WO2024011805A1

WO2024011805A1 - Wear-resistant pvc plastic and preparation method therefor

Info

Publication number: WO2024011805A1
Application number: PCT/CN2022/132693
Authority: WO
Inventors: 张光宝; 张煜晗
Original assignee: 浙江煜华车饰有限公司
Priority date: 2022-07-15
Filing date: 2022-11-17
Publication date: 2024-01-18
Also published as: CN115073871A

Abstract

Disclosed in the present invention is a wear-resistant PVC plastic, which is prepared from a functional polyvinyl chloride masterbatch, a filler and a stabilizer, wherein methyl methacrylate, cementing liquid, nano-diamond and a wear resistance enhancer are added into the functional polyvinyl chloride masterbatch, so that the degree of crosslinking and compatibility of the PVC plastic are improved, and the wear resistance is enhanced. The PVC plastic disclosed by the present invention has high stability, has no pungent smell and is harmless to human bodies during long-time use.

Description

Wear-resistant PVC plastic and preparation method thereof

Technical field

The invention belongs to the technical field of PVC plastics, and specifically relates to a wear-resistant PVC plastic and a preparation method thereof.

Background technique

Polyvinyl chloride (PVC) does not specifically refer to the polymer itself, but also includes blends based on PVC resin. Other components are generally stabilizers, plasticizers, fillers, etc. Polyvinyl chloride, abbreviated as PVC in English, is a polymer formed by polymerizing vinyl chloride monomer (VCM) with initiators such as peroxides and azo compounds or under the action of light and heat according to the free radical polymerization reaction mechanism. . Polyvinyl chloride has excellent physical and chemical properties. It was once the most widely produced general plastic in the world and is widely used.

Chinese patent CN 109762287 A discloses a wear-resistant polyvinyl chloride plastic, including the following raw material components: modified polyvinyl chloride, phenolic resin modified polyvinyl chloride, epoxy resin modified polyvinyl chloride and aluminum trioxide Modified polyvinyl chloride was invented to have better wear resistance. Four kinds of modified polyvinyl chloride are mixed and granulated to obtain wear-resistant polyvinyl chloride plastic. The preparation process is complicated, and the wear-resistant mechanism of polyvinyl chloride plastic is not yet understood. clear.

Chinese patent CN103937128 B discloses a PVC plastic floor and its preparation method. The weight parts of the raw materials of the PVC plastic floor are: 100 parts of polyvinyl chloride resin, 20 to 30 parts of chlorinated polyethylene, and tribasic lead sulfate. 4 to 6 parts, 2 to 4 parts of stearic acid, 0.6 to 1.4 parts of stearic acid, 80 to 120 parts of calcium carbonate, 1 to 2 parts of 3-aminopropyltrimethoxysilane, and 1 to 3 parts of methyl silicone oil. The PVC plastic floor of this invention has good wear resistance, stain resistance and anti-slip properties. However, the tribasic lead sulfate added to it is easy to absorb moisture, has poor stability and is toxic, which makes it unsafe for long-term use.

Contents of the invention

A preparation method of wear-resistant PVC plastic, including the following steps:

(1) According to parts by mass, put 80 to 90 parts of functional polyvinyl chloride masterbatch and 18 to 25 parts of filler into a ball mill, grind at a speed of 200 to 300 rpm for 1 to 2 hours, and pass through a 550 to 600 mesh sieve to obtain a mixed powder. ;

(2) According to parts by mass, place 90 to 100 parts of mixed powder and 7 to 12 parts of stabilizer in an internal mixer, and mix at 130 to 140°C and 40 to 50 rpm for 5 to 8 minutes to obtain mixture A;

(3) Feed mixture A into a twin-screw extruder with a processing temperature of 220 to 240°C and a main engine speed of 330 to 360 rpm for extrusion and granulation; injection molding to obtain wear-resistant PVC plastic.

The filler is at least one of carbon black, calcium carbonate, clay, barium sulfate, and talcum powder; preferably, the filler is a mixture obtained by mixing calcium carbonate and barium sulfate in a mass ratio of (8 to 10): 1 .

