阅读说明：本技术 一种高粘耐久免钉胶 (High-viscosity durable nail-free glue ) 是由 蔡思韵 于 2019-11-06 设计创作，主要内容包括：本发明公开了一种高粘耐久免钉胶,属于胶粘剂制备技术领域。本发明以蓖麻油、预处理埃洛石等为原料,滴加β-环糊精水溶液热混处理,提高组分间的相容性,胆固醇起到界面改性的作用,协同提升本发明的附着性和耐久性。制嵌段共聚物,并通过对其结构状态的调节,结合生物胶体构成高耐久性的复合胶体基料,在埃洛石碳纳米管中热分散硬脂酸锌,作为骨架结合胶体形成有机-无机互穿的网络,提高本免钉胶的使用效果。以具有活性基团的虫胶、壶藤胶和钠基膨润土共混研磨,使得胶体内部发生迅速被撑大,在后续的超声处理下,稳定结合构成复合胶体基料,便于进一步提高本胶体的附着性和耐久性。本发明解决了目前常用免钉胶的附着力和耐久性不佳的问题。(The invention discloses a high-viscosity durable nail-free adhesive, and belongs to the technical field of adhesive preparation. According to the invention, castor oil, pretreated halloysite and the like are used as raw materials, and a beta-cyclodextrin aqueous solution is added dropwise for hot mixing treatment, so that the compatibility among the components is improved, cholesterol plays a role in interface modification, and the adhesiveness and durability of the composition are synergistically improved. Preparing a segmented copolymer, combining with a biological colloid to form a high-durability composite colloid base material by adjusting the structural state of the segmented copolymer, thermally dispersing zinc stearate in the halloysite carbon nanotube to form an organic-inorganic interpenetrating network as a framework combined colloid, and improving the using effect of the nail-free glue. The shellac, the caraway gum and the sodium bentonite with active groups are mixed and ground, so that the interior of the colloid is rapidly expanded, and the shellac, the caraway gum and the sodium bentonite are stably combined to form a composite colloid base material under subsequent ultrasonic treatment, thereby being convenient for further improving the adhesiveness and the durability of the colloid. The invention solves the problem that the conventional nail-free glue is poor in adhesive force and durability.)

1. The high-viscosity durable nail-free glue comprises, by weight, 2 ~ 4 parts of polyethylene wax, 1 ~ 3 parts of titanium dioxide, 2 ~ 5 parts of sodium benzoate, 3 ~ 7 parts of a plasticizer, 5 ~ 8 parts of a thixotropic agent, 40 ~ 60 parts of a composite colloid base material, and 20 ~ 35 parts of a modification additive.

2. The high-viscosity durable nail-free glue according to claim 1, wherein the preparation method of the composite colloid base material comprises the following steps:

(1) mixing polyethylene glycol, toluene, lactide and stannous octoate according to the mass ratio of 3: 10 ~ 15: 2 ~ 4: 0.03 under the nitrogen atmosphere, keeping the temperature and mixing at 65 ~ 75 ℃, heating to 150 ~ 160 ℃, keeping the temperature and cooling to obtain a reaction material, adding dichloromethane and dodecyl hexaethylene glycol ether according to the mass ratio of 15 ~ 25: 4: 1 into the reaction material, mixing and stirring, adding a reagent accounting for 45 ~ 60% of the mass of the reaction material, centrifuging, collecting a centrifugal substance, washing with water, and drying to obtain a block copolymer;

(2) mixing and stirring the block copolymer, the glycerol solution and the sodium sulfate at the temperature of 30 ~ 45 ℃ according to the mass ratio of 1: 5 ~ 8: 0.03, heating to 55 ~ 70 ℃, adding the pretreated biological glue and the regulator, mixing, shearing and dispersing to obtain bulk materials, performing ultrasonic treatment and dialyzing to obtain the composite colloidal base material.

3. The high-viscosity durable nail-free glue according to claim 2, wherein the reagent in the step (1) is prepared by mixing diethyl ether and petroleum ether according to a volume ratio of 3: 1 ~ 2.

