CN114854188B - Pyrophyllite/polyurethane composite film and preparation method and application thereof - Google Patents

Pyrophyllite/polyurethane composite film and preparation method and application thereof Download PDF

Info

Publication number
CN114854188B
CN114854188B CN202210459602.8A CN202210459602A CN114854188B CN 114854188 B CN114854188 B CN 114854188B CN 202210459602 A CN202210459602 A CN 202210459602A CN 114854188 B CN114854188 B CN 114854188B
Authority
CN
China
Prior art keywords
pyrophyllite
polyurethane
polyurethane composite
film
modified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210459602.8A
Other languages
Chinese (zh)
Other versions
CN114854188A (en
Inventor
詹瑛瑛
任坤
黄睿
王世萍
江莉龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuzhou University
Original Assignee
Fuzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuzhou University filed Critical Fuzhou University
Priority to CN202210459602.8A priority Critical patent/CN114854188B/en
Publication of CN114854188A publication Critical patent/CN114854188A/en
Application granted granted Critical
Publication of CN114854188B publication Critical patent/CN114854188B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/10—Solid or semi-solid fertilisers, e.g. powders
    • C05G5/12—Granules or flakes
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings
    • C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings
    • C05G5/38—Layered or coated, e.g. dust-preventing coatings layered or coated with wax or resins
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Abstract

The invention discloses a pyrophyllite/polyurethane composite film and a preparation method and application thereof. The pyrophyllite with a layered structure is stripped in a simple ball milling mode to improve the specific surface area of the pyrophyllite, the surface of the pyrophyllite is activated by monoalkoxy pyrophosphate titanate through further ball milling, the modified pyrophyllite is dispersed in a polyurethane precursor through ultrasonic treatment, and a film is directly formed through in-situ polymerization. The pyrophyllite/polyurethane composite coating film can be applied to the field of controlled release. Compared with the common polyurethane coating, the natural mineral pyrophyllite adopted by the invention is cheap and easy to obtain, the pyrophyllite structure and the surface modification are realized by using a very small amount of monoalkoxy pyrophosphate titanate through simple mechanical treatment, the controlled release performance and the mechanical performance of the pyrophyllite/polyurethane film are improved, and no waste liquid is generated in the whole modification and film forming process.

