CN111944473A

CN111944473A - Bi-component strippable daub and preparation method thereof

Info

Publication number: CN111944473A
Application number: CN202010840611.2A
Authority: CN
Inventors: 袁振; 王宏伟; 郭子慧; 王少华; 张海凤; 王宇川
Original assignee: Cetc Baoli Beijing Technology Co ltd
Current assignee: Cetc Baoli Beijing Technology Co ltd
Priority date: 2020-08-20
Filing date: 2020-08-20
Publication date: 2020-11-17
Anticipated expiration: 2040-08-20
Also published as: CN111944473B

Abstract

The invention provides a bi-component strippable daub which 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, a catalyst, a chain extender, surface hydroxyl modified paraffin, a thickening agent and a solid filler; the chain extender comprises castor oil. According to the invention, the paraffin with hydroxyl on the surface is introduced into the double components, so that an operator can not stick hands when kneading; meanwhile, as the hydroxyl on the surface of the daub can react with isocyanate, the daub has good compatibility after being cured, does not cause material drying crack, pulverization and deformation due to migration, 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 for a long time in severe environments. Meanwhile, the chain extender contains a certain amount of castor oil, so that the daub can be integrated into glass during stripping, and basically has no residue on a protected device.

Description

Bi-component strippable daub and preparation method thereof

Technical Field

The invention belongs to the field of high-molecular functional materials, and particularly relates to a bi-component fast-curing plastic cement and a preparation method thereof.

Background

In order to prevent electrical equipment and electric wires from leaking electricity, an anti-electricity-leakage adhesive tape is generally used for plugging and protecting. However, this method cannot isolate the electrical equipment from the contact of water vapor, and cannot achieve the effect of complete sealing. The long-time use has great potential safety hazard of short circuit. Meanwhile, after the wires are oxidized, the resistance of some devices, including the connectors, is increased, the heat productivity is obviously increased, the service life of the cables and the wires is influenced, and the wires are easily burnt out to cause accidents.

In the prior art, some daub is often adopted to plug and protect electrical equipment and wire joints. Red mud and the like are traditionally used for dehydration curing, the curing speed is slow, and the cured red mud has high hardness and is crisp. At present, high-molecular daub, generally epoxy resin, is generally used as base glue, filler, curing agent and auxiliary agent. For example, patent CN102993579A discloses an insulating waterproof daub, which comprises, by weight: butyl rubber: 60-70%; reinforcing agent: 5-10%; filling: 20-25%; flame retardant: 0.5-5%; curing agent: 0.2-2%; water-proofing agent: 5 to 20 percent. However, the single-component daub is inconvenient to use, and the components need to be kneaded, so that the formed daub has uneven components, thickness and density, and is difficult to achieve effective protection of electric appliances. At present, a two-component daub product is generally adopted, and CN102504487A discloses an insulating sealing daub for wire joints, wherein the daub is composed of A, B two components, the colors of the two components are obviously different, and the two components are respectively composed of the following raw materials: the component A comprises: 40-60% of epoxy resin, 5-8% of toughening agent, 20-40% of thixotropic agent and 20-30% of inert filler; and B component: 15-20% of modified amine, 30-60% of a tough curing agent, 3-6% of a curing accelerator, 20-30% of a flame retardant, 0.1-0.3% of a pigment and 20-30% of an inert filler. However, the amine curing agent has an irritating odor before curing, which has health risks to constructors and adverse effects on the environment. CN109897584A discloses a bi-component daub, which is composed of a component A and a component B according to the mass ratio of 1: 1; the component A comprises the following raw materials in parts by weight: 20-30 parts of epoxy resin, 40-70 parts of insulating filler and 10-30 parts of diluent; the component B comprises the following raw materials in parts by weight: 10-20 parts of toughening curing agent, 10-20 parts of colorless curing agent, 5-10 parts of curing accelerator, 1-3 parts of color filler and 30-50 parts of insulating filler. The colorless curing agent is used to replace common amine curing agent, eliminating strong pungent taste during construction. In addition, the daub adopting the epoxy resin has high strength, but low toughness, difficult capacity expansion of a finished product, poor plasticity, frangibility and easy pulverization.

