CN115925507A - Preparation method of high-stability chlorinated alkane - Google Patents
Preparation method of high-stability chlorinated alkane Download PDFInfo
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- CN115925507A CN115925507A CN202211664447.XA CN202211664447A CN115925507A CN 115925507 A CN115925507 A CN 115925507A CN 202211664447 A CN202211664447 A CN 202211664447A CN 115925507 A CN115925507 A CN 115925507A
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Abstract
The invention discloses a preparation method of high-stability chlorinated alkane, and relates to the technical field of chlorinated alkane. The preparation method comprises the following steps: the molten paraffin and chlorine gas are subjected to chlorination reaction in the material dispersion system and the initiation system; after the chlorination reaction is finished, refining and deacidifying a product to obtain the high-stability chlorinated alkane, wherein the material dispersion system comprises: water, sodium silicate, tetrachloroethane, and sodium polymethacrylate; the initiation system comprises: isopropyl thioxanthone, dibenzoyl peroxide and lauroyl peroxide. The preparation method of the invention improves the mass transfer of a dispersion system, effectively improves the stability of chlorinated alkane, does not need to add a stabilizer and saves the cost.
Description
Technical Field
The invention relates to the technical field of chlorinated alkanes, in particular to a preparation method of high-stability chlorinated alkanes.
Background
The chlorinated alkane is prepared by chlorination reaction of alkane, and has the advantages of good flame retardant property, aging resistance, static resistance, electric insulation, good material compatibility and low price, so the chlorinated alkane is widely applied to the fields of rubber tapes, tires, vehicle floors, cables, paint, adhesives and the like with flame retardant requirements as an additive for improving the performance, and a main product obtains good flame retardant property. In addition, the application in fireworks and crackers is also available.
Because a series of processing such as mixing, rubber mixing, extrusion and the like is generally required in the processing process of rubber and plastic products, the processing procedures often have certain temperature rise, and the temperature rise generated in the processing process of different products is different, and some products can even reach more than 200 ℃. Therefore, thermal stability is required for chlorinated alkanes. During processing, chlorinated alkanes undergo various degrees of decomposition due to the effect of temperature, and the higher the temperature, the longer the processing time, the more severe the decomposition. The decomposition and carbonization of the chlorinated alkane can deepen the color and luster of a main product, increase the acidity, generate bubbles, even corrode the surface of a machine to generate a sticking and rolling phenomenon, cause the processing difficulty and reduce the product performance besides causing the loss of effective components, changing the formula proportion and influencing the flame retardant effect.
According to the industry standard, the thermal stability of common chlorinated alkanes can meet the requirements of products with common purposes. However, the requirements for high-end products at home and abroad, for example, in some occasions with high requirements, can impose severe requirements on the thermal stability of the chlorinated alkane. In order to improve the thermal stability of chlorinated alkane, a mode of adding a thermal stabilizer is commonly adopted at present, and the commonly adopted thermal stabilizer is ethylene glycol diglycidyl ether. The heat stabilizer needs to have the following properties: (1) rapidly combines with the generated hydrogen chloride to avoid the acidity of the medium; (2) rapidly reacting with the oxidation active substance to prevent further reaction, and (3) reacting with the polyene structure to generate a stable substance to prevent further dehydrochlorination. In addition, the impurities in the materials are reduced, and the opportunity of contacting with iron is reduced, so that the stability of the product can be improved.
However, the above methods are limited in the range of improvement in stability or avoidance of instability factor from the external condition, and most of the stabilizers are added in a large amount and at high cost. Therefore, it is very important to improve the stability of the chlorinated alkane itself.
In view of the above, the present invention provides a method for stabilizing chlorinated alkane itself to meet the production requirement.
Disclosure of Invention
The invention aims to provide a preparation method of high-stability chlorinated alkane, which can greatly improve the stability of the chlorinated alkane. The inventor finds that when the chlorine content of the product is about 74 percent in research, the chlorine-hydrogen ratio in the molecule is close to 1: the chlorine and hydrogen are distributed in a staggered way in space and constrained with each other, so that the initial decomposition temperature of chlorinated alkane is effectively reduced, the thermal decomposition temperature is increased, the decomposition speed at high temperature is obviously reduced, the thermal stability index is improved, the stability of the chlorinated alkane is effectively improved from two aspects, and a stabilizer does not need to be added.
