阅读说明：本技术 一种防潮钙锌稳定剂及制备方法 (Moistureproof calcium-zinc stabilizer and preparation method thereof ) 是由 洪颖 吴蔚 胡佩 晏敏辉 于 2021-09-03 设计创作，主要内容包括：本发明就是要提供一种防潮钙锌稳定剂及制备方法,属于稳定剂技术领域。防潮钙锌稳定剂的制备,按重量百分比计包含以下组分：硬脂酸锌22％、赛克10％、沸石35％、多元醇8％、硬脂酸钙5％、氢氧化钙5％、乙酰丙酮锌5％、乙酰丙酮钙5％、与水滑石5％、抗氧剂3％、尿嘧啶2％。制备的钙锌稳定剂,环保无异味,在大批量应用在PVC制品造粒后,能确保产品在一个月内不吸潮,保证生产正常使用。(The invention provides a moisture-proof calcium-zinc stabilizer and a preparation method thereof, belonging to the technical field of stabilizers. The preparation method of the moisture-proof calcium-zinc stabilizer comprises the following components in percentage by weight: 22% of zinc stearate, 10% of seek, 35% of zeolite, 8% of polyhydric alcohol, 5% of calcium stearate, 5% of calcium hydroxide, 5% of zinc acetylacetonate, 5% of calcium acetylacetonate, 5% of hydrotalcite, 3% of antioxidant and 2% of uracil. The prepared calcium-zinc stabilizer is environment-friendly and free of peculiar smell, and can ensure that the product does not absorb moisture within one month and ensure normal use of production after being applied to granulation of PVC products in large batches.)

1. The preparation method of the moisture-proof calcium-zinc stabilizer is characterized in that the moisture-proof calcium-zinc stabilizer comprises the following components in percentage by weight:

23-29% of stearate, 8-11% of cycico, 30-36% of zeolite, 5-10% of polyol, 3-6% of calcium hydroxide, 3-6% of zinc acetylacetonate, 3-6% of calcium acetylacetonate, 3-6% of hydrotalcite, 1-4% of antioxidant and 1-2% of uracil.

2. The process for preparing a moisture-resistant calcium-zinc stabilizer as claimed in claim 1, which comprises the following steps:

1) mixing the raw materials, and stirring stearate, saxok, polyalcohol and uracil at 45-50 deg.C for 8-9 min; 2) Performing catalytic reaction, adding water zeolite and calcium hydroxide, adding a catalyst at the same time, and continuously stirring for 18-20 min; 3) Preparing a damp-proof calcium-zinc stabilizer, finally adding zinc acetylacetonate, calcium acetylacetonate, hydrotalcite and an antioxidant according to the proportion of the components, stirring and reacting for 9-10min at the temperature of 50-65 ℃ under the condition of protective gas, stopping stirring, standing and cooling to obtain a damp-proof calcium-zinc stabilizer product.

3. The method for preparing a moisture-proof Ca-Zn stabilizer as claimed in claim 1, wherein the stirring in step 1) is intermittent and/or continuous stirring, and the stirring rate is controlled at 100-250 r/min.

4. The process for preparing a moisture-proof Ca-Zn stabilizer as claimed in claim 1, wherein the continuous stirring rate in step 2) is 80-150 r/min.

5. The method for preparing the moisture-proof calcium-zinc stabilizer according to claim 1, wherein the catalyst in the step 2) is a dilute acetic acid aqueous solution with the concentration of 0.02-0.08 mol/L; meanwhile, the adding speed of the catalyst dilute acetic acid aqueous solution is controlled to be 0.03ml/1s-0.03ml/10 s.

6. The process of claim 1, wherein said protective gas of step 3) is nitrogen or argon.

7. The process of claim 1, wherein said antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].

The technical field is as follows:

the invention belongs to the technical field of stabilizers for PVC materials, and provides a preparation method of a stabilizer amount, in particular to a moisture-proof calcium-zinc stabilizer and a preparation method thereof.

Background art:

it is known that the performance of the stabilizer has a great influence on the stability of the PVC material in the preparation process of the PVC material. The calcium-zinc heat stabilizer containing the metal soap gradually becomes a mainstream product in the heat stabilizer in recent decades due to the advantages of no toxicity, environmental protection, moderate price, good stabilizing effect and the like. The stabilizing/lubricating system plays a certain positive role in improving the processing fluidity and the thermal stability of PVC. However, there are also disadvantages that are not easily overcome.

