阅读说明：本技术 一种重软pvc材料及其制备方法与应用 (Heavy-soft PVC material and preparation method and application thereof ) 是由 �谷洋 陈光勤 常雪松 于 2021-08-19 设计创作，主要内容包括：本发明公开了一种重软PVC材料,其包括如下重量份的组分：PVC 50～60份、液体增塑剂20～30份、固体增塑剂1～5份、增强剂10～20份、稳定剂1～5份、增韧剂1～10份、润滑剂0.1～0.5份和抗氧剂0.1～0.5份。本发明通过特定种类的液体增塑剂和固体增塑剂对PVC进行协同改性,显著降低了PVC的玻璃化温度,获得高弹性软质PVC；同时还通过特定种类的增强剂对PVC进行补强,进一步提高了PVC的强度、硬度和密度；通过上述两种途径同时作用,对PVC进行塑化增强改性,最终获得高弹性、高密度和中硬度的重软PVC材料,其能有效吸收冲击能量,达到与橡胶减震块相同的缓冲减震效果,且成本比橡胶减震块更低,可替代橡胶减震块用于冰箱等家电中。(The invention discloses a heavy soft PVC material which comprises the following components in parts by weight: 50-60 parts of PVC, 20-30 parts of liquid plasticizer, 1-5 parts of solid plasticizer, 10-20 parts of reinforcing agent, 1-5 parts of stabilizer, 1-10 parts of toughening agent, 0.1-0.5 part of lubricant and 0.1-0.5 part of antioxidant. According to the invention, the liquid plasticizer and the solid plasticizer of a specific kind are used for carrying out synergistic modification on PVC, so that the glass transition temperature of the PVC is obviously reduced, and high-elasticity soft PVC is obtained; meanwhile, the PVC is reinforced by a specific type of reinforcing agent, so that the strength, hardness and density of the PVC are further improved; the two ways act simultaneously to plasticize, enhance and modify PVC, finally obtain the heavy and soft PVC material with high elasticity, high density and medium hardness, which can effectively absorb impact energy, achieve the same buffering and damping effect as the rubber damping block, has lower cost than the rubber damping block, and can replace the rubber damping block to be used in household appliances such as refrigerators.)

1. The heavy soft PVC material is characterized by comprising the following components in parts by weight: 50-60 parts of PVC, 20-30 parts of liquid plasticizer, 1-5 parts of solid plasticizer, 10-20 parts of reinforcing agent, 1-5 parts of stabilizer, 1-10 parts of toughening agent, 0.1-0.5 part of lubricant and 0.1-0.5 part of antioxidant.

2. A heavy, flexible PVC material according to claim 1, wherein the liquid plasticizer comprises at least one of diisononyl phthalate, polyester plasticizer, epoxidized soybean oil, trioctyl trimellitate, and octyl epoxidized fatty acid.

3. A heavy flexible PVC material according to claim 1, wherein the solid plasticizer comprises at least one of the following designations B-02, YH-1800, HLM-401Z.

4. A heavy flexible PVC material according to claim 1, wherein the reinforcing agent comprises at least one of nano-activated calcium carbonate, ground calcium carbonate, iron powder.

5. A heavy flexible PVC material according to claim 1, wherein the stabilizer comprises at least one of a complex heat stabilizer, an organotin heat stabilizer, and a stearate.

6. A heavy flexible PVC material as claimed in claim 1, wherein said toughening agent comprises at least one of nitrile rubber scrap, epoxy natural rubber scrap.

7. A heavy, flexible PVC material according to claim 1, wherein the lubricant comprises at least one of calcium stearate, pentaerythritol stearate, low molecular weight polyethylene, paraffin wax.

8. The heavy, flexible PVC material of claim 1, wherein said antioxidant comprises at least one of antioxidant CA, antioxidant 264, antioxidant 2246, and antioxidant 1076.

