CN114044842B - Efficient anti-freezing emulsion antioxidant terminator for PVC (polyvinyl chloride) and preparation method thereof - Google Patents
Efficient anti-freezing emulsion antioxidant terminator for PVC (polyvinyl chloride) and preparation method thereof Download PDFInfo
- Publication number
- CN114044842B CN114044842B CN202111393431.5A CN202111393431A CN114044842B CN 114044842 B CN114044842 B CN 114044842B CN 202111393431 A CN202111393431 A CN 202111393431A CN 114044842 B CN114044842 B CN 114044842B
- Authority
- CN
- China
- Prior art keywords
- antioxidant
- stirring
- emulsifier
- reaction kettle
- terminator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an efficient anti-freezing emulsion antioxidant terminator for PVC and a preparation method thereof, belonging to the technical field of antioxidant terminator preparation. The antioxidant comprises the following components in percentage by mass: 10-20% of hindered phenol antioxidant, 10-20% of phosphite antioxidant, 10-20% of sulfate antioxidant, 5-8% of amine antioxidant, 5-8% of piperidine free radical antioxidant, 5-8% of antifreeze agent, 1-3% of emulsifier, 2-3% of dispersant, 1-5% of zinc stabilizer and the balance deionized water, wherein the emulsifier is a combination of emulsifier A and emulsifier B, and the dispersant is a combination of dispersant A and dispersant B. The invention adopts the A/B kettle production process, firstly heats and melts the oil phase, then preheats the oil phase before adding the water phase, strictly controls the emulsification temperature to be 70-80 ℃, adopts the process of adding the water phase in stages for multiple times during emulsification, has good emulsification effect and excellent product stability, does not delaminate after being placed for more than one year, and has excellent low-temperature frost resistance of the product.
Description
Technical Field
The invention belongs to the technical field of preparation of antioxidant terminators, and particularly relates to an efficient anti-freezing emulsion antioxidant terminator for PVC and a preparation method thereof.
Background
During each stage of the life cycle of the PVC resin product, namely the production, storage, processing and use processes of the PVC resin product, oxidation occurs due to self or external factors, so that the PVC resin and the PVC resin product gradually turn yellow, become hard and crisp, and scorch and turn black at higher temperature. In order to inhibit or delay the oxidative degradation of the PVC resin in the production, processing and use processes, an antioxidant terminator is generally required to be added into the PVC resin in the polymerization stage, the selection of the antioxidant is very important, and the proper antioxidant can effectively improve the aging resistance of the PVC resin and prolong the service life. In order to meet the pursuit of people on high performance and high added value of PVC products, many auxiliary agent manufacturers in China carry out research on the antioxidant, and the synergistic effect of the antioxidant is mainly utilized to fully exert the characteristics of each product so as to achieve the ideal antioxidant effect.
When the PVC suspension polymerization is terminated, an antioxidant terminator is required to be added, active ingredients added into the antioxidant terminator consume free radicals in a system to generate a stable structure, so that the purpose of terminating the polymerization reaction is achieved, and meanwhile, terminator molecules are blocked at the tail end of a polymerization long chain, so that the thermal stability and the anti-aging capability of the PVC resin are improved. The main problems of the antioxidant terminating agent in the prior industry are as follows:
(1) The freezing point is about 0 ℃, and the product is usually found to be solidified and can not be poured out in the use process in winter, so the heat preservation transportation at 20 ℃ is adopted in the industry at present, and the cost is increased.
(2) The stability is poor, the preparation process in the emulsion antioxidant industry is prepared by melting and then emulsifying the solid antioxidant, but the requirement on a dispersion system is extremely high due to the high melting point of the antioxidant, otherwise, the fluidity is influenced and even the oil phase is separated out due to the overlarge liquid drop. Meanwhile, the emulsification process is phase inversion emulsification, so that the requirements on various parameters and equipment in the emulsification process are high, and the defective rate is obviously increased when the dispersion system is poor.