4. The high-viscosity durable nail-free glue according to claim 2, wherein the pretreated biological glue obtained in the step (2) is prepared by mixing lacca, balanus and sodium bentonite according to a mass ratio of 5 ~ 8: 1: 0.01.

5. The high-viscosity durable nail-free glue according to claim 2, wherein the regulator in the step (2) is prepared by mixing calcium acetylacetonate and epoxy resin according to a mass ratio of 1: 4 ~ 8.

6. The high-viscosity durable nail-free glue according to claim 1, wherein the modified additive is prepared by mixing and stirring castor oil, cholesterol and pretreated halloysite at 35 ~ 45 ℃ according to a mass ratio of 7 ~ 13: 2: 4, heating to 60 ~ 75 ℃, preserving heat to obtain a heat treatment material, adding an ethanol solution into the heat treatment material according to a mass ratio of 1: 4 ~ 8, mixing to obtain a diluent, dripping a beta-cyclodextrin aqueous solution into the diluent according to a volume ratio of 6 ~ 10: 1, preserving heat and stirring at 45 ~ 55 ℃, cooling, performing suction filtration, collecting, filtering, crushing, sieving to obtain a sieved material, adding auxiliary materials into the sieved material according to a mass ratio of 8 ~ 14: 1 ~ 3, mixing and grinding to obtain the modified additive.

7. The high-viscosity durable nail-free glue according to claim 6, wherein the pretreated halloysite is prepared by crushing and sieving halloysite, collecting sieved substances, adding zinc stearate according to the mass ratio of 6 ~ 10: 1, mixing and grinding the mixture to obtain a grinding material, performing heat preservation treatment on the grinding material at 120 ~ 130 ℃ and cooling the heat preservation treatment.

8. The high-viscosity durable nail-free glue according to claim 6, wherein the auxiliary material is prepared by mixing calcium stearate and pentaerythritol according to a mass ratio of 1: 2 ~ 5.

9. The high-viscosity durable nail-free glue according to claim 1, wherein the plasticizer is obtained by mixing epoxidized soybean oil and triethyl citrate according to a mass ratio of 3 ~ 7: 1.

10. The high-viscosity durable nail-free glue according to claim 1, wherein the thixotropic agent is prepared by mixing polyvinyl alcohol, white carbon black and attapulgite according to a mass ratio of 1 ~ 3: 1: 5 ~ 8.

Technical Field

The invention belongs to the technical field of adhesive preparation, and particularly relates to a high-viscosity durable nail-free adhesive.

Background

The nail-free glue is a multifunctional building structure strong glue with strong adhesive force. The nail is generally called liquid nail at foreign countries, and is called nail-free glue at home. Nail-free glues are used in many industries, furniture manufacturing: bonding mercury lenses, aluminum edge seals, handles, crystal plates, marble, plate bonding, and the like; decoration industry: various wood lines, door pocket lines, plaster lines, floor tiles, various interior decoration hanging parts, various wallboard projects and the like are bonded and fixed; exhibition display industry: various calligraphy and painting, labels, acrylic, bay, etc. are adhered and fixed. The cabinet door plate industry: bonded grain steel plates, and the like.

The building adhesive can well adhere the same and different building materials together, replaces the original processes of nailing, riveting, welding and the like, greatly saves resources, improves the construction speed, reduces the construction cost and the like. In recent years, the value added range of the building adhesive is far beyond that of other products, the application range of the building adhesive is expanded to various fields such as roads, bridges, subways, culverts, tunnels, dams and the like from the application of single existing buildings such as reinforcement, earthquake resistance and the like, even all newly-built high-speed railway projects are bonded by using a large amount of building structure adhesives, and along with the technical progress, the adhesive is changed to special functional projects such as heat resistance, low temperature resistance, insulation, fast curing, green and environment protection and the like.