9. Use of a heavy flexible PVC material according to any one of claims 1 to 8 for the manufacture of a seismic-damping rubber block.

10. A cushion rubber block, characterized in that, it is made of the heavy soft PVC material according to any claim 1-8.

Technical Field

The invention belongs to the technical field of modified plastics, and particularly relates to a heavy and soft PVC material, and a preparation method and application thereof.

Background

Polyvinyl chloride (PVC) has excellent characteristics of light weight, good wear resistance, weathering resistance, corrosion resistance and the like, also has good mechanical strength and toughness, can meet the use requirements of various fields, is widely applied to various fields such as floors, living goods, building materials, industrial goods and the like, and gradually replaces the traditional materials such as metal, wood and the like. In addition, PVC also has the great advantage that PVC materials with different hardness can be obtained by adjusting the formula. The PVC plastics are divided according to the amount of the contained plasticizer, and are often divided into: hard PVC, the plasticizer content is less than 10 wt%; semi-hard PVC, the plasticizer content is 10 wt% -30 wt%; the plasticizer content of the soft PVC is 30-70 wt%. For example, the sealing strip of the refrigerator door is made of soft PVC, and is used for blocking air from entering the refrigerator and realizing the heat preservation effect of the refrigerator.

At present, most of shock-absorbing rubber blocks (for example, shock-absorbing blocks used in refrigerators) used in the household appliance industry are made of rubber materials, such as natural rubber, nitrile rubber and the like. However, the rubber cushion rubber block has a good damping effect, but is expensive. Therefore, the inventor of the application plans to optimize and improve the cheap PVC material, and uses the PVC material to replace the rubber material to prepare the damping rubber block so as to reduce the manufacturing cost of the damping rubber block on the premise of not reducing the damping effect of the damping rubber block.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide a heavy soft PVC material and a preparation method and application thereof.

In order to realize the purpose, the technical scheme adopted by the invention is as follows:

a heavy soft PVC material comprises the following components in parts by weight: 50-60 parts of PVC, 20-30 parts of liquid plasticizer, 1-5 parts of solid plasticizer, 10-20 parts of reinforcing agent, 1-5 parts of stabilizer, 1-10 parts of toughening agent, 0.1-0.5 part of lubricant and 0.1-0.5 part of antioxidant.

Preferably, the liquid plasticizer includes at least one of diisononyl phthalate (DINP), polyester plasticizer, Epoxidized Soybean Oil (ESO), trioctyl trimellitate (TOTM), and epoxidized octyl fatty acid (ED 3).

Preferably, the solid plasticizer comprises at least one of the following designations B-02, YH-1800, HLM-401Z.

The inventor finds that the liquid plasticizer and the solid plasticizer are compounded according to the proportion of the invention, so that a synergistic interaction effect can be exerted, the molecular chain spacing of PVC is effectively increased and the acting force among PVC molecular chains is weakened under the condition of a small using amount, the vitrification temperature of PVC is remarkably reduced, high-elasticity soft PVC is obtained, the high-elasticity soft PVC can better absorb impact energy, and the same buffering and damping effect as a rubber damping block is achieved.

The inventor also finds that although the damping effect of the damping block is closely related to the high elasticity of the material, the strength, hardness and density of the material also have an important effect on the damping effect of the damping block. Therefore, the PVC material is further reinforced by the reinforcing agent, so that the strength, the hardness and the density of the PVC are improved, and the damping effect of the PVC material is further improved.

Preferably, the reinforcing agent comprises at least one of nano active calcium carbonate, heavy calcium carbonate and iron powder. The inventor finds that the material can effectively reinforce PVC by using the material as a reinforcing agent.

Preferably, the PVC is injection molded grade polyvinyl chloride, preferably of the following grades: at least one of Qilu petrochemical S-1000, Xinjiang celestial PVC-SG3 and Xinjiang celestial PVC-SG 5. The PVC of the grades has better processability, and can achieve the same buffering and damping effect as the rubber damping block after being modified by the plasticizer and the reinforcing agent.

