阅读说明：本技术 一种纳米改性高密度聚乙烯波纹管 (Nano modified high-density polyethylene corrugated pipe ) 是由 夏新华 叶林杰 吴迪高 谢纯辉 杨湘刚 于 2021-08-26 设计创作，主要内容包括：本发明涉及一种纳米改性高密度聚乙烯波纹管,其由包含纳米材料改性高密度聚乙烯、马来酸酐接枝聚乙烯和助剂的原料制成,所述纳米材料改性高密度聚乙烯和马来酸酐接枝聚乙烯的质量比为(12.0-14.0)：1.0,所述助剂的重量占所述纳米材料改性高密度聚乙烯和马来酸酐接枝聚乙烯的总重的10-23%；所述助剂由包含以下重量份的原料组成,碳酸钙无机填料10-15份；色母粒5-10份；润滑剂2-5份；分散剂1-3份；增塑剂4-6份；光稳定剂2-5份；抗氧化剂2-4份。本发明通过优化纳米材料改性高密度聚乙烯、马来酸酐接枝聚乙烯和助剂的种类及配比,能提高波纹管的抗紫外线、抗氧化和耐热性能,具有延缓波纹管老化并延长其使用寿命的优点。(The invention relates to a nano modified high-density polyethylene corrugated pipe which is prepared from raw materials comprising nano material modified high-density polyethylene, maleic anhydride grafted polyethylene and an auxiliary agent, wherein the mass ratio of the nano material modified high-density polyethylene to the maleic anhydride grafted polyethylene is (12.0-14.0): 1.0, wherein the weight of the auxiliary agent accounts for 10-23% of the total weight of the nano material modified high-density polyethylene and the maleic anhydride grafted polyethylene; the auxiliary agent comprises the following raw materials in parts by weight, 10-15 parts of calcium carbonate inorganic filler; 5-10 parts of color master batch; 2-5 parts of a lubricant; 1-3 parts of a dispersant; 4-6 parts of a plasticizer; 2-5 parts of a light stabilizer; and 2-4 parts of an antioxidant. According to the invention, through optimizing the types and the proportion of the nano material modified high-density polyethylene, the maleic anhydride grafted polyethylene and the auxiliary agent, the ultraviolet resistance, the oxidation resistance and the heat resistance of the corrugated pipe can be improved, and the corrugated pipe has the advantages of delaying the aging of the corrugated pipe and prolonging the service life of the corrugated pipe.)

1. A nanometer modified high density polyethylene corrugated pipe is characterized in that: the polyethylene is prepared from raw materials including nano-material modified high-density polyethylene, maleic anhydride grafted polyethylene and an auxiliary agent, wherein the mass ratio of the nano-material modified high-density polyethylene to the maleic anhydride grafted polyethylene is (12.0-14.0): 1.0, wherein the weight of the auxiliary agent accounts for 10-23% of the total weight of the nano material modified high-density polyethylene and the maleic anhydride grafted polyethylene; the auxiliary agent comprises the following raw materials in parts by weight,

10-15 parts of calcium carbonate inorganic filler;

5-10 parts of color master batch;

2-5 parts of a lubricant;

1-3 parts of a dispersant;

4-6 parts of a plasticizer;

2-5 parts of a light stabilizer;

and 2-4 parts of an antioxidant.

2. The nano-modified high-density polyethylene corrugated pipe as claimed in claim 1, wherein: the polyethylene is prepared from raw materials including nano-material modified high-density polyethylene, maleic anhydride grafted polyethylene and an auxiliary agent, wherein the mass ratio of the nano-material modified high-density polyethylene to the maleic anhydride grafted polyethylene is 13.4: 1.0, wherein the weight of the auxiliary agent accounts for 17% of the total weight of the nano material modified high-density polyethylene and the maleic anhydride grafted polyethylene; the auxiliary agent comprises the following raw materials in parts by weight,

12 parts of calcium carbonate inorganic filler;

9 parts of color master batch;

3 parts of a lubricant;

2 parts of a dispersing agent;

5 parts of a plasticizer;

4 parts of light stabilizer;

and 3 parts of an antioxidant.

3. The nano-modified high-density polyethylene corrugated pipe according to any one of claims 1-2, characterized in that: the nano material modified high-density polyethylene comprises the following raw materials in parts by weight,

15-25 parts of nano barium sulfate modified high-density polyethylene;

15-25 parts of nano silicon dioxide modified high-density polyethylene;

50-70 parts of nano titanium dioxide modified high-density polyethylene.