The stabilizer is at least one of barium stearate, lead stearate, cadmium stearate, and lead dibasic phosphite.

The preparation method of the functional polyvinyl chloride masterbatch includes the following steps:

S1: According to parts by mass, combine 80 to 90 parts of polyvinyl chloride masterbatch, 5 to 10 parts of methyl methacrylate, 0.3 to 2 parts of initiator, 7 to 10 parts of emulsifier, 20 to 30 parts of cementing fluid, 1 Add ~3 parts of nanodiamond and 50~80 parts of water into the reaction kettle, react at 110~120°C for 3~6 hours, and cool to room temperature to obtain mixture I;

S2: According to parts by mass, stir 100 to 120 parts of mixture I at 50 to 60°C and 200 to 300 rpm. Add 1 to 3 mol/L of dilute hydrochloric acid at a dropping speed of 0.3 to 0.5 mL/10s to adjust the pH to 2.3. ~3.3, continue the reaction for 2~3 hours, filter, wash with water until neutral, extrusion and granulation to obtain functional polyvinyl chloride masterbatch.

In the present invention, methyl methacrylate is first grafted on PVC to improve the toughness and compatibility of PVC plastic. The grafted PVC reacts with the cementing liquid and nanodiamonds. The nanodiamonds have high surface activity and can fully contact the cementing liquid. At the same time, the compatibility of the polyvinyl chloride masterbatch and the cementing liquid is improved, and the nanodiamonds are dripped into the cementing liquid. After adding hydrochloric acid to adjust the pH, the silicate ions and hydrogen ions in the cementing solution react to form cement. The particle size of the cement has good roundness and good sorting properties, so that it can be evenly interspersed in the structure of PVC plastic, which can improve the quality of plastic products. Rigidity, hardness and wear resistance improve the strength and geometric stability of plastic products. In addition, due to the uniform distribution of nanodiamonds in the cement, the compatibility and stability of the cement and PVC plastic are enhanced. At the same time, it has high hardness and can effectively Improve the strength, toughness and wear resistance of PVC masterbatch.

Preferably, the preparation method of the functional polyvinyl chloride masterbatch includes the following steps:

S1: In terms of parts by mass, combine 80 to 90 parts of polyvinyl chloride masterbatch, 5 to 10 parts of methyl methacrylate, 0.3 to 2 parts of initiator, 7 to 10 parts of emulsifier, 20 to 30 parts of cementing fluid, 5 ~7 parts of wear-resistant enhancer, 1-3 parts of nanodiamond and 50-80 parts of water are added to the reaction kettle, react at 110-120°C for 2-3 hours, and cool to room temperature to obtain mixture I;

S2: According to parts by mass, stir 100 to 120 parts of mixture I at 50 to 60°C and 200 to 300 rpm. Add 1 to 3 mol/L of dilute hydrochloric acid at a dropping speed of 0.3 to 0.5 mL/10s to adjust the pH to 2.3. ~3.3, continue the reaction for 3 ~ 6 hours, filter, wash with water until neutral, extrusion and granulation, to obtain functional polyvinyl chloride masterbatch.

Furthermore, the present invention also adds a wear-resistant reinforcing agent in the preparation of functional polyvinyl chloride masterbatch. The wear-resistant reinforcing agent is composed of sisal fiber and diabase fiber. Among them, the sisal fiber has gaps and holes in varying degrees, and there is an elongated cavity in the center. The cavity is connected to the gaps and holes on the surface, and has a large specific surface area. The sisal fiber and the PVC plastic matrix are cross-linked, thereby increasing the resistance of the PVC plastic. Wearability; diabase fiber has the advantages of strong stiffness, tensile properties and good dispersion. It is interwoven into a network during the cementing process of the cementing solution, which increases the degree of cross-linking inside the PVC plastic, thus increasing the wear resistance of the PVC plastic. properties and mechanical properties; at the same time, under the action of initiator, sisal fiber can also be grafted to the surface of diabase fiber to form a multi-dimensional cross-linked network structure. The synergistic effect further enhances the interface compatibility between the wear-resistant reinforcement and PVC plastic. properties and cross-linking degree to improve the wear resistance of PVC plastics.