Through retrieval, chinese patent document CN101805458 discloses a preparation method of an emulsion type composite antioxidant, namely, DLTDP: (wingstay.L: 1076) =4:2, wherein wingstay.l:1076= (0.5 to 1.5): (1.5-0.5) adding stearic acid 3-8% and C4-C18 straight chain or branched chain alcohol 0.5-1.5% or their mixture, based on the total weight of the raw material A as 100%, heating to react under the stirring of 300-400 r/min, adding KOH when the temperature reaches 70-90 deg.C, and controlling the pH value at 7-11; adding deionized water to make the solid content of the whole system be 53% -56%, firstly adding 30% of deionized water, regulating stirring speed to 180-250 rpm, adding the rest deionized water, naturally cooling to room temperature. The method provides a new idea for preparing the composite antioxidant, but the application of the antioxidant is limited due to single type, and the antioxidant is only applied to the post-processing process of PVC and cannot be applied to the polymerization process of PVC.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defects that the application effect of the traditional antioxidant is relatively poor and the stability of the traditional antioxidant needs to be further improved, and provides an efficient anti-freezing emulsion antioxidant terminator for PVC and a preparation method thereof. By adopting the technical scheme of the invention, the problems can be effectively solved, and the thermal stability and the aging whiteness index of the polymerized PVC powder are greatly improved; meanwhile, the product of the invention also has excellent frost resistance and emulsion stability, simple production process and low requirement on equipment capacity.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to an efficient anti-freezing emulsion antioxidant terminator for PVC, which comprises the following components in percentage by mass: 10-20% of hindered phenol antioxidant, 10-20% of phosphite antioxidant, 10-20% of sulfate antioxidant, 5-8% of amine antioxidant, 5-8% of piperidine free radical antioxidant, 5-8% of antifreeze agent, 1-3% of emulsifier, 2-3% of dispersant, 1-5% of zinc stabilizer and the balance of deionized water, wherein the emulsifier is the combination of emulsifier A and emulsifier B, and the dispersant is the combination of dispersant A and dispersant B.
Furthermore, the emulsifier A is isomeric tridecanol polyoxyethylene ether monophosphate E1310P, and the emulsifier B is fatty alcohol polyoxyethylene ether lacto-bailing; wherein, the ratio of the emulsifier A to the emulsifier B meets 1: (0.8-1.2).
Furthermore, the dispersing agent A is PVA-4788, the dispersing agent B is PVA-4040, and the mixture ratio of the dispersing agent A to the dispersing agent B meets (1.2-1.8): 1.
further, the hindered phenol antioxidant is one or more of antioxidants 1010, 1098, 1076 and the like.
Still further, the phosphite antioxidants are one or more combinations of 168, 618, TNP, and the like; the sulfate antioxidant is one or a combination of DLTP, DSTP and the like.
Further, the amine antioxidant is N-N diethylhydroxylamine; the piperidine free radical type antioxidant is 4-hydroxy-2, 6-tetramethyl piperidine-1-oxygen free radical.
Further, the antifreeze is ethylene glycol; the zinc stabilizer is fatty acid zinc.
The preparation method of the efficient anti-freezing emulsion antioxidant terminator for PVC comprises the following steps:
firstly, adding hindered phenol antioxidant, phosphorous acid antioxidant, sulfate antioxidant, piperidine free radical antioxidant and emulsifier A into a reaction kettle A, then heating, stirring, and preserving heat until the materials in the kettle are completely melted and then cooling;
step two, sequentially adding a dispersing agent A, an emulsifying agent B, a zinc stabilizing agent, deionized water and the like into a reaction kettle B, starting stirring, and continuously stirring for 25-30 min after heating;
thirdly, when the temperature of the materials in the reaction kettle A is reduced to 70-80 ℃, adding the materials in the reaction kettle B;
step four, adding a dispersant B into the mixed material treated in the step three, and preserving heat and stirring;
step five, adding the amine antioxidant into the mixed material treated in the step four, preserving heat and stirring;
and step six, adding an antifreeze into the mixed material treated in the step five, preserving heat, stirring, and then shearing for emulsification to obtain the antioxidant terminator.
Furthermore, in step three, the method for adding the materials in the reaction kettle B into the reaction kettle A is as follows:
s1, adding 20% of the total weight of the materials in the reaction kettle B at a constant speed, controlling the adding time to be 5-10min, and stirring for 10min;
s2, adding 20% of the total weight of the materials in the reaction kettle B at a constant speed, controlling the adding time to be 5-10min, and stirring for 10min;
s3, adding 40% of the total weight of the materials in the reaction kettle B at a constant speed, controlling the adding time to be 10-20min, and stirring for 15min;
s4, adding the residual materials in the reaction kettle B at one time, and stirring for 25-30 min;
wherein in the steps S1-S4, the feeding temperature is controlled to be 70-80 ℃.
Furthermore, in the first step, the temperature is raised to 140-150 ℃; in the second step, the temperature rise is 55-60 ℃; in the fourth step, the temperature is kept at 50-60 ℃, and the stirring time is 30-35 min; in the fifth step, the temperature is kept at 40-50 ℃, and the stirring time is 30-35 min; in the sixth step, the temperature is kept at 30-40 ℃, the stirring time is 30-35 min, and the shearing time is 25-30 min.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the efficient anti-freezing emulsion antioxidant terminator for PVC, the component composition and the proportion thereof are optimally designed, especially, the amine antioxidant and the piperidine free radical antioxidant are continuously introduced into the components of the traditional antioxidant, so that the efficient anti-freezing emulsion antioxidant terminator can play a synergistic effect with other components, the antioxidant and terminating performance of the product is further improved, and the thermal stability and the aging whiteness index of the polymerized PVC powder can be greatly improved after the efficient anti-freezing emulsion antioxidant terminator is used. Meanwhile, compared with the conventional antioxidant terminator, the product of the invention has excellent frost resistance and emulsion stability, can be stored at minus 35 ℃, and does not delaminate after being placed for more than one year.
