阅读说明：本技术 一种轻质环保pvc管件用组合物及其制备方法 (Composition for light environment-friendly PVC pipe fitting and preparation method thereof ) 是由 高虎 李其建 任仰省 徐伟伟 马洁 刘宏旭 从宪玲 于 2021-07-09 设计创作，主要内容包括：本发明涉及一种轻质环保PVC管件用组合物及其制备方法,属于PVC材料的技术领域。包括重量份的以下组分：PVC树脂80～100份、稳定剂1.5～3.5份、内润滑剂1～1.6份、外润滑剂0.6～1.28份,空心玻璃微珠5～15份,加工助剂1.5～3.0份、增韧剂3～8份、填料为5～10份、色粉0.08～0.15份。本发明通过在体系中添加处理后的空心玻璃微珠,利用其珠状结构提高了配方体系的流动性；同时还可以有效提高PVC材料的稳定性、力学性能、热稳定性和阻燃性能,同时产品密度降低,降低生产设备的负荷,提高了生产效率。(The invention relates to a composition for a light environment-friendly PVC pipe fitting and a preparation method thereof, belonging to the technical field of PVC materials. Comprises the following components in parts by weight: 80-100 parts of PVC resin, 1.5-3.5 parts of stabilizer, 1-1.6 parts of internal lubricant, 0.6-1.28 parts of external lubricant, 5-15 parts of hollow glass microsphere, 1.5-3.0 parts of processing aid, 3-8 parts of toughening agent, 5-10 parts of filler and 0.08-0.15 part of toner. According to the invention, the treated hollow glass beads are added into the system, and the bead-shaped structure of the hollow glass beads is utilized to improve the fluidity of the formula system; meanwhile, the stability, mechanical property, thermal stability and flame retardant property of the PVC material can be effectively improved, the product density is reduced, the load of production equipment is reduced, and the production efficiency is improved.)

1. The composition for the light environment-friendly PVC pipe fitting is characterized by comprising the following components in parts by weight: 80-100 parts of PVC resin, 1.5-3.5 parts of stabilizer, 1-1.6 parts of internal lubricant, 0.6-1.28 parts of external lubricant, 5-15 parts of hollow glass microsphere, 1.5-3.0 parts of processing aid, 3-8 parts of toughening agent, 5-10 parts of filler and 0.08-0.15 part of toner.

2. The composition for the light environment-friendly PVC pipe fitting as claimed in claim 1, is characterized by comprising the following components in parts by weight: 90-100 parts of PVC resin, 2-2.8 parts of stabilizer, 1.2-1.4 parts of internal lubricant, 0.72-1.12 parts of external lubricant, 6-10 parts of hollow glass microsphere, 2.0-3.0 parts of processing aid, 6-8 parts of toughening agent, 5-8 parts of filler and 0.08-0.12 part of toner.

3. The composition for the light and environment-friendly PVC pipe fitting as claimed in any one of claims 1 or 2, wherein the hollow glass beads are activated for 10-20 hours by 25 wt% of ammonia water, and the activated glass beads are pretreated by 5-30 per mill of titanate coupling agent; and washing the treated product with deionized water for 2-3 times, drying the product in an oven at 80-100 ℃ for 2-3 h, taking out the product and placing the product in a drying place for later use.

4. The composition for lightweight and environment-friendly PVC pipe fittings according to any one of claims 1 or 2, wherein the polymerization degree of the PVC resin is 650 to 740; the particle size range of the PVC resin is 120-160 mu m.

5. The composition for lightweight and environment-friendly PVC pipe fittings according to any one of claims 1 or 2, wherein the particle size distribution of the hollow glass beads is as follows: d10 is less than 10 μm, D50 is 18-24 μm, D90 is less than 32 μm, and D100 is less than 40 μm.

6. The composition for lightweight and environment-friendly PVC pipe fittings according to any one of claims 1 or 2, wherein the true density of the hollow glass beads is 0.12-0.70 g/cm³(ii) a The compressive strength of the hollow glass beads is more than or equal to 8000 PSI.

