CN112625640A - Rat hole plugging daub and preparation method thereof - Google Patents
Rat hole plugging daub and preparation method thereof Download PDFInfo
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- CN112625640A CN112625640A CN202011335939.5A CN202011335939A CN112625640A CN 112625640 A CN112625640 A CN 112625640A CN 202011335939 A CN202011335939 A CN 202011335939A CN 112625640 A CN112625640 A CN 112625640A
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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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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- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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Abstract
The invention provides a rat hole plugging daub and a preparation method thereof. The daub consists of a component A and a component B, wherein the component A comprises: polyether polyol, isocyanate, surface hydroxyl modified paraffin, a thickening agent and a solid filler; the component B comprises: polyether polyol, surface hydroxyl modified paraffin, a catalyst, a chain extender and a composite filler. According to the invention, through the surface hydroxyl modified paraffin, as the hydroxyl on the surface of the surface hydroxyl modified paraffin can react with isocyanate, the cured paraffin has good compatibility, and the daub obtained after curing has good weather resistance under the environments of high temperature, high humidity, high salt and the like, and can play a role in protecting and plugging electrical equipment for a long time under severe environments. Meanwhile, the invention achieves the purpose of expelling mice by introducing the composite filler which can generate the gas for expelling mice, thereby achieving the effect of preventing the power station equipment from being damaged by the mice.
Description
Technical Field
The invention relates to the technical field of materials, in particular to rat hole plugging daub and a preparation method thereof.
Background
With the development of economic technology and the improvement of living standard of people, electric energy becomes essential secondary energy in production and life of people, and brings endless convenience to production and life of people. The essential part of the long-distance power transmission of the transformer substation is also an important component of the power system, and the safe and reliable operation of the transformer substation is an important guarantee for the safe and reliable operation of the power system.
Because the transformer substation generally occupies a large area, is provided with a large number of devices and has high risk, the transformer substation is generally arranged in suburbs, mountainous areas and other areas relatively far away from people. Therefore, the environment in which the substation is located is relatively harsh. Under severe environment, rats are a huge problem faced by a power station, on one hand, the rats not only bite cables and secondary wires of a terminal box, but also climb in equipment sleeves and equipment, possibly causing accidents such as short circuit and tripping, or causing misoperation and rejection of relay protection and automatic devices, even causing fire or burning out and breakdown of electrical equipment; on the other hand, the rats themselves are also the transmission carriers of various diseases, which not only hurt the equipment, but also damage the health of operators, and must be rejected outdoors. Therefore, for the murine animals of the power station, the traditional practice is as follows: building a rat-proof baffle, arranging a rat trap or a rat sticking plate and the like.
However, the rat bites very strongly, and can bite barriers such as the rat guard and the like again or damage equipment at other positions, and the moving range of the rat is very large, and the rat trap can be avoided perfectly, so that the problem that the rat damages the power station equipment cannot be solved well in the prior art.
Therefore, in order to solve the above problems, there is a strong need in the art for a new method for preventing rats from damaging the substation.
Disclosure of Invention
In order to solve the problems, the invention provides a rat hole plugging daub and a preparation method thereof.
In a first aspect, the invention provides a rat hole plugging daub, which comprises a component A and a component B;
based on 100 parts by weight of the component A, the component A comprises: 20-35 parts of polyether polyol, 12-25 parts of isocyanate, 12-25 parts of surface hydroxyl modified paraffin, 0.5-2 parts of thickening agent and 30-40 parts of solid filler;
based on 100 parts by weight of the component B, the component B comprises: 15-30 parts of polyether polyol, 10-25 parts of surface hydroxyl modified paraffin, 0.5-2 parts of catalyst, 4-6 parts of chain extender, 0.5-2 parts of thickener, 25-30 parts of solid filler and 25-30 parts of composite filler; the composite filler is used for generating gas for repelling rats.
Preferably, the polyether polyol comprises at least one of propylene oxide polyether polyol and polytetrahydrofuran polyol;
the hydroxyl value of the polyether polyol is 10-100 mgKOH/g;
the number of the surface hydroxyl modified paraffin is 0.05-0.2 mmol/g.
Preferably, the isocyanate comprises: at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate; the diphenylmethane diisocyanate is liquefied modified diphenylmethane diisocyanate; the liquefaction modification comprises carbodiimide modification.
Preferably, the solid filler comprises: at least one of titanium dioxide, clay, talcum powder, light calcium carbonate, heavy calcium carbonate, fumed silica and quartz powder;
the mass ratio of the light calcium carbonate to the fumed silica is 12-18: 1-2; the particle size of the light calcium carbonate is 20-60 nm, and the specific surface area of the fumed silica is 170-220m2/g。
Preferably, the thickening agent comprises a cellulose ether;
the cellulose ether comprises: at least one of hydroxyethyl methyl cellulose ether and hydroxypropyl methyl cellulose ether.
