CN114805721A - Self-closing aeration hose and preparation method thereof - Google Patents

Self-closing aeration hose and preparation method thereof Download PDF

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Publication number
CN114805721A
CN114805721A CN202210412722.2A CN202210412722A CN114805721A CN 114805721 A CN114805721 A CN 114805721A CN 202210412722 A CN202210412722 A CN 202210412722A CN 114805721 A CN114805721 A CN 114805721A
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CN
China
Prior art keywords
self
aeration hose
closing
closing aeration
parts
Prior art date
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Pending
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CN202210412722.2A
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Chinese (zh)
Inventor
张雷
刘莉
潘建通
陈凯华
迟金宝
黄文涛
汪翠萍
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Beijing Jiarunjie Environmental Protection Technology Co ltd
Beijing Bohuite Environmental Technology Co ltd
Original Assignee
Beijing Jiarunjie Environmental Protection Technology Co ltd
Beijing Bohuite Environmental Technology Co ltd
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Application filed by Beijing Jiarunjie Environmental Protection Technology Co ltd, Beijing Bohuite Environmental Technology Co ltd filed Critical Beijing Jiarunjie Environmental Protection Technology Co ltd
Priority to CN202210412722.2A priority Critical patent/CN114805721A/en
Publication of CN114805721A publication Critical patent/CN114805721A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4804Two or more polyethers of different physical or chemical nature
    • C08G18/4808Mixtures of two or more polyetherdiols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4854Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • C08L75/08Polyurethanes from polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/18Applications used for pipes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The invention relates to the field of high polymer materials, and provides a self-closing aeration hose and a preparation method thereof, wherein the self-closing aeration hose comprises the following raw materials: isocyanate: diphenylmethane-4, 4' -diisocyanate; polyol: polytetrahydrofuran ether glycol 1000 and polytetrahydrofuran ether glycol 2000 in the mass ratio of 0.4-0.5: 1; chain extender: plastic polyether ER-85. The MDI, the PTMG mixed with specific molecular weight and the ER-85 are compounded, and the prepared self-closing aeration hose is resistant to hydrolysis, not easy to pollute and block, high in oxygen utilization rate and obviously superior to the prior art.