The chlorination reaction is a chain reaction initiated by free radicals, materials and products in the process are subjected to gas-liquid phase reaction with chlorine in a molten state, the early-stage reaction has low system viscosity and high mass transfer speed, no repulsive groups are on raw material molecules, and few products are beneficial to reaction balance, so that the reaction speed is high, the heat release is large, the temperature rise speed is high, the molecular motion is accelerated due to the temperature rise, the activity of the groups is enhanced, free radicals can be generated under the thermal initiation effect, the reaction speed is accelerated, the reaction time is shortened, but the chemical balance is not facilitated, the partial pressure of chlorine in the reaction system is reduced at high temperature, the reaction is not facilitated, the dehydrochlorination speed is remarkably increased, side reactions are increased, the products are subjected to bond breaking and isomerization in advance, the byproducts are increased, and even the products are yellowed and the later-stage reaction is difficult to be smoothly carried out. In the later stage of the reaction, the partial pressure of chlorine is reduced due to the approach of the reaction end point, the viscosity of the system is increased, the mass transfer is difficult, the molecular chlorine atoms are close to saturation, the reaction power is reduced due to the space effect obstruction and the repulsion between groups, and the chlorine atoms are difficult to replace hydrogen atoms, so the reaction speed is slow, the control of the chlorine content is very difficult, and therefore, in order to obtain the target chlorine content, the reaction system needs to be improved so as to improve the mass transfer effect of the reaction materials.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in one aspect, the present invention provides a method for preparing a high-stability chlorinated alkane, comprising the steps of:
(1) The molten paraffin and chlorine gas are subjected to chlorination reaction in the material dispersion system and the initiation system;
(2) After the chlorination reaction is finished, the product is refined and deacidified to obtain the high-stability chlorinated alkane,
wherein the content of the first and second substances,
the material dispersion comprises: water, sodium silicate, tetrachloroethane, and sodium polymethacrylate; preferably, the ratio of the water, the sodium silicate, the tetrachloroethane and the sodium polymethacrylate is 2000-4000:10-30:500-1500:15-35 (kg: kg: mL: kg), most preferably 3000:20:1000:25 (kg: kg: mL: kg).
Preferably, the dispersion is carried out in an enamel reactor, stirred with an impeller stirrer, at a speed of 150 to 170r/m.
The initiation system comprises: isopropyl thioxanthone, dibenzoyl peroxide and lauroyl peroxide; preferably, the mass ratio of 1105, dibenzoyl peroxide and lauroyl peroxide is 40-60:80-120:40-60, most preferably 50:100:50.
preferably, the initiation system is carried out under ultraviolet irradiation. Preferably, the parameters of the ultraviolet irradiation are: 320-400nm, 30-40W ultraviolet lamp.
Preferably, in step (1), the temperature of the molten paraffin does not exceed 60 ℃.
Preferably, in the step (1), the chlorine gas is introduced at a speed of 20-70L/s.
Preferably, in step (1), the chlorination reaction conditions are as follows: the reaction temperature is gradually increased from 80 ℃ to 145 ℃ and is not more than 145 ℃ at most; the reaction pressure is gradually increased from the normal pressure to 0.6MPa, and the highest pressure is not more than 0.6MPa.
Preferably, in the step (1), when the reaction rate of the chlorination reaction is reduced to 10.0L/s, the introduction of chlorine is stopped. To control the progress of the chlorination reaction.
In the step (1), as a preferable mode, the paraffin is melted and then subjected to a refining treatment.
Further, the impurity removal mode is as follows: washing and refining with water containing a small amount of sulfuric acid.
In the step (1), as a preferable mode, the chlorine gas is subjected to impurity removal treatment.
Further, the impurity removal mode is as follows: impurity removal is realized through a buffer tank and a filter in sequence.
