Solid additive for PVC (polyvinyl chloride) synthesis as well as preparation method and application of solid additive

Abstract

The invention discloses a solid additive for PVC (polyvinyl chloride) synthesis as well as a preparation method and application thereof, and belongs to the fields of organic chemistry and fine chemical engineering. The solid additive for PVC synthesis is micron-scale and / or nano-scale powder particles, and comprises: a) an effective component comprising one or more of a hindered phenol antioxidant, an auxiliary antioxidant, a heat stabilizer, a light stabilizer, a plasticizer or a terminating agent; and b) an emulsifier adhered to the surface of the active ingredient. The preparation method is simple, the obtained solid additive powder for PVC synthesis is micron-scale and / or nano-scale, the particle size state is stable, and the solid additive powder can be applied to preparation of PVC, so that a terminator for PVC is continuously maintained and transported in a solid powder form, and the weather resistance and the stability of the terminator are greatly improved.

Description

Technical Field

[0001] The present invention relates to the fields of organic chemistry and fine chemical industry, and specifically relates to a solid auxiliary agent for PVC synthesis and a preparation method and application thereof. Background Art

[0002] Commonly used additives in the preparation process of PVC include antioxidant terminators, plasticizers, stabilizers, lubricants, fillers and flame retardants. These additives play a vital role in the production of PVC products and can significantly improve the performance and processing characteristics of PVC. Antioxidant terminators for PVC are also called environmentally friendly terminators, which are used to control the rate of chemical reactions or terminate reactions. Depending on their functions, they may contain one or more of antioxidants, terminators, heat stabilizers, light stabilizers, plasticizers and other ingredients. Existing environmentally friendly terminators are generally made into liquid preparations such as solutions, suspensions or emulsions, because the liquid state makes it easier to add and disperse the effective ingredients of the terminator into the PVC polymerization system. However, these preparations contain a large amount of water, which leads to some limitations on the weather resistance and shelf life of the terminator under certain special working conditions (such as high temperature demulsification, low temperature phase change, and long-term storage stratification), which will incur additional costs in transportation and storage. In addition, the material compatibility of the suspension or emulsion will be further limited, resulting in taboos in the combination of materials in the formula.

[0003] The applicant tried to add antifreeze agents to the antioxidant terminator to increase the antifreeze performance, such as: the Chinese patent application number is 202111393431.5, and the patent application document with the application publication date of February 15, 2022 discloses a high-efficiency antifreeze emulsion antioxidant terminator for PVC and its preparation method. The antioxidants in this patent are composed of the following components by mass percentage: 10% to 20% hindered phenol antioxidants, 10% to 20% phosphite antioxidants, 10% to 20% thioester antioxidants, 5% to 8% amine antioxidants, 5% to 8% piperidine free radical antioxidants, 5% to 8% antifreeze agents, 1% to 3% emulsifiers, 2% to 3% dispersants, 1% to 5% zinc stabilizers, and the balance is deionized water. Although the product has good low-temperature storage performance and high antifreeze performance, it is not stable enough in hot summer environments.

[0004] Therefore, in order to improve the storage stability in extremely low temperature or high heat environment, it is urgent to develop a solid additive for PVC synthesis and its preparation method and application. Summary of the invention

[0005] 1. Problem to be solved

[0006] One of the purposes of the present invention is to provide a solid additive for PVC synthesis, aiming to enable the solid additive for PVC synthesis to be continuously maintained and transported in the form of solid powder, reduce the possibility of powder agglomeration, and reduce the impact of taboo compatibility.

[0007] Another object of the present invention is to provide a method for preparing a solid additive for PVC synthesis, so that the obtained solid additive powder for PVC synthesis is micrometer-level and / or nanometer-level, and the particle size is stable. Further, the application of the solid additive for PVC synthesis is provided, which can be compounded with a solvent and added to the PVC preparation system.

[0008] 2. Technical solution

[0009] In order to solve the above problems, the technical solution adopted by the present invention is as follows:

[0010] According to the purpose of the present invention, the first aspect of the present invention provides a solid additive for PVC synthesis, which is a micron-scale and / or nano-scale powder particle, comprising:

[0011] a) Active ingredients, including one or more of hindered phenol antioxidants, auxiliary antioxidants, heat stabilizers, light stabilizers, plasticizers or terminators;

[0012] b) Emulsifier, adheres to the surface of the active ingredient.

[0013] When the above technical solution is adopted, the active ingredient is controlled to be in the form of solid powder and must be in the form of micron-sized and / or nano-sized particles. The surface of the active ingredient is connected with an emulsifier, which reduces the particle size of the active ingredient while also reducing the risk of secondary agglomeration, thereby improving the storage stability of the antioxidant terminator powder.

[0014] As a possible implementation scheme, the hindered phenol antioxidant is β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester (1076), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (245), 3,5-di-tert-butyl-4-hydroxyphenyl propionate octyl ester (1135), tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester (1 010), 2,6-di-tert-butyl-p-cresol (264), 2,2′-methylenebis(4-methyl-6-tert-butylphenol) (2246), 4,4′-thiobis(6-tert-butyl-3-methylphenol) (300), 4,6-bis(octylthiomethyl)-o-cresol (1520), 2,2′-mercaptoethylene glycol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (1035) or more thereof.