7. The composition for lightweight, environmentally friendly PVC pipe as claimed in any one of claims 1 or 2, wherein the weight ratio of the internal lubricant to the external lubricant is 1: 0.6 to 0.8; the internal lubricant is at least one of stearic acid, glyceryl monostearate or butyl stearate, and the external lubricant is at least one of oxidized polyethylene wax, PE wax or PPA.

8. The composition for lightweight and environment-friendly PVC pipe as claimed in any one of claims 1 or 2, wherein the processing aid is one of methyl methacrylate-acrylate copolymer, MMA-styrene copolymer or acrylonitrile-styrene copolymer.

9. The composition for lightweight and environment-friendly PVC pipe according to any one of claims 1 or 2, wherein the toughening agent is at least one of chlorinated polyethylene, acrylonitrile-styrene-butadiene copolymer or methacrylic acid-butadiene-styrene copolymer.

10. The preparation method of the composition for the light environment-friendly PVC pipe fitting is characterized by comprising the following specific steps of:

(1) adding PVC resin, a stabilizer and an internal lubricant into a high-speed and low-speed mixer, heating to 60-80 ℃, mixing for 1-2 min at a stirring speed of 475-950 r/min;

(2) 1/2 of toner, a toughening agent, a processing aid and a filler is added into a high-speed and low-speed mixer, the rotating speed is increased to 90-100 ℃, the mixture is mixed for 3-5 min, and the stirring speed is 875-950 r/min;

(3) adjusting the stirring speed to 600-900 r/min, adding an external lubricant, hollow glass beads and the rest of filler, and mixing for 1-3 min at a stirring speed of 875-950 r/min for 1-3 min; heating to 120-130 ℃, transferring to a low-speed mixer for cold mixing to 40-50 ℃, controlling the rotating speed to be 300-500 r/min, controlling the cold mixing time to be 5-15 min, and standing for 24 hours for later use;

(4) and (4) granulating by using a conical double-screw extruder.

Technical Field

The invention belongs to the technical field of PVC materials, and particularly relates to a composition for a light environment-friendly PVC pipe fitting and a preparation method thereof.

Background

PVC (polyvinyl chloride) is one of five general resins, has excellent physical properties, corrosion resistance and flame resistance, and has the advantage of low price compared with other materials, so that the PVC is widely applied. However, the existing PVC resin has the defects of poor molding processability, poor fluidity, low thermal stability and the like, and the defects have adverse effects on the production and processing of PVC products. In order to improve the defects of the PVC resin and improve the application range of products, the PVC can be subjected to chemical modification and physical modification, and the physical modification of the PVC is more widely applied in production.

The glass beads are nano-scale inorganic materials with smooth surfaces, the main chemical component is borosilicate glass, and the glass beads are hollow transparent positive beads observed under an electron microscope. Has various performances of low density, high strength, high temperature resistance and the like, has good fluidity and chemical stability, and is a novel multifunctional material across fields. The hollow glass beads can be used in the industries of rubber and plastic, ocean resource development, aerospace, 5G communication, light weight of vehicles, coatings, sports equipment, artificial stone and the like.

The application of the hollow glass beads has important significance on the strategies of performance improvement and optimization, light weight and energy conservation and emission reduction of various materials. The prepared composite material of the hollow glass beads and the PVC can improve the fluidity and the molding processability of PVC products. At present, the flowability of a formula system of the hard injection-molded PVC composite material is improved by adding a plasticizer and a large amount of internal lubricant, but the method is easy to cause the reduction of the stability and the mechanical property of a product.

The invention discloses a preparation method of a low-specific-gravity high-wear-resistance PVC cable material, provides a method capable of effectively reducing the use of high-density filler and reducing the specific gravity of a product, and mainly relates to application of light physical properties of hollow glass microspheres and weight reduction. However, it does not relate to how to improve the melt flow properties. The invention of China with the application number of CN202010357626.3 provides an enhanced cable, which mainly utilizes the strong strength of hollow glass beads and can further enhance the strength of the cable. However, the matrix mainly involved is soft PVC material, and the improvement of the performance of hard PVC injection molding pipe in terms of fluidity is not disclosed. The Chinese invention with the application number of CN202011461074.7 discloses a resin composition and application thereof, wherein the dielectric property and the pressure resistance of the resin composition are improved by optimizing the particle size distribution of hollow glass beads. It does not disclose whether hollow glass microspheres can improve the stability and flow properties in rigid PVC systems.