Description

Pyrophyllite/polyurethane composite membrane and preparation method and application thereof
Technical Field
The invention belongs to the technical field of membrane materials, and particularly relates to a pyrophyllite/polyurethane composite coating and a preparation method thereof.
Background
Polyurethane is a high polymer material with rubber elasticity and plastic strength, is concerned in a plurality of fields due to certain strength, toughness, wear resistance, low temperature resistance, oil resistance and environmental resistance, and the modified composite material is applied to the controlled release of fertilizers besides the biomedical fields of combustion-supporting building materials, drug-loaded controlled release, wound repair, tissue engineering and the like. Polyurethanes can be classified into petroleum-based polyurethanes and bio-based polyurethanes according to their origin. The polyurethane prepared by using the petroleum products and the derivatives thereof as raw materials has higher cost and is not degradable, and the residual film material after the fertilizer is released can cause secondary pollution to the environment. Compared with petroleum-based polyurethane, the bio-based polyurethane material is easier to degrade and has wide and various sources. In order to improve the controlled release performance and the mechanical performance of the polyurethane membrane material and achieve ecological and cost-friendly properties, the invention focuses on expanding the selection range of membrane materials and the synthesis process. The patent CN101323545A covers all biological grease developed and utilized by human beings and all isocyanates, so researchers seek to develop innovation from the main materials of polyurethane precursors. In patent CN 110218121, the mechanical property and the processing property of the film layer are improved by adding chain extenders, auxiliaries and catalysts, and a polyurethane coating film with high strength, good toughness, improved controlled release performance and a maximum release period of 70 days is obtained. Patent CN 103421161 adopts mixed polyol to make the polyurethane molecular chain have different soft segment and hard segment, so as to improve controllability. The patent CN 103319252 introduces herbicide into polyurethane coating liquid to realize double functions of weeding and slow release, and introduces paraffin as lubricant. Patent CN105111402 introduces polycarbodiimide or monocarbodiimide as hydrolysis stabilizer in vegetable oil polyol. In patent CN 106800472, attapulgite is added to vegetable oil, cardanol is used for modifying isocyanic acid to obtain a bio-based hybrid composite modified polyurethane controlled release fertilizer, wherein the castor oil-based controlled release fertilizer with the coating amount of 3% can last for 60 days. Patent CN 103145138A discloses a method for dissociating attapulgite by gamma rays and high-energy electron radiation, which is further applied to the field of chemical fertilizers.
Pyrophyllite is a clay mineral with a layered structure, and its molecular formula is Al 2 [Si 4 O 10 ](OH) 2 There are both monoclinic and triclinic crystal structures, with monoclinic pyrophyllite being more common. The pyrophyllite resources in China are rich, the pyrophyllite resources are one of a few countries which produce pyrophyllite ores in the world, the pyrophyllite resources are mainly distributed in the southeast coastal areas, and the newly increased pyrophyllite storage amount in the Fujian province in 2017 reaches 4353 ten thousand tons. While the amount of pyrophyllite mineral exploration is increased, the application of pyrophyllite is gradually developed from the industries of architectural ceramics, refractory materials and glass fibers to more than ten fields of papermaking, plastics, rubber, candies, medicines, lubricants, cosmetics and the like, but most of the fields have higher requirements on the grade of pyrophyllite and low-grade pyrophyllite (Al) 2 O 3 The content is less than 20 percent) and aluminum is also supplemented. The direct application of low-grade pyrophyllite is expanded, resources are fully and reasonably utilized, and the direction of field research motivation is also provided. In view of the reports of natural minerals in the field of application to polyurethane films, it is only rare to find an application of pyrophyllite in this field. Therefore, the invention develops innovative research of the composite application of the low-grade pyrophyllite and the polyurethane film based on resource ecological friendliness and process cost friendliness.
Disclosure of Invention
The invention integrates excellent controlled release property, resource ecological friendliness and process cost friendliness, develops innovative research on the composite application of low-grade pyrophyllite and polyurethane film, and provides the pyrophyllite/polyurethane composite film and a preparation method thereof. By comparing the influence of the property of the modifier, the content of the modifier and the modification method on the performance of the pyrophyllite/polyurethane composite membrane, the novel composite membrane based on vegetable oil-based polyurethane and low-grade pyrophyllite as main materials and the preparation method thereof are innovatively developed.
In order to achieve the purpose, the invention adopts the technical scheme that:
a pyrophyllite/polyurethane composite membrane is prepared by modifying pyrophyllite with monoalkoxy pyrophosphate titanate, wherein the mass percent of the modified pyrophyllite in the composite membrane is 5-9%, preferably 7%; the dosage of the monoalkoxy pyrophosphate titanate is 0.3-0.4% of the weight of the pyrophyllite.