In addition to epoxy resin cements, polymer cements also include polyurethane cements, which are polymer-based cements formed by polymerizing polyhydroxy compounds and isocyanate. The polyurethane has excellent mechanical properties, is resistant to extrusion and stretching, has good plasticity, and is convenient to protect and plug various special-shaped materials; meanwhile, the polyurethane has better corrosion resistance, and can keep good weather resistance under the conditions of acidity, alkalinity and high salt. For example, CN105061723A and CN105694796A disclose a polyurethane cement respectively, but such a cement is mainly used for plugging areas and large-sized materials such as buildings, ships, chimneys, chemical pipelines, and the like.

The daub related to in the prior art has strong bonding force, has higher strength after curing, but can not be peeled off immediately when needed, so that secondary construction is complex during construction, and controllability is not high.

In patent CN109913033A of Hainan BiKa waterborne new material Co., Ltd, a hand inkpad which is not sticky to hands is developed, epoxy resin is used as base glue, and an anti-sticking auxiliary agent compounded by paraffin and vaseline is adopted, but the addition of the anti-sticking auxiliary agent can lead the curing material of the inkpad to be unstable, and the components can migrate along with the time, thereby reducing the mechanical strength and shortening the service life; and its peeling force is too low to secure sufficient strength.

CN103038283A discloses a strippable insulation sheath for cable wires, which uses chlorinated polyolefin as glass control additive in the strippable sheath, and simultaneously adds organosilicon. Promotes the incompatibility of nonpolar polyolefin in thermodynamics, reduces the interface crosslinking force, further can reduce the adhesion force between the layers of the cable and the wire, and further improves the strippability of the protective sleeve. Although the organosilicon compound can achieve the strippable effect, the finished product has high brittleness, poor durability, long base surface curing time and difficult construction due to the characteristic of the hardness of the epoxy group material. The protective sleeve obtained in the patent is a rigid structure, and cannot effectively protect a special-shaped electric device; and weather resistance may not be durable in some severe environments due to the inclusion of various fillers.

Therefore, in order to meet the requirements of insulation protection for wires and cables of current special-shaped electrical equipment, a novel daub is continuously developed, has the advantages of insulation and water resistance, strong plasticity, difficult pulverization and fragmentation, and can be directly kneaded by hands to be rapidly cured and molded after two components are mixed; the weather resistance is good, and the coating can be safely and permanently used in various harsh environments; the paint has good strippability while ensuring mechanical properties, can be easily stripped when needed, and is convenient for secondary construction.

Disclosure of Invention

In order to overcome the defects that the common daub in the prior art has poor toughness, poor plasticity and difficult dilatation, is easy to pulverize and crush after long-time work, has long curing time and complicated application steps, the invention provides the polyurethane-based high-molecular daub, which has two components, can directly knead the two components into a proper shape by hands during use, has quick curing time, good mechanical property after curing and satisfactory hardness and toughness; corrosion resistance and good weather resistance; the adhesive force is moderate, and the adhesive has good strippability while ensuring the mechanical strength; meanwhile, the material has strong cohesion, can be conveniently stripped from the whole protected electric appliance, basically has no residue, is convenient for secondary construction, and is novel polyurethane cement with excellent comprehensive performance.

In order to solve the technical problems, the first object of the invention is to provide a two-component peelable daub, which consists of two components A and 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, a catalyst, a chain extender, surface hydroxyl modified paraffin, a thickening agent and a solid filler; the chain extender comprises castor oil.

Further, the component A comprises the following raw materials in parts by weight: 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 30-40 parts of solid filler; 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 and 30-50 parts of solid filler.

Preferably, the chain extender may further include an amine chain extender or a polyol chain extender, provided that the content of castor oil in the chain extender is 10 to 50 wt%, preferably 25 to 35 wt%. The amine chain extender is at least one selected from ethylenediamine, propylenediamine, N, N-dihydroxy (diisopropyl) aniline, diethyltoluenediamine, 3,3 '-dichloro-4, 4' -diamino-diphenylmethane (MOCA), 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 polyalcohol chain extender is at least one selected from ethylene glycol, 1, 4-butanediol, diethylene glycol, dipropylene glycol, 1, 6-hexanediol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-cyclohexanediol, trimethylpentanediol, resorcinol bis (2-hydroxyethyl) ether, p-phenol dihydroxyethyl ether and trimethylolpropane.