Preferably, the stabilizer comprises at least one of a composite heat stabilizer, an organotin heat stabilizer and a stearate.

Preferably, the toughening agent comprises at least one of nitrile rubber scrap (NBR) and epoxy natural rubber scrap (ENR).

Preferably, the lubricant comprises at least one of calcium stearate, pentaerythritol stearate (PETS), low molecular weight polyethylene (with the molecular weight of 1000-10000 Da) and solid paraffin.

Preferably, the antioxidant comprises at least one of antioxidant CA, antioxidant 264, antioxidant 2246 and antioxidant 1076.

The invention also provides a preparation method of the heavy soft PVC material, which comprises the following steps:

(1) uniformly mixing PVC, a reinforcing agent, a stabilizing agent and a toughening agent to obtain a mixture A;

(2) uniformly mixing the mixture A, the liquid plasticizer, the solid plasticizer, the lubricant and the antioxidant to obtain a mixture B;

(3) and adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the heavy soft PVC material.

Preferably, the temperature of the twin-screw extruder is set to: the temperature of the first area is 135-145 ℃, the temperature of the second area is 145-160 ℃, the temperature of the third area is 160-170 ℃, the temperature of the fourth area is 155-165 ℃, and the temperature of the discharge hole is 145-160 ℃; the rotating speed of the screw is 20-35 RPM.

The invention also provides application of the heavy soft PVC material in preparation of the damping rubber block.

The invention also provides a damping rubber block which is made of the heavy soft PVC material.

Compared with the prior art, the invention has the beneficial effects that: according to the invention, the liquid plasticizer and the solid plasticizer of the specific types are used for carrying out synergistic modification on PVC, so that the glass transition temperature of PVC is remarkably reduced, and high-elasticity soft PVC is obtained; meanwhile, the special type of reinforcing agent is used for reinforcing PVC, so that the strength, hardness and density of the PVC are further improved; the two ways act simultaneously to plasticize, enhance and modify PVC, finally obtain the heavy and soft PVC material with high elasticity, high density and medium hardness, which can effectively absorb impact energy, achieve the same buffering and damping effect as the rubber damping block, has lower cost than the rubber damping block, and can replace the rubber damping block to be used in household appliances such as refrigerators.

Detailed Description

The present invention will be described in detail with reference to specific embodiments in order to make the above objects, features and advantages more comprehensible. It is apparent that the following examples are only a part of the embodiments of the present invention, and not all of them. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. The methods employed in the examples of the present invention are all conventional in the art unless otherwise specified, the equipment, reagents, starting materials used are commercially available, and the starting materials used in the same name in each example and comparative example are all the same.

Example 1

Weighing the following raw materials in parts by weight:

PVC: 55 portions of

Liquid plasticizer: 25 portions of

Solid plasticizer: 3 portions of

Reinforcing agent: 15 portions of

Compound heat stabilizer: 3 portions of

NBR toughening agent: 5 portions of

PETS lubricant: 0.2 part

Antioxidant: 0.2 part

Wherein the PVC is PVC-SG3 which is purchased from Xinjiang province.

The liquid plasticizer is a mixture of DINP, a polyester plasticizer (with the molecular weight of 2500-5000 Da) and ESO, and the mass ratio of the DINP to the polyester plasticizer to the ESO is 6:3: 1.

The solid plasticizer is B-02 which is purchased from Jiangsu Aite En high polymer materials GmbH.

The reinforcing agent is a mixture of nano active calcium carbonate and heavy calcium carbonate, and the mass ratio of the nano active calcium carbonate to the heavy calcium carbonate is 1: 1.

The composite heat stabilizer is purchased from Guangdong Weilinnan New materials science and technology Co., Ltd, and is in a model of WWP-G03B.