Stripping a lamellar structure of the low-grade pyrophyllite by a mechanical ball milling method, improving the specific surface area of the pyrophyllite, adding monoalkoxy pyrophosphate titanate, and further performing ball milling to realize organization of the surface of the pyrophyllite; the modified pyrophyllite is dispersed in a polyurethane precursor solution through ultrasonic treatment, a film precursor is atomized and attached to the surface of urea particles by means of high-pressure gas, and a film is directly formed on the surface of the urea particles after heating. When the urea coating agent is applied to urea coating, urea is pretreated; after the urea is preheated to 65-70 ℃, 0.5 wt% of zinc lactate aqueous solution is sprayed on the surface of the urea particles to improve the surface smoothness of the urea particles, trace elements are introduced, and the hydrolysis in the polymerization process is inhibited by utilizing the characteristic of strong water absorption of the zinc lactate, so that the controlled release performance of the composite membrane is improved.
The preparation method of the pyrophyllite/polyurethane composite film comprises the following steps:
(1) Taking a proper amount of monoalkoxy pyrophosphate type titanate and isopropanol according to the mass ratio of 1. After 10 g of dried pyrophyllite and 60 g of agate balls (large ball: medium ball: small ball =1 3).
(2) Adding modified pyrophyllite with the mass being 5-9% of that of the polyurethane precursor into the polyurethane precursor, stirring, and placing in an ultrasonic cleaner for ultrasonic treatment for 20 min to uniformly disperse the modified pyrophyllite in the polyurethane precursor solution, wherein the preferred ultrasonic frequency is 37 Hz, so as to achieve the optimal dispersion effect.
(3) Putting the large granular urea into a rotary drum coating machine, opening the rotary drum coating machine to rotate and preheating the large granular fertilizer, wherein the rotating speed of the coating machine is 40 rmp, stopping heating when the surface temperature of urea granules reaches 65-70 ℃, spraying 0.5 wt% of zinc lactate aqueous solution (the mass of the aqueous solution is 1% of the mass of the urea) on the surfaces of the urea granules, and reheating the urea granules to enable the surface temperature to reach 65-70 ℃ after 5 min.
(4) Adding the mixture of the modified pyrophyllite and the polyurethane precursor into a spray gun, spraying the mixture onto the surface of urea particles through high-pressure gas, and continuously heating to solidify the mixture into a film. And after the polyurethane is completely cured, spraying again, and repeating for three times, so that the mass of the pyrophyllite/polyurethane composite membrane reaches 3% of the mass of the urea particles.
Further, the polyurethane precursor is formed by mixing vegetable oil-based polyol and isocyanate according to the molar ratio of hydroxyl in the polyol to isocyanate in the isocyanate of 1. The vegetable oil-based polyol is one or more of castor oil, soybean oil-based polyol, palm oil-based polyol and rapeseed oil-based polyol, and castor oil is preferred. The isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and polymethylene polyphenyl polyisocyanate, and toluene diisocyanate is preferred.
The invention has the following remarkable advantages:
1. the characteristic of rich pyrophyllite resources in Fujian province is exerted, and low-grade pyrophyllite with low price is used as a filler;
2. compared with other surface modifiers, the modifier has a plurality of hydrophobic carbon chains on the molecule, and can effectively improve the lipophilicity of the pyrophyllite surface under the condition of extremely small addition amount; the complex carbon chains can be physically entangled with polyurethane molecular chains more, so that the mechanical property and the controlled release property of the composite film can be effectively improved;
3. the lamella of the pyrophyllite is peeled by a two-step mechanical ball milling method, the specific surface area of the pyrophyllite is improved, the particle size of particles is reduced, the dispersion of a modifier is promoted, and the reactive sites are increased. The method has low requirement on equipment, simple preparation process, no waste liquid generated in the modification process, high utilization rate of the modifier and higher economic benefit;
4. the surface of urea particles is modified by using 0.5 wt% of zinc lactate aqueous solution, so that the surface smoothness of urea is improved, beneficial trace elements are introduced, and hydrolysis in the polymerization process is inhibited by utilizing the characteristic of strong water absorption of the urea, so that the controlled release performance of the composite membrane is improved.
Drawings
FIG. 1 is an XRD spectrum of a low grade pyrophyllite; quantification by the K-value methodAnalyzing to obtain Al in the used low-grade pyrophyllite 2 O 3 The content of (D) is 7 wt%;
FIG. 2 is an SEM image of a modified pyrophyllite; (a) is the modified pyrophyllite obtained in example 2; (b) is the modified pyrophyllite obtained in comparative example 4; (c) is the modified pyrophyllite obtained in comparative example 8;
FIG. 3 is an SEM image of the urea surface before and after 0.5 wt% zinc lactate treatment; in the figure, (a) is the surface micro-topography of urea; and (b) the microscopic morphology of the urea surface after zinc lactate treatment.
Detailed Description
In order to make the content of the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Taking a proper amount of monoalkoxy pyrophosphate type titanate and isopropanol according to a mass ratio of 1. 50 g of dried pyrophyllite and 300 g of agate ball milling beads (macrobeads: mesobeads: bead =1 = 3) were dry-milled in a ball mill at 500 rpm for 45min, then 0.30g of a monoalkoxy pyrophosphate type titanate solution was added, and further dry-milled at 500 rpm for 45min to obtain a modified pyrophyllite.
