CN115304813B - Greening tree watering heat preservation bag and preparation method and application thereof - Google Patents
Greening tree watering heat preservation bag and preparation method and application thereof Download PDFInfo
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- CN115304813B CN115304813B CN202210999227.6A CN202210999227A CN115304813B CN 115304813 B CN115304813 B CN 115304813B CN 202210999227 A CN202210999227 A CN 202210999227A CN 115304813 B CN115304813 B CN 115304813B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/05—Forming flame retardant coatings or fire resistant coatings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01C—PLANTING; SOWING; FERTILISING
- A01C23/00—Distributing devices specially adapted for liquid manure or other fertilising liquid, including ammonia, e.g. transport tanks or sprinkling wagons
- A01C23/006—Distribution of liquid fertilisers by gravity flow
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0237—Devices for protecting a specific part of a plant, e.g. roots, trunk or fruits
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G25/00—Watering gardens, fields, sports grounds or the like
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
- A01M7/00—Special adaptations or arrangements of liquid-spraying apparatus for purposes covered by this subclass
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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Abstract
The invention discloses a greening tree watering heat-preserving bag and a preparation method and application thereof, and relates to the technical field of heat-preserving materials. When the thermal insulation bag for watering the greening trees is prepared, firstly, ethylene glycol formate, polypropylene and polyvinyl chloride are mixed and blown into a bag for heat sealing to prepare the watering bag, allyl alcohol glycidyl ether and triethoxysilane are reacted to prepare epoxy silane, the epoxy silane, diphenyl diethoxy silane and hydroxymethyl triethoxy silane are reacted to prepare epoxy polysiloxane polyol, the epoxy polysiloxane polyol is reacted with diethyl phosphate and triphenylphosphine to prepare modified polysiloxane polyol, and the modified polysiloxane polyol, propylene glycol polyether, a foam stabilizer, N-dimethyl cyclohexylamine, a foaming agent and diphenylmethane diisocyanate are mixed and then are scraped on the surface of the watering bag to prepare the thermal insulation bag for watering the greening trees. The greening tree watering heat-insulating bag prepared by the invention has excellent heat-insulating performance and flame-retardant performance.
Description
Technical Field
The invention relates to the technical field of heat preservation materials, in particular to a greening tree watering heat preservation bag and a preparation method and application thereof.
Background
The afforestation tree watering bag is a high-efficiency practical product for afforestation and off-season tree planting in arid areas. When the tree is planted, the greening tree watering bag is used, watering is not needed again in two months of the live period of the tree seedling after watering fully, the water utilization rate and the tree planting efficiency are greatly improved, the tree planting cost is reduced, and the greening tree watering bag contains a water retaining agent and a plant nutrient; not only can keep moisture from losing, but also can promote the rooting development of the sapling. Application range: 1. afforestation of barren mountains, returning to forests, sand lands and beach lands; 2. off-season tree planting; planting, transplanting and supplementing street trees; 3. planting and supplementing highway hedgerow; planting and supplementing the side net green belt.
In the environment with larger temperature difference between cold and day and night, heat preservation and protection are also needed, so the invention provides a greening tree watering bag capable of carrying out heat preservation, which is required by the market.
Disclosure of Invention
The invention aims to provide a greening tree watering heat-preserving bag and a preparation method and application thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the greening tree watering thermal insulation bag is characterized in that the greening tree watering thermal insulation bag is prepared by mixing modified polysiloxane polyol, propylene glycol polyether, foam stabilizer, N-dimethylcyclohexylamine, foaming agent and diphenylmethane diisocyanate and then scraping the mixture on the surface of the watering bag.
Preferably, the modified polysiloxane polyol is prepared by reacting epoxy polysiloxane polyol with diethyl phosphate and triphenylphosphine.
Preferably, the epoxy polysiloxane polyol is prepared by reacting allyl alcohol glycidyl ether with triethoxysilane to prepare epoxy silane, and reacting the epoxy silane, diphenyl diethoxysilane and hydroxymethyl triethoxysilane.
Preferably, the pouring bag is made of ethylene glycol formate, polypropylene and polyvinyl chloride mixed blowing bag by heat sealing.