4. The nano-modified high-density polyethylene corrugated pipe as claimed in claim 3, wherein: the calcium carbonate inorganic filler is composed of the following raw materials in parts by weight,

40-60 parts of superfine heavy calcium carbonate;

25-30 parts of silicon dioxide substrate single-layer graphene;

and 15-30 parts of nano titanium dioxide loaded silver ions.

5. The nano-modified high-density polyethylene corrugated pipe as claimed in claim 3, wherein: the particle size of the color master batch is less than 1 mu m.

6. The nano-modified high-density polyethylene corrugated pipe as claimed in claim 3, wherein: the lubricant is one or a combination of more of mineral oil, palm oil and stearate.

7. The nano-modified high-density polyethylene corrugated pipe as claimed in claim 3, wherein: the dispersing agent is polyethylene wax.

8. The nano-modified high-density polyethylene corrugated pipe as claimed in claim 3, wherein: the plasticizer is one or a composition of more of di-n-butyl phthalate, tolyl butyl phthalate, dioctyl phthalate and diisononyl phthalate.

9. The nano-modified high-density polyethylene corrugated pipe as claimed in claim 3, wherein: the light stabilizer is one or a composition of more of benzotriazolyl dodecyl p-cresol, methylene bis-benzotriazolyl tetramethyl butyl phenol and benzotriazolyl butyl phenol sodium sulfonate.

10. The nano-modified high-density polyethylene corrugated pipe as claimed in claim 3, wherein: the antioxidant is one or a composition of more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (nonylphenol) phosphite ester and ditridecyl thiodipropionate.

Technical Field

The invention relates to the technical field of corrugated pipes, in particular to a nano modified high-density polyethylene corrugated pipe.

Background

With the rapid development of municipal engineering and infrastructure construction, the demand for prestressed corrugated pipes is on a rapidly increasing trend. The corrugated pipe as a pore-forming material of a prestress post-tensioning method is an important component of a prestress system, is developed from the earliest drawn pipe to a metal corrugated pipe and then to the current plastic corrugated pipe, and can be widely applied to the fields of bridges, highways, railways, high-rise buildings, hydropower, nuclear power, sewage treatment plants and the like.

At present, the prestressed plastic corrugated pipe mainly produced by using High Density Polyethylene (HDPE) as a main material generally has the quality defects of low ring stiffness, structural layering, poor heat resistance and fire resistance and the like due to the influence of the physical and chemical properties of the HDPE main material, the existing high density polyethylene corrugated pipe is relatively light, and is easy to float during the concrete pouring process, in addition, the price of the corrugated pipe product is high due to the high HDPE raw material cost, China enters a new economic normal state, the building market is recovered and weak, and further the HDPE prestressed plastic corrugated pipe obviously lacks the market competitiveness.

Therefore, the Chinese patent with the publication number of CN102070810B discloses a special material for a corrugated pipe for high-density polyethylene prestressed concrete, which comprises the following components in parts by weight: 100 parts of regenerated high-density polyethylene, 5-20 parts of mica powder, 0.1-0.5 part of silane coupling agent KH570, 1-6 parts of maleic anhydride grafted polyethylene, 1-3 parts of PE wax, 0.3-1.5 parts of white mineral oil and 0.2-0.5 part of color master batch.

The special material not only can enhance the overall mechanical property of the corrugated pipe, but also has the weight increasing effect by adding the mica powder which is a mineral enhancing mode, and can improve the defects that the prior polyethylene corrugated pipe has light weight and is easy to float in concrete construction. However, the above prior art solutions have the following drawbacks: when the corrugated pipe produced by the special material is actually used, the inside of the corrugated pipe is in a through hole state, the corrugated pipe is easy to age under the action of light and oxygen, and the corrugated pipe is easy to heat and age when concrete is poured due to the defect that the high-density polyethylene material is not heat-resistant, so that the service life of the corrugated pipe is influenced and needs to be improved.

Disclosure of Invention

The invention aims to solve the problems of the prior art and provides a nano modified high-density polyethylene corrugated pipe, which achieves the purposes of delaying the aging of the corrugated pipe and prolonging the service life of the corrugated pipe by improving the ultraviolet resistance, oxidation resistance and heat resistance of the corrugated pipe.