(2) Weighing 19.3995 g of castor oil and 1.2185 g of modified pyrophyllite obtained in the step (1), mixing, performing ultrasonic treatment for 20 min at 37 Hz, adding 5.0g of toluene diisocyanate, stirring to obtain a film precursor, and standing for later use.
(3) 200 g of large-particle urea is put into a rotary drum coating machine, the surface of the urea particles is heated to 65-70 ℃ at the rotating speed of 40 rmp, then the heating is stopped, 2.0 g of 0.5 wt% zinc lactate aqueous solution is sprayed on the surface of the urea particles, and after the treatment for 5min, the heating is carried out again to ensure that the surface temperature of the urea reaches 65-70 ℃.
(4) And adding the film precursor into a spray gun, spraying the film precursor onto the surface of urea particles through high-pressure gas, continuously heating, curing to form a film, spraying again after the polyurethane is completely cured, and repeating for three times to ensure that the mass of the pyrophyllite/polyurethane composite film reaches 3% of the mass of the urea particles.
Example 2
The pyrophyllite/polyurethane composite film provided in this example is different from example 1 in that the mass of the monoalkoxy pyrophosphate titanate solution in the pyrophyllite/polyurethane composite film preparation step (1) is 0.40 g.
Example 3
The pyrophyllite/polyurethane composite membrane provided in this example is different from example 1 in that the amount of monoalkoxy pyrophosphate titanate added in the pyrophyllite/polyurethane composite membrane preparation step (1) was 0.40 g, and the amount of modified pyrophyllite added in the preparation step (2) was 1.7055 g.
Example 4
The pyrophyllite/polyurethane composite membrane provided in this example is different from example 1 in that the amount of monoalkoxy pyrophosphate titanate added in the pyrophyllite/polyurethane composite membrane preparation step (1) was 0.40 g, and the amount of modified pyrophyllite added in the preparation step (2) was 2.1930 g.
Comparative example 1
The pyrophyllite/polyurethane composite membrane provided by this comparative example is different from example 1 in that the amount of the monoalkoxy pyrophosphate type titanate solution added in the pyrophyllite/polyurethane composite membrane preparation step (1) is 0.10 g.
Comparative example 2
Compared with example 1, the pyrophyllite/polyurethane composite membrane provided by the comparative example is different in that the addition amount of the monoalkoxy pyrophosphate titanate solution in the pyrophyllite/polyurethane composite membrane preparation step (1) is 0.20 g.
Comparative example 3
Compared with example 1, the pyrophyllite/polyurethane composite membrane provided by the comparative example is different in modification process parameters of the monoalkoxy pyrophosphate titanate solution in the preparation step (1) of the pyrophyllite/polyurethane composite membrane, the pyrophyllite is not subjected to ball milling in advance, and the modified pyrophyllite is obtained by directly adding 0.30g of the monoalkoxy pyrophosphate titanate solution into the pyrophyllite and performing ball milling for 90 min.
Comparative example 4
Compared with example 2, the pyrophyllite/polyurethane composite membrane provided by the comparative example is different in modification process parameters of the monoalkoxy pyrophosphate titanate solution in the preparation step (1) of the pyrophyllite/polyurethane composite membrane, the pyrophyllite is not subjected to ball milling in advance, and the modified pyrophyllite is obtained by directly adding 0.40 g of the monoalkoxy pyrophosphate titanate solution into the pyrophyllite and performing ball milling for 90 min.
Comparative example 5
Compared with example 2, the pyrophyllite/polyurethane composite membrane provided by the comparative example is different in that the modifier added in the preparation step (1) of the pyrophyllite/polyurethane composite membrane is monoalkoxy titanate.
Comparative example 6
Compared with example 2, the pyrophyllite/polyurethane composite membrane provided by the comparative example is different in that the modifier added in the preparation step (1) of the pyrophyllite/polyurethane composite membrane is epoxy silane.
Comparative example 7
Compared with example 2, the pyrophyllite/polyurethane composite membrane provided by the comparative example is different in that the modifier added in the preparation step (1) of the pyrophyllite/polyurethane composite membrane is vinyl silane.
Comparative example 8
(1) Taking 50 g of dried pyrophyllite, mixing with 250 mL of isopropanol, carrying out ultrasonic treatment for 10 min, adding 0.2 g of monoalkoxy pyrophosphate titanate, mechanically stirring at 80 ℃ for 3 h, carrying out centrifugal separation, washing with isopropanol, and carrying out vacuum drying at 80 ℃ for 24 h to obtain the modified pyrophyllite.
(2) Weighing 19.3995 g of castor oil and 1.2185 g of the modified pyrophyllite obtained in the step (1), mixing, performing ultrasonic treatment for 20 min at 37 Hz, adding 5.0g of toluene diisocyanate, stirring to obtain a film precursor, and standing for later use.
(3) 200 g of large-particle urea is put into a rotary drum coating machine, the surface of the urea particles is heated to 65-70 ℃ at the rotating speed of 40 rmp, then the heating is stopped, 2.0 g of 0.5 wt% zinc lactate aqueous solution is sprayed on the surface of the urea particles, and after the treatment for 5min, the heating is carried out again to ensure that the surface temperature of the urea reaches 65-70 ℃.
