阅读说明：本技术 一种97%矿物油乳剂 (97% mineral oil emulsion ) 是由 路宽 贾威阵 徐冰冰 莫学坤 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种97％矿物油乳剂,以质量百分数计,组分为：97wt.％的精炼矿物油和3wt.％乳化剂。本发明中对精炼矿物油的赛波特颜色,相对正构烷烃平均碳数,相对正构烷烃碳数范围差,非磺化物含量,链烷烃含量等指标进行限制,且对乳化剂进行了严格筛选,乳化剂配方选用不同乳化剂单剂复配。本发明的精炼矿物油乳剂具有最合理的乳化稳定性能,在农业使用时可避免药害的同时,发挥最佳药效。此外,本发明97％矿物油乳剂配方为无色无味透明液体、物理化学性质稳定,不会对生产者、使用者及环境造成危害,符合环保要求。(The invention discloses 97% mineral oil emulsion which comprises the following components in percentage by mass: 97 wt.% refined mineral oil and 3 wt.% emulsifier. The invention limits indexes of the refined mineral oil such as Saybolt color, average carbon number relative to normal paraffin, poor carbon number range relative to normal paraffin, non-sulfonated content, paraffin content and the like, strictly screens the emulsifier, and adopts different emulsifier single agents for compounding in the formula of the emulsifier. The refined mineral oil emulsion has the most reasonable emulsification stability, and can avoid phytotoxicity and simultaneously exert the best pesticide effect in agricultural use. In addition, the 97% mineral oil emulsion formula is colorless, tasteless and transparent liquid, has stable physical and chemical properties, does not cause harm to producers, users and the environment, and meets the requirement of environmental protection.)

1. 97% mineral oil emulsion, characterized by comprising, by weight, 97% refined mineral oil, 3% emulsifier; wherein the physical and chemical property indexes of the refined mineral oil are as follows: the appearance is clear and transparent, the Saybolt color is more than or equal to +30, the average carbon number of the relative normal paraffin is 21-24, the carbon number range difference of the relative normal paraffin is less than or equal to 8, the non-sulfonated content is more than or equal to 99%, and the paraffin content is more than or equal to 70%.

2. 97% mineral oil emulsion according to claim 1 wherein the emulsifier is one or more of sorbitan monolaurate, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol distearate, polyethylene glycol monostearate, fatty alcohol polyoxyethylene ether, sucrose monostearate, polyethylene glycol monooleate, polyethylene glycol dioleate, castor oil polyoxyethylene ether.

Technical Field

The invention belongs to refined mineral oil emulsion, and particularly relates to 97% mineral oil emulsion which is colorless odorless oily liquid, is stable in physical and chemical properties, has reasonable emulsion stability, and can avoid phytotoxicity and simultaneously exert optimal drug effect in agricultural use.

Background

The mineral oil emulsions have a long history of use in crop protection and were first used to control scale insects on citrus. As early as the 18 th century, there was literature mentioning that petroleum could be used as an insecticide; in the early 60 s of the 19 th century, people began to paint kerosene on sweet oranges and lemons to control coccid with the first oil well in the world. Later in the 80's of the 19 th century, emulsions composed of kerosene and whale oil soap became a popular means of controlling overwintering aphids and other citrus pests. The oil film formed by the mineral oil emulsion can suffocate pests and invade the bodies of the pests, so that the pests are killed. Similarly, the oil film formed by the mineral oil emulsion can inhibit the transpiration of crops, especially under severe conditions such as high temperature and high humidity, and therefore, the use of the mineral oil emulsion is also required to bear a great risk of phytotoxicity.

The key reason for generating the oil film by the mineral oil emulsion is the emulsion breaking time, so that the optimization of the emulsifying performance of the mineral oil emulsion is the key point for controlling the insecticidal effect and the phytotoxicity, but the earlier research in the field of the mineral oil emulsion is shallow, the technology of emulsifying the mineral oil is laggard, so that the quality of the mineral oil emulsion product in the market is obviously not up to the standard, the emulsifying stability is unreasonable, the product appearance is not transparent, a cosolvent with strong pungent smell is added, the product is placed for a period of time or meets the temperature change, the product is unstable, the phenomenon of precipitation of the emulsifier appears, and the use effect is seriously. The condition that the leaves of crops are damaged in a large area is inevitably caused when farmers apply the mineral oil missible oil, and finally, the yield of the crops is seriously influenced, and a great amount of economic loss is caused.

In order to improve the quality of mineral oil emulsion products, the national ministry of agriculture issued No. 1133 bulletin, "bulletin about matters related to mineral oil pesticide registration management", in 2008, the research on the drug effect and the cause of phytotoxicity of mineral oil emulsion products is also emphasized, and the technical requirements of mineral oil emulsions are gradually increased.