Preferably, the catalyst comprises: at least one of tertiary amine catalyst and organic metal catalyst;
the tertiary amine catalyst comprises: at least one of triethylamine, tributylamine, triethylenediamine, and N, N-dimethylaniline;
the organometallic catalyst includes: at least one of organic bismuth and organic tin;
the organic bismuth comprises: at least one of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate and bismuth naphthenate;
the organic tin comprises at least one of tin octoate, tin ethylhexanoate, tin laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate and dioctyltin diacetate;
when the catalyst comprises a tertiary amine catalyst and an organic metal catalyst, the mass ratio of the tertiary amine catalyst to the organic metal catalyst is 6-10: 1-2.
Preferably, the chain extender comprises at least one of amine chain extender and polyalcohol chain extender;
the amine chain extender comprises: at least one of ethylenediamine, propylenediamine, N-dihydroxy (diisopropyl) aniline, diethyltoluenediamine, 3 '-dichloro-4, 4' -diamino-diphenylmethane, 3, 5-dimethylthiotoluenediamine, 3, 5-diethyl-2, 4-toluenediamine, 3, 5-diethyl-2, 6-toluenediamine, divinyltriamine, tetraethylenepentamine, diethylenetriamine isophorone diamine, and di-N-butylamine;
the polyol-based chain extender includes: at least one of ethylene glycol, butanediol, diethylene glycol, dipropylene glycol, 1, 6-hexanediol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-cyclohexanediol, and trimethylpentanediol.
Preferably, the composite filler is obtained by wrapping a composite inorganic salt system by the surface hydroxyl modified paraffin;
the composite inorganic salt system comprises: persulfates and chlorites; the mass ratio of the persulfate to the chlorite is 1.1: 1-2: 1.
preferably, the rat hole plugging daub further comprises: an auxiliary agent;
the auxiliary agent comprises: at least one of a toughening agent, a plasticizer, a stabilizer, a flame retardant, a mildew preventive and color paste.
In a second aspect, the present application provides a method for preparing the rat hole plugging daub of the first aspect, wherein the method comprises:
step one, preparing a component A:
a1, adding isocyanate into dehydrated polyether polyol to obtain a first mixed system, and carrying out heating reaction on the first mixed system to obtain a prepolymer;
a2, dehydrating the solid filler at high temperature to obtain a dehydrated solid filler;
a3, mixing the prepolymer, the dehydration filler, the hydroxyl surface modified paraffin and the thickening agent, and stirring to obtain a daub-shaped component A;
step two, preparing a component B:
b1, heating and dehydrating a second mixed system mixed by polyether polyol, a catalyst and a chain extender under the negative pressure condition to obtain a B component semi-finished product;
b2, dehydrating the solid filler and the composite filler at a high temperature to obtain a dehydrated solid filler and a dehydrated composite filler;
b3, mixing the semi-finished product of the component B, the dehydrated solid filler, the dehydrated composite filler, the hydroxyl surface modified paraffin and the thickening agent, and stirring to obtain a daub-shaped component B;
and step three, at room temperature, mixing the component A prepared in the step one and the component B prepared in the step two according to the mass ratio of 1-1.2: 1-1.2, and obtaining the rat hole plugging daub.
The embodiment of the invention provides rat hole plugging daub and a preparation method thereof. Wherein the rat hole plugging daub comprises a component A and a component B; based on 100 parts by weight of the component A, the component A comprises: 15-20 parts of polyether polyol, 8-13 parts of isocyanate, 8-12 parts of surface hydroxyl modified paraffin, 0.5-1 part of thickening agent and 20-30 parts of solid filler; based on 100 parts by weight of the component B, the component B comprises: 15-20 parts of polyether polyol, 7-12 parts of surface hydroxyl modified paraffin, 0.5-1 part of catalyst, 3-5 parts of chain extender, 0.5-1 part of thickener, 20-30 parts of solid filler and 20-30 parts of composite filler; the composite filler is used for generating gas for repelling rats. Compared with the prior art, the invention has the following advantages:
1. according to the invention, the paraffin is modified by surface hydroxyl, so that the prepared daub has surface lubricity, the purpose of no sticking is achieved, and the operation of a user is convenient; on the other hand, as the hydroxyl on the surface of the surface hydroxyl modified paraffin can react with isocyanate, the cured paraffin has good compatibility, and the daub obtained after curing has good weather resistance under the environments of high temperature, high humidity, high salt and the like, and can play a role in protecting and plugging electrical equipment for a long time under severe environments.
2. According to the invention, the composite filler capable of generating the gas for repelling the mice is introduced, and the pungent smell emitted by the filler stimulates the smell of the mice, so that the effect of repelling the mice is achieved, and the effect of preventing the transformer substation from being damaged by the mice is achieved.
