CN108822433A - A kind of dedicated low smell of toy film is without phenol barium zinc stabilizer and preparation method thereof - Google Patents

Abstract

The invention relates to the field of heat stabilizers for polyvinyl chloride, in particular to a special low-odor phenol-free barium-zinc stabilizer for toy films and a preparation method thereof. The stabilizer comprises by weight: 100 parts of main stabilizer; 10-15 parts of thiophene porous polymer; 5-8 parts of lubricant; 4-9 parts of phenol-free antioxidant; and 20-30 parts of auxiliary stabilizer. Added thiophene porous polymer in the formula of the present invention, has bigger BET value, and high specific surface area makes it have enrichment effect, and adsorption capacity is big, and the thermal stability in PVC processing process is significantly improved, and is not easy to change color; Polymer The rigid structure is beneficial to the improvement of mechanical and mechanical properties and weather resistance of the product; the heat stabilizer provided by the invention has a simple preparation method, is convenient to operate, and is environmentally friendly, and the prepared heat stabilizer has good heat stability and processability.

Description

A special low-odor phenol-free barium-zinc stabilizer for toy films and its preparation method

technical field

The invention relates to the field of heat stabilizers for polyvinyl chloride, in particular to a special low-odor phenol-free barium-zinc stabilizer for toy films and a preparation method thereof.

Background technique

Polyvinyl chloride (PVC) has the advantages of good processability, high strength, corrosion resistance, good insulation, and flame retardant, and is widely used in industrial and agricultural production. However, there are some defects in the PVC molecular chain, such as allyl chloride, etc. The processing temperature of PVC is generally above 170°C. At this high temperature, active Cl atoms such as allyl chloride are easily removed in the form of HCl, resulting in " "zipper" type chain reaction, making the color of PVC turn yellow or even black. And the generated HCl will further promote the thermal degradation of PVC. Therefore, heat stabilizers need to be added during PVC processing. Commonly used heat stabilizers include lead salt stabilizers, metal soaps, organotin compounds, organic stabilizers and composite stabilizers. With the enhancement of people's awareness of environmental protection, toxic heat stabilizers containing lead and cadmium are gradually banned, and environmentally friendly heat stabilizers will gain new development. Among them, organotin-based and zinc-based heat stabilizers are the most promising heat stabilizer systems. The price of organic tin base is high, while the relatively cheap calcium zinc base has broad-spectrum applicability and has more room for development. Due to its non-toxic and high-efficiency characteristics, calcium-zinc heat stabilizers have become the most active field and the most competitive product among composite stabilizers in recent years. However, calcium-zinc heat stabilizers still have defects such as poor stabilizing effect, initial coloring, and "zinc burning".

Composed of light elements such as carbon, hydrogen, oxygen, nitrogen, boron, etc., connected by covalent bonds, and have a large specific surface area and a large number of micropores, such polymers are called organic porous materials. Compared with traditional porous materials (such as activated carbon, zeolite, molecular sieve), organic porous polymer is a new type of porous material because of its lower skeleton density, higher specific surface area, higher chemical and thermal Stability and diverse skeleton molecular structure and other characteristics. These excellent characteristics make organic porous materials widely used in heterogeneous catalysis, gas adsorption and separation, energy storage and so on. Therefore, as a research hotspot, organic porous materials have been developed rapidly in recent years. Sulfur in thiophene has a lone pair of electrons, which can generate dipole-to-dipole interactions with gas molecules. If thiophene is introduced into porous materials, it can increase the adsorption of porous materials to gases, thereby further increasing its adsorption capacity.

Contents of the invention

The purpose of the present invention is to address the deficiencies in the prior art, to provide a special low-odor phenol-free barium-zinc stabilizer for toy films and a preparation method thereof. The stabilizer provided by the present invention has good heat resistance, good weather resistance, and is not easy to change color.

In order to achieve the above object, the present invention adopts the following technical solutions:

A special low-odor phenol-free barium-zinc stabilizer for toy films, comprising by weight:

Further, the main stabilizer described above is prepared by the following method:

Add glycerol and organic carboxylic acid into the stirred reactor at a molar ratio of 1: (1-5), react at normal pressure and 100-130°C for 5-10 hours to obtain glycerol organic carboxylic acid ester; Add zinc oxide to glycerol organic carboxylate, react at normal pressure, 160-180°C for 3-5h, cool down to 100°C, add triglycidyl isocyanurate with a molar ratio of (0.1-0.5):1 to glycerol , Continue to react for 1-2h, the obtained product is dried and pulverized to obtain the main stabilizer.