The inventors have unexpectedly discovered that the addition of a chain extender in an amount of castor oil increases the cohesion of the material without affecting the peelability of the mastic, allowing the mastic of the invention to be peeled off intact from the electrical appliance to be protected, substantially without residue. The castor oil is a renewable biological resource, contains double bonds and a plurality of hydroxyl groups, and can react with isocyanate to generate a certain cross-linked structure. In the prior art, castor oil is used as an auxiliary material component of the modified polyurethane, but the castor oil is generally used for improving the heat resistance and the mechanical strength of the material. No prior art has been found to disclose the addition of castor oil as a chain extender which improves the integrity of the peelable material when peeled without adversely affecting the peelability.

Preferably, the number of hydroxyl groups on the surface of the modified paraffin is 0.05 to 0.2mmol/g, preferably 0.08 to 0.15 mmol/g.

The hydroxyl surface modified paraffin is obtained by a preparation method comprising the following steps: 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.

Preferably, the reaction condition is that the reaction is carried out for 5 to 30min at the temperature of between 40 and 60 ℃, and the concentration of the hydrogen peroxide is between 5 and 20 percent by weight.

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 the hydrogen peroxide is between 10 and 15 percent by weight.

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 of the paraffin is modified 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.

The inventor has also unexpectedly found that, after the surface hydroxyl modification is carried out on the paraffin by hydrogen peroxide or ozone, a small amount of hydroxyl is carried 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 can not 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.

The polyether polyol is at least one of polyoxyalkylene polyol and polytetrahydrofuran polyol. Preferably, the polyether polyol is prepared by using glycerol as an initiator, and the hydroxyl value is 30-120 mgKOH/g.

The isocyanate is selected from at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI) and Lysine Diisocyanate (LDI); preferably a liquefied modified diphenylmethane diisocyanate, more preferably a carbodiimide modified MDI.

The catalyst is a tertiary amine catalyst and/or an organic metal catalyst, the tertiary amine catalyst is selected from triethylamine, tributylamine, triethylene diamine and N, N-dimethylaniline, the organic metal catalyst is organic bismuth and/or organic tin, the organic bismuth is selected from at least one of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate and bismuth naphthenate, and the organic tin is selected from at least one of tin octoate, tin ethylhexanoate, tin laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate and dioctyltin diacetate.

Preferably, the catalyst is a compound of a tertiary amine catalyst and an organic metal catalyst according to the mass ratio of 6-10: 1-2. The compounded catalyst can effectively control the reaction speed, so that the whole reaction is rapid and controllable, the curing time is 1-30 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.

The solid filler is at least one selected from titanium dioxide, clay, talcum powder, light calcium, heavy calcium, fumed silica and quartz powder, preferably the light calcium and the fumed silica are compounded according to the mass ratio of 12-18:1-2, the particle size of the light calcium is 20-60 nm, and the specific surface area of the fumed silica is 170-220m²/g。

The thickening agent is selected from cellulose ethers, preferably hydroxyethyl methyl cellulose ether and/or hydroxypropyl methyl cellulose ether.

In the two-component daub provided by the invention, some auxiliary agents can be added according to actual requirements, and the types and the use amounts of the auxiliary agents are well known in the field. For example, the additives include, but are not limited to, flame retardants, mold inhibitors, color pastes, and the like.

For example, in one embodiment of the present invention, the amounts of the toughening agent and the plasticizer are independently 0.5 to 1 part, the amount of the stabilizer is 0.1 to 0.3 part, the amount of the flame retardant is 2 to 10 parts, the amount of the mildewproof agent is 1 to 2 parts, and the amount of the color paste is 1 to 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 and hydrated zinc borate.

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.

