1. The high-temperature-resistant acrylic pressure-sensitive adhesive is characterized by comprising the following raw materials in parts by weight:

2. the high-temperature-resistant acrylic pressure-sensitive adhesive as claimed in claim 1, wherein the phosphogypsum whisker comprises the following raw materials in parts by weight:

3. the high-temperature-resistant acrylic pressure-sensitive adhesive as claimed in claim 2, wherein the solvent-type acrylic pressure-sensitive adhesive is prepared from the following raw materials in parts by mass:

4. the high temperature resistant acrylic pressure sensitive adhesive of claim 1, wherein the whisker modifier is a polyurethane LH3721A adhesive and LH3721B curing agent.

5. The high temperature resistant acrylic pressure sensitive adhesive of claim 2 wherein the whisker turning agent is at least one of citric acid, sodium dodecyl sulfate or magnesium sulfate and the whisker modifier is stearic acid.

6. The high temperature resistant acrylic pressure sensitive adhesive of claim 3 wherein the soft acrylic monomer is at least one of butyl acrylate or isooctyl acrylate, the hard monomer is at least one of vinyl acetate or methyl acrylate, and the functional monomer is at least one of acrylic acid, hydroxyethyl acrylate or glycidyl acrylate.

7. The high temperature resistant acrylic pressure sensitive adhesive of claim 1 wherein the first solvent and the second solvent are both at least one of toluene or ethyl acetate.

8. The high temperature resistant acrylic pressure sensitive adhesive of claim 1 wherein the hardener is an isocyanate.

9. The high temperature resistant acrylic pressure sensitive adhesive of claim 1 wherein the initiator is AIBN.

10. The preparation method of the high temperature resistant acrylic pressure sensitive adhesive according to claim 3 or 6, characterized by comprising the following steps:

(1) adding the phosphogypsum and water into a reaction kettle respectively according to the mass part ratio, adding the crystal whisker transfer agent at a certain temperature and pressure, stirring at a speed of 100-300 r/min, reacting for 2-9 h, then adding the crystal whisker regulator, preserving heat for 1h, neutralizing to be neutral by using saturated lime water, then discharging, spin-drying and dehydrating the phosphogypsum crystal whisker suspension, drying after dehydration to obtain the phosphogypsum crystal whisker, mixing 10 parts of first solvent and crystal whisker modifier, stirring for 10min, adding the mixture into the phosphogypsum crystal whisker for mixing, stirring for 0.5h, drying for 30min at 100 ℃, curing for 7 days at 50 ℃ to obtain the modified phosphogypsum crystal whisker, mixing the modified phosphogypsum crystal whisker with the rest 20 parts of first solvent, and stirring for 10 min;

(2) mixing the second solvent, the soft acrylic monomer, the hard monomer and the functional monomer according to the mass part ratio, and mixing 50 volume percent of the monomersPouring the solution into a container, and introducing N into the container₂Heating to 66-68 ℃ for 0.5-2 h, adding 0.15 part of initiator, reacting for 1-3 h, dripping the residual 50% of monomer mixture into the container, dripping for 1-4 h at 70-72 ℃, adding the residual 0.1 part of initiator while dripping the monomer mixture, keeping the temperature for 2-7 h after all the solution is dripped, cooling to 30 ℃ after the reaction is finished, and discharging;

(3) adding the modified phosphogypsum whiskers obtained in the step (1) into the solvent type acrylic pressure-sensitive adhesive obtained in the step (2) according to the mass part ratio, stirring for 5min, adding a hardening agent, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Background

At present, about 2 hundred million tons of accumulated phosphogypsum in China is added, about 8000 million tons of phosphogypsum is newly added every year along with the development of high-efficiency compound fertilizers, the utilization rate is about 20 percent, and the technical problem to be solved is urgently needed for ecological environment protection and high-value effective utilization of resource-saving phosphogypsum. The whisker is a fibrous single crystal with a fixed cross section shape, a complete appearance, a perfect internal structure and a length-diameter ratio of 5-1000, and the gypsum whisker is a fibrous single crystal of semi-hydrated or anhydrous calcium sulfate and is a novel functional material with excellent performance and low price. The gypsum whisker can be used as a high-value industrial material, has low price, and is widely applied to the fields of paper making, plastics, buildings, coatings and the like. The high added value gypsum whisker integrates the advantages of reinforcing fiber and superfine inorganic filler, and has excellent mechanical property, good compatibility and excellent smoothness.

In addition, the solvent type acrylic pressure-sensitive adhesive has the advantages of high wettability, high drying speed, high water resistance and the like, and is widely applied to aviation, aerospace, automobiles, electronic and electric appliances and daily life due to the excellent performance of the solvent type acrylic pressure-sensitive adhesive. However, the general solvent-based acrylic pressure-sensitive adhesive has poor heat resistance, and has the problems of reduced peel strength and permanent adhesion, and separation and migration of adhesive layers after high-temperature treatment or use at high temperature.