3, the rat hole plugging daub provided by the invention has plasticity, so that the rat hole plugging daub can be changed according to the form of the rat hole, and the aim of good plugging property of irregular rat holes is fulfilled; the rat-hole plugging daub provided by the invention belongs to polymer microspheres, and has long-term durability and can play a good protection role on power station equipment based on the stability of a polymer.
Drawings
Fig. 1 shows a flow chart of a preparation method of the rat hole plugging daub in the embodiment of the invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below. The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
The applicant of the present invention has found that in order to prevent rats from damaging the power station equipment in the substation, the following solutions are proposed by those skilled in the art:
scheme 1, a deratization method for outdoor rat holes, comprising the following steps in sequence: a. firstly, throwing rodenticide aluminum phosphide into the deep position of an outdoor rat hole; b. then a mud blocking object for preventing the silt from covering the aluminum phosphide is plugged into the hole; c. then pouring an initiator for accelerating the aluminum phosphide reaction; d. then blocking the hole with soil; e. then adding an oxidant into the hole; f. and finally, covering the opening with stones, bricks and concrete, and sealing the opening. Although the scheme can effectively kill the rats in the outdoor rat hole under various climatic conditions, the method has complex and troublesome procedures and is difficult to operate.
Scheme 2, a cave formula rat killer, has functions such as rain-proof, dampproofing, sun-proof, theftproof, is applicable to indoor deratization, also can be used to outdoor, field and any environment deratization. The cave type mouse killer is a box body, a plurality of mouse holes are formed in the periphery of the bottom of the box body, a movable door is arranged on the side face of the box body, a poison bait bin is suspended on the inner side of the box body, a feeding port is formed in the top face of the poison bait bin, and a discharging port is formed in the lower portion of the poison bait bin. Although the scheme is easily accepted by the masses, the equipment structure is fine and easy to damage, and the scheme has high manufacturing cost and is difficult to popularize.
In order to solve the problems, the invention provides the rat hole plugging daub which comprises a component A and a component B; based on 100 parts by weight of the component A, the component A comprises the following components: 20-35 parts of polyether polyol, 12-25 parts of isocyanate, 12-25 parts of surface hydroxyl modified paraffin, 0.5-2 parts of thickening agent and 30-40 parts of solid filler; based on 100 parts by weight of the component B, the component B comprises: 15-30 parts of polyether polyol, 10-25 parts of surface hydroxyl modified paraffin, 0.5-2 parts of catalyst, 4-6 parts of chain extender, 0.5-2 parts of thickener, 25-30 parts of solid filler and 25-30 parts of composite filler; the composite filler is used for generating gas for repelling rats.
When implemented, preferably, the polyether polyol comprises at least one of propylene oxide polyether polyol and polytetrahydrofuran polyol; the hydroxyl value of the polyether polyol is 10-100 mgKOH/g; the number of the surface hydroxyl modified paraffin is 0.05-0.2 mmol/g.
The hydroxyl surface modified paraffin is prepared by the following preparation method: reacting hydrogen peroxide or ozone with paraffin wax which is heated and liquefied, cooling to room temperature, condensing the paraffin wax into particles again, filtering, and washing with water until the pH value is neutral to obtain the hydroxyl surface modified paraffin wax.
In the step of modifying the surface of the paraffin wax by the hydroxyl group, the reaction is carried out for 5-30min at the temperature of 40-60 ℃, and the concentration of hydrogen peroxide is 5-20 wt%; more preferably, the reaction condition is that the reaction is carried out for 10 to 20min at the temperature of between 40 and 60 ℃, and the concentration of hydrogen peroxide is between 10 and 15 percent by weight.
In this embodiment, the amount of the hydrogen peroxide is not particularly limited, and the number of the hydroxyl groups on the surface of the paraffin after the surface modification of the paraffin depends on the concentration of the hydrogen peroxide and the reaction time. The amount of hydrogen peroxide is enough to completely immerse the paraffin. The volume dosage of the hydrogen peroxide is 2 to 5 times (ml/g) of the mass of the paraffin generally.
In addition, in the embodiment, after the surface hydroxyl of the paraffin is modified by hydrogen peroxide or ozone, a small amount of hydroxyl is arranged on the surface of the paraffin, so that on one hand, certain surface lubricity can be provided when the two components are not cured, and an operator cannot stick hands when kneading; on the other hand, after the final curing, the paraffin plays a plasticizing effect, and because the interface is fully wetted, the hydroxyl on the surface is combined with the isocyanate of the curing agent, so the paraffin has good bonding force with a base surface, the compatibility is good, the material cannot crack due to migration after the curing, the pulverization and the deformation are also good, and the daub obtained after the curing has good weather resistance under the environments of high temperature, high humidity, high salt and the like, and can play a role in protecting and plugging electrical equipment for a long time in severe environment.