The second purpose of the invention is to provide a preparation method of the two-component strippable daub, which comprises the following steps:

preparing a component A:

(A1) adding polyether polyol and optionally adding an auxiliary agent, heating and dehydrating under the condition of negative pressure, cooling, adding isocyanate, and heating to react to obtain a prepolymer;

(A2) dehydrating the solid filler at high temperature;

(A3) stirring the prepolymer obtained in the step (A1), the dehydrated filler obtained in the step (A2), hydroxyl surface modified paraffin and a thickening agent into a puddle to obtain a component A;

preparing a component B:

(B1) adding polyether polyol, a catalyst and a chain extender, optionally adding an auxiliary agent, and heating and dehydrating under the negative pressure condition to obtain a B component semi-finished product;

(B2) dehydrating the filler at high temperature;

(B3) and (C) stirring the semi-finished product of the component B obtained in the step (B1), the dehydrated filler obtained in the step (B2), the hydroxyl surface modified paraffin and the thickening agent into a puddle to obtain the component B.

And the heating dehydration under the negative pressure condition is to heat the mixture to 90-110 ℃ for 2-4 hours under the vacuum pressure of 0.05MPa to 0.1 MPa.

The filler is dehydrated at high temperature, namely heated at 150-220 ℃ for 3-6 hours.

The dual-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 curing time of the two-component daub provided by the invention is controllable, and can be adjusted within 1-30 min by adjusting the dosage of the catalyst. Meanwhile, the component A and the component B of the bi-component daub are not sticky, can be directly kneaded by hand without special equipment, and has the convenience in operation and industry.

The obtained daub after curing has excellent comprehensive performance and strong plasticity, the elongation at break is more than 100%, the preferred embodiment can reach more than 120%, and the volume can be conveniently expanded; 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.

Compared with the prior art, the invention has the following technical advantages:

the paraffin with certain hydroxyl groups on the surface is introduced into the double components, so that certain surface lubricity is provided, and an operator cannot stick hands when kneading; meanwhile, as the hydroxyl on the surface of the material can react with isocyanate, the cured material has good compatibility and cannot cause material drying crack, pulverization and deformation due to migration. In addition, due to good compatibility, the cured daub has good weather resistance in high-temperature, high-humidity, high-salt and other environments, and can play a role in protecting and plugging electrical equipment for a long time in severe environments.

Secondly, the chain extender containing a certain amount of castor oil is added, so that crosslinking with a proper degree is generated during curing, the strippability of the daub after curing is not influenced, the internal cohesion of the material is greatly improved, and the daub can be integrated into glass during stripping, and basically has no residue on a protected device.

Thirdly, through adopting the compounded catalyst, the proportion is adjusted, so that the material reaction is relatively smooth, the later-stage curing speed is high, a certain operation time is reserved for facilitating curing and forming, and meanwhile, the later-stage curing speed is high, so that the whole curing time can still be controlled within 30 min.

And fourthly, the selection of the flexible chain polymer, the isocyanate and the cross-linking agent can give consideration to the surface strength, and meanwhile, the material has excellent toughness, strong plasticity and easy cutting, so that the material is convenient for the requirements of removal, drilling and other capacity expansion after curing.

Detailed Description

The present invention will be further described with reference to the following examples, but the present invention is not limited to the descriptions in the following. Unless otherwise specified, "parts" in the examples of the present invention are parts by weight unless otherwise specified, and% are mass percentages unless otherwise specified. All reagents used are commercially available in the art.

In the examples of the present invention, the number of hydroxyl groups on the surface of paraffin wax was measured by a method described in patent document CN 104761929A: the number of surface hydroxyl groups of the paraffin was measured by grignard reagent titration.

The refined paraffin is purchased from Kunlun, trade name 52 #; polyoxyalkylene 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 200M²(ii)/g; carbodiimide modified MDI was purchased from Tahitian Chemicals and had an NCO content of 30%.

Preparation exampleSurface hydroxyl modification of paraffin wax

Preparation example 1

Heating 20g Kunlun No. 52 paraffin to above 60 ℃, liquefying the paraffin, putting into 40mL10 wt% hydrogen peroxide, stirring and reacting for 10min at 40 ℃, quickly transferring into an ice water bath, cooling to room temperature, condensing the paraffin into particles, filtering, washing with water to be neutral, 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 0.083 mmol/g.