The antioxidant is a mixture of antioxidant CA and antioxidant 264, and the mass ratio of the antioxidant CA to the antioxidant 264 is 1: 1.

(1) Putting PVC, a reinforcing agent, a stabilizing agent and a toughening agent into a high-speed mixer, and uniformly mixing (stirring and mixing for 15min) to obtain a mixture A;

(2) putting the mixture A, the liquid plasticizer, the solid plasticizer, the lubricant and the antioxidant into a high-speed mixer, and stirring and mixing for 10min at 75 ℃ to obtain a mixture B;

(3) and adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the heavy and soft PVC material. Wherein the temperature of the twin-screw extruder is set as follows: the temperature of the first zone is 140 ℃, the temperature of the second zone is 160 ℃, the temperature of the third zone is 170 ℃, the temperature of the fourth zone is 160 ℃, and the temperature of the discharge port is 155 ℃; the screw speed was 27 RPM.

Example 2

Weighing the following raw materials in parts by weight:

PVC: 50 portions of

Liquid plasticizer: 20 portions of

Solid plasticizer: 1 part of

Reinforcing agent: 20 portions of

Compound heat stabilizer: 2 portions of

NBR toughening agent: 7 portions of

PETS lubricant: 0.1 part

Antioxidant: 0.1 part

The PVC, liquid plasticizer, solid plasticizer, reinforcing agent, composite heat stabilizer and antioxidant used in example 2 were the same as those used in example 1.

(1) Putting PVC, a reinforcing agent, a stabilizing agent and a toughening agent into a high-speed mixer, and uniformly mixing (stirring and mixing for 20min) to obtain a mixture A;

(2) putting the mixture A, the liquid plasticizer, the solid plasticizer, the lubricant and the antioxidant into a high-speed mixer, and stirring and mixing for 10min at 85 ℃ to obtain a mixture B;

(3) and adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the heavy and soft PVC material. Wherein the temperature of the twin-screw extruder is set as follows: the temperature of the first zone is 140 ℃, the temperature of the second zone is 160 ℃, the temperature of the third zone is 170 ℃, the temperature of the fourth zone is 160 ℃, and the temperature of the discharge port is 155 ℃; the screw speed was 26 RPM.

Example 3

Weighing the following raw materials in parts by weight:

PVC: 60 portions of

Liquid plasticizer: 30 portions of

Solid plasticizer: 5 portions of

Reinforcing agent: 10 portions of

Compound heat stabilizer: 1 part of

NBR toughening agent: 3 portions of

PETS lubricant: 0.2 part

Antioxidant: 0.2 part

The PVC, liquid plasticizer, solid plasticizer, reinforcing agent, composite heat stabilizer and antioxidant used in example 3 were the same as those used in example 1.

(1) Putting PVC, a reinforcing agent, a stabilizing agent and a toughening agent into a high-speed mixer, and uniformly mixing (stirring and mixing for 20min) to obtain a mixture A;

(2) putting the mixture A, the liquid plasticizer, the solid plasticizer, the lubricant and the antioxidant into a high-speed mixer, and stirring and mixing for 10min at 80 ℃ to obtain a mixture B;

(3) and adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the heavy and soft PVC material. Wherein the temperature of the twin-screw extruder is set as follows: the temperature of the first zone is 140 ℃, the temperature of the second zone is 160 ℃, the temperature of the third zone is 170 ℃, the temperature of the fourth zone is 160 ℃, and the temperature of the discharge port is 155 ℃; the screw speed was 35 RPM.

Example 4

Example 4 differs from example 1 only in the solid plasticizer used, which is YH-1800 from shanghai crane chemical, in example 4.

Example 5

Example 5 differs from example 1 only in the solid plasticizer used, which was HLM-401Z, available from shandongyi chemical, used in example 4.

Comparative example 1

Weighing the following raw materials in parts by weight:

PVC: 40 portions of

Liquid plasticizer: 15 portions of

Solid plasticizer: 7 portions of

Reinforcing agent: 20 portions of

Compound heat stabilizer: 1 part of

NBR toughening agent: 3 portions of

PETS lubricant: 0.2 part

Antioxidant: 0.2 part

The PVC, liquid plasticizer, solid plasticizer, reinforcing agent, composite heat stabilizer and antioxidant used in comparative example 1 were the same as those used in example 1. PVC material was obtained according to the preparation of example 2.

Comparative example 2

Weighing the following raw materials in parts by weight:

PVC: 70 portions of

Liquid plasticizer: 35 portions of

Solid plasticizer: 1 part of

Reinforcing agent: 20 portions of

Compound heat stabilizer: 1 part of

NBR toughening agent: 3 portions of

PETS lubricant: 0.2 part

Antioxidant: 0.2 part

The PVC, liquid plasticizer, solid plasticizer, reinforcing agent, composite heat stabilizer and antioxidant used in comparative example 2 were the same as those used in example 1. PVC material was obtained according to the preparation of example 3.

Comparative example 3

Comparative example 3 differs from example 1 only in the solid plasticizer used, which is dupont HP441 in comparative example 3.

Comparative example 4

Comparative example 4 differs from example 1 only in that: in comparative example 4, no solid plasticizer was added, and 28 parts of liquid plasticizer was added, and the composition and the component ratio of the liquid plasticizer were the same as those of example 1.

Comparative example 5

Comparative example 5 differs from example 1 only in that: in comparative example 5, no liquid plasticizer was added, and 28 parts of solid plasticizer was added, and the solid plasticizer was the same as in example 1.

Comparative example 6

Comparative example 6 differs from example 1 only in that: in comparative example 6 no reinforcing agent was added.

Performance testing

The physical and chemical properties of the PVC materials prepared in examples 1-5 and comparative examples 1-6 were tested, and the commercially available nitrile rubber shock-absorbing block for refrigerator was used as a control.

The method of each test item is as follows:

1. tensile strength was tested according to ISO 527;

2. elongation at break was tested according to ISO 527;

3. the shore hardness is tested according to ISO 7619;

4. the damping coefficient is tested according to GB/T18258-2000;

5. the density was tested according to ISO 2781.

The test results are shown in the following table:

and (4) analyzing results: as can be seen from the test data of the examples 1-5 and the reference, the damping coefficients of the heavy soft PVC rubber blocks of the examples 1-5 are equivalent to those of the rubber damping block made of NBR material, and the mechanical property of the heavy soft PVC rubber blocks is slightly superior to that of the rubber damping block made of NBR material; the formula of the damping rubber block is optimized, so that the low-cost PVC heavy soft rubber block can be used for replacing a high-cost NBR rubber block and can be used as a damping rubber block of household appliances such as a refrigerator, the same damping effect as that of the rubber damping block is achieved, and the cost of the damping rubber block is reduced.

Through comparison of performance parameters of examples 1-5 and comparative examples 1-2, it can be found that the change of the component content can affect the performance of the prepared PVC material, and the damping coefficient of the PVC material prepared in examples 1-5 is obviously higher than that of comparative examples 1-2, which shows that when the formula disclosed by the invention is used for preparing the PVC material, the damping effect of the PVC material can be obviously improved.

The comparison of the performance parameters of the example 1, the examples 4-5 and the comparative example 3 shows that the damping coefficient of the examples 1 and the examples 4-5 is obviously higher than that of the comparative example 3, thereby showing that only the heavy soft PVC modified by the solid plasticizer of the grade of the invention has better damping effect. By comparing the performance parameters of the example 1 and the comparative examples 4 to 6, it can be seen that the advantages of the liquid plasticizer and the solid plasticizer are complemented with each other only by the synergistic effect of the liquid plasticizer and the solid plasticizer and the reinforcing effect of the reinforcing agent, so that the heavy and soft PVC with excellent performance and good damping effect can be obtained.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.