Due to the continuous development of the technology of adhesion by adhesives in recent years, the industry and the field of application thereof are also continuously expanding, and are one of the indispensable materials particularly in the building, decoration and industrial fields. Meanwhile, with the personalized demands on decoration and fitment, the rapid improvement of the living standard of people and the rapid development of building material, decoration and advertisement industries, the use of traditional materials such as iron nails, bolts and the like is more and more abandoned, and an adhesive product is selected for substitution. And the advantages of convenient construction of the nail-free glue material and beautiful bonding without nail holes are gradually used by people. That is to say, the nail-free glue has better adhesive property, and avoids the defects of nail hole or punching fixation and the problem of influencing the aesthetic property.

The nail-free glue is generally divided into a water-based glue, a solvent-based glue and a body-based glue, and volatile solvents which comprise aldehydes, benzenes, chlorinated organic solvents and the like and are harmful to human bodies and the environment are often used for convenience of construction and bonding.

The existing nail-free glue mostly adopts solvent-type chloroprene rubber, solvent-type SBS rubber, solvent-type styrene rubber and the like as adhesive materials, although the nail-free glue has a certain gluing effect, the nail-free glue still contains toxic and harmful or low-toxic solvents, the total content of the solvents is more than 10%, and some solvents even reach 50%, and the harm of the solvents to the health of people and the environment is not negligible.

The nail-free glue in the current market has low bonding strength, weak adhesive force and poor durability, and is easy to fall off after being used for a period of time.

Disclosure of Invention

The technical problems to be solved by the invention are as follows: aiming at the problems of poor adhesive force and poor durability of the existing common nail-free glue, the high-viscosity durable nail-free glue is provided.

In order to solve the technical problems, the invention adopts the following technical scheme:

the high-viscosity durable nail-free glue comprises 2 ~ 4 parts of polyethylene wax, 1 ~ 3 parts of titanium dioxide, 2 ~ 5 parts of sodium benzoate, 3 ~ 7 parts of plasticizer, 5 ~ 8 parts of thixotropic agent, 40 ~ 60 parts of composite colloid base material and 20 ~ 35 parts of modified additive.

The preparation method of the composite colloidal base material comprises the following steps:

(1) mixing polyethylene glycol, toluene, lactide and stannous octoate according to the mass ratio of 3: 10 ~ 15: 2 ~ 4: 0.03 under the nitrogen atmosphere, keeping the temperature and mixing at 65 ~ 75 ℃, heating to 150 ~ 160 ℃, keeping the temperature and cooling to obtain a reaction material, adding dichloromethane and dodecyl hexaethylene glycol ether according to the mass ratio of 15 ~ 25: 4: 1 into the reaction material, mixing and stirring, adding a reagent accounting for 45 ~ 60% of the mass of the reaction material, centrifuging, collecting a centrifugal substance, washing with water, and drying to obtain a block copolymer;

(2) mixing and stirring the block copolymer, the glycerol solution and the sodium sulfate at the temperature of 30 ~ 45 ℃ according to the mass ratio of 1: 5 ~ 8: 0.03, heating to 55 ~ 70 ℃, adding the pretreated biological glue and the regulator, mixing, shearing and dispersing to obtain bulk materials, performing ultrasonic treatment and dialyzing to obtain the composite colloidal base material.

And (2) mixing the diethyl ether and the petroleum ether according to the volume ratio of 3: 1 ~ 2 to obtain the reagent in the step (1).

And (3) mixing the pretreated biological glue obtained in the step (2) with shellac, caraway gum and sodium bentonite according to the mass ratio of 5 ~ 8: 1: 0.01 to obtain the pretreated biological glue.

And (3) mixing the regulator in the step (2) with calcium acetylacetonate and epoxy resin according to the mass ratio of 1: 4 ~ 8 to obtain the regulator.