Further, the above-mentioned organic carboxylic acid is one of formic acid, acetic acid, glutaconic acid, and crotonic acid.

Further, the BET specific surface area of the above-mentioned thiophene porous polymer is 1150-1200 m ² ·g ^-1 .

Further, the above-mentioned thiophene porous polymer is tetrathieno[1,2-b:4,3-b':5,6-b":8,7-b"'] cyclooctatetraene.

Further, the above-mentioned thiophene porous polymer can also be prepared by the following method:

Add 1,3,5-tris(2-thienyl)benzene into 1,2-dichloroethane solvent, stir to dissolve, then add anhydrous FeCl ₃ , stir at room temperature for 24-36h; add volume Anhydrous methanol twice as much as 1,2-dichloroethane, continue to stir for 1-3 hours, filter under reduced pressure, wash and dry to obtain the thiophene porous polymer.

Further, the above-mentioned 1,3,5-tris(2-thienyl)benzene and anhydrous FeCl ₃ have a molar ratio of 1:(1-5).

Further, the above-mentioned lubricant is one of butyl stearate, paraffin wax, polyethylene wax, and amide wax.

Further, the above-mentioned phenol-free antioxidant is one of furanone, phthalide, and N,N-dibenzylhydroxylamine.

Further, the auxiliary stabilizer mentioned above is one of triphenyl phosphite, epoxidized soybean oil, sorbitol, dibenzoylmethane, and stearyl benzoylmethane.

Further, a method for preparing a special low-odor phenol-free barium-zinc stabilizer for toy films, specifically comprising the following steps:

(1) Put the main stabilizer and lubricant into the reaction kettle and mix well; take the mixed material, add it to the kneader and heat it to 70-80°C and stir, add phenol-free antioxidant, and knead at 90-120°C for 30- 40min;

(2) Add thiophene porous polymer and auxiliary stabilizer to the kneader of step (1), knead and stir for 40-50min; discharge, press, sieve, pack, and obtain the PVC heat stabilizer comprising a covalent organic framework . The beneficial effect that the present invention has:

(1) In the present invention, the zinc components and calcium components in the system are crosslinked and combined, which can effectively inhibit "zinc burning" and improve the initial effect of PVC processing heat stability.

(2) Added thiophene porous polymer in the formula of the present invention, has bigger BET value, and high specific surface area makes it have enrichment effect, and adsorption capacity is big, and the sulfur in thiophene has lone pair electron, can and HCl gas molecule The interaction between dipole and dipole is generated. If thiophene is introduced into the porous material, it can increase the adsorption of the porous material to HCl gas, thereby further increasing its adsorption capacity, significantly improving the thermal stability during PVC processing, and not easy to change color; The rigid structure of the polymer is conducive to the improvement of the mechanical and mechanical properties and weather resistance of the product.

(3) The preparation method of the thermal stabilizer provided by the invention is simple, easy to operate, and environmentally friendly, and the prepared thermal stabilizer has good thermal stability and processability.

Detailed ways

The present invention is described in further detail now in conjunction with embodiment.

Example 1

A special low-odor phenol-free barium-zinc stabilizer for toy films, comprising by weight:

The main stabilizer described above is prepared by the following method:

Glycerin (purchased from Yangzhou Feiyang Chemical Co., Ltd.) and formic acid (purchased from Shanghai Zhanyun Chemical Co., Ltd.) were added into the stirred reactor at a molar ratio of 1:3, and reacted at normal pressure and 100°C for 10 hours to obtain glycerol formate; Add calcium oxide (purchased from Suzhou Bosheng Industry and Trade Co., Ltd.) and zinc oxide (purchased from Seoul International Trade (Shanghai) Co., Ltd.) that are equimolar to glycerin into glycerol formate and react at normal pressure and 160°C for 5 hours , lower the temperature to 100°C, add triglycidyl isocyanurate (purchased from Suzhou Fulu Biotechnology Co., Ltd.) with a molar ratio of 0.1:1 to glycerol, and continue the reaction for 1 hour. The obtained product is dried and crushed and passed through a 100-mesh sieve That is, the main stabilizer is obtained.