As optimization, the preparation method of the greening tree watering heat preservation bag comprises the following preparation steps:
(1) Ethylene glycol formate, polypropylene and polyvinyl chloride are mixed according to the mass ratio of 1:1: 1-2: 3:3, uniformly mixing, heating, melting, injecting into a mould, cooling to form a bag blank, sending into a blowing machine for blowing bags, wherein the blowing air pressure is 1.5-1.8 MPa, blow molding, heat sealing, processing into a required specification model, and the heat sealing strength is not lower than 12N/15mm, and the distance between the formed heat sealing edge and the bag edge is not greater than 4mm, so as to prepare the pouring bag;
(2) Toluene and epoxy polysiloxane polyol are mixed according to a mass ratio of 3: 4-3: 5, uniformly mixing, heating to 30-40 ℃, heating the mixed solution with the mass 1.1-1.2 times of that of the epoxy polysiloxane polyol within 30-40 min, heating to 70-75 ℃, stirring for reaction for 3-4 h at 600-800 r/min, cooling to room temperature, regulating the pH value to 6.8-7.2 by using a sodium hydroxide solution with the mass fraction of 3-5%, and standing for 4-6 h at 50-60 ℃ and 1-2 kPa to obtain modified polysiloxane polyol;
(3) The modified polysiloxane polyol, propylene glycol polyether with the molecular weight of 1000-1600, foam stabilizer, N-dimethylcyclohexylamine, pure water and foaming agent are mixed according to the mass ratio of 80:80:3:2:1: 40-100: 100:5:3:1:50, uniformly mixing, stirring for 2-3 min at 10-20 ℃ at 800-1000 r/min, then adding diphenylmethane diisocyanate with the mass 2.4-2.8 times that of the modified polysiloxane polyol, continuously stirring for 8-10 s, scraping and coating the mixture on one side surface of the irrigation bag for 1-2 mm thick, heating to 42-46 ℃, and carrying out heat preservation and solidification for 20-24 h to obtain the greening tree irrigation heat preservation bag.
As an optimization, the preparation method of the epoxy polysiloxane polyol in the step (2) comprises the following steps: glycidyl allyl alcohol ether, triethoxysilane and n-hexane are mixed according to the mass ratio of 1:1: 8-1: 1:10, uniformly mixing, adding divinyl tetramethyl disiloxane platinum salt with the mass of 0.03-0.05 times of that of allyl alcohol glycidyl ether, stirring and refluxing for 4-6 hours at 70-80 ℃ and 500-800 r/min, and standing for 3-4 hours at 20-30 ℃ and 1-2 kPa to obtain epoxy silane; epoxy silane, diphenyl diethoxy silane, hydroxymethyl triethoxy silane and ethanol are mixed in a nitrogen atmosphere according to the mass ratio of 1:1:1: 6-1: 2:2:10, regulating the pH value to 2.9-3.1 by using hydrochloric acid with the mass fraction of 3-5%, stirring for 40-50 min at the temperature of 30-40 ℃ and 500-800 r/min, heating to 50-60 ℃, stirring for reacting for 2-3 h at the temperature of 500-800 r/min, heating to 70-78 ℃ and continuing to stir for reacting for 7-9 h, extracting and separating by using hexamethyldisiloxane to obtain an oil phase, and drying for 8-10 h at the temperature of 10-30 ℃ and the pressure of 1-10 Pa.
As optimization, the mixed solution in the step (2) is prepared by mixing toluene, diethyl phosphate and triphenylphosphine according to a mass ratio of 130:70:1 to 170:90:1 are evenly mixed to prepare a mixed solution.
Preferably, the foam stabilizer in the step (3) is AK8804.
Preferably, the foaming agent in the step (3) is 141B.
As optimization, the application method of the greening tree watering heat-preserving bag comprises the following steps:
(a) The shape of the greening tree watering heat preservation bag can be manufactured according to the tree;
(b) The upper part of the greening tree watering heat-preserving bag is provided with a water filling port or is open, and the bottom is provided with a drip irrigation hole capable of controlling the flow rate;
(c) The greening tree watering heat-preserving bag can be used for watering, fertilizing and spraying the greening tree in summer. Can be tied at the bottom of the tree in winter and used as a cold-proof quilt.
