peroxide, and heating in a water bath at 60 ℃ for 10 hours to obtain the colloidal electrolyte.
The ionic conductivity of the colloidal electrolyte was 1X 10-3S·cm-1。
Example 2
Putting 25g of freshly distilled methyl methacrylate monomer into a clean dry conical flask, adding 25mg of thermal initiator benzoyl peroxide, heating in a water bath at 60 ℃, intermittently oscillating the conical flask, and carrying out prepolymerization for 1h to obtain a high-molecular prepolymer;
cooling the reaction system to room temperature, adding 75g of Propylene Carbonate (PC), 10mg of lithium perchlorate and 0.5g of dibutyl phthalate, adding 2.5g of freshly distilled methyl methacrylate monomer, stirring until the monomers are completely dissolved, adding 55mg of benzoyl peroxide, and heating in a water bath at 60 ℃ for 10 hours to obtain the colloidal electrolyte.
The ionic conductivity of the colloidal electrolyte is 5X 10-5S·cm-1。
Example 3
Putting 25g of freshly distilled methyl methacrylate monomer into a clean dry conical flask, adding 25mg of azodiisobutyronitrile serving as a thermal initiator, heating in a water bath at 60 ℃, intermittently oscillating the conical flask, and carrying out prepolymerization for 1h to obtain a high-molecular prepolymer;
cooling the reaction system to room temperature, adding 75g of Propylene Carbonate (PC), 50mg of lithium perchlorate and 0.5g of dibutyl phthalate, adding 2.5g of freshly distilled methyl methacrylate monomer, stirring until the monomers are completely dissolved, adding 55mg of azobisisobutyronitrile, and heating in a water bath at 60 ℃ for 10 hours to obtain the colloidal electrolyte.
The ionic conductivity of the system is 4 multiplied by 10-4S·cm-1。
Example 4
Putting 15g of a mixed monomer of freshly distilled methyl methacrylate and 10g of methyl acrylate into a clean dry conical flask, adding 25mg of benzoyl peroxide as an initiator, heating in a water bath at 60 ℃, intermittently oscillating the conical flask, and carrying out prepolymerization for 2 hours to obtain a high-molecular prepolymer;
cooling the reaction system to room temperature, adding 75g of Propylene Carbonate (PC), 100mg of lithium perchlorate and 0.5g of dibutyl phthalate, adding 2.5g of freshly distilled methyl methacrylate monomer, stirring until the monomers are completely dissolved, adding 55mg of benzoyl peroxide, and heating in a water bath at 60 ℃ for 10 hours to obtain the colloidal electrolyte.
The ionic conductivity of the colloidal electrolyte was 1.2X 10-3S·cm-1。
Example 5
Taking 20g of a mixed monomer of freshly distilled methyl methacrylate and 5g of methyl acrylate, putting the mixed monomer into a clean dry conical flask, adding 25mg of benzoyl peroxide as an initiator, heating in a water bath at 60 ℃, intermittently oscillating the conical flask, and carrying out prepolymerization for 1h to obtain a high-molecular prepolymer;
and cooling the reaction system to room temperature, adding 75g of Propylene Carbonate (PC) and 100mg of lithium perchlorate, adding 2.5g of freshly distilled methyl acrylate monomer, stirring until the methyl acrylate monomer is completely dissolved, adding 55mg of benzoyl peroxide, and heating in a water bath at 80 ℃ for 6 hours to obtain the colloidal electrolyte.