The above-mentioned thiophene porous polymer is prepared by the following method:

Add 1,3,5-tris(2-thienyl)benzene (purchased from Shanghai Yansheng Industrial Co., Ltd.) into 1,2-dichloroethane (purchased from Taizhou Jiangping Oil Chemical Co., Ltd.) solvent, stir dissolved, then added anhydrous FeCl ₃ (purchased from Yiwu Luotian Trading Co., Ltd.) with a molar ratio of 1:3 to 1,3,5-tris(2-thienyl)benzene, and stirred at room temperature for 24 hours; then added Anhydrous methanol (purchased from Dezhou Runxin Experimental Instrument Co., Ltd.) whose volume is twice that of 1,2-dichloroethane, continued to stir for 1 hour, vacuum filtered, washed, and dried to obtain the thiophene porous polymer. The yield was 86%, and the BET specific surface area of the thiophene porous polymer was 1150 m ² ·g ^-1 .

A kind of preparation method of special low-odor phenol-free barium-zinc stabilizer for toy film, specifically comprises the following steps:

(1) Add the main stabilizer and butyl stearate (purchased from Nanjing Hand in Hand Chemical Technology Co., Ltd.) into the reaction kettle and mix thoroughly; take the mixed material, add it to a kneader and heat it to 70°C and stir, add furanone (purchased from Shanghai Exetin Fragrance Co., Ltd.), kneading at 90°C for 40min;

(2) Add thiophene porous polymer and triphenyl phosphite (purchased from Shanghai McLean Biochemical Technology Co., Ltd.) into the kneader of step (1), knead and stir for 40-50min; discharge into tablets, sieve, pack , that is, a PVC heat stabilizer containing a covalent organic framework.

Example 2

A special low-odor phenol-free barium-zinc stabilizer for toy films, comprising by weight:

The main stabilizer described above is prepared by the following method:

Glycerin (purchased from Yangzhou Feiyang Chemical Co., Ltd.) and acetic acid (purchased from Shanghai Zhanyun Chemical Co., Ltd.) were added into the stirred reactor at a molar ratio of 1:1, and reacted at normal pressure and 110°C for 8 hours to obtain glycerol acetate; Add calcium oxide (purchased from Suzhou Bosheng Industry and Trade Co., Ltd.) and zinc oxide (purchased from Shouli International Trade (Shanghai) Co., Ltd.), which are equimolar to glycerin, into glycerol acetate and react at normal pressure and 160°C for 5 hours. , lower the temperature to 100°C, add triglycidyl isocyanurate (purchased from Suzhou Fulu Biotechnology Co., Ltd.) with a molar ratio of 0.3:1 to glycerin, and continue the reaction for 2 hours. The obtained product is dried and crushed and passed through a 100-mesh sieve That is, the main stabilizer is obtained.

The above-mentioned thiophene porous polymer is prepared by the following method:

Add 1,3,5-tris(2-thienyl)benzene (purchased from Shanghai Yansheng Industrial Co., Ltd.) into 1,2-dichloroethane (purchased from Taizhou Jiangping Oil Chemical Co., Ltd.) solvent, stir dissolved, and then added anhydrous FeCl ₃ (purchased from Yiwu Luotian Trading Co., Ltd.) with a molar ratio of 1:1 to 1,3,5-tris(2-thienyl)benzene, and stirred at room temperature for 28 hours; then added Anhydrous methanol (purchased from Dezhou Runxin Experimental Instrument Co., Ltd.) whose volume is 2 times that of 1,2-dichloroethane, continued to stir for 1.5 h, filtered under reduced pressure, washed, and dried to obtain the thiophene porous polymer , the yield was 85%, and the BET specific surface area of the thiophene porous polymer was 1165m ² ·g ^-1 .