The above object of the present invention is achieved by the following technical solutions:

a nanometer modified high-density polyethylene corrugated pipe is prepared from raw materials including nanometer material modified high-density polyethylene, maleic anhydride grafted polyethylene and an auxiliary agent, wherein the mass ratio of the nanometer material modified high-density polyethylene to the maleic anhydride grafted polyethylene is (12.0-14.0): 1.0, wherein the weight of the auxiliary agent accounts for 10-23% of the total weight of the nano material modified high-density polyethylene and the maleic anhydride grafted polyethylene; the auxiliary agent comprises the following raw materials in parts by weight, 10-15 parts of calcium carbonate inorganic filler; 5-10 parts of color master batch; 2-5 parts of a lubricant; 1-3 parts of a dispersant; 4-6 parts of a plasticizer; 2-5 parts of a light stabilizer; and 2-4 parts of an antioxidant.

By adopting the technical scheme, firstly, the nano material modified high-density polyethylene and the maleic anhydride grafted polyethylene in the proportion replace the original high-density polyethylene to serve as base materials, and a light stabilizer and an antioxidant are added, so that the compatibility between the base materials and the auxiliary agent can be improved while the ultraviolet resistance, the oxidation resistance and the heat resistance of the corrugated pipe are directly improved; secondly, calcium carbonate inorganic filler and maleic anhydride grafted polyethylene can be used as fillers to be dispersed in the base material, so that the weight of the corrugated pipe is directly enhanced, and the corrugated pipe is prevented from floating upwards; in addition, the color master batch, the lubricant, the dispersant and the plasticizer can take maleic anhydride grafted polyethylene as a carrier, so that the color master batch, the lubricant, the dispersant and the plasticizer can effectively reduce the melt defect of the corrugated pipe in the processing process while ensuring the uniform dispersion in the nano material modified high-density polyethylene, thereby ensuring that the corrugated pipe has better aging resistance; in summary, by optimizing the types and the proportions of the nano material modified high-density polyethylene, the maleic anhydride grafted polyethylene and the auxiliary agent, the ultraviolet resistance, the oxidation resistance and the heat resistance of the corrugated pipe can be improved, and the corrugated pipe has the advantages of delaying the aging of the corrugated pipe and prolonging the service life of the corrugated pipe.

Preferably, the polyethylene is prepared from raw materials comprising nano-material modified high-density polyethylene, maleic anhydride grafted polyethylene and an auxiliary agent, wherein the mass ratio of the nano-material modified high-density polyethylene to the maleic anhydride grafted polyethylene is 13.4: 1.0, wherein the weight of the auxiliary agent accounts for 17% of the total weight of the nano material modified high-density polyethylene and the maleic anhydride grafted polyethylene; the auxiliary agent comprises the following raw materials in parts by weight, and 12 parts of calcium carbonate inorganic filler; 9 parts of color master batch; 3 parts of a lubricant; 2 parts of a dispersing agent; 5 parts of a plasticizer; 4 parts of light stabilizer; and 3 parts of an antioxidant.

Further, the nano material modified high-density polyethylene comprises the following raw materials in parts by weight, 15-25 parts of nano barium sulfate modified high-density polyethylene; 15-25 parts of nano silicon dioxide modified high-density polyethylene; 50-70 parts of nano titanium dioxide modified high-density polyethylene. The nano titanium dioxide modified high-density polyethylene has excellent mechanical, optical and thermal stability, the high-density polyethylene can be highly dispersed after being grafted with the nano titanium dioxide, and the nano barium sulfate modified high-density polyethylene and the nano silicon dioxide modified high-density polyethylene are enveloped on a framework formed by the nano titanium dioxide modified high-density polyethylene, so that the composite system can further improve the aging resistance and the heat resistance of the corrugated pipe, and the purpose of prolonging the service life of the corrugated pipe is achieved.

Further, the calcium carbonate inorganic filler comprises the following raw materials, by weight, 40-60 parts of ultrafine heavy calcium carbonate; 25-30 parts of silicon dioxide substrate single-layer graphene; and 15-30 parts of nano titanium dioxide loaded silver ions. The method comprises the steps of depositing a silicon dioxide thin layer on the surface of graphene, hindering the pi stacking effect among graphene sheet layers, realizing uniform dispersion of the graphene, dispersing superfine heavy calcium carbonate and silicon dioxide serving as basic frameworks in a corrugated pipe raw material, and uniformly dispersing graphene, nano titanium dioxide and nano silver serving as particle fillers on the basic frameworks, so that the weight of the corrugated pipe can be increased, the ultraviolet resistance effect can be achieved, and the service life of the corrugated pipe can be prolonged.

Further, the particle size of the color master batch is less than 1 μm. The color master batches with the particle sizes have better compatibility in the corrugated pipe material.

Further, the lubricant is one or a combination of mineral oil, palm oil and stearate. The lubricants are adhered to the surface of the calcium carbonate inorganic filler, so that the adhesive soft performance between the nano material modified high-density polyethylene and the maleic anhydride grafted polyethylene is adjusted, the lubricating purpose is achieved, and the components are promoted to be uniformly dispersed.