Description

Self-closing aeration hose and preparation method thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to a self-closing aeration hose and a preparation method thereof.
Background
The aeration hose is generally used in the field of sewage treatment, and can also be used for aeration of circulating water, high-density culture systems and common fish ponds in the aquaculture industry. The aeration hose is in an expansion state when aeration is carried out, and is flattened when the aeration is stopped, so that sewage is not easy to enter the hose. Meanwhile, compared with the traditional aeration head, the hose is simple and convenient to install and maintain, so that the hose is more and more widely applied.
At present, the most aeration hoses are made of PVC materials, a large amount of plasticizer is usually required to be added for plasticizing in the preparation process of the soft PVC pipeline, and the mass of the plasticizer is usually more than 50% of the total mass. However, during the preparation and use of the hose, plasticizers and other organic substances may migrate to the surface of the hose to provide a good growth environment for the growth of microorganisms, thereby forming a biofilm. The long-term growth of the biological membrane can not only cause the blockage of the aeration hole in the hose and influence the aeration effect and the oxygenation efficiency, but also influence the normal operation of sewage treatment; meanwhile, cell metabolites secreted in the microbial metabolism process can induce the problems of pipe wall corrosion, scaling, oxidation and the like, and the service life of the hose is influenced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a self-closing aeration hose and a preparation method thereof.
The invention provides a self-closing aeration hose, which comprises the following raw materials:
isocyanate: diphenylmethane-4, 4' -diisocyanate;
polyol (b): polytetrahydrofuran ether glycol 1000 and polytetrahydrofuran ether glycol 2000 in the mass ratio of 0.4-0.5: 1;
chain extender: plastic polyether ER-85.
According to the research of the invention, the specific isocyanate, the polyol and the chain extender are selected for combination and compounding, namely MDI, PTMG mixed with specific molecular weight and ER-85 are compounded, so that the prepared self-closing aeration hose is resistant to hydrolysis, not easy to pollute and block, high in oxygen utilization rate and obviously superior to the prior art.
According to the self-closing aeration hose provided by the invention, the mass ratio of the isocyanate to the polyol is 0.35-0.5: 1.
The self-closing aeration hose provided by the invention comprises 25-30 parts of diphenylmethane-4, 4' -diisocyanate, 60-70 parts of polytetrahydrofuran ether glycol 1000 and 2000 parts of polytetrahydrofuran ether glycol 2000 in a mass ratio of 0.4-0.5:1, and ER-8512-15 parts.
When the raw material formula of the self-closing aeration hose is shown as above, the obtained self-closing aeration hose has excellent performances of hydrolysis resistance, difficult pollution and blockage, high oxygen utilization rate and the like.
According to the self-closing aeration hose provided by the invention, the hardness of the ER-85 is 85 +/-2A.
The invention also provides a preparation method of the self-closing aeration hose.
The preparation method provided by the invention comprises the following steps:
(1) dehydrating the polyol in advance;
(2) reacting the dehydrated polyol with isocyanate to generate a prepolymer;
(3) and mixing the obtained prepolymer with a chain extender, extruding, cooling and forming.
According to the preparation method of the self-closing aeration hose provided by the invention, in the step (1), the dehydration temperature is controlled at 100 ℃ and 110 ℃, and the dehydration time is 6-8 hours.
According to the preparation method of the self-closed aeration hose provided by the invention, in the step (2), the reaction temperature is controlled at 120-130 ℃, and the reaction time is 5-6 hours.
According to the preparation method of the self-closed aeration hose provided by the invention, in the step (2), stirring is carried out in the reaction process, and the stirring speed is 400-600 r/min.
According to the preparation method of the self-closed aeration hose provided by the invention, in the step (3), the temperature control is divided into eight zones from the material inlet to the extrusion port in the extrusion process, and the eight zones are sequentially 130-.
According to the preparation method of the self-closing aeration hose provided by the invention, in the step (3), the temperature for cooling and forming is controlled to be 20-25 ℃.
The invention provides a self-closing aeration hose and a preparation method thereof. The MDI, the PTMG mixed with specific molecular weight and the ER-85 are compounded, and the prepared self-closing aeration hose is resistant to hydrolysis, not easy to pollute and block, high in oxygen utilization rate and obviously superior to the prior art.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the 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.