A kind of preparation method of special low-odor phenol-free barium-zinc stabilizer for toy film, specifically comprises the following steps:

(1) Add the main stabilizer and paraffin (purchased from Jinan Dehou Chemical Co., Ltd.) into the reaction kettle and mix thoroughly; take the mixed material, add it to a kneader and heat it to 75°C and stir, add phthalide (purchased from Guangzhou Hu Proud Chemical Co., Ltd.), kneading at 100°C for 40min;

(2) Add thiophene porous polymer and epoxidized soybean oil (purchased from Tianyuan Plastic Auxiliary Factory, Leling City, Shandong) into the kneader of step (1), knead and stir for 40-50min; , packaging, namely to obtain a PVC heat stabilizer comprising a covalent organic framework.

Example 3

A special low-odor phenol-free barium-zinc stabilizer for toy films, comprising by weight:

The main stabilizer described above is prepared by the following method:

Add glycerin (purchased from Yangzhou Feiyang Chemical Co., Ltd.) and glutaconic acid (purchased from Hubei Jusheng Technology Co., Ltd.) into the stirred reactor at a molar ratio of 1:5, and react at normal pressure and 120°C for 6 hours to obtain glycerol pentene Diacyl ester; Calcium oxide (purchased from Suzhou Bosheng Industry and Trade Co., Ltd.) and zinc oxide (purchased from Shouli International Trade (Shanghai) Co., Ltd.) equimolar with glycerol were added to glycerol glutaric acid ester in normal Pressed at 170°C for 4 hours, cooled to 100°C, added triglycidyl isocyanurate (purchased from Suzhou Fulu Biotechnology Co., Ltd.) with a molar ratio of 0.5:1 to glycerin, and continued to react for 1 hour. The obtained product was dried, After crushing, pass through a 100-mesh sieve to obtain the main stabilizer.

The above-mentioned thiophene porous polymer is prepared by the following method:

Add 1,3,5-tris(2-thienyl)benzene (purchased from Shanghai Yansheng Industrial Co., Ltd.) into 1,2-dichloroethane (purchased from Taizhou Jiangping Oil Chemical Co., Ltd.) solvent, stir dissolved, then added anhydrous FeCl ₃ (purchased from Yiwu Luotian Trading Co., Ltd.) with a molar ratio of 1:5 to 1,3,5-tris(2-thienyl)benzene, and stirred at room temperature for 32 hours; then added Anhydrous methanol (purchased from Dezhou Runxin Experimental Instrument Co., Ltd.) whose volume is twice that of 1,2-dichloroethane, continued to stir for 2 hours, vacuum filtered, washed, and dried to obtain the thiophene porous polymer. The yield was 87%, and the BET specific surface area of the thiophene porous polymer was 1180 m ² ·g ^-1 .

A kind of preparation method of special low-odor phenol-free barium-zinc stabilizer for toy film, specifically comprises the following steps:

(1) Add the main stabilizer and polyethylene wax (purchased in Yangzhou Roland New Materials Co., Ltd.) into the reaction kettle and mix thoroughly; take the mixed material, add it to a kneader and heat it to 80 ° C and stir, add phthalide (purchased in Guangzhou Huao Chemical Co., Ltd.), kneading at 110°C for 35min;

(2) Add thiophene porous polymer and sorbitol (purchased in Guangzhou Tonghang Trading Co., Ltd.) into the kneader of step (1), knead and stir for 40-50min; A PVC heat stabilizer comprising a covalent organic framework is obtained.

Example 4

A special low-odor phenol-free barium-zinc stabilizer for toy films, comprising by weight:

The main stabilizer described above is prepared by the following method:

Add glycerin (purchased from Yangzhou Feiyang Chemical Co., Ltd.) and glutaconic acid (purchased from Hubei Jusheng Technology Co., Ltd.) into the stirred reactor at a molar ratio of 1:5, and react at normal pressure and 120°C for 6 hours to obtain glycerol pentene Diacyl ester; Calcium oxide (purchased from Suzhou Bosheng Industry and Trade Co., Ltd.) and zinc oxide (purchased from Shouli International Trade (Shanghai) Co., Ltd.) equimolar with glycerol were added to glycerol glutaric acid ester in normal Pressed at 170°C for 4 hours, cooled to 100°C, added triglycidyl isocyanurate (purchased from Suzhou Fulu Biotechnology Co., Ltd.) with a molar ratio of 0.5:1 to glycerin, continued to react for 1.5 hours, and the obtained product was dried 1. After crushing, pass through a 100-mesh sieve to obtain the main stabilizer.