Preparation example 2

The other methods and conditions were the same as in preparation example 1 except that the reaction time was 15min to obtain a modified paraffin 2, and the number of surface hydroxyl groups of the obtained modified stone 2 was 0.106 mmol/g.

Preparation example 3

The other methods and conditions were the same as in preparation example 1 except that the reaction time was 20min to obtain a modified paraffin 3, and the number of surface hydroxyl groups of the obtained modified paraffin 3 was 0.137 mmol/g.

Preparation example 4

The other methods and conditions were the same as in preparation example 3 except that the hydrogen peroxide concentration was 15 wt% to obtain modified paraffin 4, and the number of surface hydroxyl groups in the obtained modified paraffin 4 was 0.152 mmol/g.

Preparation example 5

The other methods and conditions were the same as in preparation example 4 except that the hydrogen peroxide concentration was 20 wt%, the reaction time was 30min, and modified paraffin 5 was obtained, and the number of surface hydroxyl groups of the obtained modified paraffin 5 was 0.215 mmol/g.

Example 1

Preparation of component A:

(A1) adding 15 parts of polyoxyalkylene polyol R4110 and 0.4 part of benzoic acid glycol ester, and dehydrating at 110 ℃ under negative pressure of-0.08 MPa for 2 hours; cooling to 60 ℃, adding 10 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 parts of light calcium carbonate and meteorologic white carbon black are dehydrated for 4 hours at 160 ℃ according to the compound filler with the mass ratio of 15: 1;

(A3) adding the prepolymer obtained in the step (A1) and the dehydrated filler obtained in the step (A2) into a planetary stirring kettle, and stirring 8 parts of the modified paraffin 1 prepared in the preparation example 1 and 1 part of hydroxymethyl cellulose ether into a cement-like product to obtain a component A finished product;

preparation of the component B:

(B1) adding 15 parts of polyoxyalkylene polyol R4110, 0.8 part of triethylamine, 0.2 part of tin laurate, 1.25 parts of castor oil, 3.75 parts of diethyltoluenediamine, 0.3 part of glycol benzoate, 5 parts of triphenyl phosphate and 2 parts of potassium sorbate, and dehydrating at 90 ℃ for 2 hours under negative pressure of-0.10 MPa to obtain a B-component semi-finished product;

(B2) 40 parts of light calcium carbonate and meteorologic white carbon black are dehydrated for 4 hours at 160 ℃ according to the mixed filler with the mass ratio of 15:1

Time of flight

(B3) And (3) adding the semi-finished product of the component B obtained in the step (B1), the dehydrated filler obtained in the step (B2), 8 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 cement-like product to obtain the finished product of the component B.

Example 2

The other conditions and methods were the same as in example 1 except that the modified paraffin 1 in component a and component B was replaced with an equal part by mass of the modified paraffin 2 obtained in preparation example 2.

Example 3

The other conditions and methods were the same as in example 1 except that the modified paraffin 1 in component a and component B was replaced with an equal part by mass of the modified paraffin 3 obtained in preparation example 2.

Example 4

The other conditions and methods were the same as in example 1 except that the modified paraffin 1 in component a and component B was replaced with an equal part by mass of the modified paraffin 4 obtained in preparation example 2.

Example 5

The other conditions and methods were the same as in example 1 except that the modified paraffin 1 in component a and component B was replaced with an equal part by mass of the modified paraffin 5 obtained in preparation example 2.

Example 6

The other conditions and methods were the same as in example 3 except that polyoxyalkylene polyol R4110 in component A and component B was replaced with an equal mass part of polytetrahydrofuran polyol PTMEG 250.

Example 7

The other conditions and the method are the same as the example 3, and the difference is that 40 parts of light calcium carbonate and the fumed silica in the component A and the component B are replaced by equal parts of light calcium carbonate according to the mass ratio of 15: 1.

Example 8

The other conditions and procedure were the same as in example 3 except that the catalyst in component A and component B, i.e., 0.8 parts of triethylamine, was replaced with 1 part of triethylamine in place of 0.2 parts of tin laurate.