Unless otherwise specified, the starting materials used in the examples of the present invention are all commercially available.
In the following examples, the raw materials are all abbreviated:
MDI, diphenylmethane-4, 4' -diisocyanate;
PTMG, polytetrahydrofuran ether glycol;
ER-85 is namely plastic polyether (ER-85) -Taiwan Gangding;
TDI, toluene diisocyanate;
ER-801 is namely plastic polyether (ER-801) -Taiwan ancient cooking vessel.
Example 1
The embodiment provides a self-closing aeration hose which comprises the following raw materials:
MDI 28 parts
PTMG (PTMG1000/2000 ═ 0.45) 65 parts
ER-8514 parts.
The embodiment also provides a preparation method of the self-closing aeration hose, which comprises the following specific steps:
(1) dehydrating the polyol in advance; the dehydration temperature was controlled at 105 ℃ and the dehydration time was 7 hours.
(2) Reacting the dehydrated polyol with isocyanate to generate a prepolymer; the reaction temperature is controlled at 125 ℃, the reaction time is 5 hours, and the stirring speed is 500r/min during the reaction process.
(3) Mixing the obtained prepolymer with a chain extender, extruding, cooling and forming; in the extrusion process, the temperature control is divided into eight zones from the material inlet to the extrusion port, wherein the eight zones are 130-140 ℃, 150-155 ℃, 165-175 ℃, 185-195 ℃, 155-145 ℃ and 110-120 ℃ in sequence; the temperature for cooling and forming is controlled at 20 ℃.
Example 2
The embodiment provides a self-closing aeration hose which comprises the following raw materials:
25 parts of MDI
PTMG (PTMG1000/2000 ═ 0.5) 60 parts
ER-8512 parts.
The embodiment also provides a preparation method of the self-closing aeration hose, which comprises the following specific steps:
(1) dehydrating the polyol in advance; the dehydration temperature is controlled at 100 ℃, and the dehydration time is 8 hours.
(2) Reacting the dehydrated polyol with isocyanate to generate a prepolymer; the reaction temperature is controlled at 120 ℃, the reaction time is 6 hours, and the stirring speed is 500r/min during the reaction process.
(3) Mixing the obtained prepolymer with a chain extender, extruding, cooling and forming; in the extrusion process, the temperature control is divided into eight zones from the material inlet to the extrusion port, wherein the eight zones are 130-140 ℃, 150-155 ℃, 165-175 ℃, 185-195 ℃, 155-145 ℃ and 110-120 ℃ in sequence; the temperature for cooling and forming is controlled at 20 ℃.
Example 3
The embodiment provides a self-closing aeration hose which comprises the following raw materials:
MDI 30 parts
PTMG (PTMG1000/2000 ═ 0.4) 70 parts
ER-8515 parts.
The embodiment also provides a preparation method of the self-closing aeration hose, which comprises the following specific steps:
(1) dehydrating the polyol in advance; the dehydration temperature is controlled at 110 ℃, and the dehydration time is 6 hours.
(2) Reacting the dehydrated polyol with isocyanate to generate a prepolymer; the reaction temperature is controlled at 130 ℃, the reaction time is 5 hours, and the stirring speed is 500r/min during the reaction process.
(3) Mixing the obtained prepolymer with a chain extender, extruding, cooling and forming; in the extrusion process, the temperature control is divided into eight zones from the material inlet to the extrusion port, wherein the eight zones are 130-140 ℃, 150-155 ℃, 165-175 ℃, 185-195 ℃, 155-145 ℃ and 110-120 ℃ in sequence; the temperature for cooling and forming is controlled at 25 ℃.
Comparative example 1
The comparative example provides a self-closing aeration hose, which comprises the following raw materials:
TDI 28 parts
PTMG (PTMG1000/2000 ═ 0.45) 65 parts
ER-8514 parts.
The preparation method is the same as that of example 1.
Comparative example 2
The comparative example provides a self-closing aeration hose, which comprises the following raw materials:
MDI 28 parts
PTMG 100065 parts
ER-8514 parts.
The preparation method is the same as that of example 1.
Comparative example 3
The comparative example provides a self-closing aeration hose, which comprises the following raw materials:
MDI 28 parts
PTMG 200065 parts
ER-8514 parts.
The preparation method is the same as that of example 1.
Comparative example 4
The comparative example provides a self-closing aeration hose, which comprises the following raw materials:
MDI 28 parts
PTMG (PTMG1000/2000 ═ 0.45) 65 parts
ER-80114 parts.
The preparation method is the same as that of example 1.
Comparative example 5
The comparative example provides a self-closing aeration hose, which comprises the following raw materials:
MDI 32 parts
PTMG (PTMG1000/2000 ═ 0.45) 58 parts
ER-8510 parts.
The preparation method is the same as that of example 1.
Performance testing
The self-closing aeration hoses obtained in the examples and the comparative examples were subjected to performance tests. The test items and methods were as follows:
hardness: a shore durometer;
tensile strength, elongation at break, tear strength: test Standard "Experimental methods for tension of vulcanized rubber and thermoplastic Elastomers";