Disclosure of Invention

Aiming at the problems that the flowability and stability of hard injection-molded PVC materials are poor and the stability and mechanical property of the products are easily reduced in the prior art, the invention provides a composition for a light environment-friendly PVC pipe fitting and a preparation method thereof, so as to solve the problems. According to the invention, the treated hollow glass beads are added into the system, and the bead shape of the hollow glass beads is utilized to improve the fluidity of the formula system; meanwhile, the stability, mechanical property, thermal stability and flame retardant property of the PVC material can be effectively improved, the product density is reduced, the load of production equipment is reduced, and the production efficiency is improved.

The technical scheme of the invention is as follows:

the composition for the light environment-friendly PVC pipe fitting comprises the following components in parts by weight: 80-100 parts of PVC resin, 1.5-3.5 parts of stabilizer, 1-1.6 parts of internal lubricant, 0.6-1.28 parts of external lubricant, 5-15 parts of hollow glass microsphere, 1.5-3.0 parts of processing aid, 3-8 parts of toughening agent, 5-10 parts of filler and 0.08-0.15 part of toner. The hollow glass beads are activated by ammonia water and then treated by a titanate coupling agent to obtain the hollow glass beads.

Preferably, the hollow glass beads are activated for 10-20 hours by 25 wt% of ammonia water, and the activated glass beads are pretreated by 5-30 per mill of titanate coupling agent. And washing the treated product with deionized water for 2-3 times, drying the product in an oven at 80-100 ℃ for 2-3 h, taking out the product and placing the product in a drying place for later use. The pretreatment is that the titanate coupling agent is directly coupled with trace amino or hydroxyl adsorbed on the surfaces of the glass beads through the alkoxy of the titanate coupling agent.

The hollow glass beads have smooth surfaces and bead-shaped particle shapes. The addition of the proper amount can improve the flowability of a formula system, and the mechanical property of a rigid PVC injection molding system product cannot be influenced, once the addition of the glass microspheres in the PVC rigid injection molding product exceeds the range, the mechanical property of the product can be greatly influenced, for example, the tensile strength, the bending strength, the notch impact strength and the like can be greatly reduced, and the product is unqualified.

Preferably, the composition comprises the following components in parts by weight: 90-100 parts of PVC resin, 2-2.8 parts of stabilizer, 1.2-1.4 parts of internal lubricant, 0.72-1.12 parts of external lubricant, 6-10 parts of hollow glass microsphere, 2.0-3.0 parts of processing aid, 6-8 parts of toughening agent, 5-8 parts of filler and 0.08-0.12 part of toner.

Preferably, the polymerization degree of the PVC resin is 650-740; the particle size range of the PVC resin is 120-160 mu m.

Preferably, the particle size distribution of the hollow glass beads is as follows: d10 is less than 10 μm, D50 is 18-24 μm, D90 is less than 32 μm, and D100 is less than 40 μm.

Preferably, the true density of the hollow glass beads is 0.12-0.70 g/cm³Preferably 0.35 to 0.6g/cm³。

Preferably, the compressive strength of the hollow glass beads is more than or equal to 8000PSI, preferably more than or equal to 10000 PSI.

Preferably, the stabilizer is at least one of a calcium-zinc composite stabilizer or an organic tin stabilizer.

Preferably, the weight ratio of the internal lubricant to the external lubricant is 1: 0.6 to 0.8; the internal lubricant is at least one of stearic acid, glyceryl monostearate or butyl stearate, and the external lubricant is at least one of oxidized polyethylene wax, PE wax or PPA.

Preferably, the processing aid is one of methyl methacrylate-acrylate copolymer, MMA-styrene copolymer or acrylonitrile-styrene copolymer. The processing aid can improve the strength of the melt and improve the plasticizing time.