The PVC stabilizer used in the market at present is added with a large amount of zeolite, the water content of the zeolite is higher and is usually about 5-8%, the formula contains substances with strong water absorption such as calcium oxide, calcium hydroxide and the like, the water absorption substances need to be reduced or removed when the formula needs to achieve better moisture resistance, but the stability of the material is unfavorable, in order to solve the problem that part of hydrotalcite, zinc acetylacetonate, calcium acetylacetonate and the like which have good temperature resistance and compatibility and little precipitation amount need to be added in the formula of the stabilizer of the system of the contradiction to replace the materials, the heat stability is improved, the adding amount of the stabilizer in a PVC product is relatively small, the contradiction of high selling price is balanced, and the moisture-proof calcium-zinc composite stabilizer prepared according to the method is suitable for soft and semi-hard full-color environment-friendly PVC products without peculiar smell and toxicity, and is particularly suitable for nontoxic wires and cables with the specification of 70-105 ℃.

For example, in chinese patent application publication No. CN111793198A, a calcium salt suitable for PVC calcium zinc stabilizer and a preparation method thereof, the raw material used for preparing the PVC environment-friendly calcium zinc stabilizer is calcium hydroxide or calcium oxide, and the calcium hydroxide or calcium oxide has strong water absorption, so the method is to heat the raw material in a reaction kettle by a heating device at a temperature higher than 100 ℃ to remove the water in the raw material, thereby preparing the calcium zinc stabilizer. The method used in the method needs to use a heating device for production, so that the production cost is increased, the operation intensity of workers is higher, and the prepared thermal stability is insufficient, so that the stability of the moisture-proof calcium-zinc stabilizer is influenced.

Also, as disclosed in chinese patent application publication No. CN112250970A, "high stability environment-friendly calcium zinc stabilizer for PVC" and its preparation method ", the preparation method uses calcium stearate and zinc stearate as raw materials, and prepares the calcium zinc stabilizer by heating and stirring, and the above preparation methods cannot solve the problems of incomplete conversion rate of stearate preparation, high preparation cost, and the like.

Therefore, how to provide a preparation method of the moisture-proof calcium-zinc stabilizer can solve the problem that a large amount of zeolite is added in the formula of the conventional stabilizer, and the moisture content of the zeolite is higher and is usually as high as about 5% -8%; after the stabilizer is applied to PVC product granulation in large batch, the product can be ensured not to absorb moisture within one month, and the normal use of production is ensured. Is especially suitable for soft and semi-hard full-color environment-friendly nontoxic PVC products and nontoxic wires and cables with the specification of 70-105 ℃.

The invention content is as follows:

the invention provides a preparation method of a moistureproof calcium-zinc stabilizer, which mainly comprises the following components: stearate, mosaic, zeolite, polyalcohol, calcium hydroxide, zinc acetylacetonate, calcium acetylacetonate, hydrotalcite, uracil and the like, and the prepared moisture-proof calcium-zinc stabilizer can solve the problem that a large amount of zeolite is added in the formula of the conventional stabilizer, and the moisture content of the zeolite is higher and is usually as high as about 5-8 percent; after the stabilizer is applied to PVC product granulation in large batch, the product can be ensured not to absorb moisture within one month, and the normal use of production is ensured.

The invention discloses a preparation method of a damp-proof calcium-zinc stabilizer, which comprises the following components in percentage by weight:

23-29% of stearate, 8-11% of cycico, 30-36% of zeolite, 5-10% of polyol, 3-6% of calcium hydroxide, 3-6% of zinc acetylacetonate, 3-6% of calcium acetylacetonate, 3-6% of hydrotalcite, 1-4% of antioxidant and 1-2% of uracil.

The preparation method of the damp-proof calcium-zinc stabilizer is prepared according to the following steps:

1) mixing the raw materials, and stirring stearate, saxok, polyalcohol and uracil at 45-50 deg.C for 8-9 min;

2) performing catalytic reaction, adding water zeolite and calcium hydroxide, adding a catalyst at the same time, and continuously stirring for 18-20 min;

3) preparing a damp-proof calcium-zinc stabilizer, finally adding zinc acetylacetonate, calcium acetylacetonate, hydrotalcite and an antioxidant according to the proportion of the components, stirring and reacting for 9-10min at the temperature of 50-65 ℃ under the condition of protective gas, stopping stirring, standing and cooling to obtain a damp-proof calcium-zinc stabilizer product.

In the preparation method of the moisture-proof calcium-zinc stabilizer, the stirring in the step 1) is preferably interrupted and/or continuous, and the stirring speed is controlled at 100-250 r/min.

Further, the continuous stirring speed of the step 2) is 80-150 r/min.

Preferably, the catalyst in the step 2) is a dilute acetic acid aqueous solution with the concentration of 0.02-0.08 mol/L; meanwhile, the adding speed of the catalyst dilute acetic acid aqueous solution is controlled to be 0.03ml/1s-0.03ml/10 s.

Preferably, the protective gas in step 3) is nitrogen or argon.

The antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.