(2) According to the efficient anti-freezing emulsion antioxidant terminator for PVC, the antifreeze agent is added into a system, particularly, the selection and the proportion of the antifreeze agent are optimized, and particularly, the antifreeze agent is ethylene glycol, so that the lowest storage temperature of the product can be improved on the basis of keeping the stability of the obtained product, and the use requirement of Xinjiang area at the air temperature in winter can be effectively met.
(3) According to the efficient anti-freezing emulsion antioxidant terminator for PVC, the composition of the emulsifier and the dispersant is optimized, particularly, the emulsifier adopts an emulsification composite system, and the dispersant adopts a dispersion composite system, so that the emulsification and dispersion effects of the product can be ensured during preparation, and the emulsion stability of the finally obtained antioxidant product is improved. Meanwhile, the invention optimizes the type selection and the proportion of the emulsifier and the dispersant, thereby further ensuring the emulsification and dispersion effects of the system, further improving the stability of the product, effectively improving the aging resistance of the PVC resin when used in the PVC resin, and prolonging the service life of the PVC resin.
(4) The preparation method of the efficient anti-freezing emulsion antioxidant terminator for PVC provided by the invention optimizes the types and proportions of the components and specific process parameters, particularly adopts an A/B reaction kettle production process during preparation, heats and melts the oil phase, pre-heats the oil phase before adding the water phase, strictly controls the emulsification temperature to be 70-80 ℃, and in addition, the preparation method adopts a process of adding the water phase in stages for multiple times during emulsification, so that the phenomena of viscosity abnormal increase and the like caused by failure of a phase-change emulsification process can be avoided, the emulsification effect is good, and the stability of an emulsified product is excellent.
(5) According to the preparation method of the efficient anti-freezing emulsion antioxidant terminator for PVC, disclosed by the invention, the mixing temperature and the stirring time of the raw materials are strictly controlled, so that the feasibility of the process is effectively ensured, the emulsification failure is avoided, the finally obtained product has excellent termination performance, the whiteness and the heat stability time of PVC resin are effectively improved, and the emulsion stability of the obtained product is also greatly improved.
Drawings
FIG. 1 shows the stability and usage of the antioxidant terminators obtained in each example of the present invention and comparative example;
Detailed Description
The invention relates to an efficient anti-freezing emulsion antioxidant terminator for PVC, which comprises the following components in percentage by mass: 10-20% of hindered phenol antioxidant, 10-20% of phosphite antioxidant, 10-20% of sulfate antioxidant, 5-8% of amine antioxidant, 5-8% of piperidine free radical antioxidant, 5-8% of antifreeze agent, 1-3% of emulsifier, 2-3% of dispersant, 1-5% of zinc stabilizer and the balance of deionized water.
Specifically, the hindered phenol antioxidant is one or more of antioxidants 1010, 1098, 1076 and the like. The phosphite antioxidant is one or more of 168, 618, TNP and the like; the sulfate antioxidant is one or a combination of DLTP, DSTP and the like. The amine antioxidant is N-N diethylhydroxylamine; the piperidine free radical type antioxidant is 4-hydroxy-2, 6-tetramethyl piperidine-1-oxygen free radical. The antifreeze agent is ethylene glycol. The zinc stabilizer is fatty acid zinc.
Firstly, on the basis of traditionally using hindered phenol antioxidants, phosphite antioxidants, sulfate antioxidants and the like, the product of the invention is added with two antioxidants of N-N diethylhydroxylamine and 4-hydroxy-2, 6-tetramethylpiperidine-1-oxyl, on one hand, the two antioxidants can be compounded with the fatty acid zinc stabilizer to effectively improve the oxidation resistance and termination performance of the product; on the other hand, in the addition system of the two antioxidants and the fatty acid zinc, the antioxidant can play a synergistic role with the traditional hindered phenol antioxidant, so that compared with the traditional antioxidant, the thermal stability and the aging whiteness index of the polymerized PVC powder can be greatly improved, and the requirements of customers and the high-quality production of PVC resin are effectively met.