Compared with the prior art, the invention has the following beneficial effects:
when the greening tree watering thermal insulation bag is prepared, the watering bag is prepared by mixing and blowing ethylene glycol formate, polypropylene and polyvinyl chloride, and then the greening tree watering thermal insulation bag is prepared by mixing and scraping modified polysiloxane polyol, propylene glycol polyether, foam stabilizer, N-dimethyl cyclohexylamine, foaming agent and diphenylmethane diisocyanate on the surface of the watering bag.
Firstly, allyl alcohol glycidyl ether and triethoxysilane are reacted to prepare epoxy silane, the epoxy silane, diphenyl diethoxy silane and hydroxymethyl triethoxysilane are reacted to prepare epoxy polysiloxane polyol, the epoxy polysiloxane polyol, diethyl phosphate and triphenylphosphine are reacted to prepare modified polysiloxane polyol, phosphorus element is introduced, and flame retardance is carried out in coordination with a polysiloxane chain segment at high temperature, so that the flame retardance of the greening tree watering thermal insulation bag is improved.
And secondly, mixing the modified polysiloxane polyol, propylene glycol polyether, a foam stabilizer, N-dimethylcyclohexylamine, a foaming agent and diphenylmethane diisocyanate, and then scraping the mixture on the surface of the irrigation bag to form a foaming surface, thereby improving the heat preservation performance of the greening tree irrigation heat preservation bag.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the method for testing each index of the greening tree watering heat preservation bag manufactured in the following examples is as follows:
thermal insulation performance: the greening tree watering thermal insulation bags obtained in each example and the comparative example materials are taken to have the same size, shape and thickness, the thermal insulation side is wrapped with hot water with the same temperature, the hot water is placed in the same room temperature environment, the water temperature is measured after a period of time, and Wen Bianliang =initial temperature-environment temperature is recorded.
Flame retardant properties: the greening tree watering thermal insulation bags obtained in each example are taken to be the same in size, shape and thickness as those of the comparative example materials, and the polar oxygen index is measured according to the GB/T2406 standard method to test the flame retardance.
Example 1
The preparation method of the greening tree watering heat-preserving bag mainly comprises the following preparation steps:
(1) Ethylene glycol formate, polypropylene and polyvinyl chloride are mixed according to the mass ratio of 1:1:1, uniformly mixing, heating, melting, injecting into a mould, cooling to form a bag blank, sending into a blowing machine for blowing bags, wherein the blowing air pressure is 1.5MPa, performing blow molding, performing heat seal processing to form a required specification model, and the heat seal strength is not lower than 12N/15mm, and the distance between the formed heat seal edge and the bag edge is not greater than 4mm to prepare a pouring bag;
(2) Glycidyl allyl alcohol ether, triethoxysilane and n-hexane are mixed according to the mass ratio of 1:1:8, uniformly mixing, adding divinyl tetramethyl disiloxane platinum salt with the mass of 0.03 times of that of allyl alcohol glycidyl ether, stirring and refluxing at 70 ℃ and 500r/min for 6 hours, and standing at 20 ℃ for 4 hours under 1kPa to obtain epoxy silane; epoxy silane, diphenyl diethoxy silane, hydroxymethyl triethoxy silane and ethanol are mixed in a nitrogen atmosphere according to the mass ratio of 1:1:1:6, uniformly mixing, regulating the pH to 2.9 by using hydrochloric acid with the mass fraction of 3%, stirring for 50min at 30 ℃ and 500r/min, heating to 50 ℃, stirring for 3h at 500r/min, heating to 70 ℃, continuously stirring for 9h, extracting and separating by using hexamethyldisiloxane to obtain an oil phase, and drying at 10 ℃ and 1Pa for 10h to obtain epoxy polysiloxane polyol; toluene, diethyl phosphate and triphenylphosphine are mixed according to the mass ratio of 130:70:1, uniformly mixing to prepare a mixed solution, and mixing toluene and epoxy polysiloxane polyol according to a mass ratio of 3:4, uniformly mixing, heating to 30 ℃ and keeping the mixed solution with the mass 1.1 times of that of the epoxy polysiloxane polyol within 40min, heating to 70 ℃, stirring for reaction for 4h at 600r/min, cooling to room temperature, adjusting the pH to 6.8 by using a sodium hydroxide solution with the mass fraction of 3%, and standing for 6h at 50 ℃ and 1kPa to obtain the modified polysiloxane polyol;
(3) The modified polysiloxane polyol, propylene glycol polyether with the molecular weight of 1000, foam stabilizer AK8804, N-dimethylcyclohexylamine, pure water and foaming agent 141B are mixed according to the mass ratio of 80:80:3:2:1:40, stirring for 3min at 10 ℃ at 800r/min, adding diphenylmethane diisocyanate with the mass 2.4 times of that of the modified polysiloxane polyol, stirring for 8s, scraping and coating the mixture on one side surface of the irrigation bag for 2mm thick, heating to 42 ℃, preserving heat, and curing for 24h to obtain the greening tree irrigation heat-preserving bag.