The wear-resistant reinforcing agent is composed of diabase fiber and sisal fiber according to the mass ratio of 1: (3-5).

The initiator is one of potassium persulfate and dicumyl hydrogen peroxide-ferrous sulfate complex.

The emulsifier is at least one of oleic acid, potassium stearate, potassium disproportionated rosinate, and sodium dodecyl sulfonate.

The preparation process of the cementing solution includes the following steps: add quartz sandstone powder into a 1-3 mol/L sodium hydroxide aqueous solution according to the material-to-liquid ratio of 1g: (15-20) mL, and stir at 30-40°C and 200-300 rpm. Stir at a rotating speed for 3 to 4 hours, filter and collect the filtrate to obtain a cementing liquid.

Beneficial effects of the present invention:

The invention discloses a wear-resistant PVC plastic, which is made of functional polyvinyl chloride masterbatch, filler and stabilizer. The functional polyvinyl chloride masterbatch is composed of polyvinyl chloride masterbatch, methyl methacrylate and cementing liquid. , obtained by the reaction of nanodiamond and wear-resistant reinforcing agent. The wear-resistant reinforcing agent uses both diabase fiber and sisal fiber, which are interwoven into a network during the cementing process of the cementing solution, which improves the cross-linking degree and compatibility of PVC plastic. Enhance its wear resistance; the PVC plastic has high stability, no irritating odor, and is harmless to the human body after long-term use.

Detailed ways

Some raw materials are introduced as follows:

PVC masterbatch, brand number: 46518, Dongguan Jinsuyan Plastic Technology Co., Ltd.

Nanodiamond, particle size: 100nm, Zhecheng County Zhongyuan Superabrasives Co., Ltd.

Quartz sandstone powder, particle size: 300 mesh, Lingshou County Shengbang Mineral Products Processing Factory.

Diabase fiber is prepared by the following method: wash the diabase with water, dry it, crush it and pass it through a 40-mesh sieve to obtain diabase powder. Add the diabase powder to the rock wool production device and process it at 500 Melt extrusion at ℃ to obtain diabase fibers with a diameter of 6 μm and a length of 3 mm. Among them, diabase, item number: 768, Lingshou County Huimao Mineral Products Processing Factory.

Sisal fiber, item number: SFA01, Nanning Jebsen Trading Co., Ltd.

Comparative example 1

(1) In terms of parts by mass, put 80 parts of polyvinyl chloride masterbatch and 20 parts of filler into a ball mill, grind at a speed of 200 rpm for 1 hour, and pass through a 600-mesh sieve to obtain a mixed powder;

(2) According to parts by mass, place 90 parts of mixed powder and 7 parts of stabilizer in an internal mixer, and mix at 140°C and 40 rpm for 5 minutes to obtain mixture A;

(3) Feed mixture A into a twin-screw extruder with a processing temperature of 220°C and a main engine speed of 360 rpm for extrusion and granulation; injection molding to obtain wear-resistant PVC plastic.

The filler is a mixture obtained by mixing calcium carbonate and barium sulfate at a mass ratio of 10:1.

The stabilizer is barium stearate.

Comparative example 2

(1) According to parts by mass, put 80 parts of functional polyvinyl chloride masterbatch and 20 parts of filler into a ball mill, ball mill at a speed of 200 rpm for 1 hour, and pass through a 600-mesh sieve to obtain a mixed powder;

(2) In terms of parts by mass, place 90 parts of mixed powder and 7 parts of stabilizer in an internal mixer, and mix at 140°C and 40 rpm for 5 minutes to obtain mixture A;

The filler is a mixture of calcium carbonate and barium sulfate with a mass ratio of 10:1.

The stabilizer is barium stearate.