However, mineral oil emulsions still suffer from the following problems: (1) the emulsion stability of most products in the market is unreasonable, on one hand, emulsion breaking of the emulsion of many products is too fast, a large amount of floating oil can be separated out in a short time, so that the emulsion is sprayed to cause the oil content of the local part of the blade to be too high, and the blade is burnt; on the other hand, the emulsion stability of more mineral oil emulsion is also taught to be too good, floating oil cannot be demulsified and separated out within a long period of time, and an oil film cannot be formed on the surfaces of crops and insects after application, so that the effects of killing insects and protecting crops cannot be achieved, and the waste of mineral oil is caused; (2) at present, many products in the market have the defects that the matching of an emulsifier formula and mineral oil is poor, the appearance is opaque, some products need to be added with a solvent with strong pungent smell for assisting dissolution, and some products, including some foreign imported brands, have unstable product properties and generate the phenomenon of emulsifier precipitation when the products are placed for a period of time or subjected to temperature change, so that the use effect is seriously influenced. The above problems all indicate that the mineral oil emulsion product emulsification technology has a certain gap.

Therefore, aiming at the two technical problems of unscientific demulsification time and immature emulsifying technology, a technical attack is carried out, and a 97% mineral oil emulsion is developed.

Disclosure of Invention

Aiming at the problems of the existing mineral oil emulsion products, the invention provides 97% mineral oil emulsion, the refined mineral oil emulsion is colorless and odorless oily liquid, has stable physical and chemical properties and reasonable emulsion stability, and can avoid phytotoxicity and simultaneously exert the optimal drug effect in agricultural use.

The 97% mineral oil emulsion comprises 97% of refined mineral oil and 3% of emulsifier by weight; the refined mineral oil strictly meets the notice requirement of national Ministry of agriculture No. 1133, and has the physical and chemical property index characteristics that: the appearance is clear and transparent, the Saybolt color is more than or equal to +30, the average carbon number of the relative normal paraffin is 21-24, the carbon number range difference of the relative normal paraffin is less than or equal to 8, the non-sulfonated content is more than or equal to 99%, and the paraffin content is more than or equal to 70%. The emulsifier is one or more of sorbitan monolaurate, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol distearate, polyethylene glycol monostearate, fatty alcohol-polyoxyethylene ether, sucrose monostearate, polyethylene glycol monooleate, polyethylene glycol dioleate and castor oil polyoxyethylene ether.

The refined mineral oil emulsion is colorless and odorless oily liquid, and when the refined mineral oil emulsion is used, the emulsion breaking time of the emulsion is reasonable, the phytotoxicity can be avoided, and the insecticidal effect can be exerted to the greatest extent.

The refined mineral oil emulsion disclosed by the invention is proved to have good matching property with mineral oil through high-temperature storage stability and low-temperature storage stability experiments.

The refined mineral oil emulsion is uniform in liquid phase and stable. When the water is added for use, the emulsion is uniformly dispersed in water, no floating oil appears on the surface of the emulsion, an oil layer is gradually separated out after the emulsion is stood for 15 minutes in a thermostatic water bath, the phytotoxicity to leaves or plants of the plants can not be caused, a layer of oil film can be formed on the surface of the plants to protect the plants after the water is evaporated, and the oil film can be formed on the body surface of the insects to block air pipes of the insects to play an insecticidal role if the oil film is distributed on the body surface.

Detailed Description

The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.

The 97% mineral oil emulsion comprises 97% of refined mineral oil and 3% of emulsifier by weight; as examples, a 3% polyethylene glycol monooleate solution can be formulated with refined mineral oil as the solvent, or a mineral oil emulsion can be formulated with sorbitan monolaurate (Span80), polyoxyethylene sorbitan fatty acid ester (Tween80) as the emulsifier, such as: respectively preparing 3% Span80 emulsion and 3% Tween80 emulsion by using refined mineral oil as a solvent, and mixing the two emulsions according to a specific ratio (for example, 20ml of 3% Span80 emulsion is mixed with 4-10ml of 3% Tween80 emulsion) to obtain the 97% mineral oil emulsion of the compound emulsifier. The following is a further description of the mineral oil emulsion of the compound emulsifier.

Example 1:

the invention is compared with the foreign brand 97% mineral oil emulsion product (Daodall)

(1) Compatibility of mineral oil with emulsifiers

The results of comparing the thermal storage stability and the low temperature stability of the products with the foreign brand 97% mineral oil emulsion by using the national standards GB/T19136-2003 and GB/T19137-2003 are shown in the following table 1:

TABLE 1 comparative test results of heat storage stability and Low temperature stability

As a result, the heat storage stability and the low temperature stability of the foreign brand 97% mineral oil emulsion are both qualified, and the physical and chemical properties are poor.