In specific embodiments, the isocyanate comprises: at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI); preferably a liquefied modified diphenylmethane diisocyanate, more preferably a carbodiimide modified MDI.
In specific implementation, the solid filler comprises: at least one of titanium dioxide, clay, talcum powder, light calcium carbonate, heavy calcium carbonate, fumed silica and quartz powder;
wherein the mass ratio of the light calcium carbonate to the fumed silica is 12-18: 1-2; the particle size of the light calcium carbonate is 20-60 nm, and the specific surface area of the gas-phase white carbon black is 170-220m2/g。
In specific embodiments, the thickening agent comprises a cellulose ether; wherein the cellulose ether comprises: at least one of hydroxyethyl methyl cellulose ether and hydroxypropyl methyl cellulose ether.
In specific implementations, the catalyst includes: tertiary amine catalyst and/or organic metal catalyst.
Wherein the tertiary amine catalyst comprises: at least one of triethylamine, tributylamine, triethylenediamine, and N, N-dimethylaniline; the organometallic catalyst includes: at least one of organic bismuth and organic tin; the organic bismuth comprises: at least one of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate and bismuth naphthenate; the organic tin comprises at least one of tin octoate, tin ethylhexanoate, tin laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate and dioctyltin diacetate.
And when the catalyst comprises a tertiary amine catalyst and an organic metal catalyst, the mass ratio of the tertiary amine catalyst to the organic metal catalyst is 6-10: 1-2. The compounded catalyst can effectively control the reaction speed, so that the overall reaction is rapid and controllable, the surface drying time is 1-60 min, the curing time is 30-120 min, the reaction is smooth, and the operator can be left for enough time to knead and shape. The curing time can be specifically adjusted according to the amount of the catalyst.
In specific implementation, the chain extender comprises at least one of an amine chain extender and a polyalcohol chain extender;
wherein, the amine chain extender comprises: at least one of ethylenediamine, propylenediamine, N-dihydroxy (diisopropyl) aniline, diethyltoluenediamine, 3,3 '-dichloro-4, 4' -diamino-diphenylmethane, 3, 5-dimethylthiotoluenediamine, 3, 5-diethyl-2, 4-toluenediamine, 3, 5-diethyl-2, 6-toluenediamine, divinyltriamine, tetraethylenepentamine, diethylenetriamine isophorone diamine, di-N-butylamine; the polyol chain extender includes: at least one of ethylene glycol, butanediol, diethylene glycol, dipropylene glycol, 1, 6-hexanediol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-cyclohexanediol, and trimethylpentanediol.
In specific implementation, the composite filler is obtained by wrapping a composite inorganic salt system by surface hydroxyl modified paraffin.
Wherein, the composite inorganic salt system is obtained by mixing sodium persulfate and sodium chlorite according to a certain proportion (the mass ratio is close to 1.1: 1-2: 1), and the system reacts to generate ClO in the presence of water2：2NaClO2+Na2S2O8→2ClO2↑+2Na2SO4. Thus, upon exposure to air, a gas phase of matter is obtained: chlorine dioxide stimulates the sense of smell of the mice, thereby playing a role in preventing the mice from being damaged.
In this example, the composite filler was prepared by the following method:
and (3) placing the composite inorganic salt system in molten surface hydroxyl modified paraffin, uniformly mixing, performing suction filtration at a melting temperature (50-100 +/-5 ℃) in a 500-mesh filter screen under a vacuum condition, cooling and solidifying, and crushing to obtain the composite filler particles of the composite inorganic salt system wrapped by the modified paraffin. The dosage of the surface hydroxyl modified paraffin can be determined according to the dosage of the composite inorganic salt system, so that each particle in the obtained composite filler is completely wrapped by the paraffin, and the composite inorganic salt system is prevented from being exposed in the air in advance.
The actual rat repelling effect is realized by the following steps: when a mouse bites the mouse hole plugging plaster at the mouse hole, the composite filler in the plaster can be bitten by the mouse, and after the mouse bites the modified paraffin on the surface layer of the composite filler particles, the composite inorganic salt system on the inner layer can be exposed in the air, so that the composite inorganic salt system reacts in the air and releases irritant and toxic chlorine dioxide, and the purpose of repelling the mouse is achieved through the released chlorine dioxide.
In practice, the addition amount of the composite filler in the rat hole plugging daub has an obvious relation with the rat repelling effect, the rat repelling effect can be achieved when the addition amount reaches a certain threshold value, and the effect increase exceeding the threshold value is not obvious, so that the addition amount of the composite filler is generally 25-30 parts based on economic consideration.
In specific implementation, some additives can be added into the rat hole plugging cement provided by the invention according to actual requirements, and the types and the dosage of the additives are well known in the field. For example, the additives include, but are not limited to, toughening agents, plasticizers, stabilizers, flame retardants, mold inhibitors, color pastes, and the like.