S1: According to parts by mass, add 90 parts of polyvinyl chloride masterbatch, 10 parts of methyl methacrylate, 1 part of initiator, 8 parts of emulsifier, 1 part of nanodiamond and 80 parts of water into the reaction kettle, and react at 120°C 4h, cool to room temperature to obtain mixture I;

S2: According to parts by mass, stir 100 parts of mixture I at 60°C and 200 rpm. Add 1 mol/L dilute hydrochloric acid at a dropping speed of 0.5 mL/10 s to adjust the pH to 2.3. Continue the reaction for 2 hours, filter, and wash with water until medium. properties, extrusion and granulation to obtain functional polyvinyl chloride masterbatch.

The initiator is potassium persulfate.

The emulsifier is oleic acid.

Example 1

The stabilizer is barium stearate.

S1: In terms of parts by mass, add 90 parts of polyvinyl chloride masterbatch, 10 parts of methyl methacrylate, 1 part of initiator, 8 parts of emulsifier, 30 parts of cementing fluid, 1 part of nanodiamond and 80 parts of water into the reactor. medium, react at 120°C for 4 hours, and cool to room temperature to obtain mixture I;

S2: According to parts by mass, stir 100 parts of mixture I at 60°C and 200 rpm, then add 1 mol/L dilute hydrochloric acid at a dropping speed of 0.5 mL/10 s to adjust the pH to 2.3, continue the reaction for 2 hours, filter, and wash with water. Neutral, extrusion and granulation to obtain functional polyvinyl chloride masterbatch.

The initiator is potassium persulfate.

The emulsifier is oleic acid.

The preparation process of the cementing solution includes the following steps: add quartz sandstone powder to a 3 mol/L sodium hydroxide aqueous solution according to a material-to-liquid ratio of 1g:15 mL, stir for 3 hours at 40°C and 300 rpm, filter and collect the filtrate to obtain Cementing liquid.

Example 2

(1) According to parts by mass, put 80 parts of functional polyvinyl chloride masterbatch and 20 parts of filler into a ball mill, ball mill at 200 rpm for 1 hour, and pass through a 600-mesh sieve to obtain a mixed powder;

The stabilizer is barium stearate.

S1: In terms of parts by mass, combine 90 parts of polyvinyl chloride masterbatch, 10 parts of methyl methacrylate, 1 part of initiator, 8 parts of emulsifier, 30 parts of cementing fluid, 5 parts of wear-resistant enhancer, and 1 part of nanodiamond and 80 parts of water were added to the reaction kettle, reacted at 120°C for 4 hours, and cooled to room temperature to obtain mixture I;

The initiator is potassium persulfate.

The emulsifier is oleic acid.

The preparation process of the cementing liquid includes the following steps:

Add quartz sandstone powder to 3 mol/L sodium hydroxide aqueous solution according to the material-to-liquid ratio of 1g:15 mL, stir at 40°C and 300 rpm for 3 hours, filter and collect the filtrate to obtain a cementing liquid.

The wear-resistant reinforcing agent is diabase fiber.

Example 3

The stabilizer is barium stearate.

The initiator is potassium persulfate.

The emulsifier is oleic acid.

The preparation process of the cementing liquid includes the following steps:

The wear-resistant reinforcing agent is sisal fiber.

Example 4

The stabilizer is barium stearate.

The initiator is potassium persulfate.

The emulsifier is oleic acid.

The preparation process of the cementing solution includes the following steps: add quartz sandstone powder to a 3 mol/L sodium hydroxide aqueous solution according to a material-to-liquid ratio of 1g:15 mL, stir at 40°C and 300 rpm for 3 hours, filter and collect the filtrate to obtain Cementing liquid.

The wear-resistant reinforcing agent is composed of diabase fiber and sisal fiber in a mass ratio of 1:4.