[0015] As a possible implementation scheme, the auxiliary antioxidant is one or more of dilauryl thiodipropionate (DLTP), distearyl thiodipropionate (DSTP), and pentaerythritol tetrakis (3-lauryl thiopropionate) (412S).

[0016] As a possible implementation scheme, the heat stabilizer is one or more of sodium perchlorate, mono- / di-pentaerythritol, hydrotalcite, and epoxidized soybean oil.

[0017] As a possible implementation scheme, the light stabilizer includes one or more of 2-hydroxy-4-octyloxybenzophenone (UV-531), 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (UV-326), and hindered amine light stabilizer (GW-540).

[0018] As a possible implementation scheme, the plasticizer includes one or more of di(2-ethylhexyl) phthalate (DOP), diethylhexyl phthalate (DEHP), triglycerides, fatty acid methyl esters, tributyl citrate, and cyclohexyl hexanoate.

[0019] As a possible implementation scheme, the terminator includes one or more of diethylhydroxylamine and ATSC.

[0020] As a possible implementation scheme, the emulsifier is one or more of polyvinyl alcohol, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, polyoxyethylene sorbitan monooleate, sorbitan trioleate, polyoxyethylene lauryl ether, octylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether.

[0021] As a possible implementation scheme, the solid additive for PVC synthesis also includes: c) a pH regulator, which adheres to the surface of the emulsifier to enable the emulsifier to play a better role.

[0022] As a possible implementation scheme, the pH adjuster includes one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sulfuric acid, hydrochloric acid, phosphoric acid, and stearic acid.

[0023] As a possible implementation scheme, when the active ingredient contains one or more of liquid (diethylhydroxylamine terminator, plasticizer, epoxy soybean oil) or low melting point substance (DLTP auxiliary antioxidant), the solid additive for PVC synthesis also includes: d) carrier material, the active ingredient is loaded in the carrier material, and the carrier is not used unless necessary. In the case of adopting the above technical scheme, since diethylhydroxylamine is volatile and will escape when processed into powder, plasticizer and epoxy soybean oil liquid are easy to agglomerate, and DLTP has a low melting point, even after forming micron-level and / or nano-level powder, it will melt and agglomerate during storage or transportation under hot summer conditions, making it difficult to use the active ingredient later, increasing storage or transportation costs, and loading the above active ingredient on a carrier material is conducive to improving stability.

[0024] As a possible implementation scheme, the carrier material is one or more of nano-silicon dioxide, montmorillonite, and zeolite.

[0025] As a possible implementation scheme, the solid additive for PVC synthesis also includes: e) an anti-caking agent, and / or, f) a rheological additive, which has a dispersing effect between the active ingredients and / or an adhesion effect on the surface of the active ingredients, reduces the particle size of the active ingredients, prevents the secondary agglomeration of the active ingredients, and increases fluidity.

[0026] As a possible implementation scheme, the anti-caking agent includes one or more of potassium ferrocyanide, sodium aluminosilicate, tricalcium phosphate, microcrystalline cellulose, calcium stearate, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and hypromellose.

[0027] As a possible implementation scheme, the rheological additive includes one or more of fumed silica, bentonite, polyamide wax, and hydroxypropyl guar gum.

[0028] As a possible implementation scheme, the preferred composition and mass fraction of the solid additive for PVC synthesis include:

[0029]

[0030] The second aspect of the present invention provides a method for preparing a solid additive for PVC synthesis, comprising the steps of:

[0031] S1, dispersion step: dispersing and / or dissolving the active ingredient, emulsifier, and pH adjuster in a solvent, and controlling the particle size of the active ingredient to be less than 100 μm by emulsification or sand milling, preferably the particle size of the active ingredient is controlled to be less than 10 μm, to obtain a dispersion;

[0032] S2, drying process: if the dispersion does not contain an antioxidant and the active ingredient is insoluble in water, the dispersion in step S1 is vacuum filtered to obtain a filtrate, and the filtrate is vacuum dried to obtain a solid additive for PVC synthesis;

[0033] If the active ingredient contains an antioxidant or is soluble in water, spray drying is performed to obtain a solid additive for PVC synthesis. This is because antioxidants or components that are easily soluble in water tend to agglomerate during vacuum drying;

[0034] Among them, the anti-caking agent and the rheological additive can be added during the dispersion process of step S1 or after the drying process of step S2 is completed.