The moisture-proof calcium-zinc stabilizer and the preparation method thereof disclosed by the invention have the following beneficial effects that the preparation method of the moisture-proof calcium-zinc stabilizer is low in cost, energy consumption and water consumption, low in pollution, environment-friendly and free of peculiar smell; secondly, the moisture-proof calcium-zinc composite stabilizer prepared by the method is strong, is suitable for soft and semi-hard full-color environment-friendly nontoxic PVC products, and is particularly suitable for nontoxic electric wires and cables with the specification of 70-105 ℃. Thirdly, the moisture-proof calcium-zinc stabilizer prepared by the invention can ensure that the product does not absorb moisture within one month and ensure the normal use of the product after being applied to the granulation of PVC products in batches.

The specific implementation mode is as follows:

the present invention will be described in further detail with reference to specific embodiments, and the respective compositions of the present invention can be commercially available. The mass portion or the mass percentage of the mixture,

the invention provides a preparation method of a moistureproof calcium-zinc stabilizer, which comprises the following components in percentage by weight:

27% of stearate, 10% of seek, 35% of zeolite, 8% of polyhydric alcohol, 5% of calcium hydroxide, 3-8% of zinc acetylacetonate, 3-8% of calcium acetylacetonate, 3-8% of hydrotalcite, 3% of antioxidant and 2% of uracil;

the preparation method of the damp-proof calcium-zinc stabilizer is characterized by comprising the following steps:

1) according to the component proportion, stearate, cecum, polyalcohol and uracil are intermittently and/or continuously stirred for 8-9min at the temperature of 45-50 ℃, and the stirring speed is controlled at 250 r/min;

2) adding zeolite and calcium hydroxide, adding dilute acetic acid aqueous solution with concentration of 0.02-0.08mol/L, controlling the speed of adding dilute acetic acid aqueous solution to be 0.03ml/1s-0.03ml/10s, continuously stirring for 18-20min, and controlling the stirring speed to be 80-150 r/min;

3) and finally adding zinc acetylacetonate, calcium acetylacetonate, hydrotalcite and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester according to the component proportion, stirring for 9-10min at the temperature of 75-80 ℃ under the condition of matching with nitrogen protection, and cooling to obtain the calcium-zinc stabilizer.

The moisture-proof calcium-zinc heat stabilizer has the beneficial effects that a large amount of zeolite is added in a conventional stabilizer formula, the content of calcium oxide and calcium hydroxide needs to be removed or reduced due to high moisture content of the zeolite, and the production efficiency is improved by adding the materials of hydrotalcite, zinc acetylacetonate and calcium acetylacetonate in a specific proportion and a catalyst in a specific content, so that the heat stabilizer can be effectively prevented from absorbing external moisture, reworking and hot drying are not needed, processes such as reworking and hot drying of PVC products and vacuum packaging are omitted, the cost is saved for enterprises, and the PVC products are bright and have no pores. Meanwhile, the technology has wide adaptability, can select different types of calcium-zinc heat stabilizers as the main body, and is easy to industrialize and popularize. After the preparation method is applied to the preparation of nontoxic electric wires and cables with the specification of 70-105 ℃, the quality indexes of the electric wires and cables can completely reach the specified national quality requirements through detection. Meanwhile, after the PVC granulation liquid is applied to granulation of PVC products, the prepared PVC products are ensured not to absorb moisture within one month, and normal use of production is ensured.

In the following examples, the same as the above-described embodiments are not described except for the following description of examples.

Example 1:

the invention provides a preparation method of a damp-proof calcium-zinc stabilizer, which comprises the following components in percentage by weight:

27% of stearate, 10% of seek, 35% of zeolite, 8% of polyhydric alcohol, 5% of calcium hydroxide, 3-8% of zinc acetylacetonate, 3-8% of calcium acetylacetonate, 3-8% of hydrotalcite, 3% of antioxidant and 2% of uracil;

the preparation method of the moisture-proof calcium-zinc stabilizer is characterized by comprising the following steps:

1) according to the component proportion, stearate, cecum, polyalcohol and uracil are intermittently and/or continuously stirred for 8-9min at the temperature of 45-50 ℃, and the stirring speed is controlled at 250 r/min;

2) adding zeolite and calcium hydroxide, adding dilute acetic acid aqueous solution with concentration of 0.02-0.08mol/L, controlling the speed of adding dilute acetic acid aqueous solution to be 0.03ml/1s-0.03ml/10s, continuously stirring for 18-20min, and controlling the stirring speed to be 80-150 r/min;

3) and finally adding zinc acetylacetonate, calcium acetylacetonate, hydrotalcite and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester according to the component proportion, stirring for 9-10min at the temperature of 75-80 ℃ under the condition of matching with nitrogen protection, and cooling to obtain the calcium-zinc stabilizer.

The samples are respectively added into PVC, and meanwhile, plasticizer, calcium carbonate, pigment and the like are added, stirred and granulated on an extruder. PVC particles are put in 70 ℃ water for 72 hours, and the weight increase ratio is 0.01 percent;

the moisture-proof calcium-zinc stabilizer product prepared by the method and the components effectively solves the problem that partial hydrotalcite, zinc acetylacetonate, calcium acetylacetonate and other materials with excellent temperature resistance and compatibility and less precipitation amount need to be added in the formula of the stabilizer in a system product for replacement, improves the thermal stability of the product, and relatively less addition amount is added in a pvc product, so that the contradiction of high selling price is balanced, and the product performance is greatly improved.

In the case of the example 2, the following examples are given,

this example is the same as example 1 above except for the following explanation,

the contents of zinc acetylacetonate, calcium acetylacetonate, and hydrotalcite used in this example in the components are preferably changed, and the specific mass percentages of the components are as follows; 25% of stearate, 10% of seek, 32% of zeolite, 8% of polyol, 5% of calcium hydroxide, 5% of zinc acetylacetonate, 5% of calcium acetylacetonate, 5% of hydrotalcite, 3% of antioxidant and 2% of uracil.

The preparation method of the moisture-proof calcium-zinc stabilizer is characterized by comprising the following steps:

1) according to the component proportion, the stearate, the saxok, the polyalcohol and the uracil are intermittently and/or continuously stirred for 8-9min at the temperature of 45-50 ℃, and the stirring speed is controlled at 200 r/min;

2) adding zeolite and calcium hydroxide, adding dilute acetic acid aqueous solution with concentration of 0.02-0.08mol/L, controlling the speed of adding dilute acetic acid aqueous solution to be 0.03ml/1s-0.03ml/10s, continuously stirring for 20min, and controlling the stirring speed to be 120 r/min;

3) and finally, adding zinc acetylacetonate, calcium acetylacetonate, hydrotalcite and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester according to the component proportion, stirring for 9-10min at the temperature of 80 ℃ under the condition of matching argon protection, and cooling to obtain the calcium-zinc stabilizer.

Comparative example 1:

the comparative example does not add zinc acetylacetonate, calcium acetylacetonate, and hydrotalcite;

the comparative example of the invention comprises the following components in percentage by weight:

30% of stearate, 10% of seek, 40% of zeolite, 10% of polyol, 5% of calcium hydroxide, 3% of antioxidant and 2% of uracil. The preparation of the comparative examples is carried out according to the process of the invention or according to the processes of the prior art or modified on the basis of the process of the invention,

the preparation method of the calcium zinc stabilizer comprises the following steps:

1) according to the component proportion, the stearate, the saxok, the polyalcohol and the uracil are intermittently and/or continuously stirred for 8-9min at the temperature of 45-50 ℃, and the stirring speed is controlled at 80 r/min;

2) then adding zeolite and calcium hydroxide, simultaneously adding a dilute acetic acid aqueous solution with the concentration of 0.01mol/L, simultaneously controlling the speed of adding the dilute acetic acid aqueous solution to be 0.03ml/1s-0.03ml/10s, and continuously stirring;

3) finally, adding tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester according to the proportion of the components, stirring for 9-10min at the temperature of 75-80 ℃ under the protection of nitrogen, and cooling to obtain a calcium-zinc stabilizer;

and respectively adding the calcium-zinc stabilizer samples into PVC, adding a plasticizer, calcium carbonate, pigment and the like, stirring materials, and granulating on an extruder. The PVC particles were placed in 70 ℃ water for 72 hours, the weight gain being 3.7%.

Application examples

The moistureproof calcium zinc stabilizer prepared by the method is applied to PVC product forming agents, and the moistureproof calcium zinc stabilizer product prepared by the method is provided for some detection technology company Limited in Shanghai for detection according to a detection report of the detection technology company Limited in Shanghai:

and (3) checking and detecting basis: the PV3900:2000, model,

detecting items: the odor test was conducted on a sample of a sample,

sample storage conditions: 23 +/-2 ℃ of the temperature of the reaction kettle,

relative humidity: 50 percent plus or minus 5 percent,

the detection device comprises: constant temperature forced air drying case LRH-250, equipment number: TTE20164629 and the like,

in the context of Table 1, the following examples are,

the moisture-proof calcium-zinc stabilizer prepared by the method is applied to PVC product forming agents, all technical indexes meet requirements, for example, the thermal stability time of 200 ℃ is more than twice of that of the prior art, and the product thermal stability is high. Meanwhile, the problems that partial hydrotalcite, zinc acetylacetonate, calcium acetylacetonate and the like need to be added in a stabilizer formula of a system product, the characteristics of high temperature resistance, excellent compatibility and the like are solved, the heat stabilizer is effectively prevented from absorbing external moisture, reworking and hot drying are not needed, the processes of reworking, hot drying, vacuum packaging and the like of PVC products are omitted, the cost is saved for enterprises, and the PVC products are bright and have no air holes.