Further, the dispersing agent is polyethylene wax. The polyethylene wax has excellent cold resistance, heat resistance, chemical resistance and wear resistance, and can promote the high dispersion of the nano material modified high-density polyethylene and the maleic anhydride grafted polyethylene.

Further, the plasticizer is one or a combination of more of di-n-butyl phthalate, tolyl butyl phthalate, dioctyl phthalate and diisononyl phthalate. Through the synergistic effect of the plasticizer and the nano-silica modified high-density polyethylene, the water resistance, alkali resistance, weather resistance and hardness of the corrugated pipe can be improved while the self-plasticizing property is ensured, and the service life of the corrugated pipe is further prolonged.

Further, the light stabilizer is one or a composition of a plurality of benzotriazole-based dodecyl p-cresol, methylene bis-benzotriazole-based tetramethyl butyl phenol and benzotriazole-based butyl phenol sodium sulfonate. The light stabilizer belongs to a high-molecular-weight benzotriazole light stabilizer, is beneficial to environmental protection, and is beneficial to improving the thermal stability of an auxiliary agent and the compatibility with nano-material modified high-density polyethylene, so that an excellent ultraviolet resistance function is achieved.

Further, the antioxidant is one or a composition of more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (nonylphenol) phosphite ester and ditridecyl thiodipropionate. On one hand, the antioxidant performance and the long-acting stability of the raw material of the corrugated pipe can be improved through the synergistic effect of the components in a high-density polyethylene system; on the other hand, the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester can be compounded with the nano titanium dioxide modified high-density polyethylene to form a multifunctional antioxidant, so that the anti-aging effect of the corrugated pipe can be further improved.

In conclusion, the beneficial technical effects of the invention are as follows: by optimizing the types and the proportion of the nano material modified high-density polyethylene, the maleic anhydride grafted polyethylene and the auxiliary agent, the ultraviolet resistance, the oxidation resistance and the heat resistance of the corrugated pipe can be improved, and the corrugated pipe has the advantages of delaying the aging of the corrugated pipe and prolonging the service life of the corrugated pipe.

Detailed Description

In order to make the technical means, the creation features, the achievement purposes and the functions of the invention clearer and easier to understand, the invention is further described in the following with the specific embodiments.

Examples

Example 1: the invention discloses a nano modified high-density polyethylene corrugated pipe which is prepared from raw materials comprising nano material modified high-density polyethylene, maleic anhydride grafted polyethylene and an auxiliary agent. The preparation method comprises the following steps of,

s1, preparing nano material modified high-density polyethylene, and mixing 22 parts of nano barium sulfate modified high-density polyethylene, 18 parts of nano silicon dioxide modified high-density polyethylene and 63 parts of nano titanium dioxide modified high-density polyethylene to obtain nano material modified high-density polyethylene;

s2, preparing an auxiliary raw material, namely mixing 50 parts of superfine heavy calcium carbonate, 27 parts of silicon dioxide substrate single-crystal single-layer graphene and 22 parts of nano titanium dioxide loaded silver ions to obtain a calcium carbonate inorganic filler; selecting color master batches with the particle size of less than 1 mu m, selecting mineral oil as a lubricant, selecting polyethylene wax as a dispersant, selecting di-n-butyl phthalate as a plasticizer, selecting benzotriazolyl dodecyl p-cresol as a light stabilizer, and selecting tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester as an antioxidant;

s3, preparing an auxiliary agent, namely mixing 12 parts of calcium carbonate inorganic filler prepared in S2, 9 parts of color master batch, 3 parts of lubricant, 2 parts of dispersant, 5 parts of plasticizer, 4 parts of light stabilizer and 3 parts of antioxidant to obtain the auxiliary agent;

s4 mixing the nanomaterial modified high-density polyethylene obtained in S1 and maleic anhydride grafted polyethylene according to the weight ratio of 13.4: the mass ratio of 1.0 and the auxiliary agent obtained in S3 are mixed according to the weight accounting for 17 percent of the total weight of the nano material modified high-density polyethylene and the maleic anhydride grafted polyethylene, and then the mixture is put into a double-screw extruder to be melted and extruded into a tube blank, and the tube blank is spirally wound, cooled and formed, cut at fixed length and inspected to obtain the corrugated tube.

Example 2: the invention discloses a nano modified high-density polyethylene corrugated pipe, which is different from the corrugated pipe in example 1 in that the weight parts and weight ratios of the components in the raw materials are shown in table 1.