Disclosure of Invention

The first technical problem to be solved by the invention is to provide a high-temperature-resistant acrylic pressure-sensitive adhesive aiming at the prior art, which can avoid the damage of an adhesive layer under the action of high temperature and has better viscosity and lasting viscosity performance under the high temperature.

The second technical problem to be solved by the invention is to provide a preparation method of the high-temperature-resistant acrylic pressure-sensitive adhesive aiming at the prior art.

The technical scheme adopted by the invention for solving the first technical problem is as follows: the high-temperature-resistant acrylic pressure-sensitive adhesive is characterized by comprising the following raw materials in parts by weight:

further, the phosphogypsum whisker comprises the following raw materials in parts by weight:

further, the solvent type acrylic pressure-sensitive adhesive is prepared from the following raw materials in parts by weight:

further, the whisker modifier is polyurethane LH3721A adhesive and LH3721B curing agent.

Further, the whisker crystal modifier is at least one of citric acid, sodium dodecyl sulfate or magnesium sulfate, and the whisker regulator is stearic acid.

Further, the acrylic soft monomer is at least one of butyl acrylate or isooctyl acrylate, the hard monomer is at least one of vinyl acetate or methyl acrylate, and the functional monomer is at least one of acrylic acid, hydroxyethyl acrylate or glycidyl acrylate.

Further, the first solvent and the second solvent are both at least one of toluene or ethyl acetate.

Further, the hardener is an isocyanate.

Further, the initiator is AIBN (azobisisobutyronitrile).

The technical solution adopted to further solve the second technical problem is as follows: the preparation method of the high-temperature-resistant acrylic pressure-sensitive adhesive is characterized by comprising the following steps of:

(1) according to the weight portion ratio, the phosphogypsum and water are respectively added into a reaction kettle, the crystal whisker transfer agent is added under certain temperature and pressure, the stirring speed is 100-300 r/min, after reaction for 2-9 h, the crystal whisker regulator is added, after heat preservation for 1h, the mixture is neutralized to be neutral by saturated lime water, then discharging is carried out, the phosphogypsum crystal whisker suspension is dried by spin drying, and the phosphogypsum crystal whisker is obtained after dehydration and drying.

And mixing 10 parts of first solvent and the whisker modifier, stirring for 10min, adding the mixture into the prepared phosphogypsum whisker, stirring for 0.5h, drying at 100 ℃ for 30min, and curing at 50 ℃ for 7 days to obtain the modified phosphogypsum whisker.

The phosphogypsum whisker is prepared by a hydrothermal method, a water-insoluble substance is formed under the action of stearic acid, the hydration of the hemihydrate gypsum whisker is prevented, a whisker modifier (polyurethane adhesive) can be firmly adsorbed on the surface of the phosphogypsum whisker and can react with-COOH in the stearic acid to form a special protective layer, the surface area of the whisker is increased, and the solvent resistance and the rigidity of the whisker are improved.

(2) Mixing the soft acrylic monomer, the hard monomer and the functional monomer according to the mass part ratio, pouring 50 percent of monomer mixed solution into a container, and introducing N into the container₂And (3) heating for 0.5-2 h, heating to 66-68 ℃, adding 0.15 part of initiator, reacting for 1-3 h, dripping the residual 50% of monomer mixture into the container, dripping for 1-4 h at 70-72 ℃, adding the residual 0.1 part of initiator while dripping the monomer mixture, preserving heat for 2-7 h after all the solution is dripped, and cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of the first solvent according to the mass part ratio, stirring for 10min, adding into the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding the hardener, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Compared with the prior art, the invention has the advantages that: the ardealite whisker is added into the acrylic pressure-sensitive adhesive, can be effectively embedded into the acrylic pressure-sensitive adhesive, improves the interface bonding between the whisker and the acrylic acid, and can react a little on the polyurethane coating part on the surface of the whisker to ensure that the interfaces are connected more firmly.

The high-temperature-resistant acrylic pressure-sensitive adhesive disclosed by the invention has the advantages that the preparation method is simple, the high-temperature-resistant acrylic pressure-sensitive adhesive takes the phosphogypsum whisker as one of main functional raw materials, and the phosphogypsum whisker integrates the properties of fiber and filler.

Detailed Description

The present invention will be described in further detail with reference to examples.