In one embodiment of the invention, the dosage of the toughening agent and the plasticizer is 0.5-1 part independently, the dosage of the flame retardant is 2-10 parts, the dosage of the mildew preventive is 1-2 parts, and the dosage of the color paste is 1-5 parts. These auxiliaries can be present as constituents of the A component and/or of the B component, provided that the total amount is ensured within a certain value range.
The flame retardant is not particularly limited, and may be an organic flame retardant or an inorganic flame retardant, and the organic flame retardant is preferably a phosphorus flame retardant, such as at least one of TCEP, TCPP, TDCPP, DMMP, triphenyl phosphate, and MPP; and the inorganic flame retardant is at least one selected from hydrated aluminum hydroxide, hydrated magnesium hydroxide, monoammonium phosphate, diammonium phosphate, ammonium chloride, boric acid, hydrated zinc borate and expanded graphite.
The toughening agent is at least one selected from methacrylate, ethylene octene copolymer, ethylene butene copolymer and ethylene propylene copolymer.
The plasticizer is at least one of phthalic acid ester, aliphatic diacid ester, phosphoric acid ester or benzoic acid diol ester.
The mildew preventive is an inorganic mildew preventive or an organic mildew preventive, and the organic mildew preventive comprises at least one of sodium diacetate, potassium sorbate, sodium sorbate, potassium citrate, sodium citrate, calcium propionate, sodium ascorbate, potassium ascorbate, sodium salicylate, dodecylalanine, cason, methylparaben, ethylparaben and lysozyme; the inorganic mildew preventive comprises at least one of nano silver, nano zinc oxide and nano titanium dioxide.
The color paste is selected from at least one of red phthalocyanine blue, permanent red, carbon black, titanium dioxide, complex dye, phthalocyanine green, medium yellow, scarlet, iron yellow, carbon black and permanent red.
In a second aspect, the present application provides a preparation method of a rat hole plugging daub, including:
step one, preparing a component A:
a1, adding an auxiliary agent into dehydrated polyether polyol, optionally adding an isocyanate to obtain a first mixed system, and carrying out heating reaction on the first mixed system to obtain a prepolymer;
a2, dehydrating the solid filler at high temperature to obtain a dehydrated solid filler;
a3, mixing the prepolymer, the dehydration filler, the hydroxyl surface modified paraffin and the thickening agent, and stirring to obtain a daub-shaped component A;
step two, preparing a component B:
b1, heating and dehydrating a second mixed system mixed by polyether polyol, a catalyst and a chain extender under the negative pressure condition, and optionally adding an auxiliary agent into the second mixed system to obtain a B component semi-finished product;
b2, dehydrating the solid filler at high temperature to obtain a dehydrated filler;
b3, mixing the semi-finished product of the component B, the dehydrated filler, the composite filler, the hydroxyl surface modified paraffin and the thickening agent, and stirring to obtain a daub-shaped component B;
step three, at room temperature, mixing the component A prepared in the step one and the component B prepared in the step two according to the mass ratio of 1-1.2: 1-1.2, and obtaining the rat hole plugging daub.
In this example, the dehydration is performed by heating under negative pressure, wherein the pressure of the vacuum pumping is-0.05 MPa to-0.1 MPa, and the dehydration is performed by heating to 90-110 ℃ for 2-4 hours. The solid filler is dehydrated at high temperature, which means that the solid filler is heated at 140 ℃ and 160 ℃ for 3-6 hours.
The two-component daub provided by the method is convenient and quick to use, and only needs to mix the component A and the component B at room temperature according to the mass ratio of 1-1.2: 1-1.2, and curing to obtain the product. The two-component daub provided by the invention is quick in curing and controllable in curing time, and the surface drying time can be adjusted within 1-60 min and 30-120 min by adjusting the using amount of the catalyst. Meanwhile, the component A and the component B of the two-component daub are not sticky, can be directly kneaded by hand without special equipment, and has convenient operation. The obtained daub after curing has excellent comprehensive performance and strong plasticity; meanwhile, the paint is waterproof and anticorrosive, and can maintain mechanical properties for a long time under the conditions of high temperature, high humidity and high salt.
In the embodiment of the present invention, the number of the surface hydroxyl groups of the paraffin wax is measured by referring to a common method, for example, the number of the surface hydroxyl groups of the paraffin wax is measured by a grignard reagent titration method.
The refined paraffin wax is purchased from Kunlun, and has the trade name of 52 #. Polyether polyol, R4110 is available from Norway, Shandong, with a hydroxyl number of 440. + -. 20 mgKOH/g. Polytetrahydrofuran polyol PTMEG250 was purchased from Pasteur and has a hydroxyl number of 430. + -. 10 mgKOH/g. The light calcium carbonate is purchased from bright mineral processing company and has a particle size D50 of about 50 nm. The white carbon black is Kabot M-5, and the specific surface area is 200M 2/g; carbodiimide modified MDI was purchased from Tahitian Chemicals and had an NCO content of 30%.