The invention further discloses an antifreeze agent which is added and the type of the antifreeze agent is optimized by combining the system of the invention, and the applicant finds that not all components of the antifreeze agent can play a role under the formula system of the invention, and the invention can lead the lowest storage temperature of the product to reach 35 ℃ below zero on the premise of keeping the stability of the product by introducing the nonpolar alcohol antifreeze agent glycol, thereby obviously improving the antifreeze property of the antioxidant, effectively meeting the requirement of using the antioxidant in Xinjiang areas when the temperature is lower in winter, and the traditional emulsion type antioxidant in the market at present can not be transported and stored at the temperature.
Finally, the emulsifying system and the dispersing system both adopt a composite system, specifically, the emulsifier is the combination of an emulsifier A and an emulsifier B, the dispersing agent is the combination of a dispersing agent A and a dispersing agent B, and the ratio of the emulsifier A to the emulsifier B is controlled to meet 1: (0.8-1.2), and the proportion of the dispersant A and the dispersant B meets (1.2-1.8): 1, can effectively improve various properties of the antioxidant finally prepared, especially the stability of emulsion. Furthermore, the emulsifier A is isomeric tridecanol polyoxyethylene ether monophosphate E1310P, and the emulsifier B is fatty alcohol polyoxyethylene ether lacto-bailing. The dispersing agent A is PVA-4788, and the dispersing agent B is PVA-4040. The action mechanism is as follows: because the phase change process exists in the preparation process of the product, the formula process of adding the water-in-oil emulsifier E1310P into the oil phase and adding the oil-in-water emulsifier emulsion lark into the water phase is selected, and meanwhile, the dispersing agent is also selected to be compounded by using two polyvinyl alcohol dispersing agents PVA-4788 and PVA-4040 with high and low alcoholysis degrees, so that the dispersion and glue retention capacity of the emulsion can be effectively improved. The composite emulsifier system and the composite dispersant system of the emulsification system can achieve excellent emulsification effect by matching with the emulsification preparation process, and finally the obtained product can be placed for more than 12 months without layering.
The invention relates to a preparation method of an efficient anti-freezing emulsion antioxidant terminator for PVC, which comprises the following specific operation steps:
firstly, adding hindered phenol antioxidant, phosphorous acid antioxidant, sulfate antioxidant, piperidine free radical antioxidant and emulsifier A into a reaction kettle A, then heating to 140-150 ℃, starting stirring, keeping the temperature for 60min until the materials in the kettle are completely melted, and then cooling;
step two, sequentially adding a dispersant A, an emulsifier B, a zinc stabilizer, deionized water and the like into a reaction kettle B, starting stirring, heating to 60 ℃, and then continuously stirring for 25-30 min;
step three, when the temperature of the materials in the reaction kettle A is reduced to 70-80 ℃, adding the materials in the reaction kettle B, wherein the temperature is kept at 70-80 ℃ in the whole feeding process, and the concrete operation is as follows:
s1, adding 20% of the total weight of the materials in the reaction kettle B at a constant speed, controlling the adding time to be 5-10min, and stirring for 10min;
s2, adding 20% of the total weight of the materials in the reaction kettle B at a constant speed, controlling the adding time to be 5-10min, and stirring for 10min;
s3, adding 40% of the total weight of the materials in the reaction kettle B at a constant speed, controlling the adding time to be 10-20min, and stirring for 15min;
s4, adding the residual materials in the reaction kettle B at one time, and stirring for 25-30 min;
step four, adding a dispersant B into the mixed material treated in the step three, keeping the temperature at 50-60 ℃, and stirring for 30-35 min;
step five, adding the amine antioxidant into the mixed material processed in the step four, keeping the temperature at 40-50 ℃, and stirring for 30-35 min;
step six, adding an antifreeze into the mixed material treated in the step five, keeping the temperature at 30-40 ℃, and stirring for 30-35 min; and then shearing and emulsifying for 25-30 min to obtain the antioxidant.
It should be noted that, because the formula of the invention has more raw materials and the conventional preparation method can not complete effective preparation, the invention adopts the A/B kettle production process, firstly heats up and melts the oil phase, then preheats the water phase before adding the water phase, strictly controls the emulsification temperature to be 70-80 ℃, adopts the process of adding the water phase in stages for multiple times during emulsification, can avoid the phenomena of viscosity abnormal increase and the like caused by failure of the phase-change emulsification process, and has good emulsification effect and excellent stability of the emulsified product. The antioxidant prepared by adopting the components and the process is an efficient anti-freezing emulsion antioxidant terminator, has excellent low-temperature performance, the minimum storage temperature can reach minus 35 ℃, a product can be placed for more than one year without layering, and the addition amount of the antioxidant is optimized to be as low as about 150ppm, is only one third of the common addition amount in the industry, can effectively reduce the addition amount compared with the existing common antioxidant, and has higher economic benefit.
The invention is further described with reference to specific examples.
