阅读说明：本技术 Pvc用含氮热稳定剂组合物及其应用 (Nitrogen-containing heat stabilizer composition for PVC and application thereof ) 是由 臧亚南 徐云慧 巩志行 于 2021-01-13 设计创作，主要内容包括：本发明公开了PVC用含氮热稳定剂组合物极其应用,热稳定剂组合物,包括作为主热稳定剂A的二苯胺类防老剂,作为主热稳定剂B的咪唑类防老剂,作为辅助热稳定剂A的棕榈酸锌盐,作为辅助热稳定剂B的酚类抗氧剂以及作为辅助热稳定剂C的亚磷酸酯类抗氧剂。选择橡胶二胺类防老剂和咪唑类防老剂作为PVC的主热稳定剂,拓展了橡胶防老剂的用途；所使用的防老剂均无毒环保,且能提高PVC的热稳定性。(The invention discloses a nitrogen-containing heat stabilizer composition for PVC and application thereof, wherein the heat stabilizer composition comprises a diphenylamine antioxidant serving as a main heat stabilizer A, an imidazole antioxidant serving as a main heat stabilizer B, a zinc palmitate antioxidant serving as an auxiliary heat stabilizer A, a phenol antioxidant serving as an auxiliary heat stabilizer B and a phosphite antioxidant serving as an auxiliary heat stabilizer C. Rubber diamine age resisters and imidazole age resisters are selected as main heat stabilizers of PVC, and the application of the rubber age resisters is expanded; the used anti-aging agents are nontoxic and environment-friendly, and can improve the thermal stability of PVC.)

The nitrogenous heat stabilizer composition for PVC is characterized in that: the heat stabilizer composition comprises diphenylamine type anti-aging agents serving as a primary heat stabilizer A, imidazole type anti-aging agents serving as a primary heat stabilizer B,

zinc palmitate as an auxiliary heat stabilizer A, a phenol antioxidant as an auxiliary heat stabilizer B and a phosphite antioxidant as an auxiliary heat stabilizer C.

2. The nitrogen-containing heat stabilizer composition for PVC according to claim 1, wherein: the main heat stabilizer A is as follows: 4,4' -bis (phenylisopropyl) diphenylamine or a combination of 4,4' -bis (phenylisopropyl) diphenylamine and 4,4' -dioctyldiphenylamine.

3. The nitrogen-containing heat stabilizer composition for PVC according to claim 2, wherein: the main heat stabilizer B is as follows: 2-mercaptobenzimidazole zinc salt or 2-mercaptobenzimidazole;

when the 2-mercaptobenzimidazole is used, the zinc palmitate serving as the auxiliary heat stabilizer A needs to be used together;

the 2-mercaptobenzimidazole zinc salt is used without adding zinc palmitate as an auxiliary heat stabilizer A.

4. The nitrogen-containing heat stabilizer composition for PVC according to claim 3, wherein: the auxiliary heat stabilizer B is as follows: tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester or 6- (4-hydroxy-3, 5-di-tert-butylphenylamino) -2, 4-di-n-octylthio-1, 3, 5-triazine.

5. The nitrogen-containing heat stabilizer composition for PVC according to claim 4, wherein: the auxiliary heat stabilizer C is as follows: pentaerythritol diisodecyl diphosphite, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite or dioctadecyl pentaerythritol diphosphite.

6. The use of the nitrogen-containing heat stabilizer composition for PVC according to claim 5, wherein:

when the PVC is 100 parts, the heat stabilizer composition added into the PVC comprises the following components in parts by mass:

the main heat stabilizer A is 4,4' -bis (phenylisopropyl) diphenylamine, and the dosage of the main heat stabilizer A is 1-1.5 parts;

when the 4,4 '-di (phenylisopropyl) diphenylamine and the 4,4' -dioctyl diphenylamine are used together, the mass part ratio of the two is (0.8-1.2): (0.3-0.7);

the main heat stabilizer B is 2-mercaptobenzimidazole zinc salt, the dosage of the main heat stabilizer B is 0.5-1.5 parts, and an auxiliary heat stabilizer A, namely zinc palmitate, is not added;

when the main heat stabilizer B is 2-mercaptobenzimidazole, the main heat stabilizer B and the auxiliary heat stabilizer A zinc palmitate need to be used together, and the using amount of the main heat stabilizer B and the auxiliary heat stabilizer A zinc palmitate is 0.5-1.0 part;

