阅读说明：本技术 一种pvc发泡功能母粒及其制备方法 (PVC foaming functional master batch and preparation method thereof ) 是由 何志兰 聂志军 章超 高亮 杨阳 于 2020-03-31 设计创作，主要内容包括：本发明提供了一种PVC发泡功能母粒,以及提供了所述PVC发泡功能母粒的制备方法,所述PVC发泡功能母粒包括PVC树脂,发泡剂,发泡助剂,稳定剂和增塑剂,其中基于100重量份的所述PVC树脂,所述发泡剂为1-4重量份,所述发泡助剂为1.5-2.2重量份,所述稳定剂为2-2.6重量份,所述增塑剂为85-95重量份。本发明的PVC发泡功能母粒具有无毒环保、发泡效果好等特点,本发明PVC发泡功能母粒的发泡制品气泡分布规整,能有效的降低PVC发泡制品的密度和收缩率。(The invention provides a PVC foaming functional master batch and a preparation method of the PVC foaming functional master batch, wherein the PVC foaming functional master batch comprises 1-4 parts by weight of a PVC resin, 1.5-2.2 parts by weight of a foaming agent, 2-2.6 parts by weight of a stabilizer and 85-95 parts by weight of a plasticizer based on 100 parts by weight of the PVC resin. The PVC foaming functional master batch has the characteristics of no toxicity, environmental protection, good foaming effect and the like, and the foamed product of the PVC foaming functional master batch has regular bubble distribution and can effectively reduce the density and shrinkage rate of the PVC foamed product.)

1. A PVC foaming functional master batch, which comprises:

PVC resin, a foaming agent, a foaming auxiliary agent, a stabilizing agent and a plasticizing agent,

wherein based on 100 parts by weight of the PVC resin, the foaming agent is 1-4 parts by weight, the foaming auxiliary agent is 1.5-2.2 parts by weight, the stabilizer is 2-2.6 parts by weight, and the plasticizer is 85-95 parts by weight.

2. The PVC foaming functional masterbatch of claim 1, wherein the PVC resin is selected from the group consisting of SG-5, SG-7, and combinations thereof.

3. The PVC foaming concentrate of claim 1, wherein the foaming agent is a combination of thermally expandable microspheres and one or more of azo compounds, nitroso compounds or hydrazide compounds, wherein the thermally expandable microspheres are formed by a polymer shell with a volatile expanding agent encapsulated therein as a core agent.

4. The PVC foaming functional masterbatch of claim 3, wherein the shell is formed by polymerizing a monomer mixture of polymerizable monomers, wherein the polymerizable monomers are at least one of acrylonitrile monomers, acrylate monomers, acrylamide monomers and acrylic monomers.

5. The PVC foaming functional masterbatch of claim 1, wherein the foaming auxiliary agent is one or more of ZB530, K400, ZnO, PE wax and paraffin wax.

6. The PVC foaming functional masterbatch of claim 1, wherein the stabilizer is a zinc soap stabilizer, a calcium soap stabilizer or a complex of a calcium zinc composite stabilizer and an auxiliary stabilizer.

7. The PVC foaming functional masterbatch of claim 6, wherein the secondary stabilizer is one or more of hydrotalcite, epoxidized soybean oil, phosphite, epoxidized linseed oil, epoxidized butyl stearate, and epoxidized octyl stearate.

8. The PVC foaming functional masterbatch of claim 3, wherein the foaming agent is a compound of thermally expandable microspheres and an azo compound, and the azo compound is an AC foaming agent.

9. The PVC foaming functional masterbatch of claim 8, wherein the thermally expandable microspheres are 0.8 to 1 part by weight and the AC foaming agent is 0.2 to 3 parts by weight, based on 100 parts by weight of the PVC resin.