The above-mentioned thiophene porous polymer is prepared by the following method:

Add 1,3,5-tris(2-thienyl)benzene (purchased from Shanghai Yansheng Industrial Co., Ltd.) into 1,2-dichloroethane (purchased from Taizhou Jiangping Oil Chemical Co., Ltd.) solvent, stir dissolved, then added anhydrous FeCl ₃ (purchased from Yiwu Luotian Trading Co., Ltd.) with a molar ratio of 1:5 to 1,3,5-tris(2-thienyl)benzene, and stirred at room temperature for 32 hours; then added Anhydrous methanol (purchased from Dezhou Runxin Experimental Instrument Co., Ltd.) whose volume is twice that of 1,2-dichloroethane, continued to stir for 2 hours, vacuum filtered, washed, and dried to obtain the thiophene porous polymer. The yield was 87%, and the BET specific surface area of the thiophene porous polymer was 1180 m ² ·g ^-1 .

A kind of preparation method of special low-odor phenol-free barium-zinc stabilizer for toy film, specifically comprises the following steps:

(1) Add the main stabilizer and polyethylene wax (purchased from Yangzhou Roland New Material Co., Ltd.) into the reaction kettle and mix thoroughly; take the mixed material, add it to a kneader and heat it to 80°C and stir, add N,N-dibenzyl Hydroxylamine (purchased from Shanghai Hongshun Biotechnology Co., Ltd.), kneading at 120°C for 30min;

(2) Add thiophene porous polymer and dibenzoylmethane (purchased from Lianyungang Xingang Chemical Co., Ltd.) to the kneader of step (1), knead and stir for 40-50min; discharge into tablets, sieve, pack, That is, a PVC heat stabilizer comprising a covalent organic framework is obtained.

Example 5

A special low-odor phenol-free barium-zinc stabilizer for toy films, comprising by weight:

The main stabilizer described above is prepared by the following method:

Add glycerin (purchased from Yangzhou Feiyang Chemical Co., Ltd.) and butenedioic acid (purchased from Hubei Jusheng Technology Co., Ltd.) into the stirred reactor at a molar ratio of 1:3, and react at normal pressure and 130°C for 5 hours to obtain glycerol butene Diacid ester; Calcium oxide (purchased from Suzhou Bosheng Industry and Trade Co., Ltd.) and zinc oxide (purchased from Seoul International Trade (Shanghai) Co., Ltd.) equimolar with glycerin were added to glycerin butenedioic acid ester in normal pressure, 180°C for 2h, lower the temperature to 100°C, add triglycidyl isocyanurate (purchased from Suzhou Fulu Biotechnology Co., Ltd.) with a molar ratio of 0.4:1 to glycerin, continue to react for 1.5h, and the obtained product is dried 1. After crushing, pass through a 100-mesh sieve to obtain the main stabilizer.

The BET specific surface area of the thiophene porous polymer is 1050m ² ·g ^-1 .

A kind of preparation method of special low-odor phenol-free barium-zinc stabilizer for toy film, specifically comprises the following steps:

(1) Add the main stabilizer and amide wax (purchased from Guangzhou Yirui New Material Co., Ltd.) into the reaction kettle and mix thoroughly; take the mixed material, add it to a kneader and heat it to 80°C and stir, add N,N-di Benzylhydroxylamine (purchased from Shanghai Hongshun Biotechnology Co., Ltd.), kneaded at 120°C for 30min;

(2) Add thiophene porous polymer and stearyl benzoylmethane (purchased from Anhui Jiaxian Functional Auxiliary Co., Ltd.) into the kneader of step (1), knead and stir for 40-50min; Sieve and pack to obtain a PVC heat stabilizer containing a covalent organic framework.

Comparative example 1 is compared with embodiment 5, and difference is:

Comparative example 1

A kind of PVC thermal stabilizer, comprises by weight:

The main stabilizer described above is prepared by the following method:

Add glycerin (purchased from Yangzhou Feiyang Chemical Co., Ltd.) and butenedioic acid (purchased from Hubei Jusheng Technology Co., Ltd.) into the stirred reactor at a molar ratio of 1:3, and react at normal pressure and 130°C for 5 hours to obtain glycerol butene Diacid ester; Calcium oxide (purchased from Suzhou Bosheng Industry and Trade Co., Ltd.) and zinc oxide (purchased from Seoul International Trade (Shanghai) Co., Ltd.) equimolar with glycerin were added to glycerin butenedioic acid ester in normal pressure, 180°C for 2h, lower the temperature to 100°C, add triglycidyl isocyanurate (purchased from Suzhou Fulu Biotechnology Co., Ltd.) with a molar ratio of 0.4:1 to glycerin, continue to react for 1.5h, and the obtained product is dried 1. After crushing, pass through a 100-mesh sieve to obtain the main stabilizer.