Example 1
Firstly, 15 percent of hindered phenol antioxidant (1010) is added into a reaction kettle A, 15 percent of phosphorous antioxidant (168) is added, 15 percent of sulfate antioxidant (DLTP) is added, 6.5 percent of 4-hydroxy-2, 6-tetramethyl piperidine-1-oxygen free radical and 1 percent of emulsifier E1310P are added, the temperature is raised to 140-150 ℃, the stirring is started, the temperature is maintained for 60min to ensure that the materials in the kettle are completely melted, and then the temperature is reduced.
And (3) sequentially adding 1.5% of dispersing agent PVA-4788, 1% of emulsifier lacto, 2.5% of fatty acid zinc, deionized water and the like into the reaction kettle B, starting stirring, heating to 60 ℃, and stirring for 30min.
When the temperature of the materials in the reaction kettle A is reduced to 75 ℃, the materials in the reaction kettle B are added into the reaction kettle A, 20 percent of the total weight of the materials in the reaction kettle B is added at a constant speed during feeding, and the feeding time is controlled for 6min; then stirring for 10min, then adding 20% of the total weight of the materials in the reaction kettle B at a constant speed, controlling the feeding time for 8min, and stirring for 10min; then adding 40 percent of the total weight of the materials in the reaction kettle B, and controlling the feeding time for 15min; then stirring for 15min; and finally, adding the rest 20 percent of the materials in the reaction kettle B at one time, stirring for 30min after the addition is finished, and keeping the temperature at 75 ℃ in the whole feeding process.
Then 1% PVA-4040 was added, the temperature was maintained at 55 ℃ and stirring was carried out for 30min.
Then 6.5% N-N diethylhydroxylamine was added, the temperature was kept at 45 ℃ and the mixture was stirred for 30min.
Then 6.5 percent of glycol as an antifreeze is added, the temperature is kept at 35 ℃, and the mixture is stirred for 30min.
Then starting shearing to emulsify, and finishing the preparation after shearing for 30min.
Example 2
The difference between this example and example 1 is that one or more combinations of 1010, 1098 and 1076 (excluding the option of selecting 1010 alone) are used as hindered phenolic antioxidants, the rest components are the same as those in example 1, and the compounding ratio is slightly adjusted on the basis of example 1 (but the range requirement of the invention is met, the ratio of emulsifier a to emulsifier B is controlled to be 1.
Example 3
The difference between this example and example 1 is that the phosphite antioxidant is one or a combination of 168, 618 and TNP (excluding the scheme of selecting 168 alone), the rest of the components are the same as example 1, the ratio thereof is slightly adjusted on the basis of example 1 (but the scope requirement of the present invention is satisfied, and the ratio of the emulsifier a to the emulsifier B is controlled to be 1.
Example 4
The difference between the present example and example 1 is that the sulfate antioxidant is DSTP and/or a mixture of DLTP and DSTP, the rest components are the same as example 1, the mixture ratio is slightly adjusted on the basis of example 1 (but the range requirement of the present invention is satisfied, the ratio of the emulsifier a to the emulsifier B is controlled to be 1.0, the ratio of the dispersant a to the dispersant B is controlled to be 1.4.
Comparative example 1
The formula of the antioxidant of the comparative example is as follows: 1010 15%, DLTP 15%,168 15%, polyvinyl alcohol 4788% and the balance of deionized water.
The preparation method of the antioxidant comprises the following steps: adding 1010 and DLTP into a reaction kettle, heating to 100 ℃ for melting, preserving heat for 30min, then cooling to 80 ℃, adding polyvinyl alcohol and deionized water, keeping the temperature at 70-80 ℃, stirring for 30min, shearing for 30min, and cooling to normal temperature to complete the preparation.
Comparative example 2
The components and the proportion of the antioxidant of the comparative example are basically the same as those of the example 1, and the main difference is that the components do not contain fatty acid zinc, and the preparation process is basically the same as that of the example 1.
Comparative example 3
The components and the proportion of the antioxidant of the comparative example are basically the same as those of the example 1, and the main difference is that the components do not contain 4-hydroxy-2, 6-tetramethyl piperidine-1-oxygen free radical, and the preparation process is basically the same as that of the example 1.
Comparative example 4
The antioxidant of this comparative example, whose composition and formulation are substantially the same as those of example 1, is mainly different in that its composition does not contain N-N diethylhydroxylamine, and its preparation process is substantially the same as that of example 1.
Comparative example 5
The components and the proportion of the antioxidant of the comparative example are basically the same as those of the example 1, and the main difference is that the components do not contain the emulsifier lacto-lark, and the preparation process is basically the same as that of the example 1.
Comparative example 6
The components and the proportion of the antioxidant of the comparative example are basically the same as those of the example 1, and the main difference is that the components do not contain the emulsifier E1310P, and the preparation process is basically the same as that of the example 1.