Example 1:

(1) preparing phosphogypsum whiskers: the preparation method comprises the steps of adding 2 parts of phosphogypsum (produced by Jiangsu Yifu science and technology Co., Ltd., the same below) and 16 parts of tap water into a reaction kettle, controlling the reaction temperature to be 155 ℃ and the pressure to be 0.3MPa, adding 0.6 part of sodium dodecyl sulfate and 0.3 part of citric acid, reacting and stirring at 200r/min for 3h, adding 0.72 part of stearic acid, preserving heat for 1h, neutralizing with 0.6 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whiskers into a 200 ℃ drying box for drying for 3h to obtain the phosphogypsum whiskers. Adding 10 parts of ethyl acetate, 0.1 part of polyurethane LH3721A adhesive (Jiangsu Liangfu adhesive Co., Ltd., the same below) and 0.02 part of LH3721B curing agent (Jiangsu Liangfu adhesive Co., Ltd., the same below), stirring for 10min, mixing with 0.1 part of phosphogypsum whisker, stirring for 0.5h, drying at 100 ℃ for 30min, and curing at 50 ℃ for 7 days to obtain the modified phosphogypsum whisker. The diameter of the modified phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: butyl acrylate 175 parts, isooctyl acrylate 97 parts, acrylic acid 14 parts, glycidyl acrylate 1 part, methyl acrylate 13 parts and ethyl acetate 366.6 parts are mixed to form a monomer mixture, and 50% by volume of the monomer is mixedAdding the solution into a four-neck flask, introducing N₂Heating to 66-68 ℃ for 0.5h, adding 0.15 part of AIBN initiator, reacting for 1h, dropwise adding the residual 50% of monomer mixed solution into a four-neck flask, dropwise adding at 70-72 ℃ for 2h, dropwise adding the mixed monomer while supplementing the residual 0.1 part of AIBN initiator, preserving heat for 3h after dropwise adding all the solutions, and cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into 100 parts of the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding 1 part of a hardening agent L-75, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Example 2:

(1) preparing phosphogypsum whiskers: the preparation method is characterized by adopting a hydrothermal method, adding 2 parts of phosphogypsum and 16 parts of tap water into a reaction kettle, controlling the reaction temperature at 155 ℃ and the pressure at 0.3MPa, adding 0.6 part of sodium dodecyl sulfate and 0.3 part of citric acid, stirring at 200r/min for reaction for 3 hours, adding 0.72 part of stearic acid, preserving heat for 1 hour, neutralizing with 0.6 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whisker into a 200 ℃ drying box for drying for 3 hours to obtain the phosphogypsum whisker. Adding 10 parts of ethyl acetate, 0.1 part of polyurethane LH3721A adhesive and 0.02 part of LH3721B curing agent, stirring for 10min, mixing with 0.5 part of phosphogypsum whisker, stirring for 0.5h, drying at 100 ℃ for 30min, and curing at 50 ℃ for 7 days to obtain the modified phosphogypsum whisker. The diameter of the modified phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: 175 parts of butyl acrylate, 97 parts of isooctyl acrylate, 14 parts of acrylic acid, 1 part of glycidyl acrylate, 13 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50 volume percent of the monomer mixed solution is added into a four-neck flask, and N is introduced into the four-neck flask₂Heating to 66-68 ℃ for 0.5h, adding 0.15 part of AIBN initiator, reacting for 1h, and adding the monomer with the volume of 50% of that of the restAnd dropwise adding the mixed solution into a four-neck flask, dropwise adding at 70-72 ℃ for 2h, adding the rest 0.1 part of AIBN initiator while dropwise adding the mixed monomer, preserving heat for 3h after dropwise adding all the solutions, cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into 100 parts of the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding 1 part of a hardening agent L-75, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Example 3:

(1) preparing phosphogypsum whiskers: the preparation method is characterized by adopting a hydrothermal method, adding 2 parts of phosphogypsum and 16 parts of tap water into a reaction kettle, controlling the reaction temperature at 155 ℃ and the pressure at 0.3MPa, adding 0.6 part of sodium dodecyl sulfate and 0.3 part of citric acid, stirring at 200r/min for reaction for 3 hours, adding 0.72 part of stearic acid, preserving heat for 1 hour, neutralizing with 0.6 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whisker into a 200 ℃ drying box for drying for 3 hours to obtain the phosphogypsum whisker. Adding 10 parts of ethyl acetate, 0.2 part of polyurethane LH3721A adhesive and 0.02 part of LH3721B curing agent, stirring for 10min, mixing with 1.0 part of phosphogypsum whisker, stirring for 0.5h, drying for 30min at 100 ℃, and curing for 7 days at 50 ℃ to obtain the modified phosphogypsum whisker. The diameter of the modified phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: 175 parts of butyl acrylate, 97 parts of isooctyl acrylate, 14 parts of acrylic acid, 1 part of glycidyl acrylate, 13 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50 volume percent of the monomer mixed solution is added into a four-neck flask, and N is introduced into the four-neck flask₂Heating to 66-68 ℃ for 0.5h, adding 0.15 part of AIBN initiator, reacting for 1h, dropwise adding the residual 50% of monomer mixed solution into a four-neck flask, dropwise adding at 70-72 ℃ for 2h, adding the residual 0.1 part of AIBN initiator while dropwise adding the mixed monomer, and finishing dropwise adding all the solutionsThen preserving heat for 3h, cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into 100 parts of the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding 1 part of a hardening agent L-75, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Example 4:

(1) preparing phosphogypsum whiskers: the preparation method is characterized by adopting a hydrothermal method, adding 2 parts of phosphogypsum and 16 parts of tap water into a reaction kettle, controlling the reaction temperature at 155 ℃ and the pressure at 0.3MPa, adding 0.6 part of sodium dodecyl sulfate and 0.3 part of citric acid, stirring at 200r/min for reaction for 3 hours, adding 0.72 part of stearic acid, preserving heat for 1 hour, neutralizing with 0.6 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whisker into a 200 ℃ drying box for drying for 3 hours to obtain the phosphogypsum whisker. Adding 10 parts of ethyl acetate, 0.2 part of polyurethane LH3721A adhesive and 0.02 part of LH3721B curing agent, stirring for 10min, mixing with 1.5 parts of phosphogypsum whisker, stirring for 0.5h, drying for 30min at 100 ℃, and curing for 7 days at 50 ℃ to obtain the modified phosphogypsum whisker. The diameter of the modified phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: 175 parts of butyl acrylate, 97 parts of isooctyl acrylate, 14 parts of acrylic acid, 1 part of glycidyl acrylate, 13 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50 volume percent of the monomer mixed solution is added into a four-neck flask, and N is introduced into the four-neck flask₂Heating to 66-68 ℃ for 0.5h, adding 0.15 part of AIBN initiator, reacting for 1h, dropwise adding the residual 50% of monomer mixed solution into a four-neck flask, dropwise adding at 70-72 ℃ for 2h, dropwise adding the mixed monomer while supplementing the residual 0.1 part of AIBN initiator, preserving heat for 3h after dropwise adding all the solutions, and cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into 100 parts of the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding 1 part of a hardening agent L-75, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Example 5:

(1) preparing phosphogypsum whiskers: the preparation method is characterized by adopting a hydrothermal method, adding 2 parts of phosphogypsum and 16 parts of tap water into a reaction kettle, controlling the reaction temperature at 155 ℃ and the pressure at 0.3MPa, adding 0.6 part of sodium dodecyl sulfate and 0.3 part of citric acid, stirring at 200r/min for reaction for 3 hours, adding 0.72 part of stearic acid, preserving heat for 1 hour, neutralizing with 0.6 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whisker into a 200 ℃ drying box for drying for 3 hours to obtain the phosphogypsum whisker. Adding 10 parts of ethyl acetate, 0.2 part of polyurethane LH3721A adhesive and 0.02 part of LH3721B curing agent, stirring for 10min, mixing with 2.0 parts of phosphogypsum whisker, stirring for 0.5h, drying at 100 ℃ for 30min, and curing at 50 ℃ for 7 days to obtain the modified phosphogypsum whisker. The diameter of the modified phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: 175 parts of butyl acrylate, 97 parts of isooctyl acrylate, 14 parts of acrylic acid, 1 part of glycidyl acrylate, 13 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50 volume percent of the monomer mixed solution is added into a four-neck flask, and N is introduced into the four-neck flask₂Heating to 66-68 ℃ for 0.5h, adding 0.15 part of AIBN initiator, reacting for 1h, dropwise adding the residual 50% of monomer mixed solution into a four-neck flask, dropwise adding at 70-72 ℃ for 2h, dropwise adding the mixed monomer while supplementing the residual 0.1 part of AIBN initiator, preserving heat for 3h after dropwise adding all the solutions, and cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into 100 parts of the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding 1 part of a hardening agent L-75, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Example 6:

(1) preparing phosphogypsum whiskers: the preparation method is characterized by adopting a hydrothermal method, adding 2 parts of phosphogypsum and 16 parts of tap water into a reaction kettle, controlling the reaction temperature at 155 ℃ and the pressure at 0.3MPa, adding 0.6 part of sodium dodecyl sulfate and 0.3 part of citric acid, stirring at 200r/min for reaction for 3 hours, adding 0.72 part of stearic acid, preserving heat for 1 hour, neutralizing with 0.6 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whisker into a 200 ℃ drying box for drying for 3 hours to obtain the phosphogypsum whisker. Adding 10 parts of ethyl acetate, 0.3 part of polyurethane LH3721A adhesive and 0.06 part of LH3721B curing agent, stirring for 10min, mixing with 2.5 parts of phosphogypsum whisker, stirring for 0.5h, drying for 30min at 100 ℃, and curing for 7 days at 50 ℃ to obtain the modified phosphogypsum whisker. The diameter of the modified phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: 175 parts of butyl acrylate, 97 parts of isooctyl acrylate, 14 parts of acrylic acid, 1 part of glycidyl acrylate, 13 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50 volume percent of the monomer mixed solution is added into a four-neck flask, and N is introduced into the four-neck flask₂Heating to 66-68 ℃ for 0.5h, adding 0.15 part of AIBN initiator, reacting for 1h, dropwise adding the residual 50% of monomer mixed solution into a four-neck flask, dropwise adding at 70-72 ℃ for 2h, dropwise adding the mixed monomer while supplementing the residual 0.1 part of AIBN initiator, preserving heat for 3h after dropwise adding all the solutions, and cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into 100 parts of the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding 1 part of a hardening agent L-75, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Example 7:

(1) preparing phosphogypsum whiskers: the preparation method comprises the steps of adding 1 part of phosphogypsum and 6 parts of tap water into a reaction kettle, controlling the reaction temperature to be 155 ℃ and the pressure to be 0.3MPa, adding 0.6 part of sodium dodecyl sulfate and 0.4 part of citric acid, stirring at 200r/min for reaction, reacting for 3 hours, adding 0.1 part of stearic acid, preserving heat for 1 hour, neutralizing with 0.5 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whisker into a 200 ℃ drying box for drying for 3 hours to obtain the phosphogypsum whisker. Adding 10 parts of ethyl acetate, 0.2 part of polyurethane LH3721A adhesive and 0.02 part of LH3721B curing agent, stirring for 10min, mixing with 1.5 parts of phosphogypsum whisker, stirring for 0.5h, drying for 30min at 100 ℃, and curing for 7 days at 50 ℃ to obtain the modified phosphogypsum whisker. The diameter of the modified phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: 175 parts of butyl acrylate, 97 parts of isooctyl acrylate, 14 parts of acrylic acid, 1 part of glycidyl acrylate, 13 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50 volume percent of the monomer mixed solution is added into a four-neck flask, and N is introduced into the four-neck flask₂The time is 0.5h, the temperature is raised to 66-68 ℃, 0.15 part of AIBN initiator is added, after 1h of reaction, the residual 50% volume of the monomer mixed solution is dripped into a four-mouth flask, after 2h of dripping at 70-72 ℃, the residual 0.1 part of AIBN initiator is replenished while dripping the mixed monomer, after the dripping of all the solutions is finished, the temperature is maintained for 3h, and after the reaction is finished, the solution is cooled to 30 ℃ for discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into 100 parts of the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding 1 part of a hardening agent L-75, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Example 8:

(1) preparing phosphogypsum whiskers: the preparation method comprises the steps of adding 5 parts of phosphogypsum and 13 parts of tap water into a reaction kettle, controlling the reaction temperature to be 155 ℃ and the pressure to be 0.3MPa, adding 0.2 part of sodium dodecyl sulfate and 0.3 part of citric acid, stirring at 200r/min for reaction, reacting for 3 hours, adding 0.5 part of stearic acid, preserving heat for 1 hour, neutralizing with 0.1 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whisker into a 200 ℃ drying box for drying for 3 hours to obtain the phosphogypsum whisker. Adding 10 parts of ethyl acetate, 0.2 part of polyurethane LH3721A adhesive and 0.02 part of LH3721B curing agent, stirring for 10min, mixing with 1.5 parts of phosphogypsum whisker, stirring for 0.5h, drying for 30min at 100 ℃, and curing for 7 days at 50 ℃ to obtain the modified phosphogypsum whisker. The diameter of the modified phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: 175 parts of butyl acrylate, 97 parts of isooctyl acrylate, 14 parts of acrylic acid, 1 part of glycidyl acrylate, 13 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50 volume percent of the monomer mixed solution is added into a four-neck flask, and N is introduced into the four-neck flask₂Heating to 66-68 ℃ for 0.5h, adding 0.15 part of AIBN initiator, reacting for 1h, dropwise adding the residual 50% of monomer mixed solution into a four-neck flask, dropwise adding at 70-72 ℃ for 2h, dropwise adding the mixed monomer while supplementing the residual 0.1 part of AIBN initiator, preserving heat for 3h after dropwise adding all the solutions, and cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into 100 parts of the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding 1 part of a hardening agent L-75, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Example 9:

(1) preparing phosphogypsum whiskers: the preparation method is characterized by adopting a hydrothermal method, adding 10 parts of phosphogypsum and 20 parts of tap water into a reaction kettle, controlling the reaction temperature at 155 ℃ and the pressure at 0.3MPa, adding 0.1 part of sodium dodecyl sulfate, stirring at 200r/min for 3h, adding 1.0 part of stearic acid, preserving heat for 1h, neutralizing with 1.0 part of saturated lime water after the reaction is finished, discharging, dewatering the phosphogypsum whisker suspension in a spin dryer, and drying the dewatered whisker in a drying oven at 200 ℃ for 3h to obtain the phosphogypsum whisker. Adding 10 parts of ethyl acetate, 0.2 part of polyurethane LH3721A adhesive and 0.02 part of LH3721B curing agent, stirring for 10min, mixing with 1.5 parts of phosphogypsum whisker, stirring for 0.5h, drying for 30min at 100 ℃, and curing for 7 days at 50 ℃ to obtain the modified phosphogypsum whisker. The diameter of the modified phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: 175 parts of butyl acrylate, 97 parts of isooctyl acrylate, 14 parts of acrylic acid, 1 part of glycidyl acrylate, 13 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50 volume percent of the monomer mixed solution is added into a four-neck flask, and N is introduced into the four-neck flask₂Heating to 66-68 ℃ for 0.5h, adding 0.15 part of AIBN initiator, reacting for 1h, dropwise adding the residual 50% of monomer mixed solution into a four-neck flask, dropwise adding at 70-72 ℃ for 2h, dropwise adding the mixed monomer while supplementing the residual 0.1 part of AIBN initiator, preserving heat for 3h after dropwise adding all the solutions, and cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into 100 parts of the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding 1 part of a hardening agent L-75, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Example 10:

(1) preparing phosphogypsum whiskers: the preparation method is characterized by adopting a hydrothermal method, adding 2 parts of phosphogypsum and 16 parts of tap water into a reaction kettle, controlling the reaction temperature at 155 ℃ and the pressure at 0.3MPa, adding 0.6 part of sodium dodecyl sulfate and 0.3 part of citric acid, stirring at 200r/min for reaction for 3 hours, adding 0.72 part of stearic acid, preserving heat for 1 hour, neutralizing with 0.6 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whisker into a 200 ℃ drying box for drying for 3 hours to obtain the phosphogypsum whisker. Adding 10 parts of ethyl acetate, 0.2 part of polyurethane LH3721A adhesive and 0.02 part of LH3721B curing agent, stirring for 10min, mixing with 1.5 parts of phosphogypsum whisker, stirring for 0.5h, drying for 30min at 100 ℃, and curing for 7 days at 50 ℃ to obtain the modified phosphogypsum whisker. The diameter of the modified phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: 252 parts of butyl acrylate, 10 parts of acrylic acid, 10 parts of glycidyl acrylate, 5 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50% of the monomer mixed solution is added into a four-neck flask, and N is introduced₂Heating to 66-68 ℃ for 0.5h, adding 0.15 part of AIBN initiator, reacting for 1h, dropwise adding the residual 50% of monomer mixed solution into a four-neck flask, dropwise adding at 70-72 ℃ for 2h, dropwise adding the mixed monomer while supplementing the residual 0.1 part of AIBN initiator, preserving heat for 3h after dropwise adding all the solutions, and cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into 100 parts of the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding 1 part of a hardening agent L-75, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Example 11:

(1) preparing phosphogypsum whiskers: the preparation method is characterized by adopting a hydrothermal method, adding 2 parts of phosphogypsum and 16 parts of tap water into a reaction kettle, controlling the reaction temperature at 155 ℃ and the pressure at 0.3MPa, adding 0.6 part of sodium dodecyl sulfate and 0.3 part of citric acid, stirring at 200r/min for reaction for 3 hours, adding 0.72 part of stearic acid, preserving heat for 1 hour, neutralizing with 0.6 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whisker into a 200 ℃ drying box for drying for 3 hours to obtain the phosphogypsum whisker. Adding 10 parts of ethyl acetate, 0.2 part of polyurethane LH3721A adhesive and 0.02 part of LH3721B curing agent, stirring for 10min, mixing with 1.5 parts of phosphogypsum whisker, stirring for 0.5h, drying for 30min at 100 ℃, and curing for 7 days at 50 ℃ to obtain the modified phosphogypsum whisker. The diameter of the modified phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: 195 parts of butyl acrylate, 97 parts of isooctyl acrylate, 9 parts of acrylic acid, 8 parts of hydroxyethyl acrylate, 2 parts of glycidyl acrylate, 10 parts of vinyl acetate, 10 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50 volume percent of the monomer mixed solution is added into a four-neck flask, and N is introduced into the four-neck flask₂Heating to 66-68 ℃ for 0.5h, adding 0.15 part of AIBN initiator, reacting for 1h, dropwise adding the residual 50% of monomer mixed solution into a four-neck flask, dropwise adding at 70-72 ℃ for 2h, dropwise adding the mixed monomer while supplementing the residual 0.1 part of AIBN initiator, preserving heat for 3h after dropwise adding all the solutions, and cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into 100 parts of the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding 1 part of a hardening agent L-75, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Example 12:

(1) preparing phosphogypsum whiskers: the preparation method is characterized by adopting a hydrothermal method, adding 2 parts of phosphogypsum and 16 parts of tap water into a reaction kettle, controlling the reaction temperature at 155 ℃ and the pressure at 0.3MPa, adding 0.6 part of sodium dodecyl sulfate and 0.3 part of citric acid, stirring at 200r/min for reaction for 3 hours, adding 0.72 part of stearic acid, preserving heat for 1 hour, neutralizing with 0.6 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whisker into a 200 ℃ drying box for drying for 3 hours to obtain the phosphogypsum whisker. Adding 10 parts of ethyl acetate, 0.2 part of polyurethane LH3721A adhesive and 0.02 part of LH3721B curing agent, stirring for 10min, mixing with 1.5 parts of phosphogypsum whisker, stirring for 0.5h, drying for 30min at 100 ℃, and curing for 7 days at 50 ℃ to obtain the modified phosphogypsum whisker. The diameter of the modified phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: mixing 262 parts of butyl acrylate, 14 parts of acrylic acid, 12 parts of methyl acrylate and 366.6 parts of ethyl acetate to form a monomer mixed solution, adding 50% by volume of the monomer mixed solution into a four-neck flask, introducing N₂Heating to 66-68 ℃ for 0.5h, adding 0.15 part of AIBN initiator, reacting for 1h, dropwise adding the residual 50% of monomer mixed solution into a four-neck flask, dropwise adding at 70-72 ℃ for 2h, dropwise adding the mixed monomer while supplementing the residual 0.1 part of AIBN initiator, preserving heat for 3h after dropwise adding all the solutions, and cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into 100 parts of the solvent type acrylic pressure-sensitive adhesive obtained in the step (2), stirring for 5min, adding 1 part of a hardening agent L-75, and stirring for 5min to obtain the required high-temperature-resistant acrylic pressure-sensitive adhesive.

Comparative example 1:

preparation of a solvent type acrylic pressure-sensitive adhesive: 175 parts of butyl acrylate, 97 parts of isooctyl acrylate, 14 parts of acrylic acid, 1 part of glycidyl acrylate, 13 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50 volume percent of the monomer mixed solution is taken out and added into a four-neck flask, and N is introduced into the four-neck flask₂And (3) heating for 0.5h to 66-68 ℃, adding 0.15 part of AIBN for initiation, dropping the residual 50% of the volume of the monomer mixture into a four-neck flask after 1h of initiation, dropping the monomer mixture at 70-72 ℃ for 2h, adding the residual 0.1 part of AIBN while dropping the monomer mixture, preserving heat for 3h after dropping, reacting for 6h, cooling to 30 ℃ after the reaction is finished, and discharging.

Preparation of acrylic pressure-sensitive adhesive: and adding 1 part of hardening agent L-75 into 100 parts of solvent type acrylic pressure-sensitive adhesive, and stirring for 5min to obtain the acrylic pressure-sensitive adhesive.

Comparative example 2:

(1) preparing phosphogypsum whiskers: the preparation method comprises the steps of adding 2 parts of phosphogypsum and 16 parts of tap water into a reaction kettle, controlling the reaction temperature to be 155 ℃ and the pressure to be 0.3MPa, adding 0.6 part of sodium dodecyl sulfate and 0.3 part of citric acid, stirring the reaction kettle at 200r/min, reacting for 3 hours, adding 0.72 part of stearic acid, preserving heat for 1 hour, neutralizing with 0.6 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whisker into a 200 ℃ drying box for drying for 3 hours to obtain the phosphogypsum whisker. Firstly, 10 parts of ethyl acetate, 0.1 part of polyurethane LH3721A adhesive and 0.02 part of LH3721B curing agent are added, stirred for 10min, mixed with 0.08 part of phosphogypsum whisker obtained in the step, stirred for 0.5h, dried for 30min at 100 ℃, and aged for 7 days at 50 ℃. The diameter of the phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: 175 parts of butyl acrylate, 97 parts of isooctyl acrylate, 14 parts of acrylic acid, 1 part of glycidyl acrylate, 13 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50 volume percent of the monomer mixed solution is added into a four-neck flask, and N is introduced into the four-neck flask₂And (3) heating for 0.5h to 66-68 ℃, adding 0.15 part of AIBN for initiation, dropping the residual 50% of the monomer mixture into a four-neck flask after 1h of initiation, dropping the monomer mixture at 70-72 ℃ for 2h, adding the residual 0.1 part of AIBN while dropping the monomer mixture, preserving heat for 3h after dropping, reacting for 6h, cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into the 100 parts of solvent type acrylic pressure-sensitive adhesive, stirring for 5min, adding 1 part of hardener L-75, and stirring for 5min to obtain the acrylic pressure-sensitive adhesive.

Comparative example 3:

(1) preparing phosphogypsum whiskers: the preparation method comprises the steps of adding 2 parts of phosphogypsum and 16 parts of tap water into a reaction kettle, controlling the reaction temperature to be 155 ℃ and the pressure to be 0.3MPa, adding 0.6 part of sodium dodecyl sulfate and 0.3 part of citric acid, stirring the reaction kettle at 200r/min, reacting for 3 hours, adding 0.72 part of stearic acid, preserving heat for 1 hour, neutralizing with 0.6 part of saturated lime water after the reaction is finished, discharging, putting the phosphogypsum whisker suspension into a spin dryer for dehydration, and putting the dehydrated whisker into a 200 ℃ drying box for drying for 3 hours to obtain the phosphogypsum whisker. Firstly, 10 parts of ethyl acetate, 0.3 part of polyurethane LH3721A adhesive and 0.02 part of LH3721B curing agent are added, stirred for 10min, mixed with 4.0 parts of phosphogypsum whisker obtained in the step, stirred for 0.5h, dried for 30min at 100 ℃, and aged for 7 days at 50 ℃. The diameter of the phosphogypsum whisker prepared by the embodiment is 2 microns, the length is 100 microns, and the whiteness is more than or equal to 90%.