the dosage of the auxiliary heat stabilizer B is 0.4 to 0.6 part, and the dosage of the auxiliary heat stabilizer C is 0.2 to 0.5 part;

in addition, 10-50 parts of plasticizer and 0.2-1 part of lubricant are also added;

the plasticizer comprises a primary plasticizer and a secondary plasticizer; the main plasticizer is epoxidized soybean oil, and the epoxy value of the main plasticizer is greater than or equal to 6; the secondary plasticizer is trioctyl phosphate, triacetin or tributyrin; the using amount of the primary plasticizer is 8-30 parts, and the using amount of the secondary plasticizer is preferably 2-20 parts;

the lubricant is polyethylene wax and paraffin wax which are used together, and the dosage of the lubricant is 0.1 to 0.5 part;

the preparation method comprises the steps of mixing the raw materials in a high-temperature mixing machine, uniformly mixing the mixed materials in a high-temperature open mill, and controlling the roll temperature of the high-temperature open mill at 120-130 ℃; after mixing uniformly, pressing in a flat vulcanizing machine to obtain the PVC test piece.

Technical Field

The invention belongs to the field of plastic additives, and particularly relates to a nitrogen-containing heat stabilizer composition for PVC and application thereof.

Background

In recent years, nitrogen-containing heat stabilizers for PVC have attracted increasing attention. In the early days, some small molecular compounds such as thiourea, fatty amine, urea and indole were mainly used. Later, there has been a gradual development of using barbituric acid and its derivatives, phenylurea and phenylthiourea and its derivatives, certain amides and imides, anthraquinone derivatives, pyrazolone derivatives, urea derivatives, and pyrimidines, etc. CN 107129594B describes a nitrogen-containing heat stabilizer-triazole-based compound for PVC, which is mixed with zinc stearate, polyhydric alcohol, beta-diketone, epoxy compound, long-chain fatty acid and the like to prepare a composite heat stabilizer. The prepared PVC test piece is placed in an oven at 180 ℃, the color of the PVC test piece is gradually darker along with the prolonging of time, which indicates that the reaction for removing HCl from PVC is continuously carried out, and the color of the PVC test piece is blackened for 160min at the longest, which indicates that PVC is greatly degraded and completely loses the usability. CN 108329275 a describes a process for the preparation of semicarbazide pyrimidine maleamic acid and its use as a PVC heat stabilizer in combination with one or more of calcium stearate, zinc stearate, calcium acetylacetonate, zinc acetylacetonate and β -diketones. The result shows that the equilibrium time can reach 22min at the material temperature of 190-195 ℃. CN 111072574A describes a method for preparing 5, 6-diamino-1, 3-dialkyl substituted uracil, and uses the 5, 6-diamino-1, 3-dialkyl substituted uracil in combination with one or more of zinc stearate, calcium stearate and pentaerythritol as a heat stabilizer for PVC, and research results show that the color of PVC becomes darker after 65min in an oven at 180 ℃; the maximum PVC equilibration time is 4104s at the material temperature of 180 ℃ and 185 ℃.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a nitrogen-containing PVC heat stabilizer composition which can improve the static heat stability and dynamic heat stabilizer of PVC and is non-toxic and environment-friendly.

The invention is realized by the following technical scheme that the nitrogen-containing heat stabilizer composition for PVC and the heat stabilizer composition comprise diphenylamine type anti-aging agents serving as a main heat stabilizer A, imidazole type anti-aging agents serving as a main heat stabilizer B, zinc palmitate serving as an auxiliary heat stabilizer A, phenol type anti-oxidants serving as an auxiliary heat stabilizer B and phosphite type anti-oxidants serving as an auxiliary heat stabilizer C.

As a preferable embodiment of the nitrogen-containing heat stabilizer composition for PVC of the invention: the main heat stabilizer A is as follows: 4,4' -bis (phenylisopropyl) diphenylamine (KY-405) or 4,4' -bis (phenylisopropyl) diphenylamine (KY-405) and 4,4' -dioctyldiphenylamine (antioxidant ODA) are used in combination.

As a preferable embodiment of the nitrogen-containing heat stabilizer composition for PVC of the invention: the main heat stabilizer B is as follows: 2-mercaptobenzimidazole zinc salt (antioxidant MBZ) or 2-mercaptobenzimidazole (antioxidant MB);

2-mercaptobenzimidazole (an anti-aging agent MB) needs to be used together with zinc palmitate serving as an auxiliary heat stabilizer A;

when the 2-mercaptobenzimidazole zinc salt (the anti-aging agent MBZ) is used, zinc palmitate serving as an auxiliary heat stabilizer A does not need to be additionally added.