(4) Adding the film precursor into a spray gun, spraying the film precursor onto the surface of urea particles through high-pressure gas, continuously heating, curing to form a film, spraying again after the polyurethane is completely cured, and repeating for three times to ensure that the quality of the pyrophyllite/polyurethane composite film reaches 3% of the quality of the urea particles.
Compared with example 2, the pyrophyllite/polyurethane composite membrane provided by the comparative example is different in that modified pyrophyllite is prepared by a liquid phase modification method.
Comparative example 9
(1) 19.3995 g of castor oil and 5.0g of toluene diisocyanate were weighed, stirred to form a polyurethane coating solution, and left to stand for use.
(2) 200 g of large-particle urea is put into a rotary drum coating machine, the surface of the urea particles is heated to 65-70 ℃ at the rotating speed of 40 rmp, then the heating is stopped, 2.0 g of 0.5 wt% zinc lactate aqueous solution is sprayed on the surface of the urea particles, and after the treatment for 5min, the heating is carried out again to ensure that the surface temperature of the urea reaches 65-70 ℃.
(3) Adding the polyurethane coating liquid into a spray gun, spraying the polyurethane coating liquid onto the surface of urea particles through high-pressure gas, and continuously heating the urea particles to be cured into a film. And (3) after the polyurethane is completely cured, spraying again, and repeating for three times to ensure that the mass of the polyurethane coating reaches 3% of the mass of the urea particles.
The polyurethane film provided in this comparative example is different from example 1 in that no modified pyrophyllite was introduced.
And (4) performance testing:
the BET surface area and particle size of the modified pyrophyllite used in example 2 and comparative examples 4 and 8 were analyzed, and the results are shown in Table 1. The method can be obtained by adopting the mechanical ball milling pretreatment to strip the laminated structure of the pyrophyllite, dispersing the composite modifier through ball milling, and obtaining the modified pyrophyllite with larger specific surface area and smaller particle size by a two-step ball milling method.
Figure DEST_PATH_IMAGE001
The modified pyrophyllite used in example 2 and comparative examples 4,8 was analyzed for microscopic morphology, as shown in fig. 2. In comparison with the morphologies of the modified pyrophyllite samples used in comparative examples 4 and 8, which are shown in fig. 2b and 2c, it can be seen that the lamellar structure of the modified pyrophyllite used in example 2 was clearly exfoliated into thinner and smaller lamellar sheets (see fig. 2 a). The invention adopts a two-step ball milling method to optimize the texture of the pyrophyllite and effectively improve the composite crosslinking interface and action site of the pyrophyllite and the polyurethane film.
The mechanical properties of the examples and comparative examples were tested according to GB/T1040.3-2006. The mixture of the modified pyrophyllite and the polyurethane precursor was degassed and poured into a dumbbell mold to prepare a standard sample bar, and the mechanical properties of the sample bar were tested using a universal tester, with the results shown in table 2. Analysis results show that the examples show higher tensile strength and elongation at break, and show that the mechanical properties of the pyrophyllite/polyurethane composite film can be more effectively improved by the monoalkoxy pyrophosphate titanate compared with alkoxy titanate, epoxy silane and vinyl silane; the mechanical property of the pyrophyllite/polyurethane composite membrane can be further improved by adding the modifier after the pyrophyllite is subjected to ball milling treatment in advance and then performing ball milling, because the ball milling can play a role in stripping a pyrophyllite lamellar structure, the specific surface area of the pyrophyllite is improved, and the polyurethane and the pyrophyllite are combined more tightly.
Figure DEST_PATH_IMAGE002
The microscopic morphology of the urea particle surface before and after the zinc lactate solution treatment is observed by using a scanning electron microscope, as shown in fig. 3, the urea particle surface after the zinc lactate solution treatment is smoother, which is beneficial for the pyrophyllite/polyurethane composite membrane to be attached to the surface to form a more uniform coating, thereby realizing the stable release of nutrients.
The pyrophyllite/polyurethane composite membrane was tested for controlled release performance and the results are shown in table 3. Comparing examples 1-4 with comparative examples 5-7, the monoalkoxy pyrophosphate titanate is a modifier with more excellent performance, and can more effectively improve the controlled release performance of the pyrophyllite/polyurethane composite membrane; the comparison results of examples 1-2 and comparative examples 3-4 show that the two-step ball milling method obviously improves the controlled release performance of the pyrophyllite/polyurethane composite membrane; the comparison result of the example 2 and the comparative example 8 shows that the performance of the modified pyrophyllite prepared by the mechanical ball milling method is superior to that of the modified pyrophyllite prepared by the liquid phase modification method; the analysis results in table 3 show that the monoalkoxy pyrophosphate ester modified pyrophyllite prepared by two-step ball milling can significantly improve the controlled release performance of the vegetable oil-based polyurethane, prolong the nutrient release period and reduce the cost, and has higher economic value.
Figure DEST_PATH_IMAGE003
The foregoing is directed to embodiments of the present invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (5)