Example 2
The preparation method of the greening tree watering heat-preserving bag mainly comprises the following preparation steps:
(1) Ethylene glycol formate, polypropylene and polyvinyl chloride are mixed according to the mass ratio of 1.5:2:2, uniformly mixing, heating, melting, injecting into a mould, cooling to form a bag blank, sending into a blowing machine for blowing bags, wherein the blowing air pressure is 1.6MPa, performing blow molding, performing heat seal processing to form a model with a required specification, the heat seal strength is not lower than 12N/15mm, and the distance between the formed heat seal edge and the bag edge is not greater than 4mm, thus obtaining the pouring bag;
(2) Glycidyl allyl alcohol ether, triethoxysilane and n-hexane are mixed according to the mass ratio of 1:1:9, uniformly mixing, adding divinyl tetramethyl disiloxane platinum salt with the mass of 0.04 times of that of allyl alcohol glycidyl ether, stirring and refluxing at 75 ℃ and 600r/min for 5 hours, and standing at 25 ℃ and 1.5kPa for 3.5 hours to obtain epoxy silane; epoxy silane, diphenyl diethoxy silane, hydroxymethyl triethoxy silane and ethanol are mixed in a nitrogen atmosphere according to the mass ratio of 1:1.5:1.5:8, uniformly mixing, regulating the pH to 3 by using hydrochloric acid with the mass fraction of 4%, stirring for 45min at 35 ℃, heating to 55 ℃, stirring for 2.5h at 650r/min, heating to 74 ℃, continuously stirring for 8h, extracting and separating by using hexamethyldisiloxane to obtain an oil phase, and drying for 9h at 20 ℃ and 5Pa to obtain epoxy polysiloxane polyol; toluene, diethyl phosphate and triphenylphosphine are mixed according to the mass ratio of 150:80:1, uniformly mixing to prepare a mixed solution, and mixing toluene and epoxy polysiloxane polyol according to a mass ratio of 3:4.5, uniformly mixing, heating to 35 ℃, heating to a mixed solution with the mass of 1.15 times of that of the epoxy polysiloxane polyol within 35min, heating to 72 ℃, stirring at 700r/min for reaction for 3.5h, cooling to room temperature, adjusting the pH value to 7 by using a sodium hydroxide solution with the mass fraction of 4%, and standing at 55 ℃ for 5h at 1.5kPa to prepare modified polysiloxane polyol;
(3) The modified polysiloxane polyol, propylene glycol polyether with the molecular weight of 1300, foam stabilizer AK8804, N-dimethylcyclohexylamine, pure water and foaming agent 141B are mixed according to the mass ratio of 90:90:4:2.5:1:45, stirring for 2.5min at 15 ℃ at 900r/min, adding diphenylmethane diisocyanate with the mass of 2.6 times of that of the modified polysiloxane polyol, stirring for 9s, scraping and coating the mixture on one side surface of the irrigation bag for 2mm thick, heating to 44 ℃, and preserving heat and curing for 22h to obtain the greening tree irrigation heat-preserving bag.