10. The preparation method of the PVC foaming functional masterbatch according to any one of claims 1 to 9, comprising the steps of:

(1) adding PVC resin and a plasticizer into an internal mixer, mixing and heating;

(2) adding the mixed PVC resin and plasticizer from a main feeding port of a double-screw extruder, adding a stabilizer into the double-screw extruder, and adding a foaming agent and a foaming auxiliary agent into a side feeding port;

(3) the material extruded by the double-screw extruder is processed by an air-cooled hot cutting granulator to obtain high-temperature PVC foaming functional master batches; and

(4) and cooling the high-temperature PVC foaming functional master batch obtained by the air cooling hot cutting granulator by an air cooling device to obtain the PVC foaming functional master batch.

Technical Field

The invention relates to a nontoxic and environment-friendly PVC foaming functional master batch and a preparation method of the PVC foaming functional master batch, belonging to the field of functional master batch granulation.

Background

Polyvinyl chloride (PVC) is one of five synthetic resins with the largest usage in the world, and PVC materials have the characteristics of high strength, low price, good chemical corrosion resistance, good electrical insulation, difficult combustion and the like, and are widely used in the fields of shoe making industry, engineering construction, food packaging and electricity.

Certain foaming agent is required to be added in the preparation process of PVC foaming products, and the foaming agent added at present is mainly an organic chemical foaming agent, such as azodicarbonamide. Patent CN103304919B adopts azodicarbonamide as foamer preparation PVC foaming sole material, but azodicarbonamide decomposition temperature is higher to belong to exothermic foamer, constantly release heat at the decomposition in-process, make the temperature rise rapidly, the temperature range of decomposition is shorter, leads to azodicarbonamide's decomposition to have the proruption, and the pore structure is irregular.

The forming temperature of PVC products is above 170 ℃, and PVC begins to decompose when the temperature reaches about 130 ℃, so a heat stabilizer must be added in the PVC processing process, the stabilizer used in the current domestic large-scale production of PVC is a lead salt stabilizer, the plasticizer is phthalic acid, lead is toxic heavy metal, and phthalic acid is carcinogen, and along with the release of a series of environmental protection laws and standards, the solution of the problems of no toxicity and environmental protection is particularly important. The stabilizer in the patent CN104262860B adopts organic tin which is expensive and not suitable for production, and tin is a toxic metal. Patent CN110128761A adopts calcium zinc stearate as a heat stabilizer, but the calcium zinc stearate heat stabilizer has the defect of poor long-term stability. Patents CN103289243B, CN103589089B and the like adopt DOP as a plasticizer, and DOP is a carcinogen, and is easy to migrate to the surface of a product, thus being harmful to human health.

Disclosure of Invention

Therefore, in order to overcome the disadvantages of the prior art, the invention aims to provide a PVC foaming functional master batch. Compared with the existing foaming functional master batch, the PVC foaming functional master batch has the characteristics of no toxicity, environmental protection, good foaming effect and the like. The foamed product of the PVC foaming functional master batch has regular bubble distribution, and can effectively reduce the density and shrinkage rate of the PVC foamed product.

In order to achieve the purpose, the nontoxic environment-friendly PVC foaming functional master batch provided by the invention comprises PVC resin, a foaming agent, a foaming auxiliary agent, a stabilizer and a plasticizer.

Preferably, the PVC resin is one or two of SG-5 and SG-7;

the foaming agent is a compound of thermal expansion microspheres and one or more of azo compounds, nitroso compounds and yellow hydrazide compounds, wherein the thermal expansion microspheres are volatile expansion agents serving as core agents and are encapsulated in a shell formed by polymers. The shell is formed by polymerizing a monomer mixture of polymerizable monomers, and the polymerizable monomers are formed by at least one of acrylonitrile, acrylate monomers, acrylamide monomers and acrylic monomers;

the foaming auxiliary agent is one or more of ZB530, K400, ZnO, PE wax and paraffin;

the stabilizer is a zinc soap stabilizer, a calcium soap stabilizer or a complex of a calcium-zinc composite stabilizer and an auxiliary stabilizer;

the auxiliary stabilizer is one or more of hydrotalcite, epoxidized soybean oil, phosphite ester, epoxidized linseed oil, epoxidized butyl stearate and epoxidized octyl stearate;

the plasticizer is one or more of triethyl citrate (TEC), tributyl citrate (TBC), acetyl tributyl citrate (ATBC), butyryl tri-n-hexyl citrate (BTHC) and cyclohexane 1, 2-diisononyl phthalate (DINCH).