The ionic conductivity of the colloidal electrolyte was 1X 10-3S·cm-1。
Example 6
Taking 20g of a mixed monomer of freshly distilled methyl methacrylate and 5g of ethyl acrylate, putting the mixed monomer into a clean dry conical flask, adding 25mg of benzoyl peroxide as an initiator, heating in a water bath at 60 ℃, intermittently oscillating the conical flask, and carrying out prepolymerization for 1h to obtain a high-molecular prepolymer;
the reaction system was cooled to room temperature, and 75g of Propylene Carbonate (PC) was added: ethyl Methyl Carbonate (EMC): 1g of Vinylene Carbonate (VC), 300mg of lithium hexafluorophosphate and 2.5g of freshly distilled methyl methacrylate monomer are added into a mixed solution consisting of dimethyl carbonate (DMC) in a volume ratio of 1:1:1, stirred until the monomers are completely dissolved, 55mg of benzoyl peroxide is added, and the mixed solution is heated in a water bath at 60 ℃ for 12 hours to obtain the colloidal electrolyte.
The ionic conductivity of the colloidal electrolyte is 2X 10-3S·cm-1。
Experimental example 1
The temperature range in which the colloidal electrolytes obtained in examples 1 to 6 can stably work when used in a hydrazine gas sensor is examined in the experiment, and specific test data are shown in table 1 below.
TABLE 1
Lowest temperature (. degree.C.) Lowest temperature (. degree.C.)
Example 1 -40 147
Example 2 -36 120
Example 3 -29 95
Example 4 -52 180
Example 5 -45 156
Example 6 -60 200
Experimental example 2
The average weight loss of the colloidal electrolytes obtained in examples 1 to 6 after being placed at room temperature for 1 to 2 years was examined, and the specific test data are shown in table 2 below.
TABLE 2
Figure BDA0002046223080000071
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (9)

1.一种用于肼气体检测的胶体电解质的制备方法，其特征在于，将高分子单体、电解质、添加剂、热引发剂加入到有机溶剂中，进行热聚合反应，得到所述的胶体电解质；包括下列步骤：1. a preparation method for the colloidal electrolyte of hydrazine gas detection, is characterized in that, polymer monomer, electrolyte, additive, thermal initiator are joined in organic solvent, carry out thermal polymerization reaction, obtain described colloidal electrolyte ; includes the following steps: S1，取W1重量的高分子单体，加入W2重量的热引发剂，加热，进行预聚合反应，得到预聚物；S1, take W1 weight of macromolecular monomer, add W2 weight of thermal initiator, heat, carry out prepolymerization reaction, obtain prepolymer; S2，将所述预聚物加入到有机溶剂中，加入添加剂、W3重量的高分子单体、W4重量的热引发剂及电解质，加热聚合反应一定时间，即得到所述的胶体电解质；S2, adding the prepolymer into an organic solvent, adding additives, W3 weight macromolecular monomers, W4 weight thermal initiator and electrolyte, and heating the polymerization reaction for a certain period of time to obtain the colloidal electrolyte; 所述高分子单体选自新蒸馏过的甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸乙酯或丙烯酸丁酯的一种或几种的组合；Described macromolecule monomer is selected from one or more combinations of newly distilled methyl methacrylate, methyl acrylate, ethyl acrylate or butyl acrylate; 所述W1与W3的重量比为20～7:1。The weight ratio of W1 to W3 is 20-7:1. 2.根据权利要求1所述的制备方法，其特征在于，包括下列步骤：2. preparation method according to claim 1, is characterized in that, comprises the following steps: S1，取W1重量的高分子单体，加入W2重量的热引发剂，混合均匀后，在60～80℃温度下加热1～3小时，待黏度增大至50mPa·s～200Pa·s，迅速降温至室温，终止聚合反应，获得预聚物；S1, take W1 weight of polymer monomer, add W2 weight of thermal initiator, after mixing evenly, heat at 60～80℃ for 1～3 hours, when the viscosity increases to 50mPa·s～200Pa·s, quickly Cool down to room temperature, terminate the polymerization reaction, and obtain a prepolymer; S2，将所述预聚物加入到有机溶剂中，依次加入添加剂、W3重量的高分子单体和W4重量的热引发剂混合均匀，最后加入电解质，加热聚合反应一定时间，即得到所述的胶体电解质。