In order to make the present invention better understood by those skilled in the art, the method for preparing the hydroxyl surface-modified paraffin wax of the present invention will be described below by way of specific preparation examples.
Preparation example 1
Heating 20g of paraffin to above 60 ℃, liquefying the paraffin, putting into 50mL of 20 wt% hydrogen peroxide, stirring and reacting for 15min at 40 ℃, quickly transferring into an ice-water bath, cooling to room temperature, condensing the paraffin into particles, filtering, washing with water to neutrality, and then putting the paraffin with the surface hydroxyl modified into a vacuum drying oven to dry at 25-30 ℃ to obtain the modified paraffin 1. The test shows that the number of the hydroxyl on the surface of the modified paraffin is 0.132 mmol/g.
Preparation example 2
The operation of this example is similar to example 1, except that: the concentration of hydrogen peroxide is 15 wt%, the reaction temperature is 60 ℃, the reaction time is 5min, the modified paraffin 2 is obtained, and the number of surface hydroxyl groups of the modified paraffin 2 is 0.164 mmol/g.
Preparation example 3
The operation of this example is similar to example 1, except that: the concentration of hydrogen peroxide is 5 wt%, the reaction temperature is 60 ℃, the reaction time is 30min, the modified paraffin 3 is obtained, and the number of surface hydroxyl groups of the modified paraffin 3 is 0.253 mmol/g.
Preparation example 4
The operation of this example is similar to example 1, except that: replacing hydrogen peroxide with ozone, wherein the reaction temperature is 60 ℃, and the reaction time is 5min, so as to obtain the modified paraffin 4, and the number of surface hydroxyl groups of the obtained modified paraffin 4 is 0.327 mmol/g.
In order to make the present invention more understandable to those skilled in the art, the preparation method of the composite filler of the present invention is described below by specific preparation examples.
Preparation example 5
And (3) placing the composite inorganic salt system in molten surface hydroxyl modified paraffin, uniformly mixing, performing suction filtration at a melting temperature of 45 ℃ on a 500-mesh filter screen under a vacuum condition, cooling and solidifying, and crushing to obtain a modified paraffin package and an inorganic salt system.
Preparation example 6
And (3) placing the composite inorganic salt system in molten surface hydroxyl modified paraffin, uniformly mixing, filtering at a melting temperature of 70 ℃ by a 500-mesh filter screen under a vacuum condition, cooling and solidifying, and crushing to obtain a modified paraffin package and an inorganic salt system.
Preparation example 7
And (3) placing the composite inorganic salt system in molten surface hydroxyl modified paraffin, uniformly mixing, filtering at a melting temperature of 105 ℃ by a 500-mesh filter screen under a vacuum condition, cooling and solidifying, and crushing to obtain a modified paraffin package and an inorganic salt system.
In order to make the person skilled in the art better understand the present invention, the following description will be made by using specific examples to illustrate a preparation method of the rat hole plugging cement of the present invention.
Example 1
Preparation of component A:
(A1) adding 25 parts of propylene oxide polyether polyol PPG1000, and dehydrating for 2 hours at the negative pressure of-0.08 Mpa and the temperature of 110 ℃; cooling to 60 ℃, adding 15 parts of carbodiimide modified MDI, continuously stirring, slowly heating to 80 ℃, and carrying out temperature-controlled polymerization for 3 hours to obtain a prepolymer;
(A2)40 portions of light calcium with the grain diameter of 20nm and the specific surface area of 220m2The preparation method comprises the following steps of (1) dehydrating the compounded solid filler of the fumed silica according to the mass ratio of 15:1 at 160 ℃ for 4 hours;
(A3) adding the prepolymer obtained in the step (A1) and the dehydrated solid filler obtained in the step (A2), 19 parts of the modified paraffin prepared in the preparation example 1 and 1 part of hydroxymethyl cellulose ether into a planetary stirring kettle, and stirring into a cement-like product to obtain a component A finished product;
preparation of the component B:
(B1) adding 15 parts of propylene oxide polyether polyol PPG1000, 2 parts of triethylamine, 2 parts of tin laurate, 5 parts of diethyl toluene diamine, 1 part of benzoic acid glycol ester and 5 parts of triphenyl phosphate, and dehydrating at the negative pressure of-0.10 Mpa and the temperature of 90 ℃ for 2 hours to obtain a semi-finished product of the component B;
(B2) dehydrating 40 parts of light calcium carbonate, the composite filler prepared in the preparation example 5 and the gas-phase white carbon black according to the mass ratio of 8:7:1 for 4 hours at 160 ℃ to obtain a dehydrated compound solid filler;
(B3) and (3) adding the semi-finished product of the component B obtained in the step (B1), the dehydrated compound solid filler obtained in the step (B2), 29 parts of the modified paraffin 1 prepared in the preparation example 1 and 1 part of hydroxymethyl cellulose ether into a planetary stirring kettle, and stirring into a daub-shaped product to obtain the finished product of the component B.