Example 9

The other conditions and procedure were the same as in example 3 except that the catalyst in component A and component B, i.e., 0.8 parts triethylamine, was replaced with 1 part tin laurate for 0.2 parts tin laurate.

Example 10

The other conditions and method were the same as in example 3 except that the amount of the modified paraffin 3 was changed to 5 parts in the component A and the component B.

Example 11

The other conditions and method were the same as in example 3 except that the amount of the modified paraffin 3 was changed to 12 parts in the component A and the component B.

Example 12

The other conditions and the method are the same as the embodiment 3, 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.

Example 13

The other conditions and process were the same as in example 3 except that 1.25 parts of castor oil and 3.75 parts of diethyltoluenediamine in component B were replaced with 2.5 parts of castor oil and 2.5 parts of diethyltoluenediamine.

Example 14

The other conditions and procedure were the same as in example 1 except that 1.25 parts of castor oil and 3.75 parts of diethyltoluenediamine in component B were replaced with 1 part of castor oil and 4 parts of diethyltoluenediamine.

Comparative example 1

The other conditions and methods were the same as in example 1 except that the modified paraffin wax 1 in component a and component B was replaced with an equal part by mass of paraffin wax.

Comparative example 2

The other conditions and procedure were the same as in example 1 except that 1.25 parts castor oil and 3.75 parts diethyltoluenediamine were replaced with 5 parts diethyltoluenediamine in component B, i.e., castor oil was not included in the chain extender.

Effect example 1

The two-component mastic obtained in examples 1 to 12 and comparative example 1 above was rapidly kneaded by taking 20g each of the A component and the B component, and then left to stand for 24 hours. Testing various performance indexes of the condensate:

curing time: taking tensile strength of more than 0.1MPa as curing time;

the test reference test standard GB/T528-2009 for tensile strength;

the test for elongation at break is referred to test standard GB/T528-2009.

The test for flame retardancy is referred to the vertical burning test ASTM D-3801.

The insulation test was carried out with a breakdown voltage of more than 18 kV/mm.

The skin adhesion is characterized in that after the A component and the B component are mixed according to the mass ratio of 1:1, the bi-component daub is immediately tested and classified into 3 grades, the grade A is smooth in surface, the bi-component daub is not sticky to hands when being pressed forcefully during kneading, and no residue is left on the hands; grade B, the surface has slight adhesive feeling, the hand is slightly stuck by pressing hard during kneading, and a small amount of residue is left on the hand; grade C, the surface sticky feel was severe and there was more residue on the hands after kneading.

In order to test the weather resistance of the daub after curing, the mechanical property retention rate of the cured product after being placed for 1 week at 50 ℃ and RH 90% humidity was also tested. The results are shown in table 1 below:

TABLE 1

The data in Table 1 show that the bicomponent daub provided by the invention has excellent comprehensive performance, good flame retardance and mechanical property, and quick curing time, and can be conveniently regulated and controlled according to the type and the dosage of the catalyst. After high temperature and high humidity resistance, the excellent mechanical property is still maintained. The two-component daub provided by the invention is convenient to use, can be directly kneaded into a required shape and thickness by hands, and protects electrical equipment, electric wires and the like, especially special-shaped electrical devices. When kneaded by hand, the hand feeling is smooth, the hand can not be stuck, and the operation is convenient. Is a daub product with market competitiveness.

Effect example 2 weather resistance test

In order to test the weather resistance of the daub of the invention in various harsh environments, the following tests are carried out: kneading into a cuboid of 5cm multiplied by 2cm multiplied by 1 according to the mass ratio of the component A to the component B being 1:1, standing for 24 hours after curing, and performing the following weather resistance test:

1, high temperature and high humidity durability test, and test conditions are as follows: 70 ℃ and 95 RH% for 300 h. And (3) test evaluation: a, no deformation and no change in surface hardness; b, slightly changing the shape under the external force, and slightly softening the surface; and C, changing the shape under the external force, and softening the surface in a large area.