The preparation method of the modified additive comprises the steps of mixing and stirring castor oil, cholesterol and pretreated halloysite at 35 ~ 45 ℃ according to the mass ratio of 7 ~ 13: 2: 4, heating to 60 ~ 75 ℃, preserving heat to obtain a heat treatment material, adding an ethanol solution into the heat treatment material according to the mass ratio of 1: 4 ~ 8 to obtain a diluent, dropping a beta-cyclodextrin aqueous solution into the diluent according to the volume ratio of 6 ~ 10: 1, preserving heat and stirring at 45 ~ 55 ℃, cooling, performing suction filtration, collecting, freezing, crushing and sieving to obtain a filtered substance, adding auxiliary materials into the filtered substance according to the mass ratio of 8 ~ 14: 1 ~ 3, mixing and grinding to obtain the modified additive.

And (3) crushing and sieving the halloysite, collecting sieved substances, adding zinc stearate into the sieved substances according to the mass ratio of 6 ~ 10: 1, mixing and grinding to obtain a grinding material, performing heat preservation treatment on the grinding material at 120 ~ 130 ℃, and cooling to obtain the pretreated halloysite.

And the auxiliary material is prepared by mixing calcium stearate and pentaerythritol according to the mass ratio of 1: 2 ~ 5.

And the plasticizer is obtained by mixing epoxidized soybean oil and triethyl citrate according to the mass ratio of 3 ~ 7: 1.

The thixotropic agent is prepared by mixing polyvinyl alcohol, white carbon black and attapulgite according to the mass ratio of 1 ~ 3: 1: 5 ~ 8.

Compared with other methods, the method has the beneficial technical effects that:

(1) the invention uses polyethylene glycol, lactide and other blending heat treatment to prepare block copolymer, wherein, the added dodecyl hexaethylene glycol can adjust the hydrophilic hydrophobicity, so that the hydrodynamic radius of the mixed micelle is gradually reduced, the micelle structure is gradually presented to a worm-shaped structure, sodium sulfate is added to reduce the solubility of the block polymeric micelle in aqueous solution, the interaction between the micelle and water molecules is weakened, the formation of the micelle is promoted, the added glycerol can strengthen the hydrogen bond network in the liquid phase, and the separation and the stable formation of the block polyether micelle are convenient, in addition, the invention uses shellac, carapace gum and sodium bentonite with active groups to blend and grind, wherein, the amount of the sodium bentonite is less, the shellac and the carapace gum can rapidly expand under the action of water, so that the interior of the colloid is rapidly expanded, and more active sites are exposed, under the action of cavitation effect of subsequent ultrasonic treatment, the materials are stably combined to form a composite colloid base material, so that the adhesiveness and durability of the colloid are further improved;

(2) according to the invention, halloysite with a carbon nanotube structure is crushed and refined, and then is mixed and ground with zinc stearate with a melting point reduced, so that zinc stearate is dispersed among halloysite layers, and is subjected to heat preservation treatment at 120 ~ 130 ℃ to soften and disperse the zinc stearate in the zinc stearate, the arrangement of the carbon nanotubes can be more compact after solidification, the dispersion strength of halloysite is improved, the arrangement of halloysite carbon nanotubes is convenient, and the halloysite carbon nanotubes can be regularly arranged;

(3) the invention prepares the segmented copolymer, and through adjusting the structural state of the segmented copolymer, the segmented copolymer is combined with the biological colloid to form a composite colloid base material with high durability, and zinc stearate is thermally dispersed in the halloysite carbon nanotube to form an organic-inorganic interpenetrating network as a framework combined colloid, so that the use effect of the nail-free adhesive is improved.

Detailed Description

And (3) mixing diethyl ether and petroleum ether according to the volume ratio of 3: 1 ~ 2 to obtain the reagent.

And (3) mixing the shellac, the pot gamboge and the sodium bentonite according to the mass ratio of 5 ~ 8: 1: 0.01 to obtain the pretreated biological glue.

And (3) mixing the calcium acetylacetonate and the epoxy resin according to the mass ratio of 1: 4 ~ 8 to obtain the regulator.

And (3) pretreating halloysite, namely crushing halloysite in a crusher, sieving with a 80-mesh sieve, collecting sieved substances, adding zinc stearate according to the mass ratio of 6 ~ 10 to 1, mixing and grinding for 1 ~ 3h to obtain a grinding material, performing heat preservation treatment on the grinding material at 120 ~ 130 ℃ for 40 ~ 60min, and naturally cooling to room temperature to obtain the pretreated halloysite.