Example 2
The operation of this example is similar to example 1, with the following differences in the starting materials: polyether polyol is polytetrahydrofuran polyol, isocyanate is toluene diisocyanate, and the modified paraffin in the component A and the component B is the modified paraffin prepared in the preparation example 2 in equal parts by mass; the reaction conditions differ in that: the negative pressure is-0.05 Mpa, the reaction temperature under the negative pressure environment is 90 ℃, the reaction time under the negative pressure environment is 4 hours, the dehydration temperature of the solid filler is 140 ℃, and the dehydration time of the solid filler is 3 hours.
Example 3
The operation of this example is similar to example 1, with the following differences in the starting materials: the polyether polyol is polytetrahydrofuran polyol, the isocyanate is isophorone diisocyanate, and the catalyst is a mixed catalyst of triethylene diamine, bismuth isooctanoate and tin laurate (the ratio is 6:1: 1).
Example 4
The operation of this example is similar to example 1, with the following differences in the starting materials: the solid filler is talcum powder.
Example 5
The operation of this example is similar to example 1, except that 50 parts of light calcium carbonate and fumed silica in component A and component B are replaced with equal parts by mass of light calcium carbonate as the compounded filler in the mass ratio of 15: 1.
Example 6
The other conditions and method are the same as in example 2 except that the catalyst in component B is 1 part triethylamine.
Example 7
The other conditions and procedure were the same as in example 2 except that the catalyst in component B was 0.5 parts of tin laurate.
Example 8
The other conditions and method were the same as in example 2 except that the amount of the modified paraffin wax 1 used in component A was changed to 12 parts.
Example 9
The other conditions and method were the same as in example 2 except that in component A, the amount of polyether polyol was changed to 30 parts, the amount of modified paraffin 1 was changed to 20 parts, and the amount of solid filler was 30 parts.
Example 10
The other conditions and the method are the same as the embodiment 1, and the difference is that 50 parts of light calcium carbonate and the fumed silica in the component A and the component B are compounded according to the mass ratio of 15:1, and the talcum powder and the fumed silica are compounded according to the mass ratio of 15:1 and the same parts.
The applicant should note that, in each preparation example and each embodiment of the present invention, the amount of each component may be adjusted according to the needs of the user, and is not limited in the embodiment of the present invention.
In order to make the present invention more comprehensible to those skilled in the art, the rat hole plugging cement of the present invention is described below by using specific use examples.
Use example 1
Cleaning the rat hole, and breaking loose soil and concrete at the edge; mixing the A/B components prepared in the example 1 according to a ratio of 1:1, kneading for 1min, and fully mixing to obtain rat-hole plugging cement; pressing the inner wall of the rat hole to ensure compaction; filling the large blocks of the daub with the filling thickness of 10 cm; the appearance was recovered (painting paint, etc.).
Use example 2
This working example was similar to the working method of working example 1 except that the A/B components prepared in example 1 were mixed at a ratio of 1:1.2 and kneaded for 10min to be sufficiently mixed to obtain a rat-hole plugging cement; and filling the large rat hole plugging daub with the filling thickness of 20 cm.
Use example 3
This working example was similar to the working method of working example 1 except that the A/B components prepared in example 1 were mixed at a ratio of 1.2:1 and kneaded for 30 minutes to be sufficiently mixed to obtain a rat-hole plugging cement; and filling the large rat hole plugging daub, wherein the filling thickness is 15 cm.
Use example 4
This working example was similar to the working method of working example 1 except that the A/B components prepared in example 1 were mixed at a ratio of 1.2:1.2 and kneaded for 60min to be sufficiently mixed to obtain a rat-hole plugging cement; and filling the large rat hole plugging daub with the filling thickness of 30 cm.
For simplicity of explanation, the method embodiments are described as a series of acts or combinations, but those skilled in the art will appreciate that the present invention is not limited by the order of acts, as some steps may occur in other orders or concurrently in accordance with the invention. Further, those skilled in the art will appreciate that the embodiments described in the specification are preferred embodiments and that the acts and elements referred to are not necessarily required to practice the invention.
The rat hole plugging daub and the preparation method thereof provided by the invention are described in detail, the principle and the implementation mode of the invention are explained by applying specific examples, and the description of the examples is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. The rat hole plugging daub is characterized by comprising a component A and a component B;
based on 100 parts by weight of the component A, the component A comprises: 20-35 parts of polyether polyol, 12-25 parts of isocyanate, 12-25 parts of surface hydroxyl modified paraffin, 0.5-2 parts of thickening agent and 30-40 parts of solid filler;
based on 100 parts by weight of the component B, the component B comprises: 15-30 parts of polyether polyol, 10-25 parts of surface hydroxyl modified paraffin, 0.5-2 parts of catalyst, 4-6 parts of chain extender, 0.5-2 parts of thickener, 25-30 parts of solid filler and 25-30 parts of composite filler; the composite filler is used for generating gas for repelling rats.