[0035] In the case of adopting the above technical solution, by dispersing the emulsifier to the surface of the effective ingredient and reducing the particle size of the effective ingredient, the pH regulator is used to improve the effect of the emulsifier, so that the particle size of the effective ingredient is reduced to within 100 μm, preferably the particle size of the effective ingredient is controlled to be less than 10 μm, when the particle size of the effective ingredient in the dispersion is greater than 30 μm, the possibility of agglomeration in the subsequent preparation of the powder will be significantly increased; and then the solid additive for PVC synthesis is obtained by drying. It should be noted that the drying step is particularly critical. The drying method of the effective ingredient is different depending on whether it contains antioxidants or the effective ingredient is soluble in water. When there is no antioxidant and the effective ingredient is insoluble in water, vacuum drying can be used. Otherwise, spray drying is preferred to reduce the possibility of agglomeration of the active ingredient particles. In order to further improve the fluidity of the powder and strengthen the avoidance of secondary agglomeration, an anti-caking agent and / or a rheological additive are present on the surface of the effective ingredient and / or between the effective ingredients.

[0036] As a possible implementation scheme, in step S1, the solvent is an easily separable solvent, preferably one or more of water, ethanol, and methanol.

[0037] As a possible implementation scheme, in step S1, the active ingredients include one or more of a hindered phenol antioxidant, an auxiliary antioxidant, a heat stabilizer, a light stabilizer, a plasticizer or a terminator; the hindered phenol antioxidant is β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (1076), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (245), 3,5-di-tert-butyl-4-hydroxyphenyl propionate Octyl ester (1135), pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (1010), 2,6-di-tert-butyl-p-cresol (264), 2,2′-methylenebis(4-methyl-6-tert-butylphenol) (2246), 4,4′-thiobis(6-tert-butyl-3-methylphenol) (300), 4,6-bis(octylthiomethyl) o-cresol (1520), 2,2′-mercaptoethylene glycol bis[3-(3,5-di-tert-butyl-p-cresol)] The auxiliary antioxidant is one or more of dilauryl thiodipropionate (DLTP), distearyl thiodipropionate (DSTP), pentaerythritol tetrakis (3-lauryl thiopropionate) (412S); the heat stabilizer is one or more of sodium perchlorate, mono / dipentaerythritol, hydrotalcite, and epoxidized soybean oil; the light stabilizer is 2-hydroxy-4-octyloxybenzophenone (UV- 531), 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (UV-326), hindered amine light stabilizer (GW-540) one or more; the plasticizer is one or more of di-isooctyl phthalate (DOP), diethylhexyl phthalate (DEHP), triglyceride, fatty acid methyl ester, tributyl citrate, cyclohexyl hexanoate; the terminator includes one or more of diethylhydroxylamine and ATSC.

[0038] As a possible implementation scheme, in step S1, the emulsifier is one or more of polyvinyl alcohol, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, polyoxyethylene sorbitan monooleate, sorbitan trioleate, polyoxyethylene lauryl ether, octylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether; the pH adjuster includes one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sulfuric acid, hydrochloric acid, phosphoric acid, and stearic acid.

[0039] As a possible implementation scheme, in step S1, the active ingredient, emulsifier and pH adjuster are added to the solvent, and the mixture is evenly mixed by mechanical stirring for 15 to 30 minutes, and the stirring speed is set to 500 to 800 r / min; according to the purpose of the test, an emulsification or sand milling process is selected to reduce the particle size, wherein the sand milling frequency is 1500-4000 r / min, the emulsification heating temperature is 70 to 100°C, and the emulsification frequency is 2000-6000 r / min.

[0040] As a possible implementation scheme, in the drying process of step S2, the vacuum drying temperature is 50-100°C, the drying time is 30-60 minutes; the spray drying temperature is 80-150°C.

[0041] As a possible implementation scheme, the anti-caking agent includes one or more of potassium ferrocyanide, sodium aluminosilicate, tricalcium phosphate, microcrystalline cellulose, calcium stearate, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and hypromellose.

[0042] As a possible implementation scheme, the rheological additive includes one or more of fumed silica, bentonite, polyamide wax, and hydroxypropyl guar gum.

[0043] As a possible implementation scheme, in step S1, when the active ingredient contains one or more of a liquid (diethylhydroxylamine terminator, plasticizer, epoxidized soybean oil) or a low melting point substance (DLTP auxiliary antioxidant), a carrier material is also added. After the active ingredient, emulsifier, and pH adjuster are dispersed and / or dissolved in the solvent, the carrier material is added so that the active ingredient is loaded on the carrier material. The specific loading method is: stirring or ultrasonic dispersion, the dispersion time is 30 to 60 minutes, and the reaction is stirred at room temperature to 90°C for 2 to 4 hours.

[0044] When the above technical solution is adopted, since diethylhydroxylamine is volatile and will escape when processed into powder, plasticizers and epoxidized soybean oil liquids are easy to agglomerate, and DLTP has a low melting point, even after forming micron- and / or nano-scale powders, they will melt and agglomerate again during storage or transportation under hot summer conditions, making it difficult to use the active ingredients later and increasing storage or transportation costs. Loading the above active ingredients on a carrier material is beneficial to improving stability.

[0045] As a possible implementation scheme, the carrier material is one or more of nano-silicon dioxide, montmorillonite, and zeolite.