A kind of preparation method of PVC heat stabilizer, specifically comprises the steps:

(1) Add the main stabilizer and amide wax (purchased from Guangzhou Yirui New Material Co., Ltd.) into the reaction kettle and mix thoroughly; take the mixed material, add it to a kneader and heat it to 80°C and stir, add N,N-di Benzylhydroxylamine (purchased from Shanghai Hongshun Biotechnology Co., Ltd.), kneaded at 120°C for 30min;

(2) Add stearoylbenzoylmethane (purchased from Anhui Jiaxian Functional Auxiliary Co., Ltd.) into the kneader of step (1), knead and stir for 40-50min; discharge into tablets, sieve, pack, That is, a PVC heat stabilizer comprising a covalent organic framework is obtained.

Comparative example 2 is compared with embodiment 5, and difference is:

A special low-odor phenol-free barium-zinc stabilizer for toy films, comprising by weight:

The main stabilizer is 50 parts of zinc oxide and 50 parts of calcium oxide;

The BET specific surface area of the thiophene porous polymer is 1050m ² ·g ^-1 .

A kind of preparation method of special low-odor phenol-free barium-zinc stabilizer for toy film, specifically comprises the following steps:

(1) Add the main stabilizer and amide wax (purchased from Guangzhou Yirui New Material Co., Ltd.) into the reaction kettle and mix thoroughly; take the mixed material, add it to a kneader and heat it to 80°C and stir, add N,N-di Benzylhydroxylamine (purchased from Shanghai Hongshun Biotechnology Co., Ltd.), kneaded at 120°C for 30min;

(2) Add thiophene porous polymer and stearyl benzoylmethane (purchased from Anhui Jiaxian Functional Auxiliary Co., Ltd.) into the kneader of step (1), knead and stir for 40-50min; Sieve and pack to obtain a PVC heat stabilizer containing a covalent organic framework.

Comparative example 3

Example 5

A special low-odor phenol-free barium-zinc stabilizer for toy films, comprising by weight:

The main stabilizer described above is prepared by the following method:

Add glycerin (purchased from Yangzhou Feiyang Chemical Co., Ltd.) and butenedioic acid (purchased from Hubei Jusheng Technology Co., Ltd.) into the stirred reactor at a molar ratio of 1:3, and react at normal pressure and 130°C for 5 hours to obtain glycerol butene Diacid ester; Calcium oxide (purchased from Suzhou Bosheng Industry and Trade Co., Ltd.) and zinc oxide (purchased from Seoul International Trade (Shanghai) Co., Ltd.) equimolar with glycerin were added to glycerin butenedioic acid ester in normal pressure, 180°C for 2h, lower the temperature to 100°C, add triglycidyl isocyanurate (purchased from Suzhou Fulu Biotechnology Co., Ltd.) with a molar ratio of 0.4:1 to glycerin, continue to react for 1.5h, and the obtained product is dried 1. After crushing, pass through a 100-mesh sieve to obtain the main stabilizer.

The BET specific surface area of the thiophene porous polymer is 1050m ² ·g ^-1 .

A kind of preparation method of special low-odor phenol-free barium-zinc stabilizer for toy film, specifically comprises the following steps:

(1) Add the main stabilizer and amide wax (purchased from Guangzhou Yirui New Material Co., Ltd.) into the reaction kettle and mix thoroughly; take the mixed material, add it to a kneader, heat to 80°C and stir, and knead at 120°C for 30 minutes ;

(2) Add thiophene porous polymer and stearyl benzoylmethane (purchased from Anhui Jiaxian Functional Auxiliary Co., Ltd.) into the kneader of step (1), knead and stir for 40-50min; Sieve and pack to obtain a PVC heat stabilizer containing a covalent organic framework.

testing method:

Nitrogen adsorption-desorption curve: The sample was degassed at 100°C for 10 hours, the test temperature was 77K, and the specific surface area was calculated using the nitrogen adsorption-desorption isotherm of Micromeritics ASAP 2020M+C. of.