S2, adding the prepolymer into the organic solvent, adding additives, W3 weight of polymer monomer and W4 weight of thermal initiator to mix uniformly, finally adding electrolyte, heating the polymerization reaction for a certain period of time, that is, to obtain the described colloidal electrolyte. 3.根据权利要求1或2所述的制备方法，其特征在于，步骤S2中，加热聚合反应的温度为40~100℃。3. The preparation method according to claim 1 or 2, characterized in that, in step S2, the temperature of the heating polymerization reaction is 40-100°C. 4.根据权利要求3所述的制备方法，其特征在于，步骤S2为：4. preparation method according to claim 3 is characterized in that, step S2 is: 将所述预聚物加入到有机溶剂中，依次加入添加剂、W3重量的高分子单体和W4重量的热引发剂混合均匀，最后加入电解质，搅拌至完全溶解，在60～80℃下水浴加热2～24小时，至体系凝结呈弹性体，即得到所述的胶体电解质。The prepolymer is added to the organic solvent, followed by adding additives, W3 weight of polymer monomer and W4 weight of thermal initiator to mix evenly, finally adding electrolyte, stirring until completely dissolved, and heating in a water bath at 60-80 °C 2 to 24 hours, until the system coagulates into an elastomer, and the colloidal electrolyte is obtained. 5.根据权利要求1或2所述的制备方法，其特征在于，所述步骤S1中，高分子单体和热引发剂的加入量满足W1：W2=1000:1～500:1。5. The preparation method according to claim 1 or 2, characterized in that, in the step S1, the addition amount of the polymer monomer and the thermal initiator satisfies W1:W2=1000:1～500:1. 6.根据权利要求4所述的制备方法，其特征在于，预聚物与有机溶剂的重量比为2:1～1:4；高分子单体的重量W3为预聚物加入量的10%～40%；热引发剂或添加剂的添加量分别为高分子单体总量的0.1‰～2‰；电解质的加入量为原料总重量的1‰～5%。6. preparation method according to claim 4 is characterized in that, the weight ratio of prepolymer and organic solvent is 2:1～1:4; The weight W of macromolecular monomer is 10% of prepolymer addition amount ～40%; the addition amount of thermal initiator or additive is 0.1‰～2‰ of the total amount of polymer monomers; the addition amount of electrolyte is 1‰～5% of the total weight of raw materials. 7.根据权利要求6所述的制备方法，其特征在于，所述的电解质为高氯酸锂、六氟磷酸锂、四氟硼酸锂或四氟硼酸四乙基铵的一种或几种的组合。7. The preparation method according to claim 6, wherein the electrolyte is one or a combination of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate or tetraethylammonium tetrafluoroborate. 8.根据权利要求6所述的制备方法，其特征在于，所述的有机溶剂为碳酸丙烯酯、碳酸乙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、碳酸亚乙烯酯、N,N-二甲基甲酰胺或N-甲基-2-吡咯烷酮的一种或几种的组合。8. preparation method according to claim 6 is characterized in that, described organic solvent is propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, vinylene carbonate, One or more combinations of N,N-dimethylformamide or N-methyl-2-pyrrolidone. 9.根据权利要求6所述的制备方法，其特征在于，所述的热引发剂为过氧化二苯甲酰、过氧化苯甲酸叔丁酯、偶氮二异丁腈、2,2'-偶氮双（2-甲基丙腈）、过氧化苯甲酰/N，N-二甲基苯胺或过氧化二碳酸二异丙酯；9. preparation method according to claim 6 is characterized in that, described thermal initiator is dibenzoyl peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile, 2,2'- Azobis(2-methylpropionitrile), benzoyl peroxide/N,N-dimethylaniline or diisopropyl peroxydicarbonate; 所述添加剂为邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、磷酸三丁酯、柠檬酸乙酰基三辛酯、柠檬酸三乙酯或柠檬酸三丁酯的一种或几种的组合。The additive is one or more of dibutyl phthalate, dioctyl phthalate, tributyl phosphate, acetyl trioctyl citrate, triethyl citrate or tributyl citrate. The combination.
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