[0046] As a possible implementation scheme, the preferred composition and mass fraction of the solid additive for PVC synthesis include:

[0047]

[0048]

[0049] The third aspect of the present invention provides the use of the above-mentioned solid additive for PVC synthesis in the preparation of PVC resin. The solid additive for PVC synthesis of the present application can be made into a powder of mixed effective ingredients or a powder of a single effective ingredient. When used, according to the working conditions, a solvent is used to disperse and / or dissolve at least one of the solid additives for PVC synthesis, disperse and compound, so that it is convenient for the back end to add it to the reaction system for preparing PVC resin in a proportion according to the situation.

[0050] 3. Beneficial effects

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] (1) Compared with the prior art, the solid terminator of the present invention mainly solves the following technical problems:

[0053] Material compatibility issues: Existing liquid terminators, such as liquid caustic soda and sodium perchlorate, will make the emulsion unstable and unable to be stored for a long time, affecting the compatibility of the materials;

[0054] Transportation cost problem: Liquid terminators require a lot of space during transportation, which increases transportation costs;

[0055] Storage space problem: Liquid terminators require a lot of storage space, which increases storage costs and difficulty;

[0056] Weather resistance: Liquid terminators are sensitive to environmental factors such as temperature and light, especially water undergoes phase change in winter, which affects its validity period and stability;

[0057] Shelf life problem: Liquid terminators have a short shelf life and are easily affected by the environment or microorganisms.

[0058] (2) The solid additive for PVC synthesis provided by the present invention still retains the performance of the traditional terminator. For example, when the active ingredients include an antioxidant and a terminator, it has good antioxidant performance and termination properties, and can effectively improve the stability and service life of PVC.

[0059] (3) The solid additive for PVC synthesis of the present invention is solid, easy to transport, safe, highly stable, and not easily volatile; it is dispersed in water before use, and the solution, emulsion or suspension formed is well compatible with PVC, which can effectively solve the problems existing in liquid antioxidants;

[0060] (4) The addition of an emulsifier to the solid additive for PVC synthesis of the present invention can improve the compatibility of the active ingredient with PVC, and can also prevent secondary agglomeration to reduce the particle size, so that it can better play the role of antioxidant and the like; further introduction of an anti-caking agent or a rheological additive can prevent the agglomeration of the solid additive powder for PVC synthesis, which is beneficial to the later dispersion;

[0061] (5) When the solid additive for PVC synthesis of the present invention needs to use a carrier material, nano-silica, montmorillonite, zeolite, etc. are used as the carrier material, which can improve the dispersibility and stability of the antioxidant and prevent its agglomeration; and can allow the low-boiling point, liquid effective ingredients to be adsorbed and exist in the form of a solid. DETAILED DESCRIPTION

[0062] The present invention is further described below in conjunction with specific embodiments.

[0063] The present invention provides a method for preparing a solid additive for PVC synthesis, comprising the following steps:

[0064] S1, dispersion process: dispersing and / or dissolving the active ingredient, emulsifier, and pH adjuster in a solvent that is easy to separate, preferably one or more of water, ethanol, and methanol, mechanically stirring and mixing for 15 to 30 minutes, setting the stirring speed to 500 to 800 r / min, and controlling the particle size of the active ingredient to less than 100 μm by emulsification or sand milling, preferably controlling the particle size of the active ingredient to less than 10 μm, to obtain a dispersion; wherein,

[0065] The active ingredients include one or more of a hindered phenol antioxidant, an auxiliary antioxidant, a heat stabilizer, a light stabilizer, a plasticizer or a terminator; the hindered phenol antioxidant is β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl ester (1076), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (245), 3,5-di-tert-butyl-4-hydroxyphenyl propionate octyl ester (1135), tetra[β-( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester (1010), 2,6-di-tert-butyl-p-cresol (264), 2,2′-methylenebis(4-methyl-6-tert-butylphenol) (2246), 4,4′-thiobis(6-tert-butyl-3-methylphenol) (300), 4,6-bis(octylthiomethyl) o-cresol (1520), 2,2′-mercaptoethylene glycol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester (1010), 2,6-di-tert-butyl-p-cresol (264), 2,2′-methylenebis(4-methyl-6-tert-butylphenol) (2246), 4,4′-thiobis(6-tert-butyl-3-methylphenol) (300), 4,6-bis(octylthiomethyl) o-cresol (1520), ) propionate] (1035) one or more; the auxiliary antioxidant is one or more of dilauryl thiodipropionate (DLTP), distearyl thiodipropionate (DSTP), pentaerythritol tetrakis (3-lauryl thiopropionate) (412S); the heat stabilizer is one or more of sodium perchlorate, mono / dipentaerythritol, hydrotalcite, and epoxidized soybean oil; the light stabilizer is 2-hydroxy-4-octyloxybenzophenone (UV-531), 2 -(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (UV-326), hindered amine light stabilizer (GW-540) one or more; the plasticizer is one or more of di-isooctyl phthalate (DOP), diethylhexyl phthalate (DEHP), triglyceride, fatty acid methyl ester, tributyl citrate, cyclohexyl hexanoate; the terminator includes one or more of diethylhydroxylamine and ATSC. It should be noted that among the above active ingredient materials, sodium perchlorate is easily soluble in water. Even if it agglomerates after making the powder, it will not affect the use when dissolved in water when used later; mono- / di-pentaerythritol agglomerates not seriously, and hydrotalcite does not agglomerate. Therefore, when the active ingredients are only sodium perchlorate, mono- / di-pentaerythritol, and hydrotalcite, they can be directly dried into powder without additional treatment for agglomeration.