Example 3
The preparation method of the greening tree watering heat-preserving bag mainly comprises the following preparation steps:
(1) Ethylene glycol formate, polypropylene and polyvinyl chloride are mixed according to the mass ratio of 2:3:3, uniformly mixing, heating, melting, injecting into a mould, cooling to form a bag blank, sending into a blowing machine for blowing bags, wherein the blowing air pressure is 1.6MPa, performing blow molding, performing heat seal processing to form a required specification model, and the heat seal strength is not lower than 12N/15mm, and the distance between the formed heat seal edge and the bag edge is not greater than 4mm to prepare a pouring bag;
(2) Glycidyl allyl alcohol ether, triethoxysilane and n-hexane are mixed according to the mass ratio of 1:1:10, uniformly mixing, adding divinyl tetramethyl disiloxane platinum salt with the mass of 0.05 times of that of allyl alcohol glycidyl ether, stirring and refluxing at 80 ℃ and 800r/min for 4 hours, and standing at 30 ℃ and 2kPa for 3 hours to obtain epoxy silane; epoxy silane, diphenyl diethoxy silane, hydroxymethyl triethoxy silane and ethanol are mixed in a nitrogen atmosphere according to the mass ratio of 1:2:2:10, uniformly mixing, regulating the pH to 2.9 by using hydrochloric acid with the mass fraction of 5%, stirring for 40min at 40 ℃ and 800r/min, heating to 60 ℃, stirring for 2h at 800r/min, heating to 78 ℃ and continuing to stir for 7h, extracting and separating by using hexamethyldisiloxane to obtain an oil phase, and drying for 8h at 30 ℃ and 10Pa to obtain epoxy polysiloxane polyol; toluene, diethyl phosphate and triphenylphosphine are mixed according to a mass ratio of 170:90:1, uniformly mixing to prepare a mixed solution, and mixing toluene and epoxy polysiloxane polyol according to a mass ratio of 3:5, uniformly mixing, heating to 40 ℃ and keeping the mixed solution with the mass 1.2 times of that of the epoxy polysiloxane polyol within 30min, heating to 75 ℃, stirring for reaction for 3h at 800r/min, cooling to room temperature, adjusting the pH to 7.2 by using a sodium hydroxide solution with the mass fraction of 5%, and standing for 4h at 60 ℃ and 2kPa to obtain modified polysiloxane polyol;
(3) The modified polysiloxane polyol, propylene glycol polyether with molecular weight of 1600, foam stabilizer AK8804, N-dimethylcyclohexylamine, pure water and foaming agent 141B are mixed according to the mass ratio of 100:100:5:3:1:50, stirring for 2min at 20 ℃ at 1000r/min, adding diphenylmethane diisocyanate with the mass of 2.8 times of that of the modified polysiloxane polyol, stirring for 10s continuously, scraping and coating the mixture on one side surface of the irrigation bag for 2mm thick, heating to 46 ℃, preserving heat and curing for 20h, and obtaining the greening tree irrigation heat-preserving bag.
Comparative example 1
The preparation method of the greening tree watering heat-preserving bag mainly comprises the following preparation steps:
(1) Ethylene glycol formate, polypropylene and polyvinyl chloride are mixed according to the mass ratio of 1.5:2:2, uniformly mixing, heating, melting, injecting into a mould, cooling to form a bag blank, sending into a blowing machine for blowing bags, wherein the blowing air pressure is 1.6MPa, performing blow molding, performing heat seal processing to form a model with a required specification, the heat seal strength is not lower than 12N/15mm, and the distance between the formed heat seal edge and the bag edge is not greater than 4mm, thus obtaining the pouring bag;
(2) Glycidyl allyl alcohol ether, triethoxysilane and n-hexane are mixed according to the mass ratio of 1:1:9, uniformly mixing, adding divinyl tetramethyl disiloxane platinum salt with the mass of 0.04 times of that of allyl alcohol glycidyl ether, stirring and refluxing at 75 ℃ and 600r/min for 5 hours, and standing at 25 ℃ and 1.5kPa for 3.5 hours to obtain epoxy silane; epoxy silane, diphenyl diethoxy silane, hydroxymethyl triethoxy silane and ethanol are mixed in a nitrogen atmosphere according to the mass ratio of 1:1.5:1.5:8, uniformly mixing, regulating the pH to 3 by using hydrochloric acid with the mass fraction of 4%, stirring for 45min at 35 ℃, heating to 55 ℃, stirring for 2.5h at 650r/min, heating to 74 ℃, continuously stirring for 8h, extracting and separating by using hexamethyldisiloxane to obtain an oil phase, and drying for 9h at 20 ℃ and 5Pa to obtain epoxy polysiloxane polyol;
(3) Epoxy polysiloxane polyol, propylene glycol polyether with molecular weight of 1300, foam stabilizer AK8804, N-dimethylcyclohexylamine, pure water and foaming agent 141B according to the mass ratio of 90:90:4:2.5:1:45, stirring for 2.5min at 15 ℃ at 900r/min, adding diphenylmethane diisocyanate with the mass of 2.6 times of that of epoxy polysiloxane polyol, stirring for 9s, scraping and coating the mixture on one side surface of the irrigation bag for 2mm thick, heating to 44 ℃, and preserving heat and curing for 22h to obtain the greening tree irrigation heat-preserving bag.