oxygen utilization rate: refer to CJ/T475-.
The test results are shown in the following table.
TABLE 1 test table for physical and mechanical properties
Serial number Hardness Shore A Tensile strength Mpa Elongation at break% Tear Strength N/mm
Example 1 85 43 450 88
Example 2 84 40 460 85
Example 3 85 45 430 80
Comparative example 1 84 35 350 72
Comparative example 2 83 28 480 65
Comparative example 3 86 48 380 98
Comparative example 4 85 35 360 66
Comparative example 5 84 28 280 60
Note: the test environment temperature is 23 +/-2 ℃, and the test speed is 500 mm/min.
Table 2 oxygen utilization test
Serial number Flux 0.6m 3 /h*m Flux 0.9m 3 /h*m Flux 1.2m 3 /h*m
Examples1 53.17% 51.08% 47.39%
Example 2 52.12% 51.07% 48.39%
Example 3 51.08% 49.98% 47.23%
Comparative example 1 45.76% 41.08% 36.05%
Comparative example 2 54.08% 47.98% 38.23%
Comparative example 3 47.08% 44.05% 43.05%
Comparative example 4 45.86% 42.08% 35.05%
Comparative example 5 38.92% 32.98% 27.98%
Note: the test environment temperature is 15 +/-0.5 ℃, and the test water depth is 6 m.
From the above results, it can be seen that comparative example 2 has high elongation at break, good toughness rebound, high low flux oxygen utilization rate, but the utilization rate decreases rapidly with increasing flux under the same test conditions. Comparative example 3 has low elongation at break, high strength, low oxygen utilization rate, but with the flux increase, the change is smooth, but the toughness rebound is poor, and the oxygen utilization rate attenuation is fast after long-term use. Comparative examples 1, 4 and 5 had lower elongation at break and strength, lower oxygen utilization and faster decay in durability. Examples 1, 2, 3 had moderate strength and fracture, high toughness rebound, good self-closing properties, high oxygen utilization, and slow long-term decay.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A self-closing aeration hose is characterized by comprising the following raw materials:
isocyanate: diphenylmethane-4, 4' -diisocyanate;
polyol: polytetrahydrofuran ether glycol 1000 and polytetrahydrofuran ether glycol 2000 in the mass ratio of 0.4-0.5: 1;
chain extender: plastic polyether ER-85.
2. The self-closing aeration hose according to claim 1, wherein the mass ratio of the isocyanate to the polyol is 0.35 to 0.5: 1.
3. The self-closing aeration hose according to claim 2, wherein the raw materials comprise 25 to 30 parts by weight of diphenylmethane-4, 4' -diisocyanate, 60 to 70 parts by weight of polytetrahydrofuran ether glycol 1000 and 2000 parts by weight of polytetrahydrofuran ether glycol in a mass ratio of 0.4 to 0.5:1, and ER-8512 to 15 parts by weight.
4. The self-closing aeration hose of claim 3, wherein the ER-85 has a hardness of 85 ± 2A.
5. The method for preparing the self-closing aeration hose according to any one of the claims 1 to 4, which comprises the following steps:
(1) dehydrating the polyol in advance;
(2) reacting the dehydrated polyol with isocyanate to generate a prepolymer;
(3) and mixing the obtained prepolymer with a chain extender, extruding, cooling and forming.
6. The method for preparing the self-closing aeration hose according to claim 5, wherein in the step (1), the dehydration temperature is controlled at 110 ℃ and the dehydration time is 6-8 hours.
7. The method for preparing the self-closing aeration hose according to claim 5, wherein in the step (2), the reaction temperature is controlled at 120 ℃ and 130 ℃ and the reaction time is 5-6 hours.
8. The method for preparing the self-closing aeration hose according to claim 7, wherein in the step (2), stirring is performed during the reaction at a stirring speed of 400-600 r/min.
9. The method as claimed in claim 5, wherein in the step (3), the temperature control is divided into eight zones from the material inlet to the extrusion outlet during the extrusion process, and the eight zones are sequentially 130-.
10. The method for preparing a self-closing aeration hose according to claim 5, wherein in the step (3), the temperature for cooling and forming is controlled to be 20-25 ℃.
CN202210412722.2A 2022-04-19 2022-04-19 Self-closing aeration hose and preparation method thereof Pending CN114805721A (en)

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CN106966517A (en) * 2017-05-22 2017-07-21 北京得世达环保科技有限公司 A kind of TPU thin walled hoses and perforate mode for oxygenic aeration
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CN206337074U (en) * 2016-06-14 2017-07-18 江苏环川环境工程有限公司 New ultramicropore tube aerator
CN106966517A (en) * 2017-05-22 2017-07-21 北京得世达环保科技有限公司 A kind of TPU thin walled hoses and perforate mode for oxygenic aeration
JP2019030847A (en) * 2017-08-09 2019-02-28 西松建設株式会社 Aeration treatment method for contaminated water and aeration treatment device for contaminated water
CN111647124A (en) * 2020-06-04 2020-09-11 北京得世达环保科技有限公司 TPU (thermoplastic polyurethane) membrane material for sewage treatment aeration and preparation method thereof

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山西省化工研究所编: "《聚氨酯弹性体手册》", 31 January 2001, 化学工业出版社 *

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