Comparative example 7
The components and the proportion of the antioxidant of the comparative example are basically the same as those of the example 1, and the main difference is that the components do not contain VA-4040, and the preparation process is basically the same as that of the example 1.
Comparative example 8
The components and the proportion of the antioxidant of the comparative example are basically the same as those of the example 1, and the main difference is that the components do not contain VA-4788, and the preparation process is basically the same as that of the example 1.
Comparative example 9
The components, the proportion and the preparation process of the antioxidant in the comparative example are basically the same as those in example 1, and the main difference is that the addition modes of the emulsifier A and the emulsifier B are exchanged.
Comparative example 10
The components, the proportion and the preparation process of the antioxidant of the comparative example are basically the same as those of example 1, and the main difference is that the addition modes of the dispersant A and the dispersant B are exchanged.
Comparative example 11
The components, the proportion and the preparation process of the antioxidant of the comparative example are basically the same as those of the example 1, and the main difference is that methanol is used as the antifreeze agent to replace ethylene glycol.
Comparative example 12
The components, the proportion and the preparation process of the antioxidant in the comparative example are basically the same as those of example 1, and the main difference is that when materials in a reaction kettle B are added into a reaction kettle A, the materials in the reaction kettle B are not selected to be added in batches, but all the materials in the reaction kettle B are added at one time, the materials are stirred for 30min after the addition, and the rest operations are consistent with those of example 1.
Comparative example 13
The components, the proportion and the preparation process of the antioxidant in the comparative example are basically the same as those in example 1, and the main difference is that the material in the reaction kettle B is added into the reaction kettle A in two batches, specifically, the material is firstly added into the reaction kettle B at a constant speed, the total weight of the material in the reaction kettle B is 50 percent, and the feeding time is controlled for 8min; then stirring for 10min, then adding 50% of the total weight of the materials in the B kettle at a constant speed, controlling the feeding time for 6min, stirring for 30min after the feeding, keeping the temperature at 75 ℃ in the whole feeding process, and keeping the rest operations consistent with those in example 1.
Comparative example 14
The components, the proportion and the preparation process of the antioxidant in the comparative example are basically the same as those in example 1, and the main difference is that when the material in the reaction kettle B is added into the reaction kettle A, the feeding operation is started when the material in the reaction kettle A is cooled to 85 ℃, the temperature in the whole feeding process is maintained at about 85 ℃ which is higher than the emulsification temperature of the invention, and the rest operations are consistent with those in example 1.
Comparative example 15
The components, the proportion and the preparation process of the antioxidant in the comparative example are basically the same as those in example 1, and the main difference is that when the material in the reaction kettle B is added into the reaction kettle A, the feeding operation is started when the material in the reaction kettle A is cooled to 65 ℃, the temperature in the whole feeding process is maintained at about 65 ℃ and is higher than the emulsification temperature of the invention, and the rest operations are consistent with those in example 1.
The stability and the use condition of the antioxidant terminators in the above examples and comparative examples were examined, and the results are shown in FIG. 1. It should be noted that, the examples 2-4 all include a plurality of specific embodiments, including the selection of specific types of antioxidants and the specific determination of the content values of the components, and the test results are basically the same as those of example 1 (with slight variations), which is not shown in fig. 1, due to space limitations). As can be seen by combining the data in the figure 1, the antioxidant terminator product produced by adopting the raw materials, the proportion and the process method has the advantages of good emulsification effect, smooth emulsification process, good stability, no layering after being placed for more than 12 months, good low-temperature storage performance and high freezing resistance.
Claims (8)
1. An efficient anti-freezing emulsion antioxidant terminator for PVC, which is characterized in that: the coating comprises the following components in percentage by mass: 10-20% of hindered phenol antioxidant, 10-20% of phosphite antioxidant, 10-20% of sulfate antioxidant, 5-8% of amine antioxidant, 5-8% of piperidine free radical antioxidant, 5-8% of antifreeze agent, 1-3% of emulsifier, 2-3% of dispersant, 1-5% of zinc stabilizer and the balance of deionized water, wherein the emulsifier is the combination of emulsifier A and emulsifier B, and the dispersant is the combination of dispersant A and dispersant B; the emulsifier A is isomeric tridecanol polyoxyethylene ether monophosphate E1310P, and the emulsifier B is fatty alcohol polyoxyethylene ether lacto-bailing; wherein the ratio of the emulsifier A to the emulsifier B meets 1: (0.8-1.2); the dispersing agent A is PVA-4788, the dispersing agent B is PVA-4040, and the ratio of the dispersing agent A to the dispersing agent B satisfies (1.2-1.8): 1; the antifreeze agent is ethylene glycol;
the preparation method of the emulsion antioxidant terminator comprises the following steps:
firstly, adding hindered phenol antioxidant, phosphorous acid antioxidant, sulfate antioxidant, piperidine free radical antioxidant and emulsifier A into a reaction kettle A, then heating, stirring, and preserving heat until the materials in the kettle are completely molten, and then cooling;
step two, sequentially adding a dispersing agent A, an emulsifying agent B, a zinc stabilizing agent, deionized water and the like into a reaction kettle B, starting stirring, and continuously stirring for 25-30 min after heating;
thirdly, when the temperature of the materials in the reaction kettle A is reduced to 70-80 ℃, adding the materials in the reaction kettle B;
step four, adding a dispersant B into the mixed material treated in the step three, and preserving heat and stirring;
step five, adding the amine antioxidant into the mixed material treated in the step four, preserving heat and stirring;
and step six, adding an antifreeze into the mixed material treated in the step five, preserving heat, stirring, and then shearing for emulsification to obtain the antioxidant terminator.