Comparative example 2
The preparation method of the greening tree watering heat-preserving bag mainly comprises the following preparation steps:
ethylene glycol formate, polypropylene and polyvinyl chloride are mixed according to the mass ratio of 1.5:2:2, uniformly mixing, heating, melting, injecting into a mould, cooling to form a bag blank, sending into a blowing machine for blowing bags, wherein the blowing air pressure is 1.6MPa, performing blow molding, performing heat seal processing to obtain a required specification model, wherein the heat seal strength is not lower than 12N/15mm, and the distance between the formed heat seal edge and the bag edge is not greater than 4mm, thus obtaining the greening tree pouring heat-preserving bag.
The following table 1 shows the results of performance analysis of the heat insulation performance and the flame retardant performance of the greening tree watering heat insulation bags according to the embodiments 1 to 3 and the comparative examples 1 to 2.
TABLE 1
As can be seen from the comparison of the experimental data of examples 1-3 and comparative examples 1-2 in Table 1, the greening tree watering heat-insulating bag prepared by the invention has good heat-insulating performance and flame-retardant performance.
From comparison of experimental data of examples 1, 2 and 3 and comparative example 1, the examples 1, 2 and 3 have high limiting oxygen index compared with comparative example 1, which shows that after the epoxy polysiloxane polyol is modified, phosphorus element is introduced, and the epoxy polysiloxane polyol is in coordination with polysiloxane chain segments for flame retardance at high temperature, so that the flame retardance of the greening tree watering heat preservation bag is improved; from comparison of experimental data of examples 1, 2 and 3 and comparative example 2, the examples 1, 2 and 3 have small temperature variation and high limiting oxygen index compared with comparative example 2, which shows that the modified polysiloxane polyol, propylene glycol polyether, foam stabilizer, N-dimethylcyclohexylamine, foaming agent and diphenylmethane diisocyanate are mixed and then coated on the surface of a pouring bag to form a foaming surface, so that the heat insulation performance of the greening tree pouring heat insulation bag is improved, and the modified polysiloxane polyol improves the flame retardant performance of the greening tree pouring heat insulation bag.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (4)
1. The preparation method of the greening tree watering heat-preserving bag is characterized by comprising the following preparation steps of:
(1) Ethylene glycol formate, polypropylene and polyvinyl chloride are mixed according to the mass ratio of 1:1: 1-2: 3:3, uniformly mixing, heating, melting, injecting into a mould, cooling to form a bag blank, sending into a blowing machine for blowing bags, wherein the blowing air pressure is 1.5-1.8 MPa, performing blow molding, performing heat sealing processing to obtain a required specification model, wherein the heat sealing strength is not lower than 12N/15mm, and the distance between the formed heat sealing edge and the bag edge is not greater than 4mm, so as to prepare a pouring bag;
(2) Glycidyl allyl alcohol ether, triethoxysilane and n-hexane are mixed according to the mass ratio of 1:1:8~1:1:10, uniformly mixing, adding divinyl tetramethyl disiloxane platinum salt with the mass of 0.03-0.05 times of that of allyl alcohol glycidyl ether, stirring and refluxing at 70-80 ℃ and 500-800 r/min for 4-6 hours, and standing at 20-30 ℃ and 1-2 kPa for 3-4 hours to obtain epoxy silane; epoxy silane, diphenyl diethoxy silane, hydroxymethyl triethoxy silane and ethanol are mixed in a nitrogen atmosphere according to the mass ratio of 1:1:1: 6-1: 2:2:10, uniformly mixing, regulating the pH to 2.9-3.1 by using hydrochloric acid with the mass fraction of 3-5%, stirring at the temperature of 30-40 ℃ and 500-800 r/min for 40-50 min, heating