(2) Preparation of a solvent type acrylic pressure-sensitive adhesive: 175 parts of butyl acrylate, 97 parts of isooctyl acrylate, 14 parts of acrylic acid, 1 part of glycidyl acrylate, 13 parts of methyl acrylate and 366.6 parts of ethyl acetate are mixed to form a monomer mixed solution, 50 volume percent of the monomer mixed solution is added into a four-neck flask, and N is introduced into the four-neck flask₂And (3) heating for 0.5h to 66-68 ℃, adding 0.15 part of AIBN for initiation, dropping the residual 50% of the monomer mixture into a four-neck flask after 1h of initiation, dropping the monomer mixture at 70-72 ℃ for 2h, adding the residual 0.1 part of AIBN while dropping the monomer mixture, preserving heat for 3h after dropping, reacting for 6h, cooling to 30 ℃ after the reaction is finished, and discharging.

(3) Preparing high-temperature-resistant acrylic pressure-sensitive adhesive: and (2) mixing the modified phosphogypsum whisker obtained in the step (1) with the rest 20 parts of ethyl acetate, stirring for 10min, adding into the 100 parts of solvent type acrylic pressure-sensitive adhesive, stirring for 5min, adding 1 part of hardener L-75, and stirring for 5min to obtain the acrylic pressure-sensitive adhesive.

Performance evaluation:

(1)180 ° peel strength test: refer to GB/T2792-2014.

(2) And (3) testing initial adhesion: refer to GB/T4852-2002.

(3) High temperature of 120 ℃ for constant viscosity: placing a sample at the center of one end of a test steel plate, uniformly sticking the adhesive tape sample in an area of 2.5cm multiplied by 2.5cm, placing another test plate below the sample, aligning with the tail end of the test plate, sticking the rest part (2.5cm multiplied by 4.5cm area) of the sample on the other test plate, pressing the sample for 3 times in the length direction of the sample at the speed of (10 +/-0.5) mm/s by using the mass (2000 +/-100) g of a compression roller under the condition of not applying pressure, hanging (1000 +/-100) g of a weight under the other test plate after placing the test plate at the temperature of 120 ℃ for 20min, and recording the time for completely separating the sample from the test plate or the creep distance of the sample on the test plate.

(4) Whether residual glue exists at 120 ℃: a sample (2.5 cm. times.10 cm) was attached to a stainless steel plate, and the sample was pressed back 3 times at a speed of (10. + -. 0.5) mm/s with a weight of a press roll (2000. + -.100 g) in the longitudinal direction of the sample, left at 120 ℃ for 7 days, and then the tape was peeled off from the stainless steel plate to observe whether or not the stainless steel plate had residual adhesive.

The performance test results are shown in table 1, and it can be known from table 1 that the addition of a proper amount of modified phosphogypsum whiskers can not only improve the initial adhesion of the acrylic pressure-sensitive adhesive, but also improve the peel strength and elongation of the acrylic pressure-sensitive adhesive, and still have higher adhesive property and cohesive force at 120 ℃, and excessive modified phosphogypsum whiskers are not beneficial to the initial adhesion property and high temperature resistance of the high-temperature-resistant acrylic adhesive.

The working principle of the invention is as follows:

the phosphogypsum is prepared by a hydrothermal method, water-insoluble substances are formed under the action of stearic acid to prevent hydration of the semi-hydrated gypsum whiskers, a polyurethane adhesive can be firmly adsorbed on the surfaces of the gypsum whiskers and can react with-COOH in the stearic acid to form a special protective layer, the surface area of the whiskers is increased, the solvent resistance and rigidity of the whiskers are improved, the modified phosphogypsum whiskers are obtained, the modified phosphogypsum whiskers are added into acrylic pressure-sensitive adhesive and can be effectively embedded into the acrylic pressure-sensitive adhesive to improve the interface bonding between the phosphorus whiskers and acrylic acid, a polyurethane coating part on the surfaces of the whiskers can also react a small amount, the interfaces are firmly linked, the phosphogypsum whiskers can be used as fibers to play a role in bridging, when the pressure-sensitive adhesive is subjected to external force, a part of the external force can be transmitted out to play a role in buffering, and even the connection between the interiors is strengthened, thereby improving the cohesive force, the toughness and the bonding strength of the acrylic acid, and particularly under the action of high temperature, the gypsum whiskers and the part of the acrylic acid in the molecular chain network structure are mutually staggered to effectively slow down the peristalsis capability.

TABLE 1 Performance test data for each of the examples and comparative examples