1. A pyrophyllite/polyurethane composite film is characterized in that: the pyrophyllite is modified by monoalkoxy pyrophosphate titanate, and the mass percentage of the modified pyrophyllite in the composite membrane is 5-9%; the dosage of the monoalkoxy pyrophosphate titanate is 0.3 to 0.4 percent of the mass of the pyrophyllite; the preparation method of the pyrophyllite/polyurethane composite film comprises the following steps:
(1) Placing the dried pyrophyllite in a ball milling tank, dry milling for 45min at a ball-material ratio of 6:1 and a rotation speed of 500 rpm, adding monoalkoxy pyrophosphate titanate dispersed in isopropanol, continuing ball milling for 45min, and realizing modification of the pyrophyllite by a mechanochemical synthesis method;
(2) Adding the modified pyrophyllite obtained in the step (1) into a polyurethane precursor solution, carrying out ultrasonic treatment for 20 min to uniformly disperse the modified pyrophyllite in the polyurethane precursor solution, then attaching the modified pyrophyllite to a wrap in a spraying manner, and directly forming a film on the surface of the wrap through in-situ polymerization to obtain the pyrophyllite/polyurethane composite film.
2. The pyrophyllite/polyurethane composite film of claim 1, wherein: the polyurethane precursor is formed by mixing vegetable oil-based polyol and isocyanate according to the molar ratio of hydroxyl in the polyol to isocyanate of 1.
3. The pyrophyllite/polyurethane composite film of claim 2, wherein: the vegetable oil-based polyol is one or more of castor oil, soybean oil-based polyol, palm oil-based polyol and rapeseed oil-based polyol; the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and polymethylene polyphenyl polyisocyanate.
4. Use of the pyrophyllite/polyurethane composite film according to any one of claims 1-3, wherein: the composite membrane is applied to the field of controlled release.
5. Use of a pyrophyllite/polyurethane composite film according to claim 4, wherein: when large-particle urea is coated, the urea is preheated in a coating machine until the surface reaches 65-70 ℃, then an aqueous solution containing 0.5 wt% of zinc lactate is added for treatment for 5min, and then in-situ polymerization is carried out to form a film.
CN202210459602.8A 2022-04-28 2022-04-28 Pyrophyllite/polyurethane composite film and preparation method and application thereof Active CN114854188B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210459602.8A CN114854188B (en) 2022-04-28 2022-04-28 Pyrophyllite/polyurethane composite film and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210459602.8A CN114854188B (en) 2022-04-28 2022-04-28 Pyrophyllite/polyurethane composite film and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114854188A CN114854188A (en) 2022-08-05
CN114854188B true CN114854188B (en) 2023-02-24