Anti-freeze test, test conditions: storing at-10 deg.C for 300 h. And (3) test evaluation: a, no cracking and no damage; b, slight cracking or breakage; c cracking or breakage is obvious.

Ultraviolet aging test, test conditions: the power of the ultraviolet lamp in the aging box is 50W/m at room temperature²And storing for 300 h. And (3) test evaluation: a, no cracking and no damage; b, slight cracking or breakage; c cracking or breakage is obvious. The results are shown in table 2 below.

TABLE 2

Effect example 3 peelability test

The peelability test was performed as follows: the results are shown in table 3 below.

The peel integrity was rated according to the residue rate of the mastic after peeling:

a: 0-5% of daub residue after stripping;

b: the residue of the daub after stripping is more than 5-10%;

c: the residue of the daub after stripping is more than 10-15%;

d: the residue of the daub after stripping is more than 15-20%;

e: the residue of the daub after stripping is more than 20 percent.

TABLE 3

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A two-component strippable 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, a catalyst, a chain extender, surface hydroxyl modified paraffin, a thickening agent and a solid filler; the chain extender comprises castor oil.

2. The two-component peelable cement of claim 1 wherein the component a comprises the following raw materials in parts by weight: 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 30-40 parts of solid filler; 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 and 30-50 parts of solid filler.

3. The two-component peelable cement according to claim 1, wherein the chain extender further comprises an amine chain extender or a polyol chain extender, provided that the content of castor oil in the chain extender is from 10 to 50 wt%, preferably from 25 to 35 wt%; the amine chain extender is at least one selected from ethylenediamine, propylenediamine, N, N-dihydroxy (diisopropyl) aniline, diethyltoluenediamine, 3,3 '-dichloro-4, 4' -diamino-diphenylmethane (MOCA), 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 polyalcohol chain extender is at least one selected from ethylene glycol, butanediol, diethylene glycol, dipropylene glycol, 1, 6-hexanediol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-cyclohexanediol and trimethylpentanediol.

4. The two-component strippable cement of claim 1, wherein the number of hydroxyl groups on the surface of the modified paraffin wax is from 0.05 to 0.2mmol/g, preferably from 0.08 to 0.15 mmol/g.

5. The two-component strippable cement of claim 1 wherein the hydroxy surface-modified paraffin wax is obtained by a process comprising the steps of: 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.

6. The two-component peelable cement according to claim 5, wherein when the paraffin wax reacts with the hydrogen peroxide, the reaction is carried out for 5 to 30min at a temperature of between 40 and 60 ℃, and the concentration of the hydrogen peroxide is between 5 and 20 wt%; 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 the hydrogen peroxide is between 10 and 15 percent by weight.

7. The two-component peelable cement of claim 1 wherein the polyether polyol is selected from at least one of a polyoxyalkylene polyol, a polytetrahydrofuran polyol; and/or

The isocyanate is selected from at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI) and Lysine Diisocyanate (LDI); preferably a liquefied modified diphenylmethane diisocyanate, more preferably a carbodiimide-modified MDI; and/or

8. The two-component peelable mastic of claim 1 wherein the catalyst is a tertiary amine catalyst selected from the group consisting of triethylamine, tributylamine, triethylenediamine, N-dimethylaniline, and/or an organometallic catalyst selected from at least one of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate, and bismuth naphthenate, and/or an organotin selected from at least one of tin octoate, tin ethylhexanoate, tin laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, tin dibutylmaleate, and dioctyltin diacetate;

preferably, the catalyst is a compound of a tertiary amine catalyst and an organic metal catalyst according to the mass ratio of 6-10: 1-2.

9. The two-component peelable cement according to claim 1, wherein the solid filler is at least one selected from titanium dioxide, clay, talcum powder, light calcium, heavy calcium, fumed silica and quartz powder, and is preferably a combination of light calcium and fumed silica in a mass ratio of 12-18: 1-2.

10. A process for the preparation of the two-component peelable cement of any of claims 1-9 comprising the steps of:

preparing a component A:

(A2) dehydrating the solid filler at high temperature;

preparing a component B:

(B2) dehydrating the filler at high temperature;