Preferably, the toughening agent is at least one of chlorinated polyethylene, acrylonitrile-styrene-butadiene copolymer or methacrylic acid-butadiene-styrene copolymer.

Preferably, the filler is at least one of superfine light activated calcium carbonate, nano activated calcium carbonate or nano activated barium sulfate.

The invention also aims to provide a preparation method of the composition for the PVC pipe fitting, which comprises the following specific steps:

(1) adding PVC resin, a stabilizer and an internal lubricant into a high-speed and low-speed mixer, heating to 60-80 ℃, mixing for 1-2 min at a stirring speed of 475-950 r/min.

(2) 1/2 of the toner, the toughening agent, the processing aid and the filler is added into a high-speed mixer and a low-speed mixer, the temperature is increased to 90-100 ℃, the mixture is mixed for 3-5 min, and the stirring speed is 875-950 r/min.

(3) Adjusting the stirring speed to 600-900 r/min, adding an external lubricant, hollow glass beads and the rest of filler, and mixing for 1-3 min at a stirring speed of 875-950 r/min for 1-3 min; heating to 120-130 ℃, transferring to a low-speed mixer for cold mixing to 40-50 ℃, controlling the rotating speed to be 300-500 r/min, carrying out cold mixing for 5-15 min, and standing for 24 hours for later use.

(4) Granulating by a conical double-screw extruder; the granulation process of the conical double-screw extruder with the model of TDSJSZ-90 is as follows:

the extrusion screws used for the conical twin screws are free of reverse-flight zones. The reverse threads are easy to crush and break the glass beads, so that the performance of the PVC composite material is influenced.

The invention has the beneficial effects that:

(1) according to the invention, by adding the hollow glass beads, on one hand, the density of the PVC composite material is reduced, and the fluidity of a product system is improved, so that the processing performance of the PVC composite material is improved. The PVC pipe fitting injection molding process can effectively overcome the defects of poor granule fluidity, easy deformation at high temperature, poor appearance of injection molding parts and the like during PVC pipe fitting injection molding, improves the temperature resistance and pressure resistance of the pipe fitting and the attractiveness of the injection molding parts, expands the use range of the pipe fitting, reduces the production cost, can better meet the market demands, and has better economical efficiency and application prospect. On the other hand, other particle fillers such as PVC resin and the like have synergistic effect with the hollow glass beads, and the glass beads have better interface bonding force after pretreatment, and can replace the plasticizer for use. The plasticizer is not added, but the fluidity and the processing performance of the system can be ensured, and the product is environment-friendly and pollution-free.

(2) The invention selects step-by-step adding of the filler when preparing the PVC composite material. The performance of the product is improved by adding the nano inorganic filler step by step, wherein the impact strength of a cantilever beam notch and the Vicat thermal deformation temperature are improved; other fillers are combined and coated with the PVC, so that the contact range of the polar chain segment of the PVC and the glass beads is reduced, the dispersion of the glass beads is more uniform, and the combination is more comprehensive.

Detailed Description

In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The hollow glass bead treatment method used in the examples was as follows:

taking 10 parts of hollow glass beads, adding 100 parts of 25 wt% ammonia water for activation for 15 hours, and pretreating the activated glass beads by 20 per mill of titanate coupling agent. And washing the treated product with deionized water for 2-3 times, drying the product in an oven at 90 ℃ for 3h, taking out the product and placing the product in a drying place for later use.

Example 1

The composition for the light environment-friendly PVC pipe fitting comprises the following components in parts by weight: 90 parts of PVC resin, 2 parts of organic tin stabilizer, 1.2 parts of glycerin monostearate, 0.72 part of PE wax, 6 parts of hollow glass microsphere, 2 parts of methyl methacrylate-acrylate copolymer, 6 parts of chlorinated polyethylene, 3 parts of superfine light active calcium carbonate, 2 parts of nano active barium sulfate and 0.1 part of gray toner;

wherein the polymerization degree of the PVC resin is 700, and the particle size is 120-140 mu m; the hollow glass beads D10 and D50 were 9.58 μm, 20 μm, 30.25 μm and 38.85 μm, respectively, as D90.