to the temperature of 50-60 ℃, stirring at the temperature of 500-800 r/min for 2-3 h, heating to the temperature of 70-78 ℃ for continuous stirring for 7-9 h, extracting and separating by using hexamethyldisiloxane to obtain an oil phase, and drying at the temperature of 10-30 ℃ and 1-10 Pa for 8-10 h to obtain epoxy polysiloxane polyol; toluene, diethyl phosphate and triphenylphosphine are mixed according to the mass ratio of 130:70: 1-170: 90:1, uniformly mixing to prepare a mixed solution; toluene and epoxy polysiloxane polyol are mixed according to a mass ratio of 3:4~3:5, uniformly mixing, heating to 30-40 ℃, adding a mixed solution with the mass 1.1-1.2 times of that of the epoxy polysiloxane polyol in 30-40 min, heating to 70-75 ℃, stirring for reaction for 3-4 h at 600-800 r/min, cooling to room temperature, regulating the pH to 6.8-7.2 by using a sodium hydroxide solution with the mass fraction of 3-5%, and standing for 4-6 h at 50-60 ℃ at 1-2 kPa to obtain modified polysiloxane polyol;
(3) The preparation method comprises the following steps of (1) mixing modified polysiloxane polyol, propylene glycol polyether with molecular weight of 1000-1600, foam stabilizer, N-dimethylcyclohexylamine, pure water and foaming agent according to mass ratio of 80:80:3:2:1: 40-100: 100:5:3:1:50, uniformly mixing, stirring for 2-3 min at 10-20 ℃ at 800-1000 r/min, adding diphenylmethane diisocyanate with the mass 2.4-2.8 times that of the modified polysiloxane polyol, continuously stirring for 8-10 s, scraping and coating the mixture on one side surface of the irrigation bag for 1-2 mm thick, heating to 42-46 ℃, and carrying out heat preservation and solidification for 20-24 h to obtain the greening tree irrigation heat-preserving bag.
2. The method for preparing the insulation bag for watering the greening trees according to claim 1, wherein the foam stabilizer in the step (3) is AK8804.
3. The method for preparing the heat preservation bag for watering the greening trees according to claim 1, wherein the foaming agent in the step (3) is 141B.
4. The method for preparing the greening tree watering thermal insulation bag according to claim 1, wherein the method for applying the greening tree watering thermal insulation bag is as follows:
(a) The shape of the greening tree watering heat preservation bag can be manufactured according to the tree;
(b) The upper part of the greening tree watering heat-preserving bag is provided with a water filling port or is open, and the bottom is provided with a drip irrigation hole capable of controlling the flow rate;
(c) The heat-insulating bag for watering the greening trees can be used for watering the greening trees in summer, fertilizing, spraying medicines and binding at the bottoms of the trees in winter, and can be used as a cold-proof quilt.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922600A (en) * | 2019-10-22 | 2020-03-27 | 武汉大学 | Hydroxyalkyl organosilicon compounds, and preparation method and application thereof |
| CN112970401A (en) * | 2019-12-17 | 2021-06-18 | 山东海科创新研究院有限公司 | Fertilizing method, water and fertilizer slow-release bag and preparation method thereof |
| WO2021136603A1 (en) * | 2019-12-29 | 2021-07-08 | Braukmann Gmbh | A vacuum-sealable plastic pouch |
| CN114670294A (en) * | 2022-03-31 | 2022-06-28 | 安徽省科晟生态木装饰材料有限公司 | High-strength ecological plate and manufacturing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922600A (en) * | 2019-10-22 | 2020-03-27 | 武汉大学 | Hydroxyalkyl organosilicon compounds, and preparation method and application thereof |
| CN112970401A (en) * | 2019-12-17 | 2021-06-18 | 山东海科创新研究院有限公司 | Fertilizing method, water and fertilizer slow-release bag and preparation method thereof |
| WO2021136603A1 (en) * | 2019-12-29 | 2021-07-08 | Braukmann Gmbh | A vacuum-sealable plastic pouch |
| CN114670294A (en) * | 2022-03-31 | 2022-06-28 | 安徽省科晟生态木装饰材料有限公司 | High-strength ecological plate and manufacturing process |
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