As a preferable embodiment of the nitrogen-containing heat stabilizer composition for PVC of the invention: the auxiliary heat stabilizer B is as follows: tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) or 6- (4-hydroxy-3, 5-di-tert-butylphenylamino) -2, 4-di-n-octylthio-1, 3, 5-triazine (antioxidant 565).

As a preferable embodiment of the nitrogen-containing heat stabilizer composition for PVC of the invention: the auxiliary heat stabilizer C is as follows: pentaerythritol diisodecyl diphosphite (antioxidant 3010), bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite (antioxidant 626) or dioctadecyl pentaerythritol diphosphite (antioxidant 618).

When the PVC is 100 parts, the heat stabilizer composition comprises the following components in parts by weight:

the main heat stabilizer A is 4,4' -bis (phenylisopropyl) diphenylamine (KY-405) with the dosage of 1-1.5 parts;

when 4,4 '-di (phenylisopropyl) diphenylamine (KY-405) and 4,4' -dioctyl diphenylamine (antioxidant ODA) are used together, the mass part ratio of the two is (0.8-1.2): (0.3-0.7);

the main heat stabilizer B is 2-mercaptobenzimidazole zinc salt (an anti-aging agent MBZ), the dosage of the main heat stabilizer B is 0.5-1.5 parts, and an auxiliary heat stabilizer A, namely zinc palmitate, is not added;

when the main heat stabilizer B is 2-mercaptobenzimidazole (an anti-aging agent MB), the main heat stabilizer B and the auxiliary heat stabilizer A zinc palmitate need to be used together, and the usage amount of the main heat stabilizer B and the auxiliary heat stabilizer A zinc palmitate is 0.5-1.0 part;

the dosage of the auxiliary heat stabilizer B is 0.4 to 0.6 part, and the dosage of the auxiliary heat stabilizer C is 0.2 to 0.5 part;

in addition, 10-50 parts of plasticizer and 0.2-1 part of lubricant are also added;

the plasticizer comprises a primary plasticizer and a secondary plasticizer; the main plasticizer is epoxidized soybean oil, and the epoxy value of the main plasticizer is greater than or equal to 6; the secondary plasticizer is trioctyl phosphate (TOP), triacetin or tributyrin; the using amount of the primary plasticizer is 8-30 parts, and the using amount of the secondary plasticizer is preferably 2-20 parts;

the lubricant is polyethylene wax and paraffin wax which are used together, and the dosage of the lubricant is 0.1 to 0.5 part;

the preparation method comprises the steps of mixing the raw materials in a high-temperature mixing machine, uniformly mixing the mixed materials in a high-temperature open mill, and controlling the roll temperature of the high-temperature open mill at 120-130 ℃; after mixing uniformly, pressing in a flat vulcanizing machine to obtain the PVC test piece.

The invention has the beneficial effects that: rubber diamine age resisters and imidazole age resisters are selected as main heat stabilizers of PVC, and the application of the rubber age resisters is expanded; the used anti-aging agents are nontoxic and environment-friendly, and can improve the thermal stability of PVC.

Drawings

FIG. 1 is a graph showing the dynamic thermal stability analysis of PVC test pieces obtained in examples 1 to 3 and comparative example (Torque rheometer method, 185 ℃ C., 60 r/min).

Detailed Description

The present invention will be further described with reference to the following examples.

Example 1:

100 parts of PVC (polyvinyl chloride) and 100 parts of PVC (the same below) are weighed, and the dosage of the PVC heat stabilizer composition added in the PVC heat stabilizer composition is 1.0 part of age resister KY-405, 1.0 part of age resister MBZ, 0.5 part of antioxidant 1010 and 0.2 part of antioxidant 3010. In addition, 25 parts of epoxidized soybean oil (with the epoxy value of 6.5), 15 parts of TOP, 0.3 part of polyethylene wax and 0.3 part of paraffin wax are added.

The preparation method comprises the steps of adding PVC, an anti-aging agent KY405, an anti-aging agent MBZ, an antioxidant 1010, an antioxidant 3010, epoxidized soybean oil, TOP, polyethylene wax and paraffin into a high-speed mixer, and mixing. And uniformly mixing the mixed materials in a high-temperature open mill, wherein the roll temperature of the high-temperature open mill is set to be 120 ℃. After mixing uniformly, pressing in a flat vulcanizing machine to obtain the PVC test piece.