[0066] The emulsifier is one or more of polyvinyl alcohol, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, polyoxyethylene sorbitan monooleate, sorbitan trioleate, polyoxyethylene lauryl ether, octylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether;

[0067] The pH adjuster includes one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sulfuric acid, hydrochloric acid, phosphoric acid, and stearic acid;

[0068] When the active ingredient contains one or more of liquid (diethylhydroxylamine terminator, plasticizer, epoxidized soybean oil) or low melting point substance (DLTP auxiliary antioxidant), a carrier material is also added. After the active ingredient, emulsifier, and pH adjuster are dispersed and / or dissolved in the solvent, the carrier material is added so that the active ingredient is loaded on the carrier material. The specific loading method is: stirring or ultrasonic dispersion, the dispersion time is 30 to 60 minutes, and the reaction is stirred at room temperature to 90°C for 2 to 4 hours. The carrier material is one or more of nano-silica, montmorillonite, and zeolite.

[0069] S2, drying process: if the dispersion does not contain an antioxidant and the active ingredient is insoluble in water, the dispersion in step S1 is vacuum filtered to obtain a filtrate, and the filtrate is vacuum dried to obtain a solid additive for PVC synthesis;

[0070] Otherwise, spray drying is performed to obtain solid additives for PVC synthesis, because antioxidants or components that are easily soluble in water tend to agglomerate during vacuum drying.

[0071] Among them, the anti-caking agent and the rheological additive can be added during the dispersion process of step S1 or after the drying process of step S2 is completed.

[0072] Anticaking agents include one or more of potassium ferrocyanide, sodium aluminosilicate, tricalcium phosphate, microcrystalline cellulose, calcium stearate, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and hypromellose.

[0073] The rheological additive includes one or more of fumed silica, bentonite, polyamide wax, and hydroxypropyl guar gum.

[0074] Among the above-mentioned solid additives for PVC synthesis, the preferred composition and mass fractions include:

[0075]

[0076] The solid additive for PVC synthesis prepared by the present invention is micron-scale and / or nano-scale powder particles, including:

[0077] a) Active ingredients, including one or more of hindered phenol antioxidants, auxiliary antioxidants, heat stabilizers, light stabilizers, plasticizers or terminators;

[0078] b) Emulsifier, adheres to the surface of the active ingredient;

[0079] or containing, c) a pH adjusting agent, adhered to the surface of the emulsifier;

[0080] or containing, d) a carrier material, in which the active ingredient is loaded;

[0081] or containing, e) an anticaking agent, which acts on the active ingredients in a dispersing manner and / or acts on the surface of the active ingredients in an adhesive manner;

[0082] Or containing, f) a rheological additive, which has a dispersing effect between the active ingredients and / or an adhesion effect on the surface of the active ingredients.

[0083] Several embodiments are listed below. It should be noted that materials with similar structures are not listed one by one to avoid redundancy, and the embodiments of the present invention cannot be considered as a restrictive description of the scope of protection.

[0084] Example 1

[0085] This embodiment provides a method for preparing a solid auxiliary agent for PVC synthesis. The solid antioxidant terminator obtained in this embodiment is prepared as follows:

[0086] S1. Dispersion process:

[0087] S11, weigh 20 parts of 245 antioxidant, 20 parts of 1076 antioxidant, 15 parts of DSTP auxiliary antioxidant, slowly add them into a reaction bottle with 150 parts of water, then add 5 parts of emulsifier polyoxyethylene lauryl ether, place the reaction bottle in a mechanical stirrer, stir and mix evenly for 20 minutes, set the stirring speed to 500r / min, and obtain a mixed solution after stirring;

[0088] S12, adding 20 parts of nano-silicon dioxide as a carrier material to the above mixed solution, ultrasonically dispersing for 40 minutes, and then mechanically stirring the reaction at room temperature for 2 hours;

[0089] S13. The solution in step S12 is milky white. Sand grinding is selected according to the properties of the material. 1.2-1.4 mm zirconium beads are selected and sand grinding is continued until the D90 particle size is less than 20 μm.

[0090] S2, drying process: spray drying the dispersion in step S1 to finally obtain a solid antioxidant terminator for PVC.

[0091] Comparative Example 1-1

[0092] This comparative example provides a preparation method of a solid additive for PVC synthesis, which is basically the same as that of Example 1, except that: Comparative Example 1-1 does not undergo a drying process and remains in a liquid state.

[0093] Comparative Example 1-2

[0094] This comparative example provides a preparation method of a solid additive for PVC synthesis, which is basically the same as Example 1, except that: the drying method of Comparative Example 1-2 is different, high-temperature evaporation is adopted, the drying temperature is set to 105° C., and the drying time is 50 min; after drying, the mixture is ground in a mortar.