Family

ID=82632604

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210459602.8A Active CN114854188B (en) 2022-04-28 2022-04-28 Pyrophyllite/polyurethane composite film and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114854188B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1336400A (en) * 2000-08-01 2002-02-20 徐文君 Production process and use of pyrophyllite powder, and its the use thereof
JP2008174455A (en) * 2007-01-16 2008-07-31 Sumitomo Chemical Co Ltd Agrochemical granule containing coated powdery agrochemical
CN101760054A (en) * 2008-12-25 2010-06-30 温州大学 Preparation method of pyrophyllite-based nanometer composite powder
CN101831204A (en) * 2010-04-27 2010-09-15 浙江皓翔矿业有限公司 Pyrauxite-based compound titanium dioxide and chemical mechanical preparation method
JP2011140452A (en) * 2010-01-06 2011-07-21 Nissan Chem Ind Ltd Solid agrochemical preparation from which release of agrochemical active ingredient is controlled
CN102613173A (en) * 2012-02-24 2012-08-01 石家庄市龙汇精细化工有限责任公司 Granule agent for control of soil insects and preparation method thereof
CN105017814A (en) * 2014-11-26 2015-11-04 安徽池州博源非金属矿研发中心有限公司 Preparation method for active pyrophyllite micropowder
CN106883458A (en) * 2017-03-09 2017-06-23 浙江皓翔矿业有限公司 A kind of preparation method of modified pyrophyllite powder
CN113666701A (en) * 2020-05-13 2021-11-19 沈阳铸造研究所有限公司 Preparation method of casting mold material taking wollastonite gypsum associated with pyrophyllite minerals as raw material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6903879B2 (en) * 2016-07-29 2021-07-14 大日本印刷株式会社 A laminate having oxygen barrier properties and a packaging material composed of the laminate