2. A rat-hole plugging daub according to claim 1, wherein the polyether polyol comprises at least one of propylene oxide polyether polyol and polytetrahydrofuran polyol;
the hydroxyl value of the polyether polyol is 10-100 mgKOH/g;
the number of the surface hydroxyl modified paraffin is 0.05-0.2 mmol/g.
3. A rat-hole plugging mastic as claimed in claim 1, wherein the isocyanate comprises: at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate; the diphenylmethane diisocyanate is liquefied modified diphenylmethane diisocyanate; the liquefaction modification comprises carbodiimide modification.
4. A rat-hole plugging daub according to claim 1, wherein said solid filler comprises: at least one of titanium dioxide, clay, talcum powder, light calcium carbonate, heavy calcium carbonate, fumed silica and quartz powder;
the mass ratio of the light calcium carbonate to the fumed silica is 12-18: 1-2; the particle size of the light calcium carbonate is 20-60 nm, and the specific surface area of the fumed silica is 170-220m2/g。
5. A rat-hole plugging cement according to claim 1, wherein said thickening agent comprises a cellulose ether;
the cellulose ether comprises: at least one of hydroxyethyl methyl cellulose ether and hydroxypropyl methyl cellulose ether.
6. A rat-hole plugging cement according to claim 1, wherein said catalyst comprises: at least one of tertiary amine catalyst and organic metal catalyst;
the tertiary amine catalyst comprises: at least one of triethylamine, tributylamine, triethylenediamine, and N, N-dimethylaniline;
the organometallic catalyst includes: at least one of organic bismuth and organic tin;
the organic bismuth comprises: at least one of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate and bismuth naphthenate;
the organic tin comprises at least one of tin octoate, tin ethylhexanoate, tin laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate and dioctyltin diacetate;
when the catalyst comprises a tertiary amine catalyst and an organic metal catalyst, the mass ratio of the tertiary amine catalyst to the organic metal catalyst is 6-10: 1-2.
7. The rat hole plugging cement according to claim 1, wherein the chain extender comprises at least one of an amine chain extender and a polyol chain extender;
the amine chain extender comprises: at least one of ethylenediamine, propylenediamine, N-dihydroxy (diisopropyl) aniline, diethyltoluenediamine, 3 '-dichloro-4, 4' -diamino-diphenylmethane, 3, 5-dimethylthiotoluenediamine, 3, 5-diethyl-2, 4-toluenediamine, 3, 5-diethyl-2, 6-toluenediamine, divinyltriamine, tetraethylenepentamine, diethylenetriamine isophorone diamine, and di-N-butylamine;
the polyol-based chain extender includes: at least one of ethylene glycol, butanediol, diethylene glycol, dipropylene glycol, 1, 6-hexanediol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-cyclohexanediol, and trimethylpentanediol.
8. A rat hole plugging daub according to claim 1, wherein the composite filler is obtained by wrapping a composite inorganic salt system by the surface hydroxyl modified paraffin;
the composite inorganic salt system comprises: persulfates and chlorites; the mass ratio of the persulfate to the chlorite is 1.1: 1-2: 1.
9. the rat hole plugging cement according to claim 1, further comprising: an auxiliary agent;
the auxiliary agent comprises: at least one of a toughening agent, a plasticizer, a stabilizer, a flame retardant, a mildew preventive and color paste.
10. A method for preparing the rat hole plugging daub as claimed in any one of claims 1 to 9, wherein the method comprises the following steps:
step one, preparing a component A:
a1, adding isocyanate into dehydrated polyether polyol to obtain a first mixed system, and carrying out heating reaction on the first mixed system to obtain a prepolymer;
a2, dehydrating the solid filler at high temperature to obtain a dehydrated solid filler;
a3, mixing the prepolymer, the dehydration filler, the hydroxyl surface modified paraffin and the thickening agent, and stirring to obtain a daub-shaped component A;
step two, preparing a component B:
b1, heating and dehydrating a second mixed system mixed by polyether polyol, a catalyst and a chain extender under the negative pressure condition to obtain a B component semi-finished product;
b2, dehydrating the solid filler and the composite filler at a high temperature to obtain a dehydrated solid filler and a dehydrated composite filler;
b3, mixing the semi-finished product of the component B, the dehydrated solid filler, the dehydrated composite filler, the hydroxyl surface modified paraffin and the thickening agent, and stirring to obtain a daub-shaped component B;
and step three, at room temperature, mixing the component A prepared in the step one and the component B prepared in the step two according to the mass ratio of 1-1.2: 1-1.2, and obtaining the rat hole plugging daub.
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