The preparation steps are as follows:

(1) 90 parts of PVC resin, 2 parts of organic tin stabilizer and 1.2 parts of glyceryl monostearate are firstly added into a high-speed mixer and a low-speed mixer, the temperature is raised to 60-70 ℃, the mixture is mixed for 1min, and the stirring speed is 500 r/min.

(2) Mixing 3 parts of superfine light activated calcium carbonate and 2 parts of nano activated barium sulfate to obtain a filler, adding 0.1 part of gray toner, 6 parts of chlorinated polyethylene, 2 parts of methyl methacrylate-acrylate copolymer and 2.5 parts of filler into a high-speed and low-speed mixer, increasing the rotating speed to 90-95 ℃, mixing for 3min, and stirring at a speed of 875 r/min.

(3) Adjusting the stirring speed to 600r/min, adding 0.72 part of PE wax, 6 parts of hollow glass beads and the rest of filler, and mixing for 1min at a stirring speed of 875r/min for 1 min; and heating to 120-125 ℃, transferring to a low-speed mixer for cold mixing to 40-45 ℃, controlling the rotating speed at 300r/min, carrying out cold mixing for 5min, and standing for 24 hours for later use.

(4) Granulating by using a (TDSJSZ-90) conical double-screw extruder; the granulation process of the conical double-screw extruder comprises the following steps:

region(s)	Temperature of
		Charging barrel 1	157
Charging barrel 2	158
		Charging barrel 3	160
Charging barrel 4	160
		Confluence core	165
Machine head one	167
		Main unit rotating speed (Motor rotating speed)	958r/min
Rotational speed of motor of feeding motor	545r/min

Example 2

The composition for the light environment-friendly PVC pipe fitting comprises the following components in parts by weight: 95 parts of PVC resin, 2.4 parts of organic tin stabilizer, 1.3 parts of glycerin monostearate, 0.78 part of PE wax, 8 parts of hollow glass microsphere, 2.5 parts of methyl methacrylate-acrylate copolymer, 7 parts of chlorinated polyethylene, 5 parts of superfine light active calcium carbonate, 2 parts of nano active barium sulfate and 0.1 part of gray toner;

wherein the polymerization degree of the PVC resin is 700, and the particle size is 120-140 mu m; the hollow glass beads D10 and D50 were 9.58 μm, 20 μm, 30.25 μm and 38.85 μm, respectively, as D90.

The preparation steps are as follows:

(1) 95 parts of PVC resin, 2.4 parts of organic tin stabilizer and 1.3 parts of glyceryl monostearate are firstly added into a high-speed mixer and a low-speed mixer, the temperature is raised to 70-75 ℃, the mixture is mixed for 1.5min, and the stirring speed is 850 r/min.

(2) Mixing 5 parts of superfine light activated calcium carbonate and 2 parts of nano activated barium sulfate in advance to obtain a filler, adding 0.1 part of gray toner, 7 parts of chlorinated polyethylene, 2.5 parts of methyl methacrylate-acrylate copolymer and 3.5 parts of filler into a high-speed and low-speed mixer, increasing the rotating speed, heating to 95-100 ℃, mixing for 4min, and stirring at the speed of 900 r/min.

(3) Adjusting the stirring speed to 800r/min, adding 0.78 parts of PE wax, 8 parts of hollow glass beads and the rest of filler, and mixing for 2min at the stirring speed of 900r/min for 2 min; and heating to 125-130 ℃, transferring to a low-speed mixer for cold mixing to 45-50 ℃, controlling the rotating speed at 400r/min, carrying out cold mixing for 10min, and standing for 24 hours for later use.