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1336400A (en) * 2000-08-01 2002-02-20 徐文君 Production process and use of pyrophyllite powder, and its the use thereof
JP2008174455A (en) * 2007-01-16 2008-07-31 Sumitomo Chemical Co Ltd Agrochemical granule containing coated powdery agrochemical
CN101760054A (en) * 2008-12-25 2010-06-30 温州大学 Preparation method of pyrophyllite-based nanometer composite powder
JP2011140452A (en) * 2010-01-06 2011-07-21 Nissan Chem Ind Ltd Solid agrochemical preparation from which release of agrochemical active ingredient is controlled
CN101831204A (en) * 2010-04-27 2010-09-15 浙江皓翔矿业有限公司 Pyrauxite-based compound titanium dioxide and chemical mechanical preparation method
CN102613173A (en) * 2012-02-24 2012-08-01 石家庄市龙汇精细化工有限责任公司 Granule agent for control of soil insects and preparation method thereof
CN105017814A (en) * 2014-11-26 2015-11-04 安徽池州博源非金属矿研发中心有限公司 Preparation method for active pyrophyllite micropowder
CN106883458A (en) * 2017-03-09 2017-06-23 浙江皓翔矿业有限公司 A kind of preparation method of modified pyrophyllite powder
CN113666701A (en) * 2020-05-13 2021-11-19 沈阳铸造研究所有限公司 Preparation method of casting mold material taking wollastonite gypsum associated with pyrophyllite minerals as raw material

Also Published As

Publication number Publication date
CN114854188A (en) 2022-08-05

Similar Documents

Publication Publication Date Title
Gao et al. Synthesis and characterization of polyurethane/SiO2 nanocomposites
CN101565588B (en) Organic attapulgite water-borne polyurethane nano composite leather coating agent and preparation method thereof
CN102993756B (en) A kind of low-density polymer modified asphalt waterproof coiled material
CN102731989A (en) Composite material for pultrusion polyurethane resin and preparation method thereof
CN105219066B (en) A kind of polyurethane/nano hydrotalcite composite material with high-damping, UV absorption and toughness reinforcing performance and preparation method thereof
CN105670737A (en) Preparation method of graphene lubricating additive
CN103468124A (en) Waterproof and root-resistant polyurethane coating for planting roof
Wang et al. Surface modification of pyrophyllite for optimizing properties of castor oil-based polyurethane composite and its application in controlled-release fertilizer
CN101671493B (en) Coating modified material of nano calcium carbonate and modification method thereof
CN114854188B (en) Pyrophyllite/polyurethane composite film and preparation method and application thereof
Liu et al. Preparation and characterization of biodegradable polyurethane composites containing oyster shell powder
CN106554528B (en) Butadiene-styrene rubber/white carbon black/lignocellulosic/montmorillonite rubber composite material and preparation method thereof
CN1927778A (en) Composite envelope type slow release fertilizer
CN116640457A (en) Modified asphalt for waterproof coiled material and preparation method thereof
CN101696282B (en) Reinforcing filler used for rubber latex product, preparation method thereof and application thereof
CN104926693A (en) Isocyanate-group-contained modifier, and preparation and application thereof
CN110885478A (en) Preparation method of modified aramid pulp masterbatch
CN113088102B (en) Preparation method of heavy calcium carbonate for high-activation-degree silicone adhesive
Jiang et al. Surface engineering of cellulose nanocrystals via SI-AGET ATRP of glycidyl methacrylate and ring-opening reaction for fabricating self-healing nanocomposite hydrogels
JP2009503242A5 (en)
Miao et al. Castor oil and microcrystalline cellulose based polymer composites with high tensile strength
CN113429584B (en) Wear-resistant wheat straw composite board and preparation method thereof
CN113801511A (en) Preparation method of environment-friendly paint additive
CN101684170B (en) Composite material based on castor oil and microcrystalline cellulose and preparation method thereof
CN1116330C (en) Modified polyurethane elastomer material and its preparing method and use

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant