CN108990975B - Terpineol ester agricultural polymer emulsifier and preparation and use methods thereof - Google Patents
Terpineol ester agricultural polymer emulsifier and preparation and use methods thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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Abstract
The invention discloses a terpineol ester agricultural polymer emulsifier and preparation and use methods thereof, belonging to the field of polymer materials. The terpineol ester agricultural polymer emulsifier comprises the following components in parts by weight: 1-70 parts of high-molecular polymeric acid, 30-50 parts of terpineol, 0.01-10 parts of catalyst and 1-40 parts of triethanolamine. The macromolecular emulsifier prepared by the invention has larger molecular weight and long oleophylic chain, can well wrap the oil phase, and has stronger stability and excellent performance compared with the traditional micromolecular emulsifier; the preparation process is simple and environment-friendly.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a terpineol ester agricultural high polymer emulsifier and a preparation method and a use method thereof.
Background
An emulsifier is a substance used to prepare an emulsion and impart it with a minimum degree of stability, and is an essential component. Common emulsifiers are small molecular emulsifiers, mainly including nonionic emulsifiers such as alkylphenol ethoxylates and terpineol polyoxyethylene, and anionic emulsifiers such as alkylbenzene sulfonates. The polymer emulsifier generally refers to a polymer compound having a surface active function with a relative molecular mass of more than several thousands. The polymer surfactant compounds can be classified into natural polymer surfactants, natural modified (or semi-synthetic) polymer surfactants, and chemical synthetic polymer surfactants according to their sources. The natural polymer surfactant exists in animal and plant bodies, plays a very important role in the life process, and is an amphiphilic polymer compound prepared by separating and refining animals and plants; the modified high molecular surfactant comprises modified starch, cellulose, protein, chitosan and the like, and is obtained by processing natural substances serving as main raw materials; the synthetic polymer surfactant refers to a hydrophilic monomer homopolymerization or copolymerization with a hydrophobic monomer, or is prepared by chemically modifying some common polymers, and the types of the synthetic polymer surfactants are various, and generally include polymerization types (such as polyacrylates) and condensation types (such as polyamine). The polymer emulsifier is a novel emulsifier developed in 20 years, and is mainly developed by foreign and international companies, such as enterprises in Noyu, Ciba and the like. The production cycle is long, the cost is relatively high, and the method is mainly applied to industries with relatively high product price, such as the cosmetic industry. Due to cost constraints, it is rarely used in the pesticide industry.
When the micromolecule surfactant is used as an emulsifier, the micromolecule surfactant is adsorbed on an oil/water interface as a third phase, and stable emulsion is obtained by reducing interfacial tension and preventing dispersed phase droplets from aggregating. However, surfactant emulsifying systems are metastable and are thermodynamically unstable. The adsorption of the surfactant on the oil/water interface is a dynamic equilibrium, and under certain conditions, the adsorption and desorption can be fast, so that the phenomenon that surfactant molecules migrate to a body phase can occur, the long-term stability of the emulsion is poor, and the migration of small molecules can cause many negative problems. The macromolecular emulsifier has a large molecular weight and long oleophylic chains, can well wrap the oil phase, and can enhance the stability.
Terpineol is colorless viscous liquid or low-melting-point transparent crystal, and has relative density of 0.9337 deg.C, solidification point of 40 deg.C, boiling point of 220.85 deg.C, refractive index of 1.4831, and combustibility. The general commercial product is a mixture of three isomers: the alpha-terpineol has three optical isomers of levorotation, dextrorotation and racemization, wherein (+) -alpha-body exists in essential oil such as turpentine, cardamom oil, sweet orange oil and nutmeg oil; the (-) -alpha-body is present in pine needle oil, cassia leaf oil, lemon oil, lime oil and other essential oils; the (+/-) -alpha-body exists in essential oil such as geranium oil and cajeput oil; gamma-bodies have been found in oil of Tibet cypress leaves. The terpineol is colorless thick liquid, has the distillation range of 214-224 ℃ (101.3kPa), is insoluble in water, and is soluble in organic solvents such as ethanol.
Disclosure of Invention
The invention aims to solve the technical problem of providing the terpineol ester agricultural high polymer emulsifier which is simple in preparation process, environment-friendly, high in emulsifier stability and excellent in performance, and a preparation method and a use method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
on the one hand, the terpineol ester agricultural polymer emulsifier is provided, and consists of the following components in parts by weight: 1-70 parts of high-molecular polymeric acid, 30-50 parts of terpineol, 0.01-10 parts of catalyst and 1-40 parts of triethanolamine.
Further, the terpineol ester agricultural polymer emulsifier is composed of the following components in parts by weight: 50-70 parts of high-molecular polymeric acid, 30-45 parts of terpineol, 5-8 parts of a catalyst and 10-25 parts of triethanolamine.
Further, the high molecular polymeric acid is one or more of polyacrylic acid, polymethacrylic acid, acrylic acid-methacrylic acid copolymer, acrylic acid-maleic anhydride copolymer and methacrylic acid-maleic anhydride copolymer. The high molecular polymeric acid can be purchased from the market or prepared by copolymerizing monomers under the initiation of an initiator.
The high molecular polymeric acid is prepared by adopting a conventional molecular polymerization method, wherein:
the preparation method of the polyacrylic acid/polymethacrylic acid comprises the following steps: dissolving 20-60% of acrylic acid/polymethacrylic acid monomer into an ethanol solution, then adding an initiator BPO (bisphenol A O) accounting for 0.5-8% of the total mass of the monomer, heating to 60-100 ℃ to react for 1-5 h, then distilling alcohol under reduced pressure, and cooling to obtain polyacrylic acid/polymethacrylic acid; the molecular weight of polyacrylic acid/polymethacrylic acid is adjusted by the concentration of acrylic acid/polymethacrylic acid monomers, the concentration of an initiator and the reaction temperature, and the weight average molecular weight of the polyacrylic acid/polymethacrylic acid is 5000-50000.
The preparation method of the acrylic acid-methacrylic acid copolymer comprises the following steps: dissolving 20-60% of acrylic acid and polymethacrylic acid monomers (mixed in a ratio of 1: 1) into an ethanol solution, adding an initiator BPO (BPO) accounting for 0.5-8% of the total mass of the monomers, heating to 60-100 ℃ to react for 1-5 h, then distilling alcohol under reduced pressure, and cooling to obtain an acrylic acid-methacrylic acid copolymer; the molecular weight of the olefine acid-methacrylic acid copolymer is adjusted by the concentration of a monomer, the concentration of an initiator and the reaction temperature, and the weight average molecular weight of the acrylic acid-methacrylic acid copolymer is 5000-50000.
The preparation method of the acrylic acid-maleic anhydride copolymer comprises the following steps: dissolving 20-60% of acrylic acid and maleic anhydride monomers (mixed in a ratio of 1: 1) into an ethanol solution, adding an initiator BPO accounting for 0.5-8% of the total mass of the monomers, heating to 60-100 ℃ to react for 1-5 h, then distilling alcohol under reduced pressure, and cooling to obtain an acrylic acid-maleic anhydride copolymer; the molecular weight of the acrylic acid-maleic anhydride copolymer is adjusted by the concentration of a monomer, the concentration of an initiator and the reaction temperature, and the weight average molecular weight of the acrylic acid-maleic anhydride copolymer is 5000-50000.
The preparation method of the methacrylic acid-maleic anhydride copolymer comprises the following steps: dissolving 20-60% of methacrylic acid and maleic anhydride monomers (mixed in a ratio of 1: 1) into an ethanol solution, adding an initiator BPO accounting for 0.5-8% of the total mass of the monomers, heating to 60-100 ℃ to react for 1-5 h, then distilling alcohol under reduced pressure, and cooling to obtain a methacrylic acid-maleic anhydride copolymer; the molecular weight of the methacrylic acid-maleic anhydride copolymer is adjusted by the concentration of a monomer, the concentration of an initiator and the reaction temperature, and the weight average molecular weight of the methacrylic acid-maleic anhydride copolymer is 5000-50000.
Further, the catalyst is p-toluenesulfonic acid or quaternary phosphonium salt ionic liquid, and the quaternary phosphonium salt ionic liquid is prepared according to the preparation method of CN2013106849703, or purchased from Kokatco, Korea, and Mooney chemical technology (Shanghai).
Furthermore, the proportion of the agricultural polymer emulsifier in the pesticide preparation is 1-2%.
On the other hand, the invention also provides a preparation method of the terpineol ester agricultural polymer emulsifier, which comprises the following steps:
step 1: crushing the high molecular polymeric acid into powder;
step 2: adding the high-molecular polymeric acid powder prepared in the step 1, terpineol and a catalyst into a reaction kettle according to the parts by weight, and heating to a set temperature for reaction;
and step 3: and (3) carrying out reduced pressure dehydration reaction on the reaction material obtained in the step (2), adding triethanolamine for reaction, discharging and cooling to obtain the catalyst.
Wherein, in the step 1, the particle diameter D [ V,90] of the powder is 5 microns; in the step 2, the temperature is raised to 150-250 ℃, and the reaction time is 3-6 h; the reaction kettle is provided with a thermometer, a stirring device and a condensing reflux device.
Wherein in the step 3, the dehydration reaction time is 2-30 h; adding triethanolamine and reacting for 1 h.
In another aspect, the invention further provides a method for using the terpineol ester agricultural polymer emulsifier, wherein the terpineol ester agricultural polymer emulsifier is crushed into powder with the particle size of less than 20 microns by using an air flow crusher or is dispersed in water for use.
The invention has the following beneficial effects:
in the scheme, the macromolecular polymeric acid and the terpineol are esterified to form the macromolecular emulsifier under the action of the catalyst, the macromolecular emulsifier has higher molecular weight, and the esterified product has a carbon chain and an ether bond with specific lengths and has stronger lipophilicity and wraps an oil phase; and has certain steric hindrance, so that particles in an oil phase are not easy to aggregate, and the stability of the emulsifier in a pesticide system is enhanced.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
The invention provides a terpineol ester agricultural high-molecular emulsifier and a preparation method and a use method thereof, aiming at the problems of complex preparation process and poor stability of high-molecular polymerization emulsifiers in the prior art.
First, an embodiment
Example 1
The terpineol ester agricultural polymer emulsifier is composed of the following components in parts by weight: 66 parts of polyacrylic acid (weight-average molecular weight is 10000), 30 parts of terpineol, 5 parts of p-toluenesulfonic acid and 20 parts of triethanolamine.
The preparation and use method comprises the following steps:
step 1: pulverizing polyacrylic acid to particle size D90 of 5 μm;
step 2: adding polyacrylic acid, terpineol and p-toluenesulfonic acid into a reaction kettle with a thermometer, a stirring and condensing reflux device according to the weight, heating to 100 ℃, starting stirring, heating to 150 ℃, and reacting for 4 hours;
and step 3: carrying out reduced pressure dehydration reaction on the material obtained in the step 2 for 4 hours; adding triethanolamine to react for 1h, stopping the reaction, discharging materials and cooling;
and 4, step 4: the cooled material is pulverized into powder with particle size of 20 μm or less by jet mill or dispersed in water.
Example 2
The terpineol ester agricultural polymer emulsifier is composed of the following components in parts by weight: 68 parts of polymethacrylic acid (weight-average molecular weight of 15000), 40 parts of terpineol, 8 parts of p-toluenesulfonic acid and 25 parts of triethanolamine.
The preparation method is the same as that of example 1.
Example 3
The terpineol ester agricultural polymer emulsifier is composed of the following components in parts by weight: 68 parts of acrylic acid-methacrylic acid copolymer (weight-average molecular weight is 20000), 40 parts of terpineol, 6 parts of quaternary phosphonium salt ionic liquid and 25 parts of triethanolamine.
The preparation method is the same as that of example 1.
Example 4
The terpineol ester agricultural polymer emulsifier is composed of the following components in parts by weight: 60 parts of acrylic acid-maleic anhydride copolymer (weight-average molecular weight is 25000), 30 parts of terpineol, 7 parts of quaternary phosphonium salt ionic liquid and 15 parts of triethanolamine.
The preparation method is the same as that of example 1.
Example 5
The terpineol ester agricultural polymer emulsifier is composed of the following components in parts by weight: 60 parts of methacrylic acid-maleic anhydride copolymer (weight average molecular weight of 30000), 30 parts of terpineol, 6 parts of quaternary phosphonium salt ionic liquid and 15 parts of triethanolamine.
The preparation method is the same as that of example 1.
Example 6
The terpineol ester agricultural polymer emulsifier is composed of the following components in parts by weight: 28 parts of polyacrylic acid (weight average molecular weight is 5000), 28 parts of polymethacrylic acid (weight average molecular weight is 5000), 40 parts of terpineol, 6 parts of quaternary phosphonium salt ionic liquid and 23 parts of triethanolamine.
The preparation method is the same as that of example 1.
Example 7
The terpineol ester agricultural polymer emulsifier is composed of the following components in parts by weight: 28 parts of acrylic acid-maleic anhydride copolymer (weight-average molecular weight of 5000), 28 parts of acrylic acid-methacrylic acid copolymer (weight-average molecular weight of 50000), 45 parts of terpineol, 8 parts of quaternary phosphonium salt ionic liquid and 25 parts of triethanolamine.
The preparation method is the same as that of example 1.
Example 8
The terpineol ester agricultural polymer emulsifier is composed of the following components in parts by weight: 28 parts of methacrylic acid-maleic anhydride copolymer (weight-average molecular weight is 10000), 28 parts of acrylic acid-methacrylic acid copolymer (weight-average molecular weight is 40000), 45 parts of terpineol, 8 parts of quaternary phosphonium salt ionic liquid and 25 parts of triethanolamine.
The preparation method is the same as that of example 1.
Example 9
The terpineol ester agricultural polymer emulsifier comprises 28 parts by weight of methacrylic acid-maleic anhydride copolymer (weight average molecular weight is 20000), 28 parts by weight of acrylic acid-maleic anhydride copolymer (weight average molecular weight is 30000), 45 parts by weight of terpineol, 8 parts by weight of quaternary phosphonium salt ionic liquid and 25 parts by weight of triethanolamine.
The preparation method is the same as that of example 1.
Example 10
The terpineol ester agricultural polymer emulsifier is composed of the following components in parts by weight: 20 parts of acrylic acid-maleic anhydride copolymer (with the weight-average molecular weight of 10000), 20 parts of methacrylic acid-maleic anhydride copolymer (with the weight-average molecular weight of 50000), 10 parts of acrylic acid-methacrylic acid copolymer (with the weight-average molecular weight of 30000), 45 parts of terpineol, 8 parts of quaternary phosphonium salt ionic liquid and 25 parts of triethanolamine.
The preparation method is the same as that of example 1.
For the sake of brevity, to further illustrate the beneficial effects of the present invention, only the best embodiment 10 is taken as an example, and the related comparative examples are set up for performance verification. The reagents and materials used in the examples and comparative examples were commercially available unless otherwise specified. The quaternary phosphonium salt ionic liquids employed in the present invention were purchased from Kokatco Industrial products, Inc. (tributylhexylphosphonium bromide CAS105890-71-9), Lanzhou. It should be noted that modifications and adaptations may occur to those skilled in the art without departing from the principles of the present invention and should be considered within the scope of the present invention.
Comparative example 1
The emulsifier comprises the following components in parts by weight: 60 parts of terpineol polyoxyethylene ether.
Comparative example 2
The macromolecular emulsifier comprises the following components in parts by weight: 20 parts of acrylic acid-maleic anhydride copolymer (with the weight-average molecular weight of 10000), 20 parts of methacrylic acid-maleic anhydride copolymer (with the weight-average molecular weight of 50000), 20 parts of acrylic acid-methacrylic acid copolymer (with the weight-average molecular weight of 30000), 8 parts of quaternary phosphorus salt ionic liquid and 25 parts of triethanolamine.
The preparation method is the same as that of example 1.
Comparative example 3
In this comparative example, terpineol was replaced with ethanol, and the other components and contents were the same as in example 10.
The preparation method is the same as that of example 1.
Comparative example 4
In this comparative example, the acrylic acid-maleic anhydride copolymer, the methacrylic acid-maleic anhydride copolymer (weight average molecular weight of 50000), and the acrylic acid-methacrylic acid copolymer were replaced with oleic acid, and the other components and contents were the same as in example 10.
The preparation method is the same as that of example 1.
Comparative example 5
The terpineol ester emulsifier comprises the following components in parts by weight: 20 parts of acrylic acid-maleic anhydride copolymer (with the weight-average molecular weight of 10000), 20 parts of methacrylic acid-maleic anhydride copolymer (with the weight-average molecular weight of 50000), 20 parts of acrylic acid-methacrylic acid copolymer (with the weight-average molecular weight of 30000), 45 parts of terpineol and 8 parts of quaternary phosphonium salt ionic liquid.
The preparation method comprises the following steps:
step 1: pulverizing polyacrylic acid to particle size D90 of 5 μm;
step 2: adding polyacrylic acid, terpineol and quaternary phosphonium salt ionic liquid into a reaction kettle with a thermometer, a stirring and condensing reflux device according to weight, heating to 100 ℃, starting stirring, then heating to 150 ℃, carrying out reduced pressure dehydration reaction for 4 hours, and cooling;
and step 3: the cooled material is pulverized into powder with particle size of 20 μm or less by jet mill or dispersed in water.
Second, performance test
To further illustrate the advantageous effects achieved by the present invention, performance measurements were performed on the above examples and comparative examples.
1. The polymeric emulsifier prepared in example 10 and rosin-based vegetable oil (purchased from fukenuode biotechnology, ltd.) were added to water in a certain ratio to prepare a 40% emulsion, which was cut with a shear emulsifier for 5min, allowed to stand for 30min, and the stability of the emulsion was observed, the results of which are shown in table 1.
TABLE 1 emulsion stability
From the above table, it can be seen that when the addition amount of the polymeric emulsifier prepared by the present invention is more than 1%, the performance of the prepared emulsion is relatively stable.
2. The emulsifying properties of the polymeric emulsifiers prepared in examples 1 to 10 and the emulsifiers prepared in comparative examples 1 to 5 were examined
Mixing the emulsifier 1.5%, rosin-based vegetable oil 40%, and water 55% at a certain proportion, and shearing with shearing emulsifier for 5min to obtain emulsion. The emulsion stability test is carried out according to the stability of the pesticide emulsion GB/T1603-2001 and diluted by 100 times; the emulsion was tested for D [ V,50] particle size using a Mastorsizer2000 laser particle sizer and the relevant properties are shown in Table 2.
TABLE 2
| Serial number | Emulsion stability | D[V,50]Particle size/. mu.m |
| Example 1 | Good stability | 3.7 |
| Example 2 | Good stability | 3.5 |
| Example 3 | Good stability | 3.4 |
| Example 4 | Good stability | 3.1 |
| Example 5 | Good stability | 2.7 |
| Example 6 | Good stability | 2.4 |
| Example 7 | Good stability | 2.2 |
| Example 8 | Good stability | 2.0 |
| Example 9 | Good stability | 2.0 |
| Example 10 | Good stability | 1.9 |
| Comparative example 1 | Small amount of missible oil | 8.5 |
| Comparative example 2 | Large amount of emulsifiable concentrate | - |
| Comparative example 3 | Large amount of emulsifiable concentrate | - |
| Comparative example 4 | Large amount of emulsifiable concentrate | - |
| Comparative example 5 | Large amount of emulsifiable concentrate | - |
As shown in Table 2, the high molecular emulsifier prepared by the invention has good emulsion stability and smaller D [ V,50] particle size when used for emulsifying rosin-based vegetable oil. The emulsifier with large molecular weight has good emulsifying property; the emulsifying property was not good without neutralization. The emulsifier synthesized by the invention can emulsify up to 40 percent of emulsion.
3. High temperature stability test of the polymeric emulsifiers prepared in examples 1-10 and the emulsifiers prepared in comparative examples 1-5 described above
Mixing the above emulsifier 1.5%, OP-103.5%, rosin-based vegetable oil 40%, and water 55% at a certain proportion, and shearing with shearing emulsifier for 5 min. The sample is put into an ampoule bottle and sealed, and then placed in an incubator at 54 ℃ for 24h, and the change is observed. The D [ V,50] particle size of the emulsion before and after heat storage was measured using a Mastorsizer2000 laser particle sizer.
And (4) comparison treatment: proportionally mixing OP-105%, rosin-based vegetable oil 40% and water 55%, and shearing with shearing emulsifier for 5 min. The sample is put into an ampoule bottle and sealed, and then placed in an incubator at 54 ℃ for 24h, and the change is observed. The D [ V,50] particle size of the emulsion before and after heat storage was measured using a Mastorsizer2000 laser particle sizer.
Before and after the control treatment and heat storage, the D [ V,50] particle sizes were 1.0 μm and 25.4 μm, respectively, and the color became dark.
The test results of examples and comparative examples are as follows:
the results show that the high-molecular emulsifier prepared by the invention can improve the high-temperature stability of the emulsion and reduce the defect that the low-molecular emulsifier cannot resist high temperature. As can be seen from comparative examples 1 to 5, the polymeric emulsifier prepared by the invention has better stability.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. The terpineol ester agricultural polymer emulsifier is characterized by comprising the following components in parts by weight: 50-70 parts of high-molecular polymeric acid, 30-45 parts of terpineol, 5-8 parts of a catalyst and 10-25 parts of triethanolamine; the high molecular polymeric acid is one or more of polyacrylic acid, polymethacrylic acid, acrylic acid-methacrylic acid copolymer, acrylic acid-maleic anhydride copolymer and methacrylic acid-maleic anhydride copolymer; the weight average molecular weight of the high-molecular polymeric acid is 5000-50000.
2. The terpineol ester agricultural polymer emulsifier as claimed in claim 1, wherein the catalyst is p-toluenesulfonic acid or quaternary phosphonium salt ionic liquid.
3. The terpineol ester agricultural polymer emulsifier according to claim 1, wherein the proportion of the agricultural polymer emulsifier in the pesticide preparation is 1-2%.
4. The method for preparing the terpineol ester agricultural polymer emulsifier according to any one of claims 1 to 3, characterized by comprising the following steps:
step 1: crushing the high molecular polymeric acid into powder;
step 2: adding the high-molecular polymeric acid powder prepared in the step 1, terpineol and a catalyst into a reaction kettle according to the weight parts, and heating to the set temperature for reaction;
and step 3: and (3) carrying out reduced pressure dehydration reaction on the reaction material obtained in the step (2), adding triethanolamine for reaction, discharging and cooling to obtain the catalyst.
5. The method for preparing the terpineol ester agricultural polymer emulsifier according to claim 4, wherein in the step 1, the powder particle size D90 is 5 microns; in the step 2, the temperature is raised to 150-250 ℃ and the reaction time is 3-6 h.
6. The method for preparing the terpineol ester agricultural polymer emulsifier according to claim 4, wherein in the step 3, the dehydration reaction time is 2-30 h; adding triethanolamine and reacting for 1 h.
7. The method of using the terpineol ester type agricultural polymer emulsifier according to any one of claims 1 to 3, wherein the terpineol ester type agricultural polymer emulsifier is pulverized into powder having a particle size of 20 μm or less by a jet mill or dispersed in water for use.
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| US2201395A (en) * | 1938-01-26 | 1940-05-21 | Du Pont | Modified polymers of methacrylic acid esters and preparation of the same |
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| CN102039099B (en) * | 2010-11-08 | 2013-06-19 | 中国林业科学研究院林产化学工业研究所 | Self-emulsification rosinyl surfactant emulsion and preparation method thereof |
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