In S2, palm oil was selected as the lubricant, tolylbutyl phthalate as the plasticizer, methylenebis-benzotriazolyl tetramethylbutylphenol as the light stabilizer, and tris (nonylphenol) phosphite as the antioxidant.

Example 3: the invention discloses a nano modified high-density polyethylene corrugated pipe, which is different from the corrugated pipe in example 1 in that the weight parts and weight ratios of the components in the raw materials are shown in table 1.

In S2, stearate was selected as the lubricant, dioctyl phthalate as the plasticizer, sodium benzotriazolyl styrene-butadiene-phenol sulfonate as the light stabilizer, and ditridecyl thiodipropionate as the antioxidant.

Example 4: the invention discloses a nano modified high-density polyethylene corrugated pipe, which is different from the corrugated pipe in example 1 in that the weight parts and weight ratios of the components in the raw materials are shown in table 1.

In S2, stearate was selected as the lubricant, diisononyl phthalate was selected as the plasticizer, methylenebis-benzotriazolyl tetramethylbutylphenol was selected as the light stabilizer, and pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] was selected as the antioxidant.

Example 5: the invention discloses a nano modified high-density polyethylene corrugated pipe, which is different from the corrugated pipe in example 1 in that the weight parts and weight ratios of the components in the raw materials are shown in table 1.

In S2, mineral oil was selected as the lubricant, tolylbutyl phthalate was selected as the plasticizer, sodium benzotriazolyl styrene-butadiene-phenol sulfonate was selected as the light stabilizer, and ditridecylthiodipropionate was selected as the antioxidant.

TABLE 1

	Example 1	Example 2	Example 3	Example 4	Example 5
						Mass ratio of nano material modified high density polyethylene and maleic anhydride grafted polyethylene	13.4：1.0	12.0:1.0	13.5:1.0	14.0:1.0	12.7:1.0
The auxiliary agent accounts for the mass percent of the total weight of the nano material modified high-density polyethylene and the maleic anhydride grafted polyethylene	17%	23%	10%	15%	20%

TABLE 1 continuation

Components	Example 1	Example 2	Example 3	Example 4	Example 5
						Nano barium sulfate modified high-density polyethylene	22	20	15	25	18
Nano silicon dioxide modified high density polyethylene	18	25	15	20	22
						Nano titanium dioxide modified high-density polyethylene	63	60	65	50	70
Calcium carbonate inorganic filler	12	11	14	10	15
						Color master batch	9	6	5	8	10
Lubricant agent	3	4	5	2	3
						Dispersing agent	2	2	1	1	3
Plasticizer	5	6	6	5	4
						Light stabilizers	4	5	4	2	5
Antioxidant agent	3	4	3	2	2
						Superfine heavy calcium carbonate	50	40	45	60	55
Silicon dioxide-based single crystal monolayer graphene	27	25	26	28	30
						Nano titanium dioxide loaded silver ion	25	20	16	15	30

Performance test

The following test experiments were performed on the properties of the corrugated pipes produced in examples 1 to 5:

1. thermal oxidation induction period determination: a corrugated pipe with the length of 30cm is taken as a sample, the sample and an inert reference substance alumina are placed in a differential thermal analyzer, inert gas nitrogen in a sample chamber is rapidly replaced by oxygen at the temperature of 80 ℃, the change of a DTA curve (differential thermal spectrum) caused by the oxidation of the sample is tested, the thermal oxidation induction period (min) value of the corrugated pipe sample is obtained and recorded in a table 2, and the thermal aging resistance of the plastic is evaluated.

2. Ultraviolet aging measurement: a corrugated pipe with the length of 30cm is cut to serve as a sample, an ultraviolet light exposure sample is selected in an exposure chamber, the temperature of the exposure chamber is set to be 50 ℃, the exposure time is set to be 4 hours, after exposure for 4 hours, the ultraviolet aging degree of the corrugated pipe sample is detected, and data are recorded in table 2.

TABLE 2

	Example 1	Example 2	Example 3	Example 4	Example 5
						Thermal oxidation induction period (min)	27	20	25	22	22
Degree of ultraviolet ray aging (%)	0.1	0.1	0.1	0.2	0.2

As can be seen from Table 2, the bellows of the present invention can improve the ultraviolet resistance, oxidation resistance and heat resistance of the bellows by optimizing the types and the proportions of the nano material modified high density polyethylene, the maleic anhydride grafted polyethylene and the auxiliary agent, and has the advantages of delaying the bellows aging and prolonging the service life of the bellows.

Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.