(2) Comparison of emulsion stability

The emulsion stability of the above solutions was tested using the national standard GB/T1603-2001: 100mL of 30 ℃. + -. 2 ℃ standard hard water was added to a 250mL beaker, 0.5mL of the above mixed solution was sucked up with a pipette, and slowly added to the hard water with continuous stirring to prepare 100mL of an emulsion. After the emulsion addition was completed, stirring was continued for 3min at a speed of 2-3r/s, the emulsion was immediately transferred to a clean, dry 100mL graduated cylinder, and the graduated cylinder was placed in a constant temperature water bath, and the emulsion stabilization was constantly observed and the final emulsion breaking time was recorded, the results of which are given in table 2 below.

TABLE 2 emulsion stability comparative experiment results

The result shows that the emulsion stability of the foreign brand 97% mineral oil emulsion is poor, a large amount of floating oil is separated out in less than 1 minute, and the risk of phytotoxicity is high.

(3) Experiments on pesticidal effects and phytotoxicity

The insecticidal effect and the hazard risk of 97% mineral oil emulsion of a foreign brand are obtained through citrus orchard field experiments, and the red spider killing rate experiment requires that the citrus leaf surfaces of more than 100 red spiders are selected as statistical objects after spraying, and the red spider killing rate is calculated. The strength of the transpiration of the citrus leaf surface is shown in the soft and hard degree of the leaf surface, the harder the leaf surface is, the stronger the transpiration is, and conversely, the weaker the transpiration is, the strength of the transpiration can represent the risk of the phytotoxicity, and the results are shown in the following table 3:

TABLE 3 insecticidal Effect and phytotoxicity test

Through comparison, the 97% mineral oil emulsion disclosed by the invention has lower risk of phytotoxicity than a foreign brand 97% mineral oil emulsion product under the same insecticidal effect.

Example 2:

the invention is compared with the domestic brand of 97 percent mineral oil emulsion product (Guangyuan Yinong)

(1) Problem of odor

The 97% mineral oil emulsion of the invention is colorless and tasteless oily liquid, and the domestic brand 97% mineral oil emulsion has strong pungent solvent taste.

(2) Compatibility of mineral oil with emulsifiers

The results of the comparative experiments of the thermal storage stability and the low temperature stability of the mineral oil emulsion products with the national standards GB/T19136-2003 and GB/T19137-2003 and the domestic brand of 97 percent are shown in the following table 4:

TABLE 4 comparative test results of heat storage stability and Low temperature stability

The results show that the domestic brand 97% mineral oil emulsion is not qualified in heat storage stability and low temperature stability, and has poor physical and chemical properties.

(2) Comparison of emulsion stability

The emulsion stability of the above solutions was tested using the national standard GB/T1603-2001: 100mL of 30 ℃. + -. 2 ℃ standard hard water was added to a 250mL beaker, 0.5mL of the above mixed solution was sucked up with a pipette, and slowly added to the hard water with continuous stirring to prepare 100mL of an emulsion. After the emulsion addition was complete, stirring was continued for 3min at 2-3r/s, the emulsion was immediately transferred to a clean, dry 100mL graduated cylinder and the graduated cylinder was placed in a constant temperature water bath and the emulsion stabilization observed at that time and the final emulsion breaking time recorded as in table 5 below.

TABLE 5 emulsion stability comparative experiment results

The result shows that the emulsion of the domestic 97 percent mineral oil emulsion is too stable, floating oil appears in more than 30 minutes, and an oil film is not easy to form in the using process.

(3) Experiments on pesticidal effects and phytotoxicity

The killing rate of red spiders and the transpiration strength of orange leaves after application are evaluated through field experiments in a citrus orchard to obtain the insecticidal effect and the phytotoxicity risk of the red spiders and a certain brand of mineral oil emulsion in China, and the killing rate of the red spiders is calculated by selecting the orange leaves with more than 100 heads of red spiders as statistical objects after application. The strength of the transpiration of the citrus leaf surface is shown in the soft and hard degree of the leaf surface, the harder the leaf surface is, the stronger the transpiration is, and conversely, the weaker the transpiration is, the strength of the transpiration can represent the risk of the phytotoxicity, and the results are shown in the following table 3:

TABLE 6 insecticidal Effect and phytotoxicity test

Through comparison, the 97% mineral oil emulsion has a significantly higher red spider killing rate than the domestic 97% mineral oil emulsion product under the effect of less phytotoxicity risks.