Preferably, the PVC resin is SG-7, the foaming agent is a compound of thermal expansion microspheres and azo compounds, the foaming aid is ZB530, the stabilizer is a compound of a calcium-zinc composite stabilizer and an auxiliary stabilizer, and the plasticizer is one of tributyl citrate (TBC) and diisononyl cyclohexane 1, 2-Dicarboxylate (DINCH).

Preferably, the nontoxic environment-friendly PVC foaming functional master batch comprises the following components in parts by weight: 100 parts of PVC resin, 1-4 parts of foaming agent, 1.5-2.2 parts of foaming auxiliary agent, 2-2.6 parts of stabilizer and 85-95 parts of plasticizer.

Preferably, the foaming agent is a compound of thermal expansion microspheres and an azo compound, the azo compound is an AC foaming agent, and the weight parts are as follows: 100 parts of PVC resin, 1-4 parts of foaming agent (wherein the thermal expansion microspheres are 0.8-1 part, and the AC foaming agent is 0.2-3 parts), 1.5-2.2 parts of foaming auxiliary agent, 2-2.6 parts of stabilizing agent, and 85-95 parts of plasticizer.

The specific preparation method of the nontoxic environment-friendly PVC foaming functional master batch comprises the following steps:

the first step is as follows: adding PVC resin and plasticizer into an internal mixer according to the above weight parts, mixing, heating to 70-80 ℃, and stirring for 10-15 min;

the second step is that: adding the mixed PVC resin and plasticizer from a main feeding port of a double-screw extruder, adding the stabilizer in parts by weight into the double-screw extruder, adding the foaming agent and the foaming auxiliary agent in parts by weight into a side feeding port, wherein the extrusion temperature of the double-screw extruder is 100-110 ℃, and the rotating speed of the double-screw extruder is 50-150 r/min;

the third step: extruding materials by a double-screw extruder, and obtaining high-temperature PVC foaming functional master batches by an air-cooled hot-cutting granulator;

the fourth step: and cooling the high-temperature PVC foaming functional master batch obtained by the granulator to 40-50 ℃ by using an air cooling device to prepare the PVC foaming functional master batch.

The invention adopts nontoxic and environment-friendly calcium-zinc composite stabilizer as the stabilizer of PVC foaming products such as PVC foaming shoe materials, one or more of hydrotalcite, epoxidized soybean oil, phosphite ester and the like are compounded to be used as the composite stabilizer, and one or more of environment-friendly and nontoxic DINCH and citrate are adopted as the plasticizer.

In order to enable PVC foaming product manufacturers to use the thermal expansion microspheres more conveniently and quickly, simplify the production flow, improve the dispersibility of the foaming agent in PVC resin, improve the foaming effect and improve the performance of PVC foaming products, the PVC foaming functional master batch special for the PVC foaming products is prepared, and is non-toxic and environment-friendly.

Compared with the prior art, the PVC foaming functional master batch and the preparation method thereof have the following unexpected beneficial effects:

(1) the thermal expansion microspheres are used as a physical foaming agent and compounded with an AC foaming agent, so that the obtained product is uniformly and stably foamed, and the bursting property and the uncontrollable property of AC foaming are compensated.

(2) When the nontoxic environment-friendly PVC foaming master batch is used for producing PVC foaming products, the PVC raw material is directly added, and other raw materials such as foaming agent, plasticizer, stabilizer and the like do not need to be added, so that the production flow of the blow-molded slippers is greatly simplified.

(3) The calcium-zinc composite stabilizer is selected as a main stabilizer, does not contain heavy metal, and is non-toxic and environment-friendly; one or more of hydrotalcite, epoxidized soybean oil and phosphite ester are selected as auxiliary stabilizers, so that the stabilizing effect on PVC resin is enhanced; the citric acid esters are selected as the plasticizer, so that the plasticizer is non-toxic and environment-friendly.

(4) The PVC resin and the plasticizer are mixed and heated by an internal mixer, the double-screw extruder is provided with two feeding ports, the mixture of the PVC resin and the plasticizer and the stabilizing agent are added from the main feeding port, and the foaming agent and the foaming auxiliary agent are added from the side feeding port, so that the phenomenon that the thermal expansion microspheres in master batches are foamed due to the fact that the thermal expansion microspheres are in a heating state for a long time is avoided, and the foaming performance of products is influenced.

(5) The thermal expansion microspheres are used as a foaming agent of the PVC foaming material, so that gas decomposed by azodicarbonamide is prevented from being released rapidly, the structure of bubbles is more uniform and regular, the compatibility of the thermal expansion microsphere foaming agent and the PVC material is good, the density and the shrinkage rate of the PVC shoe material can be reduced, and the heat insulation property of the PVC shoe material is improved.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to specific embodiments below. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way.

The heat-expandable microspheres in the following examples were those produced by seiko chemical technology (shanghai) ltd.

Example 1

The nontoxic environment-friendly PVC foaming functional master batch comprises the following components in parts by mass: 100 parts of SG-7PVC resin, 100 parts of foaming agent compound: 0.8 part of thermal expansion microspheres, 1.2 parts of AC foaming agent, 2 parts of ZB530 foaming auxiliary agent and a stabilizer compound: 1.8 parts of calcium-zinc composite stabilizer, 0.6 part of hydrotalcite and 80 parts of plasticizer tributyl citrate (TBC).

The preparation method of the nontoxic environment-friendly PVC foaming functional master batch comprises the following steps:

the first step is as follows: adding SG-7PVC resin and plasticizer tributyl citrate (TBC) into an internal mixer according to the above weight parts, mixing, heating to 70-80 ℃, and stirring for 10-15 min;

the second step is that: adding a mixture of the mixed SG-7PVC resin and a plasticizer tributyl citrate (TBC) from a main feeding port of a double-screw extruder, adding the calcium-zinc composite stabilizer and the hydrotalcite in parts by weight into the double-screw extruder, adding the thermal expansion microspheres, the AC foaming agent and the ZB530 foaming auxiliary agent in parts by weight into a side feeding port, wherein the extrusion temperature of the double-screw extruder is 100-110 ℃, and the rotating speed is 50-150 r/min;

the third step: extruding materials by a double-screw extruder, and obtaining nontoxic and environment-friendly high-temperature PVC foaming functional master batches by an air-cooled hot cutting granulator;

the fourth step: and cooling the high-temperature PVC foaming functional master batch obtained by the granulator to 40-50 ℃ by using an air cooling device to prepare the nontoxic environment-friendly PVC foaming functional master batch.

Example 2

The nontoxic environment-friendly PVC foaming functional master batch comprises the following components in parts by mass: 100 parts of SG-7PVC resin, 100 parts of foaming agent compound: 0.8 part of thermal expansion microspheres, 1.2 parts of AC foaming agent, 2 parts of ZB530 foaming auxiliary agent and a stabilizer compound: 1 part of calcium-zinc composite stabilizer, 0.6 part of epoxidized soybean oil, 0.6 part of phosphite ester and 80 parts of tributyl citrate (TBC).

The preparation method of the nontoxic environment-friendly PVC foaming functional master batch comprises the following steps:

the first step is as follows: adding SG-7PVC resin and plasticizer tributyl citrate (TBC) into an internal mixer according to the above weight parts, mixing, heating to 70-80 ℃, and stirring for 10-15 min;

the second step is that: adding a mixture of the mixed SG-7PVC resin and a plasticizer tributyl citrate (TBC) from a main feeding port of a twin-screw extruder, adding the calcium-zinc composite stabilizer, the epoxidized soybean oil and the phosphite in parts by weight into the twin-screw extruder, adding the thermal expansion microspheres, the AC foaming agent and the ZB530 foaming auxiliary in parts by weight into a side feeding port of the twin-screw extruder, wherein the extrusion temperature of the twin-screw extruder is 100-110 ℃, and the rotating speed of the twin-screw extruder is 50-150 r/min;

the third step: extruding materials by a double-screw extruder, and obtaining nontoxic and environment-friendly high-temperature PVC foaming functional master batches by an air-cooled hot cutting granulator;

the fourth step: and cooling the high-temperature PVC foaming functional master batch obtained by the granulator to 40-50 ℃ by using an air cooling device to prepare the nontoxic environment-friendly PVC foaming functional master batch.

Example 3

The nontoxic environment-friendly PVC foaming functional master batch comprises the following components in parts by mass: 100 parts of SG-7PVC resin, 100 parts of foaming agent compound: 0.8 part of thermal expansion microspheres, 1.2 parts of AC foaming agent, 2 parts of ZB530 foaming auxiliary agent and a stabilizer compound: 1.8 parts of calcium-zinc composite stabilizer, 0.6 part of hydrotalcite and 85 parts of cyclohexane 1, 2-diisononyl phthalate (DINCH) serving as plasticizer.

The preparation method of the nontoxic environment-friendly PVC foaming functional master batch comprises the following steps:

the first step is as follows: adding SG-7PVC resin and a plasticizer cyclohexane 1, 2-diisononyl phthalate (DINCH) into an internal mixer according to the parts by weight, mixing, heating to 70-80 ℃, and stirring for 10-15 min;

the second step is that: adding a mixture of SG-7PVC resin and a plasticizer cyclohexane 1, 2-diisononyl phthalate (DINCH) from a main feeding port of a double-screw extruder, adding the calcium-zinc composite stabilizer and the hydrotalcite in parts by weight into the double-screw extruder, adding the thermal expansion microspheres, the AC foaming agent and the ZB530 foaming auxiliary in parts by weight into a side feeding port, wherein the extrusion temperature of the double-screw extruder is 100-110 ℃, and the rotating speed is 50-150 r/min;

the third step: extruding materials by a double-screw extruder, and obtaining nontoxic and environment-friendly high-temperature PVC foaming functional master batches by an air-cooled hot cutting granulator;

the fourth step: and cooling the high-temperature PVC foaming functional master batch obtained by the granulator to 40-50 ℃ by using an air cooling device to prepare the nontoxic environment-friendly PVC foaming functional master batch.

In order to better illustrate the foaming performance of the PVC foaming functional master batch prepared in the examples and the improvement of the performance of the foaming product, the foaming functional master batch and the polyvinyl chloride of the above three examples were mixed according to the following ratio of 8: 92 were blended and molded into bars in an injection molding machine and tested for properties, the results of which are shown in table 1 below.

TABLE 1

Performance index	Testing instrument	Example 1	Example 2	Example 3
					Density/g.cm-3	Electronic density instrument	0.8043	0.7466	0.7681
Tensile strength/MPa	Universal testing machine	32.72	24.50	22.86
					Elongation at break/%	Universal testing machine	235.47	102.10	137.84
Flexural Strength/MPa	Universal testing machine	37.24	29.65	27.25
					Impact strength/MPa	Universal testing machine	20.13	23.90	25.24

The results in table 1 show that the PVC foaming masterbatch of the present invention can effectively reduce the density and shrinkage of the PVC foamed product.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.