(4) Granulating by using a (TDSJSZ-90) conical double-screw extruder; the granulation process of the conical double-screw extruder comprises the following steps:

example 3

The composition for the light environment-friendly PVC pipe fitting comprises the following components in parts by weight: 100 parts of PVC resin, 2.8 parts of organic tin stabilizer, 1.4 parts of glycerin monostearate, 0.84 part of PE wax, 10 parts of hollow glass microsphere, 3 parts of methyl methacrylate-acrylate copolymer, 8 parts of chlorinated polyethylene, 6 parts of superfine light active calcium carbonate, 2 parts of nano active barium sulfate and 0.1 part of gray toner;

wherein the polymerization degree of the PVC resin is 700, and the particle size is 120-140 mu m; the hollow glass beads D10 and D50 were 9.58 μm, 20 μm, 30.25 μm and 38.85 μm, respectively, as D90.

The preparation steps are as follows:

(1) 100 parts of PVC resin, 2.8 parts of organic tin stabilizer and 1.4 parts of glyceryl monostearate are firstly added into a high-speed mixer and a low-speed mixer, the temperature is raised to 75-80 ℃, the mixture is mixed for 2min, and the stirring speed is 950 r/min.

(2) Mixing 6 parts of superfine light activated calcium carbonate and 2 parts of nano activated barium sulfate to obtain a filler, adding 0.1 part of gray toner, 8 parts of chlorinated polyethylene, 3 parts of methyl methacrylate-acrylate copolymer and 4 parts of filler into a high-speed mixer and a low-speed mixer, increasing the rotating speed, heating to 95-100 ℃, mixing for 5min, and stirring at a speed of 950 r/min.

(3) Adjusting the stirring speed to 900r/min, adding 0.84 part of PE wax, 10 parts of hollow glass beads and the rest of filler, and mixing for 3min at the stirring speed of 950r/min for 3 min; and heating to 125-130 ℃, transferring to a low-speed mixer for cold mixing to 40-45 ℃, controlling the rotating speed at 500r/min, carrying out cold mixing for 15min, and standing for 24 hours for later use.

(4) Granulating by using a (TDSJSZ-90) conical double-screw extruder; the granulation process of the conical double-screw extruder comprises the following steps:

region(s)	Temperature of
		Charging barrel 1	157
Charging barrel 2	158
		Charging barrel 3	160
Charging barrel 4	160
		Confluence core	165
Machine head one	167
		Main unit rotating speed (Motor rotating speed)	958r/min
Rotational speed of motor of feeding motor	545r/min

Comparative example

A PVC composite particle, which is different from example 1 in that nano activated calcium carbonate of the same weight is used instead of the hollow glass micro beads. The preparation method is the same as that of example 1.

Test example

1. The PVC composite particles prepared in the embodiments 1 to 3 are compared with similar products sold in the market in performance tests, and the specific test results are shown in the following table 1:

TABLE 1 Performance test results

Compared with the PVC composite particles sold on the market, the PVC composite particles prepared by the method have the performance basically same as that of the commercial products without using the plasticizer. Under the condition of not reducing the performance, the invention avoids the pollution of the plasticizer to the environment and the harm to the human body, and really plays a role in environmental protection and harmlessness.

2. The PVC composite particles prepared in example 1 and comparative example were subjected to performance tests, and the specific results are shown in table 2 below:

TABLE 2 Performance test results

Test items	Test method	Example 1	Comparative example
				Density (g/cm)3)	GB1033-2008	1.37	1.40
Melt index (190 ℃,21.6kg, g/10min)	GB/T3682-2000	13.60	11.20
				Heat distortion temperature (. degree. C.)	GB/T 1634.1-2004	61.6	61.2

According to the data analysis in table 2, compared with the comparative example, when nano active calcium carbonate with the same proportion is used to replace the hollow glass microsphere, the density data of the prepared PVC composite particle shows that the density of the PVC composite particle prepared by the invention is smaller than that of the comparative example, because the hollow glass microsphere has a smooth surface, a beaded particle shape and a small hollow specific gravity, the modified hollow glass microsphere can not only improve the flowability of the formula, but also reduce the density of the product, and can also improve the processing efficiency and stability of the injection molding product. In conclusion, the PVC injection molding pipe fitting composition can improve the fluidity of an injection molding formula, reduce the density of a product and prolong the service cycle, and the performance of the PVC injection molding pipe fitting composition is superior to that of similar products in the market.

Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.