Preferably, in the step (2), the step of refining the product is as follows: after the reaction is finished, slowly opening a pressure reduction valve, keeping the boiling state, reducing the pressure of the mixture to a condenser, condensing the mixture, and removing the micromolecule substances in a recovery system.
Preferably, in the step (2), a stabilizer is added during the deacidification and/or the pulverization.
Further preferably, the addition amount of the stabilizer is 0.01-2 per mill.
Further preferably, the stabilizer is castor oil polyoxyethylene ether.
Further preferably, in the step (2), the deacidifying step is: separating the materials after sedimentation, washing the materials once with hot water, settling and separating the materials again, and adding 4m of the materials 3 Hot air was introduced at a rate of/min to blow off residual acid for 5min.
In another aspect, the invention provides chlorinated alkanes prepared according to the above preparation method, having a chlorine content of 73-75%.
Preferably, the chlorinated alkane has the formula C 12-30 Cl 24-29 H 24-29 ，“C 12-30 "refers to any integer of 12 to 30, including 12 and 30, for example 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 30. In the examples of the present invention, chlorine was preparedBy conversion of alkanes to C 25 Cl 24-29 H 24-29 。
The invention has the beneficial effects that:
(1) The preparation process of the present invention improves the mass transfer of the dispersion to achieve a further increase in chlorine content.
(2) The invention controls the chlorine content to be about 74 percent, and ensures that the ratio of chlorine to hydrogen is close to 1: the chlorine and hydrogen are distributed in a staggered way in space and constrained with each other, so that the initial decomposition temperature of chlorinated alkane is effectively reduced, the thermal decomposition temperature is increased, the decomposition speed at high temperature is obviously reduced, the thermal stability index is improved, and the stability of the chlorinated alkane is effectively improved from two aspects.
(3) The invention does not need to add a stabilizer, thereby saving the cost.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. The following is merely an exemplary illustration of the scope of the invention as claimed, and various changes and modifications of the invention of the present application may be made by those skilled in the art based on the disclosure, which also fall within the scope of the invention as claimed.
The invention will now be further illustrated by means of specific examples. The various chemicals used in the examples of the present invention were obtained by conventional commercial routes unless otherwise specified. Unless otherwise specified, the contents are all mass contents hereinafter. Unless otherwise specified, it is understood to be carried out at room temperature.
In the following examples, the sources of the raw materials are as follows:
example 1: novel initiation System + novel Dispersion System
The novel material dispersion system is as follows: 3000kg of water +20kg of sodium silicate +1L of tetrachloroethane +25kg of sodium polymethacrylate.
Dispersing with an impeller stirrer at 160r/m.
The novel initiation system is as follows: 50g1105+100g dibenzoyl peroxide +50g lauroyl peroxide, ultraviolet irradiation, parameters are: 365nm and the rated output power of 35W.
(1) With C 25 After paraffin as the main component is melted (maximum temperature 60 ℃) and washed, 300kg of paraffin is metered and added into a 2000L enamel reactor, hot water is added, the temperature of the materials reaches 80 ℃, and then chlorine can be introduced to start chlorination reaction. Chlorine gas is subjected to preliminary impurity removal through a buffer tank, is further purified and refined through a filter, and is gradually introduced into a reaction kettle, and a novel initiation system is adopted in a novel material dispersion system to perform chlorination reaction with paraffin.
As the chlorination reaction proceeds, the temperature gradually increases and the pressure also increases. The highest temperature is controlled at 145 ℃ and the highest pressure is controlled at 0.6MPa.
(2) Refining: when the reaction speed is reduced to 10.0L/min, stopping introducing chlorine, slowly opening the pressure reduction valve, keeping the boiling state, reducing the pressure of the mixture to the condenser, condensing the mixture, and removing the micromolecule substances in the recovery system.
(3) Deacidifying: separating the materials after sedimentation, washing the materials once with hot water, settling and separating the materials again, and then adding 4m of the materials 3 Hot air was introduced at a rate of/min to blow off residual acid for 5min.
(4) Discharging after deacidification, cooling, crushing and packaging to obtain a finished product.
Example 2: novel initiating system, novel dispersing system and 1 thousandth stabilizer
The preparation method is as in example 1, except that 1 ‰ stabilizer (castor oil polyoxyethylene ether BL-40) is added after the product is refined and deacidified, and the finished product is obtained after the materials are discharged after being stirred uniformly, cooled, crushed and packaged.
Example 3: novel initiation System + common Dispersion System
The preparation is carried out as in example 1, except that the dispersion is replaced by a conventional dispersion (3000 kg of water +25kg of sodium polymethacrylate), the rest being identical.
Dispersing with an impeller stirrer at 160r/m.
Example 4: common initiation System + novel Dispersion System
Prepared according to the method of example 1, except that the dispersion was replaced with a conventional initiating system (200 g of lauroyl peroxide), the remainder being identical.
The conventional initiating system is lauroyl peroxide, UV irradiation, with the same parameters as in example 1.
Example 5
The conditions were the same as in example 1 except that the reaction was terminated when the reaction rate was decreased to 4.0L/min.
Example 6
The conditions are the same as example 5, except that 1 ‰ stabilizer (castor oil polyoxyethylene ether BL-40) is added after the product is refined and deacidified, and the product is discharged after being stirred uniformly, cooled, crushed and packaged to obtain the finished product.
Example 7
The conditions were the same as in example 1, except that the novel material dispersion was: 3000kg of water +30kg of sodium silicate +0.5L of tetrachloroethane +25kg of sodium polymethacrylate.
Dispersing with an impeller stirrer at 160r/m.
Example 8
The novel initiation system is as follows: 40g 1105+120g dibenzoyl peroxide +40g lauroyl peroxide, UV irradiation, the parameters are as in example 1.
Comparative example 1: ordinary initiation system + ordinary dispersion system
The preparation is carried out as in example 1, except that a conventional dispersion and a conventional initiator are added, the remainder being identical.
Comparative example 2: without using dispersing systems and initiating systems
The preparation is carried out as in example 1, except that no dispersion or initiator is added, the remainder being identical.
Comparative example 3: general initiation System
The preparation is carried out as in example 1, except that, without dispersion, only the conventional initiator system is added, the remainder being identical.
Comparative example 4
The conditions were the same as in example 1 except that the maximum reaction pressure was controlled to 0.4MPa. The reaction was terminated when the rate was decreased to 10.0L/min.
Comparative example 5
The conditions were the same as in example 1, except that the maximum reaction temperature reached 151 ℃. The reaction was terminated when the rate was decreased to 10.0L/min.
And (4) detecting a result:
1. the method for measuring the chlorine content comprises the following steps: the measurement was carried out according to GB1679-88 mercury method.
2. Thermal stability index determination method: the assay was performed according to GB 1680-88.
3. Thermal decomposition temperature measurement method: taking 2-5g of sample, placing the sample in a glycerol bath with heating, suspending a congo red test paper at the opening of the test tube, controlling the temperature rise rate of the oil bath to be 3 +/-0.5 ℃, and recording the temperature of the test paper when the test paper changes color. Repeating the steps once, and taking an average value to obtain the thermal decomposition temperature.
4. Chlorinated alkanes have the general formula C n H (2n+2-x) Cl x The chlorine content is a% = MCl/(MC n + MH (2n + 2-x) + MCl) = 100%,
the chlorine atom number X = a (MC + n + MH (2n + 2)/(100 MCl + a MH-a MCl),
the obtained hydrogen atom number is 2n +2-x,
wherein MC, MH and MCl are the atomic weights of carbon, hydrogen and chlorine respectively.