[0095] Example 2

[0096] This embodiment provides a method for preparing a solid auxiliary agent for PVC synthesis. The solid antioxidant terminator obtained in this embodiment is prepared as follows:

[0097] S1. Dispersion process:

[0098] S11, weigh 20 parts of 1010 antioxidant, 15 parts of 1076 antioxidant, 15 parts of 1520 antioxidant, and 10 parts of DSTP auxiliary antioxidant, slowly add them into a reaction bottle with 100 parts of water, place the reaction bottle in a mechanical stirrer, stir and mix evenly for 30 minutes, set the stirring speed to 600r / min, and obtain a mixed solution after stirring;

[0099] S12, adding 5 parts of hydroxyethyl cellulose anticaking agent and 1 part of octylphenol polyoxyethylene ether emulsifier to the mixed solution of step S11 above, ultrasonically dispersing for 60 minutes, and then mechanically stirring at 80° C. until the material is completely melted;

[0100] S13, continue to mechanically stir the mixed solution of step S12 for 1 hour, set the stirring speed to 500 r / min, and use an emulsifier for emulsification at a frequency of 3000 r / min;

[0101] S14, adding 20 parts of montmorillonite as a carrier material to the above mixed solution, ultrasonically dispersing for 40 minutes, and then mechanically stirring the reaction at room temperature for 2 hours;

[0102] S2, drying process: spray drying the dispersion in step S1 to finally obtain a solid antioxidant terminator for PVC.

[0103] Comparative Example 2-1

[0104] This comparative example provides a preparation method of a solid additive for PVC synthesis which is basically the same as that of Example 2, except that: Comparative Example 2-1 does not undergo a drying process and remains in a liquid state.

[0105] Comparative Example 2-2

[0106] This comparative example provides a preparation method of a solid additive for PVC synthesis, which is basically the same as Example 2, except that: the drying method of comparative example 2-2 is different, high-temperature evaporation is adopted, the drying temperature is set to 105° C., and the drying time is 50 min; after drying, a mortar is used for grinding.

[0107] Example 3

[0108] This embodiment provides a method for preparing a solid additive for PVC synthesis. The solid heat stabilizer obtained in this embodiment is prepared as follows:

[0109] S1. Dispersion process:

[0110] S11, weigh 50 parts of epoxidized soybean oil, slowly add it into a reaction bottle containing 100 parts of water and 5 parts of ethanol, place the reaction bottle in a mechanical stirrer, stir and mix evenly for 20 minutes, set the stirring speed to 500 r / min, and obtain a mixed solution after stirring; emulsify the above solution using an emulsifier at a frequency of 3000 r / min, so that the particle size D90 is less than 8 μm;

[0111] S12, mixing 5 parts of microcrystalline cellulose with the dispersion obtained in step S11, and stirring for 30 minutes to mix evenly;

[0112] S2, drying process: spray drying the mixed solution to finally obtain a solid antioxidant terminator for PVC.

[0113] Comparative Example 3-1

[0114] This comparative example provides a preparation method of a solid additive for PVC synthesis which is basically the same as that of Example 3, except that: Comparative Example 3-1 does not undergo a drying process and remains in a liquid state.

[0115] Comparative Example 3-2

[0116] This comparative example provides a preparation method of a solid additive for PVC synthesis, which is basically the same as Example 3, except that: the drying method of comparative example 3-2 is different, high-temperature evaporation is adopted, the drying temperature is set to 105°C, and the drying time is 50min; after drying, the mixture is ground in a mortar.

[0117] Example 4

[0118] This embodiment provides a method for preparing a solid auxiliary agent for PVC synthesis. The solid antioxidant terminator obtained in this embodiment is prepared as follows:

[0119] S1. Dispersion process:

[0120] S11, weigh 20 parts of 1010 antioxidant, 15 parts of 1076 antioxidant, 15 parts of 1520 antioxidant, and 3 parts of ATSC, slowly add them into a reaction bottle with 100 parts of water, place the reaction bottle in a mechanical stirrer, stir and mix evenly for 30 minutes, set the stirring speed to 600r / min, and obtain a mixed solution after stirring;

[0121] S12, adding 1 part of octylphenol polyoxyethylene ether emulsifier and 3 parts of sodium hydroxide to the mixed solution of step S11, ultrasonically dispersing for 60 minutes, and then mechanically stirring at 80° C. until the material is completely melted;

[0122] S13, continue to mechanically stir the mixed solution of step S12 for 1 hour, set the stirring speed to 500 r / min, and use an emulsifier for emulsification at a frequency of 3000 r / min;

[0123] S2, drying process: spray drying the mixed solution to finally obtain a solid antioxidant terminator for PVC.

[0124] Comparative Example 4-1

[0125] This comparative example provides a preparation method of a solid additive for PVC synthesis which is basically the same as that of Example 4, except that: Comparative Example 4-1 does not undergo a drying process and remains in a liquid state.