Example 2:

100 parts of PVC (polyvinyl chloride) and 100 parts of (in parts by mass, the same below) are weighed, and the dosage of the PVC heat stabilizer composition added in the PVC heat stabilizer composition is 1.0 part of age resister KY-405, 0.5 part of age resister ODA, 1.0 part of age resister MB, 0.5 part of zinc palmitate, 0.5 part of antioxidant 565, 0.5 part of antioxidant 626 and 0.2 part of antioxidant. In addition, epoxidized soybean oil (epoxy value of 6.5) 20 parts, tributyrin 20 parts, polyethylene wax 0.1 part, paraffin wax 0.1 part are added.

The preparation method specifically comprises the steps of adding PVC, an anti-aging agent KY405, an anti-aging agent ODA, an anti-aging agent MB, zinc palmitate, an antioxidant 565, an antioxidant 626, epoxidized soybean oil, tributyrin, polyethylene wax and paraffin into a high-speed mixer, and mixing. And uniformly mixing the mixed materials in a high-temperature open mill, wherein the roll temperature of the high-temperature open mill is set to be 120 ℃. After mixing uniformly, pressing in a flat vulcanizing machine to obtain the PVC test piece.

Example 3:

100 parts of PVC (polyvinyl chloride) are weighed, and the amount of the PVC heat stabilizer composition added is 1.0 part of age resister KY405, 0.5 part of age resister MBZ, 0.5 part of antioxidant 565, 0.5 part of antioxidant 618 and 0.2 part of antioxidant. In addition, epoxidized soybean oil (epoxy value of 6.5) 20 parts, triacetin 10 parts, polyethylene wax 0.2 part, paraffin wax 0.3 part are added.

The preparation method specifically comprises the steps of adding PVC, an anti-aging agent KY405, an anti-aging agent MBZ, an antioxidant 565, an antioxidant 618, epoxidized soybean oil, triacetin, polyethylene wax and paraffin into a high-speed mixer, and mixing. And (3) uniformly mixing the mixed materials in a high-temperature open mill, wherein the roll temperature of the high-temperature open mill is set to be 120 ℃. After mixing uniformly, pressing in a flat vulcanizing machine to obtain the PVC test piece.

Comparative example:

the preparation method comprises the steps of adding 100 parts of PVC, 1.5 parts of lead stearate, 1.5 parts of barium stearate, 20 parts of epoxidized soybean oil (the epoxy value is 6.5), 10 parts of TOP, 0.4 part of polyethylene wax, 0.2 part of paraffin wax and mixing in a high-speed mixer. Uniformly mixing the mixture in a high-temperature open mill, and setting the roll temperature of the high-temperature open mill to be 120 ℃; after mixing uniformly, pressing in a flat vulcanizing machine to obtain the PVC test piece.

The PVC test pieces obtained in examples 1 to 3 and comparative example were subjected to static thermal stability analysis in an oven at a temperature of 200 ℃ for 4 hours, and then sampled every 30 minutes after the first time in the oven, and the color change of the test pieces was observed, and the results are shown in Table 1.

TABLE 1 static thermal stability of PVC test pieces-oven method

As can be seen from Table 1, the samples and comparative examples were placed in an oven at 200 ℃ and the samples gradually changed from white to earthy yellow over 1320 min. Whereas the comparative example turned black-brown over only 300 min. The static thermal stability of the examples is shown to be superior to the comparative examples.

The PVC test pieces obtained in examples 1 to 3 and comparative example were subjected to dynamic thermal stability analysis-Torque rheometer method at 185 ℃ and the results are shown in FIG. 1.

When the PVC samples prepared in examples 1 to 3 and comparative example were added to a torque rheometer (185 ℃ C., 60r/min), the samples were not plasticized until the beginning, so the torque was greatly increased. As the plasticization proceeds, the torque drops. The comparative example shows an increase in torque after 1200s, indicating that the PVC is crosslinked, and a rapid decrease in torque after 2700s, indicating that the PVC begins to degrade to a large extent. The small torque increase of example 1 after 4200s and the small torque increase of example 2 after 4500s indicates that slight crosslinking of the PVC is possible, but the PVC performance is not greatly affected. Example 3 the torque dropped rapidly around 4300s, indicating that the PVC began to degrade rapidly. The dynamic thermal stability of examples 1-3 is superior to that of the comparative example.