And (3) mixing the auxiliary materials, namely mixing the calcium stearate and the pentaerythritol according to the mass ratio of 1: 2 ~ 5 to obtain the auxiliary materials.

And (3) mixing the epoxidized soybean oil and the triethyl citrate according to the mass ratio of 3 ~ 7: 1 to obtain the plasticizer.

And (3) mixing the thixotropic agent with polyvinyl alcohol, white carbon black and attapulgite according to the mass ratio of 1 ~ 3: 1: 5 ~ 8 to obtain the thixotropic agent.

The preparation method of the composite colloidal base material comprises the following steps:

(1) mixing polyethylene glycol, toluene, lactide and stannous octoate in a reaction kettle according to the mass ratio of 3: 10 ~ 15: 2 ~ 4: 0.03 under the nitrogen atmosphere, keeping the temperature and mixing for 1 ~ 13h at 65 ~ 075 ℃, heating to 150 ~ 2160 ℃, keeping the temperature for 1 ~ 2h, naturally cooling to room temperature to obtain a reaction material, adding dichloromethane and dodecyl hexaethylene glycol ether into the reaction material according to the mass ratio of 15 ~ 25: 4: 1, mixing and stirring for 25 ~ 45min, adding a reagent accounting for 45 ~ 60% by mass of the reaction material, mixing for 30 ~ 45min, transferring to a centrifuge, centrifuging for 12 ~ 20min at 3000 ~ 5000r/min, collecting a centrifuge, washing for 2 ~ 4 times, and drying to obtain a block copolymer;

(2) mixing block copolymer, glycerol solution with volume fraction of 70% and sodium sulfate at 30 ~ 45 ℃ according to the mass ratio of 1: 5 ~ 8: 0.03, magnetically stirring for 30 ~ 55min at 500 ~ 800r/min, heating to 55 ~ 70 ℃ and 70 ℃, adding pretreated biological glue and a regulator for mixing, shearing and dispersing for 10 ~ 15mnin at 2000 ~ 4000r/min, scoring a bulk material, moving to an ultrasonic oscillator, carrying out ultrasonic treatment for 15 ~ 25min at the frequency of 50 ~ 65kHz, and dialyzing for 65 ~ 70h with water to obtain the composite colloid base material.

The preparation method of the modified additive comprises the steps of mixing castor oil, cholesterol and pretreated halloysite at 35 ~ 45 ℃ according to the mass ratio of 7 ~ 13: 2: 4, stirring for 30 ~ 150min at 350 ~ 0550r/min, heating to 60 ~ 275 ℃, preserving heat for 1 ~ 33h to obtain a heat treatment material, adding 70% ethanol solution into the heat treatment material according to the mass ratio of 1: 4 ~ 8, mixing to obtain a diluent, adding 8% beta-cyclodextrin aqueous solution into the diluent according to the volume ratio of 6 ~ 10: 1, controlling the dropping rate to be 4 ~ 8mL/min, preserving heat and stirring for 1 ~ 3h at 45 ~ 55 ℃ after the dropping is completed, naturally cooling to room temperature, carrying out suction filtration, collecting filter cakes, freezing and crushing at-10 ℃, sieving with a 120-mesh sieve to obtain a sieved matter, adding auxiliary materials into a mortar at 45 ~ ℃ according to the mass ratio of 8 ~ 14: 1 ~ 3, grinding for 1 ~ 3h to obtain the modified additive.

The high-viscosity durable nail-free glue comprises, by weight, 2 ~ 4 parts of polyethylene wax, 1 ~ 3 parts of titanium dioxide, 2 ~ 5 parts of sodium benzoate, 3 ~ 7 parts of a plasticizer, 5 ~ 8 parts of a thixotropic agent, 40 ~ 60 parts of a composite colloid base material and 20 ~ 35 parts of a modification additive.