[0126] Comparative Example 4-2

[0127] This comparative example provides a preparation method of a solid additive for PVC synthesis, which is basically the same as Example 4, except that: the drying method of comparative example 4-2 is different, high-temperature evaporation is adopted, the drying temperature is set to 105°C, and the drying time is 50min; after drying, the mixture is ground in a mortar.

[0128] Example 5

[0129] This embodiment provides a method for preparing a solid auxiliary agent for PVC synthesis. The solid antioxidant terminator obtained in this embodiment is prepared as follows:

[0130] S1. Dispersion process:

[0131] S11, weigh 20 parts of 1010 antioxidant, 15 parts of 1076 antioxidant, 15 parts of 1520 antioxidant, and 1 part of octylphenol polyoxyethylene ether emulsifier, slowly add them into a reaction bottle with 100 parts of water, place the reaction bottle in a mechanical stirrer, stir and mix evenly for 30 minutes, set the stirring speed to 600r / min, and obtain a mixed solution after stirring;

[0132] S12, adding 5 parts of hydroxypropyl guar gum to the mixed solution of step S11, ultrasonically dispersing for 60 minutes, and then mechanically stirring at 80° C. until the material is completely melted;

[0133] S13, continue to mechanically stir the mixed solution of step S12 for 1 hour, set the stirring speed to 500 r / min, and use an emulsifier for emulsification at a frequency of 3000 r / min;

[0134] S2, drying process: spray drying the mixed solution to finally obtain a solid antioxidant terminator for PVC.

[0135] Comparative Example 5-1

[0136] This comparative example provides a preparation method of a solid additive for PVC synthesis which is basically the same as that of Example 5, except that: Comparative Example 5-1 does not undergo a drying process and remains in a liquid state.

[0137] Comparative Example 5-2

[0138] This comparative example provides a preparation method of a solid additive for PVC synthesis, which is basically the same as Example 5, except that: the drying method of comparative example 5-2 is different, high-temperature evaporation is adopted, the drying temperature is set to 105°C, and the drying time is 50min; after drying, the mixture is ground in a mortar.

[0139] Example 6

[0140] This embodiment provides a method for preparing a solid auxiliary agent for PVC synthesis. The solid antioxidant terminator obtained in this embodiment is prepared as follows:

[0141] S1. Dispersion process:

[0142] Weigh 20 parts of 245 antioxidant, 20 parts of 1076 antioxidant, 10 parts of DSTP antioxidant, and 10 parts of octylphenol polyoxyethylene ether, and slowly add them into a reaction bottle containing 100 parts of water and 20 parts of ethanol, place the reaction bottle in a mechanical stirrer, stir and mix evenly for 20 minutes, set the stirring speed to 500 r / min, and obtain a mixed solution after stirring; sand grind the above solution to make the particle size D90 less than 10 μm;

[0143] S2, drying process: spray drying the mixed solution to finally obtain a solid antioxidant terminator for PVC.

[0144] S3, mixing 3 parts of microcrystalline cellulose, 5 parts of hydroxypropyl guar gum and the dried product of step S2 to finally obtain a solid heat stabilizer for PVC.

[0145] Comparative Example 6-1

[0146] This comparative example provides a preparation method of a solid additive for PVC synthesis which is basically the same as that of Example 6, except that: Comparative Example 6-1 does not undergo a drying process and remains in a liquid state.

[0147] Comparative Example 6-2

[0148] This comparative example provides a preparation method of a solid additive for PVC synthesis, which is basically the same as Example 6, except that the drying method of comparative example 6-2 is different, high-temperature evaporation is used, the drying temperature is set to 105°C, and the drying time is 50 minutes. After drying, the mixture is ground using a mortar.

[0149] Performance Testing

[0150] The technical performance indicators of the solid additives for PVC synthesis obtained in the above examples and comparative examples were tested, and the testing method is as follows:

[0151] Accelerated stability assessment: Seal the sample mouth and place it at 50°C for 30 days. If the sample is liquid, place it in a sealed vial to prevent water evaporation.

[0152] Low temperature weather resistance evaluation: Seal the sample mouth and freeze it at -10℃ overnight. After it is completely solidified, return it to room temperature to allow the sample to completely melt.

[0153] For aging whiteness, refer to GB / T 15595-2008.

[0154] The results of the above tests are shown in Table 1 below:

[0155] Table 1 Test results of examples and comparative examples

[0156]

[0157] Note: The accelerated stability evaluation in the examples is to place the powder in a high temperature environment and add water to prepare an emulsion before testing the whiteness and heat stability. The aging whiteness is the test result of the PVC powder after the solid additives for PVC synthesis are compounded and used in PVC.

[0158] It can be seen from the test results in Table 1 that the solid additive for PVC synthesis prepared by the present invention has no performance degradation after high temperature or freeze-thaw damage, and the aging whiteness is generally higher than the control example. After high and low temperature damage, the embodiment and the control example show significant differences. In high and low temperature environments, the appearance of Examples 1-6 always maintains a white emulsion and is not stratified. Although the aging whiteness and thermal stability time of the PVC resin fluctuate to a certain extent, they are generally at a high level. For example, in Example 1, the aging whiteness after high temperature damage reaches 88.62% and the thermal stability time is 514s, and the aging whiteness after low temperature damage is 83.14% and the thermal stability time is 481s.