2. The efficient anti-freezing emulsion antioxidant terminator for PVC according to claim 1, which is characterized in that: the hindered phenol antioxidant is one or a combination of antioxidants 1010, 1098 and 1076.
3. The high-efficiency anti-freezing emulsion antioxidant terminator for PVC according to claim 1, which is characterized in that: the phosphite antioxidant is one or a combination of 168, 618 and TNP; the sulfate antioxidant is one or a combination of DLTP and DSTP.
4. The high-efficiency anti-freezing emulsion antioxidant terminator for PVC according to claim 1, which is characterized in that: the amine antioxidant is N-N diethylhydroxylamine; the piperidine free radical type antioxidant is 4-hydroxy-2, 6-tetramethyl piperidine-1-oxygen free radical.
5. The high-efficiency anti-freezing emulsion antioxidant terminator for PVC according to claim 1, which is characterized in that: the zinc stabilizer is fatty acid zinc.
6. A method for preparing the high-efficiency anti-freezing emulsion antioxidant terminator for PVC according to any one of claims 1 to 5, which comprises the following steps:
firstly, adding hindered phenol antioxidant, phosphorous acid antioxidant, sulfate antioxidant, piperidine free radical antioxidant and emulsifier A into a reaction kettle A, then heating, stirring, and preserving heat until the materials in the kettle are completely molten, and then cooling;
step two, sequentially adding a dispersant A, an emulsifier B, a zinc stabilizer, deionized water and the like into a reaction kettle B, starting stirring, heating and then continuously stirring for 25-30 min;
thirdly, when the temperature of the materials in the reaction kettle A is reduced to 70-80 ℃, adding the materials in the reaction kettle B;
step four, adding a dispersing agent B into the mixed material treated in the step three, and carrying out heat preservation and stirring;
step five, adding the amine antioxidant into the mixed material treated in the step four, preserving heat and stirring;
and step six, adding an antifreeze into the mixed material treated in the step five, preserving heat, stirring, and then shearing for emulsification to obtain the antioxidant terminator.
7. The preparation method of the high-efficiency anti-freezing emulsion antioxidant terminator for PVC according to claim 6, which is characterized in that: in the third step, the method for adding the materials in the reaction kettle B into the reaction kettle A is as follows:
s1, adding 20% of the total weight of the materials in the reaction kettle B at a constant speed, controlling the adding time to be 5-10min, and stirring for 10min;
s2, adding 20% of the total weight of the materials in the reaction kettle B at a constant speed, controlling the adding time to be 5-10min, and stirring for 10min;
s3, adding the materials into the reaction kettle B at a constant speed, wherein the total weight of the materials is 40%, the adding time is controlled to be 10-20min, and stirring is carried out for 15min;
s4, adding the residual materials in the reaction kettle B at one time, and stirring for 25-30 min;
wherein in the steps S1-S4, the feeding temperature is controlled to be 70-80 ℃.