Test example 1

Wear resistance test: Use abrasion meter JM-IV type, Shanghai Modern Environmental Engineering Technology Co., Ltd. Install the wear-resistant PVC plastic decorative surface with a diameter of 100mm and a thickness of 0.7mm upward on the abrasion testing machine, and install the grinding wheel on the bracket. Test under the conditions of applying 4.9N and 200r/h speed. The grinding wheel wears every time Replace it once every 100 revolutions, record the number of revolutions when it wears to the point of plastic damage, repeat the above wear resistance test 5 times, and calculate the average number of revolutions to indicate its wear resistance.

Table 1 Wear resistance test of wear-resistant PVC plastic

	耐磨性/转Wear resistance/rev
对比例1Comparative example 1	78347834
对比例2Comparative example 2	85778577
实施例1Example 1	98349834
实施例2Example 2	1089210892
实施例3Example 3	1103311033
实施例4Example 4	1156011560

Compared with Comparative Example 1, in Comparative Example 2, polyvinyl chloride was grafted with methyl methacrylate to improve the toughness and compatibility of PVC plastic; in Example 1, a cementing liquid was added, and the cement was generated as the reaction progressed It has high hardness and stable structure, which can significantly improve the wear resistance of PVC plastics. Example 2 also adds diabase fiber as a wear-resistant enhancer. Diabase fiber has good stiffness and tensile properties and can effectively improve the composite material. Mechanical properties; in Example 4, a wear-resistant reinforcing agent is added. The wear-resistant reinforcing agent uses both diabase fiber and sisal fiber. The sisal fiber has gaps and holes in varying degrees, and there is an elongated hollow in the center. The cavity is connected to the gaps and holes on the surface, with a large specific surface area. The sisal fiber and the PVC plastic matrix are cross-linked, thereby increasing the wear resistance of the PVC plastic; while the diabase fiber has strong stiffness, tensile properties and dispersion The advantage is that it is interwoven into a network during the cementing process of the cementing solution, which increases the degree of cross-linking inside the PVC plastic, thereby increasing the wear resistance and mechanical properties of the PVC plastic; at the same time, under the action of the initiator, the sisal fiber can also Grafted to the surface of diabase fiber, it forms a multi-dimensional cross-linked network structure, which acts synergistically to further enhance the interface compatibility and cross-linking degree of the wear-resistant reinforcing agent and PVC plastic, and improve the wear-resistant performance of the reinforced PVC plastic.

Test example 2

Physical performance test:

Tensile impact strength test: Refer to GB/T 13525-1992 "Plastic Tensile Impact Performance Test Method", prepare type A samples from wear-resistant PVC plastic for testing. The sample thickness is 1mm, and the tensile speed is 1mm/min. , when testing the tensile impact strength, select the T-head mass as 30g and the pendulum impact energy as 2.0J;

Bending strength test: Refer to GB/T 9341-2008 "Determination of Bending Properties of Plastics", prepare wear-resistant PVC plastic into a sample with a length of 80mm, a width of 10mm, and a thickness of 4mm. The test speed is 5mm/min.

Table 2 Physical properties test of wear-resistant PVC plastic

As can be seen from Table 2, the addition of cementing fluid effectively improves the strength and geometric stability of plastic products. As the degree of cross-linking of PVC plastic increases, its mechanical properties are significantly improved.

Claims

The preparation method of wear-resistant PVC plastic is characterized by including the following steps:

(1) Put the functional polyvinyl chloride masterbatch and filler into a ball mill for ball milling, and then sieve to obtain mixed powder;

(2) Place the mixed powder and stabilizer in an internal mixer for internal mixing to obtain mixture A;

(3) Feed mixture A into a twin-screw extruder for extrusion and granulation; injection molding to obtain wear-resistant PVC plastic.
The preparation method of wear-resistant PVC plastic as claimed in claim 1, characterized in that it includes the following steps:

(1) According to parts by mass, put 80 to 90 parts of the functional polyvinyl chloride masterbatch as claimed in claim 6 and 18 to 25 parts of filler into a ball mill, and grind it for 1 to 2 hours at a speed of 200 to 300 rpm for 550 to Sieve with 600 mesh to obtain mixed powder;

(2) According to parts by mass, place 90 to 100 parts of mixed powder and 7 to 12 parts of stabilizer in an internal mixer, and mix at 130 to 140°C and 40 to 50 rpm for 5 to 8 minutes to obtain mixture A;

(3) Feed mixture A into a twin-screw extruder with a processing temperature of 220 to 240°C and a main engine speed of 330 to 360 rpm for extrusion and granulation; injection molding to obtain wear-resistant PVC plastic.
The preparation method of wear-resistant PVC plastic as claimed in claim 1 or 2, characterized in that the preparation method of functional polyvinyl chloride masterbatch includes the following steps:

S1: According to parts by mass, combine 80 to 90 parts of polyvinyl chloride masterbatch, 5 to 10 parts of methyl methacrylate, 0.3 to 2 parts of initiator, 7 to 10 parts of emulsifier, 20 to 30 parts of cementing fluid, 1 Add ~3 parts of nanodiamond and 50~80 parts of water into the reaction kettle, react at 110~120°C for 3~6 hours, and cool to room temperature to obtain mixture I;

S2: According to parts by mass, stir 100 to 120 parts of mixture I at 50 to 60°C and 200 to 300 rpm. Add 1 to 3 mol/L of dilute hydrochloric acid at a dropping speed of 0.3 to 0.5 mL/10s to adjust the pH to 2.3. ~3.3, continue the reaction for 2~3 hours, filter, wash with water until neutral, extrusion and granulation to obtain functional polyvinyl chloride masterbatch.
The preparation method of wear-resistant PVC plastic as claimed in claim 3, characterized in that the preparation method of the functional polyvinyl chloride masterbatch includes the following steps:

S1: In terms of parts by mass, combine 80 to 90 parts of polyvinyl chloride masterbatch, 5 to 10 parts of methyl methacrylate, 0.3 to 2 parts of initiator, 7 to 10 parts of emulsifier, 20 to 30 parts of cementing fluid, 5 ~7 parts of wear-resistant enhancer, 1-3 parts of nanodiamond and 50-80 parts of water are added to the reaction kettle, react at 110-120°C for 2-3 hours, and cool to room temperature to obtain mixture I;

S2: According to parts by mass, stir 100 to 120 parts of mixture I at 50 to 60°C and 200 to 300 rpm. Add 1 to 3 mol/L of dilute hydrochloric acid at a dropping speed of 0.3 to 0.5 mL/10s to adjust the pH to 2.3. ~3.3, continue the reaction for 3 ~ 6 hours, filter, wash with water until neutral, extrusion and granulation, to obtain functional polyvinyl chloride masterbatch.
The preparation method of wear-resistant PVC plastic according to claim 3 or 4, characterized in that the preparation process of the cementing liquid includes the following steps: quartz sandstone powder according to the material-liquid ratio of 1g: (15-20) mL Add 1 to 3 mol/L sodium hydroxide aqueous solution, stir for 3 to 4 hours at 30 to 40°C and 200 to 300 rpm, filter and collect the filtrate to obtain a cementing liquid.
The preparation method of wear-resistant PVC plastic according to claim 3 or 4, wherein the initiator is one of potassium persulfate and dicumyl hydrogen peroxide-ferrous sulfate complex; The emulsifier is at least one of oleic acid, potassium stearate, potassium disproportionated rosinate, and sodium dodecyl sulfonate.
The method for preparing wear-resistant PVC plastic according to claim 4, wherein the wear-resistant reinforcing agent is at least one of diabase fiber and sisal fiber.
The preparation method of wear-resistant PVC plastic according to claim 1 or 2, characterized in that the filler is composed of calcium carbonate and barium sulfate according to a mass ratio of (8 to 10): 1;
The preparation method of wear-resistant PVC plastic according to claim 1 or 2, characterized in that the stabilizer is barium stearate, lead stearate, cadmium stearate, and lead dibasic phosphite. At least one.
Wear-resistant PVC plastic is characterized in that it is prepared by the method described in any one of claims 7-9.