The results of the examples and comparative examples are as follows:
| molecular formula | Chlorine content | Thermal stability index | Temperature of thermal decomposition | |
| Example 1 | C 25 H 25.87 Cl 26.13 | 73.95％ | 0.054％ | 206℃ |
| Example 2 | C 25 H 25.94 Cl 26.06 | 73.89％ | 0.039％ | 217℃ |
| Example 3 | C 25 H 27.70 Cl 24.30 | 72.41％ | 0.117％ | 182℃ |
| Example 4 | C 25 H 28.53 CL 23.47 | 71.66％ | 0.118％ | 176℃ |
| Example 5 | C 25 H 24.61 Cl 27.39 | 74.92％ | 0.071％ | 198℃ |
| Example 6 | C 25 H 24.35 Cl 27.65 | 75.11％ | 0.059％ | 210℃ |
| Example 7 | C 25 H 25.24 Cl 26.76 | 73.22％ | 0.064％ | 203℃ |
| Example 8 | C 25 H 25.18 Cl 26.82 | 73.17％ | 0.066％ | 202℃ |
| Comparative example 1 | C 25 H 29.38 Cl 22.62 | 70.85％ | 0.17％ | 174℃ |
| Comparative example 2 | C 25 H 31.77 Cl 20.22 | 68.33％ | 0.241％ | 162℃ |
| Comparative example 3 | C 25 H 30.10 Cl 21.90 | 70.13％ | 0.18％ | 168℃ |
| Comparative example 4 | C 25 H 27.29 Cl 24.71 | 72.77％ | 0.084％ | 193℃ |
| Comparative example 5 | C 25 H 27.46 Cl 24.54 | 72.62％ | 0.0124％ | 183℃ |
Note: because there is a trace of free chlorine in the material, the measured chlorine content will be slightly higher than the actual component, and the calculated chlorine fraction will be slightly higher than the actual fraction.
It can be seen that the proportion of the components in the novel initiation system and the novel dispersion system in the invention, the temperature and pressure control of the reaction can affect the final product, therefore, the highest temperature is controlled at 145 ℃ and the highest pressure is controlled at 0.6MPa. Compared with a comparative example 1 using a common initiation system and a common dispersion system, the novel initiation system and the novel dispersion system can obviously control the chlorine content in a final product within a certain range, and make the number ratio of hydrogen atoms to chlorine atoms closer to 1, so that the thermal decomposition index is obviously reduced, the thermal decomposition temperature is further improved, the stability of chlorinated alkane can be greatly improved, and the application requirement of high-end products is met.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. A preparation method of high-stability chlorinated alkane is characterized by comprising the following steps:
(1) The molten paraffin and chlorine gas are subjected to chlorination reaction in the material dispersion system and the initiation system;
(2) After the chlorination reaction is finished, the product is refined and deacidified to obtain the high-stability chlorinated alkane,
wherein the content of the first and second substances,
the material dispersion comprises: water, sodium silicate, tetrachloroethane, and sodium polymethacrylate; the initiation system comprises: isopropyl thioxanthone, dibenzoyl peroxide and lauroyl peroxide.
2. The method of claim 1, wherein the ratio of the water, the sodium silicate, the tetrachloroethane and the sodium polymethacrylate is 2000-4000:10-30:500-1500:15-35 (kg: kg: mL: kg).
3. The method according to claim 1, wherein the mass ratio of isopropyl thioxanthone, dibenzoyl peroxide and lauroyl peroxide is 40-60:80-120:40-60.
4. The method of claim 1, wherein the initiation system is carried out under ultraviolet irradiation.
5. The method of claim 1, wherein the dispersion is stirred using an impeller stirrer at a speed of 150 to 170r/m.
6. The method according to claim 1, wherein in the step (1), the temperature of the molten paraffin is not more than 60 ℃; the introduction speed of the chlorine is 20-70L/s; the conditions of the chlorination reaction are as follows: the reaction temperature is gradually increased from 80 ℃ to 145 ℃ and is not more than 145 ℃ at most; the reaction pressure is gradually increased from the normal pressure to 0.6MPa, and the highest pressure is not more than 0.6MPa.
7. The production method according to claim 1, wherein the introduction of chlorine is stopped when the reaction rate of the chlorination reaction is decreased to 10.0L/s in the step (1).
8. The preparation method according to claim 1, wherein in the step (2), a stabilizer is added in the deacidification and/or pulverization process, and the addition amount of the stabilizer is 0.01-2 per mill.
9. Chlorinated alkanes obtainable by the process according to any of claims 1 to 8, characterized by a chlorine content of 73 to 75%.
10. Chlorinated alkane according to claim 9, characterized in that it has the formula C 12-30 Cl 24- 29 H 24-29 。
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