Performance Testing:

The raw materials used in the PVC sample are as follows:

100 parts by mass of PVC resin;

0.5-0.8 parts by mass of low-odor phenol-free barium-zinc stabilizer for toy films;

The polyethylene wax of 3 mass parts;

The diatomite of 20 mass parts; (Hebei Maofa Mineral Products Processing Co., Ltd., 1200 orders)

3 parts by mass of KH550;

After mixing PVC resin, the low-odor phenol-free barium-zinc special-purpose stabilizer for toy films prepared in this embodiment, the addition amount is 0.6wt%, and other auxiliary agents at high speed, after kneading on a double-roller mill, plasticize, lower Slices and slices, cut into small pieces of 5mm*5mm, obtained PVC patterns, and tested, the results are shown in Table 1.

Table 1

Inspired by the above-mentioned ideal embodiment according to the present invention, through the above-mentioned description content, relevant workers can make various changes and modifications within the scope of not departing from the technical idea of the present invention. The technical scope of the present invention is not limited to the content in the specification, but must be determined according to the scope of the claims.

Claims (9)

1. a special low-odor phenol-free barium-zinc stabilizer for toy films, characterized in that it comprises by weight: 100 parts of main stabilizer; 10-15 parts of thiophene porous polymer; 5-8 parts of lubricant; 4 to 9 parts of phenol-free antioxidant; Auxiliary stabilizer 20-30 parts. 2. the special low-odor phenol-free barium-zinc stabilizer for a kind of toy film according to claim 1, is characterized in that: described main stabilizer is prepared by following method: Add glycerol and organic carboxylic acid into the stirred reactor at a molar ratio of 1: (1-5), react at normal pressure and 100-130°C for 5-10 hours to obtain glycerin organic carboxylic acid ester; Add zinc oxide to glycerol organic carboxylate, react at normal pressure, 160-180°C for 3-5h, cool down to 100°C, add triglycidyl isocyanurate with a molar ratio of (0.1-0.5): 1 to glycerol , Continue to react for 1-2h, the obtained product is dried and pulverized to obtain the main stabilizer. 3. a special low-odor phenol-free barium-zinc stabilizer for toy films according to claim 2, characterized in that: the organic carboxylic acid is one of formic acid, acetic acid, glutaconic acid, and butenedioic acid kind. The special low-odor phenol-free barium-zinc stabilizer for toy films according to claim 1, characterized in that the specific surface area of the thiophene porous polymer is 1050 m ² ·g ^-1 . 5. A special low-odor phenol-free barium-zinc stabilizer for toy films according to claim 1, characterized in that: the thiophene porous polymer is tetrathieno[1,2-b:4,3-b' :5,6-b'':8,7-b'''] cyclooctatetraene. 6. A special low-odor phenol-free barium-zinc stabilizer for toy films according to claim 1, characterized in that: the lubricant is one of butyl stearate, paraffin wax, polyethylene wax, and amide wax . 7. A special low-odor phenol-free barium-zinc stabilizer for toy films according to claim 1, characterized in that: the phenol-free antioxidant is furanone, phthalide, N,N-dibenzyl hydroxylamine kind of. 8. A special low-odor phenol-free barium-zinc stabilizer for toy films according to claim 1, characterized in that: said auxiliary stabilizer is triphenyl phosphite, epoxy soybean oil, sorbitol, diphenyl One of formylmethane and stearyl benzoylmethane. 9. A method for preparing the special low-odor phenol-free barium-zinc stabilizer for toy films as claimed in any one of claims 1-8, characterized in that it comprises the following steps: (1) Add the main stabilizer and lubricant into the reaction kettle and mix thoroughly; take the mixed material, add it to the kneader, heat it to 70-80°C and stir, add phenol-free antioxidant, and knead at 90-120°C for 30- 40min; (2) Add thiophene porous polymer and auxiliary stabilizer to the kneader in step (1), knead and stir for 40-50 min; discharge, press, sieve, and package to obtain a PVC heat-stabilized compound containing a covalent organic framework. agent.