[0159] In contrast, the comparative examples are worse. Comparative examples 1-2, 2-2, 3-2, 4-2, 5-2, and 6-2 all show complete precipitation, and some solutions turn yellow at high temperatures, indicating that they are seriously insufficient in terms of high and low temperature tolerance. In terms of performance indicators, the aging whiteness and thermal stability time of the comparative examples are significantly lower than those of the embodiments. Taking comparative example 1-2 as an example, the aging whiteness at high temperature is only 70.17% and the thermal stability time is 408s, while the aging whiteness at low temperature is 69.79% and the thermal stability time is 405s, which is significantly different from Example 1.

[0160] Although the present invention has been described in detail above by means of general description, specific implementation methods and tests, it is obvious to those skilled in the art that some modifications or improvements may be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A solid additive for PVC synthesis, characterized in that: Micron-sized and / or nano-sized powder particles, including: a) Active ingredients, including one or more of hindered phenol antioxidants, auxiliary antioxidants, heat stabilizers, light stabilizers, plasticizers or terminators; b) Emulsifier, adheres to the surface of the active ingredient.

2. A solid additive for PVC synthesis according to claim 1, characterized in that Also includes: c) pH adjuster, adhered to the surface of the emulsifier.

3. The solid additive for PVC synthesis according to claim 1, characterized in that: When the active ingredient contains one or more of liquid or low melting point substances, the solid additive for PVC synthesis further comprises: d) a carrier material, in which the active ingredient is loaded.

4. The solid additive for PVC synthesis according to claim 1, characterized in that: Solid additives for PVC synthesis also include: e) anti-caking agents, which act on the active ingredients in a dispersing manner and / or on the surfaces of the active ingredients in an adhesive manner; and / or, f) Rheological additives, which have a dispersing effect between the active ingredients and / or an adhesion effect on the surface of the active ingredients.

5. A solid additive for PVC synthesis according to any one of claims 1 to 4, characterized in that: The composition and mass fractions include: in, The hindered phenol antioxidant is one or more of 1076, 245, 1135, 1010, 264, 2246, 300, 1520, and 1035; the auxiliary antioxidant is one or more of dilauryl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetrakis (3-lauryl thiopropionate); the heat stabilizer is one or more of sodium perchlorate, mono- / di-pentaerythritol, hydrotalcite, and epoxidized soybean oil; the terminator includes one or more of diethylhydroxylamine and ATSC; The emulsifier is one or more of polyvinyl alcohol, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, polyoxyethylene sorbitan monooleate, sorbitan trioleate, polyoxyethylene lauryl ether, octylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether; The pH adjuster includes one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sulfuric acid, hydrochloric acid, phosphoric acid, and stearic acid; The carrier material is one or more of nano-silicon dioxide, montmorillonite and zeolite; Anticaking agents include one or more of potassium ferrocyanide, sodium aluminosilicate, tricalcium phosphate, microcrystalline cellulose, calcium stearate, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and hypromellose; The rheological additive includes one or more of fumed silica, bentonite, polyamide wax, and hydroxypropyl guar gum.

6. A method for preparing the solid additive for PVC synthesis according to claim 5, characterized in that: The steps are: S1, dispersion step: dispersing and / or dissolving the active ingredient, emulsifier, and pH adjuster in a solvent so that the particle size of the active ingredient is controlled to be less than 100 μm, preferably the particle size of the active ingredient is controlled to be less than 10 μm, to obtain a dispersion; S2, drying process: if the active ingredient does not contain an antioxidant and is insoluble in water, the dispersion in step S1 is vacuum filtered to obtain a filtrate, and the filtrate is vacuum dried to obtain a solid additive for PVC synthesis; If the active ingredient contains an antioxidant or is soluble in water, spray drying is performed to obtain a solid auxiliary agent for PVC synthesis.

7. The method for preparing a solid additive for PVC synthesis according to claim 6, characterized in that: During the dispersing process of step S1 or after the drying process of step S2, an anti-caking agent and a rheological aid are added.

8. The method for preparing a solid additive for PVC synthesis according to claim 6, characterized in that: In step S1, the active ingredient, emulsifier and pH adjuster are added to the solvent, and the mixture is evenly mixed by mechanical stirring for 15 to 30 minutes, and the stirring speed is set to 500 to 800 r / min; in step S2, the vacuum drying temperature is 50 to 100° C., and the drying time is 30 to 60 minutes; the spray drying temperature is 80 to 150° C.

9. The method for preparing a solid additive for PVC synthesis according to claim 6, characterized in that: When the active ingredient contains one or more of liquid or low melting point substances, a carrier material is also added so that the active ingredient is loaded on the carrier material.

10. Use of the solid additive for PVC synthesis according to claim 5 in the preparation of PVC resin, characterized in that: At least one of the solid additives for PVC synthesis is dispersed and / or dissolved in a solvent and added to the reaction system for preparing PVC resin.

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