8. The preparation method of the high-efficiency anti-freezing emulsion antioxidant terminator for PVC according to any one of claims 6 or 7, which is characterized in that: in the first step, the temperature rise is 140-150 ℃; in the second step, the temperature rise is 55-60 ℃; in the fourth step, the temperature is kept at 50-60 ℃, and the stirring time is 30-35 min; in the fifth step, the temperature is kept at 40-50 ℃, and the stirring time is 30-35 min; in the sixth step, the heat preservation temperature is 30-40 ℃, the stirring time is 30-35 min, and the shearing time is 25-30 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111393431.5A CN114044842B (en) | 2021-11-23 | 2021-11-23 | Efficient anti-freezing emulsion antioxidant terminator for PVC (polyvinyl chloride) and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111393431.5A CN114044842B (en) | 2021-11-23 | 2021-11-23 | Efficient anti-freezing emulsion antioxidant terminator for PVC (polyvinyl chloride) and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114044842A CN114044842A (en) | 2022-02-15 |
| CN114044842B true CN114044842B (en) | 2023-04-07 |
Family
ID=80210521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111393431.5A Active CN114044842B (en) | 2021-11-23 | 2021-11-23 | Efficient anti-freezing emulsion antioxidant terminator for PVC (polyvinyl chloride) and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114044842B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478841B (en) * | 2021-12-29 | 2023-07-14 | 广东希必达新材料科技有限公司 | Preparation method and application of emulsion type suspension termination liquid |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6723255B2 (en) * | 2000-03-07 | 2004-04-20 | Atofina Chemicals, Inc. | Compositions for shortstopping free radical emulsion polymerizations and stabilizing latices made therefrom |
| CN102083900A (en) * | 2008-07-11 | 2011-06-01 | 巴斯夫欧洲公司 | Storage-stable aqueous emulsions and liquid blends with low viscosity as stabilizers |
| CN102181072B (en) * | 2011-02-24 | 2013-01-16 | 常州大学 | Preparation method of emulsion antioxidant |
| CN102952219B (en) * | 2011-08-30 | 2015-05-20 | 中国石油化工股份有限公司 | Vinyl chloride monomer polymerization reaction system reaction termination method |
| CN108059779B (en) * | 2017-12-25 | 2020-12-01 | 乌鲁木齐市华泰隆化学助剂有限公司 | Environment-friendly antioxidant terminator for PVC (polyvinyl chloride) and preparation method thereof |
| CN110760021B (en) * | 2018-07-25 | 2021-10-22 | 中国石油化工股份有限公司 | Vinyl chloride polymerization terminator with good low-temperature fluidity, and preparation method and application thereof |
| CN110760019B (en) * | 2018-07-25 | 2022-01-07 | 中国石油化工股份有限公司 | Vinyl chloride polymerization terminator, preparation method and application thereof |
| CN109293806A (en) * | 2018-09-12 | 2019-02-01 | 蓝凤祥 | A kind of nontoxic high fever ageing whiteness polyvinyl chloride of anti-freeze type terminates agent emulsion and preparation method thereof |
-
2021
- 2021-11-23 CN CN202111393431.5A patent/CN114044842B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114044842A (en) | 2022-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114044842B (en) | Efficient anti-freezing emulsion antioxidant terminator for PVC (polyvinyl chloride) and preparation method thereof | |
| CN102344581B (en) | Preparation method of emulsion type low-particle-diameter high-efficiency antioxidant | |
| CN105524368A (en) | Special polyvinyl chloride sheath material for robot wires and cables and preparation method thereof | |
| CN110527020B (en) | Styrene butadiene rubber and preparation method thereof | |
| CN108003389A (en) | A kind of calcium-zinc composite stabilizing agent | |
| CN107805320B (en) | A method of preparing the aqueous antioxygen agent emulsion of high-melting-point at room temperature | |
| CN112375302A (en) | Modified insulating rubber for alternating-current cable accessories and preparation method thereof | |
| CN111909528A (en) | Antioxidant emulsion capable of being emulsified and stabilized at normal temperature and preparation method thereof | |
| CN106810889A (en) | A kind of asphalt cold repairing and preparation method thereof | |
| CN108239301A (en) | Emulsion composite antioxidant and preparation method thereof | |
| CN109553989A (en) | A kind of SBS modified pitch auxiliary agent and SBS modified pitch | |
| CN109037691A (en) | A kind of battery novel anode material additive | |
| CN108059779B (en) | Environment-friendly antioxidant terminator for PVC (polyvinyl chloride) and preparation method thereof | |
| CN115772080B (en) | Preparation method and application of acrylic acid modified sorbitol water tree inhibitor | |
| CN102702995B (en) | Preparation method of aqueous emulsion type neoprene antioxidant system product | |
| CN110760021B (en) | Vinyl chloride polymerization terminator with good low-temperature fluidity, and preparation method and application thereof | |
| CN111040188B (en) | Organic silicon emulsifier and preparation method thereof | |
| CN112708237A (en) | Antioxidant emulsion and preparation method thereof | |
| CN110327799B (en) | Water-based erucamide emulsion and preparation method thereof | |
| CN108395610A (en) | A kind of carbon nanotube shield semiconductors material and preparation method thereof | |
| CN111925604B (en) | Cable material and preparation method thereof | |
| CN113321890A (en) | Shale oil-reservoir drilling cylinder sleeve sealing ring and preparation method thereof | |
| CN114478841B (en) | Preparation method and application of emulsion type suspension termination liquid | |
| CN104672896B (en) | A kind of high temperature resistant type case for circuit breaker | |
| CN113278224A (en) | Thermal-aging-resistant PP material, preparation method thereof and plastic box |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |