CN113801615B - Dynamically crosslinked SBS hot-melt pressure-sensitive adhesive and preparation method thereof - Google Patents
Dynamically crosslinked SBS hot-melt pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a dynamically crosslinked SBS hot-melt pressure-sensitive adhesive and a preparation method thereof, belonging to the technical field of adhesives. Comprises the following raw materials: SBS thermoplastic elastomer, antioxidant, ultraviolet light initiator and phenylboronic acid ester dynamic cross-linking agent. The phenylboronic acid ester dynamic cross-linking agent participates in the construction of the SBS hot-melt pressure-sensitive adhesive cross-linking network through ultraviolet irradiation, so that the softening temperature of the SBS hot-melt pressure-sensitive adhesive is increased, and the heat resistance of the pressure-sensitive adhesive is improved. And due to the formation of a dynamic cross-linked network, the average molecular weight of the SBS hot-melt pressure-sensitive adhesive is increased, and the bulk viscosity and the cohesive strength of the pressure-sensitive adhesive are obviously improved. In addition, the phenylboronate covalent bond has excellent ester exchange capacity, a formed crosslinking network has dynamic characteristics, and the phenylboronate covalent bond is broken and recombined under a high-temperature condition, so that the crosslinking material is endowed with repeatable adhesion performance, and the practicability of the material is improved.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a dynamically crosslinked SBS hot-melt pressure-sensitive adhesive and a preparation method thereof.
Background
The hot melt pressure sensitive adhesive is a self-adhesive substance, can be coated in a molten state, can be bonded by applying pressure after being cooled and solidified, and can be widely applied to the fields of packaging, binding, heat sealing, pressure sensitive and the like. The hot-melt pressure-sensitive adhesive mainly comprises a high molecular polymer, a tackifier, an additive and the like. The SBS thermoplastic elastomer is a common adhesive high molecular polymer. The styrene-butadiene rubber adhesive not only has the thermoplasticity of styrene, but also has the flexibility and resilience of butadiene, can be compatible with various polymers, plays a skeleton role when used in an adhesive, and provides the elasticity and cohesive strength of a colloid. The SBS soft butadiene (PB) segment has high unsaturation, the performance of the adhesive can be changed by chemical crosslinking formed by unsaturated double bonds, but due to the unsaturation of the PB segment, the oxidation resistance and the ultraviolet resistance of the SBS-based hot melt adhesive at normal temperature are poor, the performance of the hot melt adhesive is rapidly reduced, and the service life is shortened. In addition, most SBS hot melt pressure sensitive adhesives are thermoplastic hot melt adhesives physically crosslinked by styrene, and the problems of low softening point, poor heat resistance, weak cohesive strength, degumming among rubbers due to external force and the like exist in the using process. Greatly limits the application range of SBS hot melt pressure sensitive adhesive.
In some of the disclosed SBS hot melt pressure sensitive adhesives, the improvement is generally achieved by adding polar tackifying resin, the method is simple to operate, but the introduction of the tackifying resin influences the cohesive strength of the adhesive, so the improvement effect is limited. For example, the Vicat softening point of the adhesive based on SBS and PS is 60-70 ℃, and the tensile shear strength of the adhesive is 0.75-0.98 MPa like the epoxy segmented copolymer adhesive and the preparation method thereof, so that the use requirement of the hot melt adhesive can not be met.
Disclosure of Invention
In order to solve the problems of low softening point, poor heat resistance and low cohesive strength of the SBS hot-melt pressure-sensitive adhesive in the current stage, and simultaneously achieve the purposes that the SBS hot-melt pressure-sensitive adhesive can be repeatedly bonded after dynamic crosslinking and the practicability of the SBS hot-melt pressure-sensitive adhesive is improved, the invention provides the SBS hot-melt pressure-sensitive adhesive subjected to dynamic crosslinking, and on the other hand, the invention provides a preparation method of the SBS hot-melt pressure-sensitive adhesive subjected to dynamic crosslinking.
A dynamically crosslinked SBS hot-melt pressure-sensitive adhesive is prepared from the following raw materials in parts by weight:
100 portions of SBS thermoplastic elastomer, 0.3 portion of antioxidant, 0.5 portion of ultraviolet initiator and 3 to 10 portions of phenylboronic acid ester dynamic cross-linking agent,
the content of styrene in the SBS thermoplastic elastomer is 28-31%;
the antioxidant is prepared by mixing tetra [ [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris [2, 4-di-tert-butylphenyl ] phosphite ester according to the mass ratio of 3: 1;
the ultraviolet initiator is 2, 2-dimethoxy-2-phenylacetophenone;
the phenylboronic acid ester dynamic cross-linking agent is a white solid, wherein the molar ratio of 1, 4-phenylboronic acid to 1-thioglycerol is 1: 2;
the SBS hot-melt pressure-sensitive adhesive is a white sheet, the shear tensile strength is higher than 2.55MPa, and the shear failure temperature is higher than 70 ℃; the shear tensile strength and the shear failure temperature recovery rate of the SBS hot-melt pressure-sensitive adhesive after re-bonding are both higher than 90%.
The re-bonding is to re-bond the waste stainless steel sheet on a flat vulcanizing machine after the stainless steel sheet bonded by the SBS hot-melt pressure-sensitive adhesive which is used is cut and stretched to lose efficacy, wherein the bonding temperature is 180 ℃, the pressure is 3MPa, and the bonding time is 20 min.
The preparation operation steps of the dynamically crosslinked SBS hot melt pressure sensitive adhesive are as follows:
(1) preparation of phenylboronic acid ester dynamic cross-linking agent
Dissolving 1, 4-phenyl diboronic acid and 1-thioglycerol in 15 times of tetrahydrofuran by mass, wherein the molar ratio of the 1, 4-phenyl diboronic acid to the 1-thioglycerol is 1: 2; adding anhydrous magnesium sulfate, wherein the mass ratio of the anhydrous magnesium sulfate to the tetrahydrofuran is 1: 4; reacting for 24 hours under the condition of nitrogen protection and 30 ℃, filtering to obtain a liquid mixture, and performing rotary evaporation to remove 80% of tetrahydrofuran to obtain a concentrated phenylboronic acid ester dynamic cross-linking agent solution; washing and precipitating for three times by using n-hexane with the mass being 50 times that of the active component to obtain a phenylboronic acid ester dynamic cross-linking agent, wherein the phenylboronic acid ester dynamic cross-linking agent is a white solid;
(2) preparation of the mixture
Taking 100 parts of SBS thermoplastic elastomer, 0.3 part of antioxidant, 0.5 part of ultraviolet initiator and 3-10 parts of phenylboronic acid ester dynamic cross-linking agent according to the formula; firstly, coating a roll with SBS thermoplastic elastomer, then adding an antioxidant, an ultraviolet light initiator and a phenylboronic acid ester dynamic cross-linking agent in sequence for mixing to obtain a mixture;
(3) preparation of dynamically crosslinked SBS hot-melt pressure-sensitive adhesive
Pouring the mixture into a mold with the volume of 100mm multiplied by 1mm, and forming on a flat vulcanizing machine, wherein the mold temperature is 180 ℃, the pressure is 5MPa, and the hot pressing time is 20-30 min; irradiating the molded sample under a low-pressure mercury lamp in a closed environment; obtaining the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive.
The preparation operating conditions are further defined as follows:
in the step (2), the temperature of a front roller and the temperature of a rear roller of the open mill are both 160 ℃, and the mixing time is 30-40 min.
In the step (3), the molding conditions are as follows: the temperature of the die is 180 ℃, the pressure is 5MPa, and the hot pressing time is 20-30 min; irradiation conditions of a low-pressure mercury lamp: the power of the low-pressure mercury lamp is 48W, the distance between the low-pressure mercury lamp and the surface of the sample is 10 cm, and the irradiation time is 20-30 min.
Compared with the prior art, the beneficial technical effects of the invention are embodied in the following aspects:
(1) in the preparation process, the phenylboronic acid ester dynamic cross-linking agent participates in the construction of the SBS hot-melt pressure-sensitive adhesive cross-linking network through ultraviolet irradiation, so that the softening temperature of the SBS hot-melt pressure-sensitive adhesive is increased, and the heat resistance of the pressure-sensitive adhesive is improved. And due to the formation of a dynamic cross-linked network, the average molecular weight of the SBS hot-melt pressure-sensitive adhesive is increased, the bulk viscosity and the cohesive strength of the pressure-sensitive adhesive are obviously improved, and the SBS hot-melt pressure-sensitive adhesive has higher mechanical properties and bonding strength.
(2) The invention relates to a dynamically crosslinked SBS hot-melt pressure-sensitive adhesive which takes phenylboronic acid ester with dynamic characteristics as a crosslinking agent. Chemical equation of phenylboronate:
under the condition of ensuring that the crosslinking density is not changed, the phenylboronic acid ester dynamic covalent bond can be reversibly broken and recombined at a higher temperature. The pressure sensitive adhesive shows a gradual viscosity change similar to Arrhenius. The pressure-sensitive adhesive is heated and melted into liquid, and is solidified again after being cooled, so that the functions of stripping and repeated adhesion can be realized, the practicability of the SBS hot-melt pressure-sensitive adhesive is improved, and the method is simple and rapid. The shear tensile strength and the shear failure temperature recovery rate of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive after re-adhesion are both higher than 90%.
(3) The shear failure temperature of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive can reach 113 ℃ at most, the shear tensile strength can reach 3.25MPa at most, and the strength can hardly be reduced after repeated bonding, so that the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive is an ideal hot-melt adhesive for bonding steel plates.
(4) The synthesis process is simple and easy to operate, environment-friendly and pollution-free, the production cost is low, the raw materials are easy to obtain, and the performance of the SBS hot-melt pressure-sensitive adhesive can be easily adjusted by adding the phenylboronic acid ester cross-linking agents with different contents.
Drawings
FIG. 1 is a graph of the shear strength on stainless steel for examples 1-4 and comparative examples 1-2.
FIG. 2 is a graph of shear failure temperatures for the bonds of examples 1-4 and comparative examples 1-2 on stainless steel.
FIG. 3 is a graph of the shear strength of example 1 after initial and re-bonding on stainless steel.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are intended for purposes of illustration and explanation only and are not intended to limit the scope of the invention.
In the examples, the SBS thermoplastic elastomer is from Corning American (D1102, D1101) with a styrene content of 28-31%; tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester and tris (2, 4-di-tert-butylphenyl) phosphite were purchased from Pasteur Inc.; 1, 4-benzenediboronic acid, 1-thioglycerol, 1, 6-hexanedithiol, 2-dimethoxy-2-phenylacetophenone were purchased from Allantin reagents Ltd.
The raw material formulations of the examples of the present invention and the comparative examples are shown in Table 1
TABLE 1 raw material formulation (parts by weight) for examples and comparative examples of dynamically crosslinked SBS hot melt pressure sensitive adhesives
Example 1
The preparation operation steps of the dynamically crosslinked SBS hot melt pressure sensitive adhesive are as follows:
(1) preparation of phenylboronic acid ester dynamic cross-linking agent
The adopted phenylboronic acid ester dynamic cross-linking agent is a reaction product of 1, 4-phenylboronic acid and 1-thioglycerol, and the preparation method comprises the following steps: 2 g (12 mmol) of 1, 4-benzenediboronic acid and 2.59 g (24 mmol) of 1-thioglycerol were dissolved in 68.9 g of tetrahydrofuran and 17.2 g of anhydrous magnesium sulfate were added and reacted at 30 ℃ for 24 hours under nitrogen protection, filtered to obtain a liquid mixture and 80% of the tetrahydrofuran was removed by rotary evaporation to obtain a concentrated solution of the phenylboronate dynamic cross-linking agent. And finally washing and precipitating for three times by using 700 g of n-hexane to obtain the phenylboronate dynamic cross-linking agent, wherein the phenylboronate dynamic cross-linking agent is a white solid.
(2) Preparation of the mixture
Weighing each raw material according to a formula, firstly wrapping 100g of SBS thermoplastic elastomer by a roller, then sequentially adding 0.3 g of antioxidant, 0.5 g of ultraviolet initiator and 3 g of phenylboronic acid ester dynamic cross-linking agent for mixing, wherein the front roller temperature and the rear roller temperature of an open mill are both 160 ℃, and the mixing time is 30min to obtain a mixture;
the mass ratio of the antioxidant is 3:1 of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite, and an ultraviolet initiator of 2, 2-dimethoxy-2-phenylacetophenone.
(3) Preparation of dynamically crosslinked SBS hot-melt pressure-sensitive adhesive
Pouring the mixture into a mold of 100mm × 100mm × 1mm, and molding on a flat vulcanizing machine at 180 deg.C under 5MPa for 20 min; sample irradiation is directly realized under the irradiation of a low-pressure mercury lamp in a closed environment; the power of the low-pressure mercury lamp is 48W; the distance between the low-pressure mercury lamp and the surface of the mixture in the mould is 10 cm, and the irradiation time is 20min, so that the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive is obtained and named as SBS-B3.
When the dynamic cross-linked SBS hot-melt pressure-sensitive adhesive needs to be repeatedly bonded and reused after being used:
the stainless steel sheet bonded by the SBS hot-melt pressure-sensitive adhesive with dynamic cross-linking is bonded on a flat vulcanizing machine after being cut and stretched out, the stainless steel sheet can be bonded again by the SBS hot-melt pressure-sensitive adhesive remained on the stainless steel sheet, the bonding temperature is 180 ℃, the pressure is 3MPa, and the bonding time is 20 min.
1. Tensile shear Strength test
(1) Test method
The test method is carried out according to the national standard GB/T7124-2008. The test specimen is of a single lap joint structure. The tensile shear strength of the adhesive is the shear stress of the single lap joint of the rigid material measured by applying a tensile force in the direction parallel to the bonding surface and along the main axis of the sample.
(2) Test specimen
The length of the bonding surface is 12.5 mm +/-0.25 mm, and the direction of the main shaft of the test piece is consistent with the cutting direction of the metal glue joint piece.
(3) Test conditions
The parking time and the test environmental conditions of the test sample meet the following requirements:
the shortest time from sample preparation to test is 16h, and the longest time is 1 month;
secondly, the test is generally carried out in the environment with the temperature of 23 +/-2 ℃ and the relative humidity of 45-55 percent;
and thirdly, during the test, the parking time of the sample under the environmental condition is not less than 12 h.
(4) Test procedure
The sample is symmetrically clamped on the clamp, and the distance from the clamping position to the nearest bonding end is 50 mm +/-1 mm. Shims may be used in the fixture to ensure that the force is in the bonding plane.
The tensile tester was run at a constant test speed, resulting in a typical failure time of 65 s ± 20 s.
If the tensile machine can be loaded at a constant speed, the change rate of the shearing force is set to be 8.3 MPa-9.8 MPa per minute.
The maximum load of the test specimen to shear failure was recorded as the failure load.
2. Heat resistance test
(1) Test method
A weight with the weight of 500g is hung below a metal lapping sample, the environment is heated at a constant speed under a specified condition, and the highest temperature which can be borne by the test sample before shear failure is the shear failure temperature.
(2) Test conditions
The temperature range of the blast oven is 30-150 ℃, and the heating rate is 10 ℃/min.
(3) Test procedure
At the temperature of 30 ℃, the metal lapping sample is hung at a proper position of a blast furnace, a weight with the weight of 500g is hung below the metal lapping sample, the temperature of the blast furnace is increased at the speed of 10 ℃/min, and the highest temperature which can be born before the shear failure of the test sample is recorded.
The tensile shear strength of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive prepared by the embodiment is 3.25MPa, the shear failure temperature is 72.6 ℃, the tensile shear strength of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive after re-bonding is 3.12MPa, and the recovery rate is 96%; the shear failure temperature was 68.2 ℃ and the recovery rate was 94%, exhibiting good repeated adhesion.
Example 2
The preparation operation steps of the dynamically crosslinked SBS hot melt pressure sensitive adhesive are as follows:
(1) preparation of phenylboronic acid ester dynamic cross-linking agent
The phenylboronic acid ester dynamic cross-linking agent used was the reaction product of 1, 4-phenylboronic acid and 1-thioglycerol, and the preparation method was the same as in example 1.
(2) Preparation of the mixture
The antioxidant is a compound of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite (the mass ratio is 3: 1), and the ultraviolet initiator is 2, 2-dimethoxy-2-phenylacetophenone.
Weighing the raw materials according to the formula, firstly wrapping 100g of SBS thermoplastic elastomer by a roller, then adding 0.3 g of antioxidant, 0.5 g of ultraviolet initiator and 5 g of phenylboronic acid ester dynamic cross-linking agent in sequence for mixing, wherein the temperature of a front roller and the temperature of a rear roller of an open mill are both 160 ℃, and the mixing time is 30min, thus obtaining the mixture.
(3) Preparation of dynamically crosslinked SBS hot-melt pressure-sensitive adhesive
Pouring the mixture into a mold of 100mm × 100mm × 1mm, and molding on a flat vulcanizing machine at 180 deg.C under 5MPa for 20 min; the irradiation is directly realized under the irradiation of a low-pressure mercury lamp in a closed environment; the power of the low-pressure mercury lamp is 48W; the distance between the low-pressure mercury lamp and the surface of the mixture in the mold is 10 cm, and the irradiation time is 20min, so that the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive is obtained and named as SBS-B5.
After 2 stainless steel sheets bonded by the SBS hot-melt pressure-sensitive adhesive with dynamic cross-linking are cut and stretched to lose efficacy, the 2 waste stainless steel sheets with the SBS hot-melt pressure-sensitive adhesive are bonded again on a flat vulcanizing machine, the bonding temperature is 180 ℃, the pressure is 3MPa, and the bonding time is 20 min.
The tensile shear strength of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive prepared by the embodiment is 2.55MPa, the shear failure temperature is 76.1 ℃, the tensile shear strength of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive after re-bonding is 2.39MPa, and the recovery rate is 94%; the shear failure temperature is 70.1 ℃, the recovery rate is 92%, and good repeated bonding capability is shown.
Example 3
The preparation operation steps of the dynamically crosslinked SBS hot melt pressure sensitive adhesive are as follows:
(1) preparation of phenylboronic acid ester dynamic cross-linking agent
The phenylboronic acid ester dynamic cross-linking agent used was the reaction product of 1, 4-phenylboronic acid and 1-thioglycerol, and the preparation method was the same as in example 1.
(2) Preparation of the mixture
The antioxidant is a compound of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite (the mass ratio is 3: 1), and the ultraviolet initiator is 2, 2-dimethoxy-2-phenylacetophenone.
Weighing the raw materials according to the formula, firstly wrapping 100g of SBS thermoplastic elastomer by a roller, then adding 0.3 g of antioxidant, 0.5 g of ultraviolet initiator and 7 g of phenylboronic acid ester dynamic cross-linking agent in sequence for mixing, wherein the temperature of a front roller and the temperature of a rear roller of an open mill are both 160 ℃, and the mixing time is 30min, thus obtaining the mixture.
(3) Preparation of dynamically crosslinked SBS hot-melt pressure-sensitive adhesive
Pouring the mixture into a mold of 100mm × 100mm × 1mm, and molding on a flat vulcanizing machine at 180 deg.C under 5MPa for 20 min; the irradiation is directly realized under the irradiation of a low-pressure mercury lamp in a closed environment; the power of the low-pressure mercury lamp is 48W; the distance between the low-pressure mercury lamp and the surface of the mixture in the mould is 10 cm, and the irradiation time is 20min, so that the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive is obtained and named as SBS-B7.
After 2 used stainless steel sheets with the SBS hot-melt pressure-sensitive adhesive in the dynamic cross-linking mode are subjected to shear stretching failure, the 2 discarded stainless steel sheets with the SBS hot-melt pressure-sensitive adhesive are re-bonded on a flat vulcanizing machine, the bonding temperature is 180 ℃, the pressure is 3MPa, and the bonding time is 20 min.
The tensile shear strength of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive prepared by the embodiment is 2.61MPa, the shear failure temperature is 94.1 ℃, the tensile shear strength of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive after re-bonding is 2.49MPa, and the recovery rate is 95%; the shear failure temperature was 88.2 ℃ and the recovery rate was 94%, exhibiting good repeated adhesion capability.
Example 4
The preparation operation steps of the dynamically crosslinked SBS hot melt pressure sensitive adhesive are as follows:
(1) preparation of phenylboronic acid ester dynamic cross-linking agent
The phenylboronic acid ester dynamic cross-linking agent used was the reaction product of 1, 4-phenylboronic acid and 1-thioglycerol, and the preparation method was the same as in example 1.
(2) Preparation of the mixture
The antioxidant is a compound of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite (the mass ratio is 3: 1), and the ultraviolet initiator is 2, 2-dimethoxy-2-phenylacetophenone.
Weighing the raw materials according to the formula, firstly wrapping 100g of SBS thermoplastic elastomer by a roller, then adding 0.3 g of antioxidant, 0.5 g of ultraviolet initiator and 10 g of phenylboronic acid ester dynamic cross-linking agent in sequence for mixing, wherein the temperature of a front roller and the temperature of a rear roller of an open mill are both 160 ℃, and the mixing time is 30min, thus obtaining the mixture.
(3) Preparation of dynamically crosslinked SBS hot-melt pressure-sensitive adhesive
Pouring the mixture into a mold of 100mm × 100mm × 1mm, and molding on a flat vulcanizing machine at 180 deg.C under 5MPa for 20 min; the irradiation is directly realized under the irradiation of a low-pressure mercury lamp in a closed environment; the power of the low-pressure mercury lamp is 48W; the distance between the low-pressure mercury lamp and the surface of the mixture in the mould is 10 cm, and the irradiation time is 20min, so that the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive is obtained and named as SBS-B10.
After 2 stainless steel sheets bonded by the SBS hot-melt pressure-sensitive adhesive with dynamic cross-linking are cut and stretched to lose efficacy, the 2 waste stainless steel sheets with the SBS hot-melt pressure-sensitive adhesive are bonded again on a flat vulcanizing machine, the bonding temperature is 180 ℃, the pressure is 3MPa, and the bonding time is 20 min.
The tensile shear strength of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive prepared by the embodiment is 3.07MPa, the shear failure temperature is 113.3 ℃, the tensile shear strength of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive after re-bonding is 2.97MPa, and the recovery rate is 97%; the shear failure temperature is 108.1 ℃, the recovery rate is 95%, and good repeated bonding capability is shown.
Comparative example 1
The traditional cross-linking agent is 1, 6-hexanedithiol; the antioxidant is a compound of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite (the mass ratio is 3: 1), and the ultraviolet initiator is 2, 2-dimethoxy-2-phenylacetophenone.
Weighing each raw material according to a formula, firstly wrapping 100g of SBS thermoplastic elastomer by a roller, then sequentially adding 0.3 g of antioxidant, 0.5 g of ultraviolet initiator and 5 g of traditional 1, 6-hexanedithiol crosslinking agent for mixing, wherein the front roller temperature and the rear roller temperature of an open mill are both 160 ℃, and the mixing time is 30min to obtain a mixture;
pouring the mixture into a mold of 100mm × 100mm × 1mm, and molding on a flat vulcanizing machine at 180 deg.C under 5MPa for 20 min; the irradiation is directly realized under the irradiation of a low-pressure mercury lamp in a closed environment; the power of the low-pressure mercury lamp is 48W; the mercury low pressure lamp was spaced 10 cm from the surface of the mixture in the mold and the irradiation time was 20min to obtain a permanently crosslinked SBS pressure sensitive adhesive named SBS-H5.
After 2 stainless steel sheets bonded by the used SBS pressure-sensitive adhesive with permanent cross-linking are cut and stretched to lose effectiveness, the 2 stainless steel sheets with the waste SBS pressure-sensitive adhesive with permanent cross-linking are bonded again on a flat vulcanizing machine, the bonding temperature is 180 ℃, the pressure is 3MPa, and the bonding time is 20 min.
The tensile shear strength of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive prepared by the embodiment is 0.3MPa, the shear failure temperature is 52.1 ℃, and the permanently crosslinked SBS pressure-sensitive adhesive after re-bonding has almost no strength and can not be repeatedly bonded.
Comparative example 2
Weighing the raw materials according to a formula without using any cross-linking agent, firstly wrapping 100g of SBS thermoplastic elastomer by a roller, then adding 0.3 g of antioxidant for mixing, wherein the temperature of a front roller and the temperature of a rear roller of an open mill are both 160 ℃, and the mixing time is 30min to obtain a mixture;
pouring the mixture into a mold of 100mm × 100mm × 1mm, and molding on a flat vulcanizing machine at 180 deg.C under 5MPa for 20min to obtain non-crosslinked SBS pressure-sensitive adhesive named SBS.
The non-crosslinked SBS pressure sensitive adhesive prepared in this example has a tensile shear strength of 0.86 MPa, a shear failure temperature of 63.7 deg.C, and both tensile shear strength and shear failure temperature are low.
TABLE 2 performances of pressure-sensitive adhesives (A) and after-reworking (B) of examples 1 to 4 and comparative examples 1 to 2
The properties of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive (a) and the reworked sample (B) prepared in examples and comparative examples were examined. The test results are shown in table 2.
The shear tensile strengths of examples 1-4 and comparative examples 1-2 are shown in FIG. 1, and the shear failure temperatures are shown in FIG. 2. Specifically, in comparative example 1, 6-hexanedithiol was used as a crosslinking agent to form permanent chemical crosslinks. At high temperature, the pressure-sensitive adhesive can not be melted, and the molecules of the pressure-sensitive adhesive are difficult to diffuse to the surface of the stainless steel metal so as to form effective bonding. Therefore, the material has extremely low tensile shear strength and shear failure temperature, and the material cannot be repeatedly bonded. In comparative example 2, the hot melt pressure sensitive adhesive did not form a crosslinked network and thus both tensile shear strength and shear failure temperature were low. In examples 1 to 4, the content of the SBS thermoplastic elastomer was 100g, and the tensile shear strength and shear failure temperature of the hot-melt pressure-sensitive adhesive were improved as a whole by the addition of the phenylboronic acid ester cross-linking agent, indicating the formation of the dynamic cross-linked network, the average molecular weight of the SBS hot-melt pressure-sensitive adhesive was increased, the bulk viscosity and the cohesive strength of the pressure-sensitive adhesive were both significantly increased, and good adhesion properties were exhibited; in addition, more importantly, the shear failure temperature of the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive is increased from 63.7 ℃ to 113.3 ℃, and the softening point and the heat resistance of the pressure-sensitive adhesive are greatly improved. Finally, the re-adhesion data for example 1 is shown in fig. 3, where it can be seen that the tensile shear strength of the sample remains substantially unchanged after re-adhesion of example 1, illustrating the dynamic nature of the phenylboronate ester dynamic cross-linking agent which imparts repeated adhesion properties to SBS hot melt pressure sensitive adhesive.
It will be understood by those skilled in the art that the foregoing is merely a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included within the scope of the present invention.
Claims (4)
1. The dynamically crosslinked SBS hot-melt pressure-sensitive adhesive is characterized by being prepared from the following raw materials in parts by weight:
100 portions of SBS thermoplastic elastomer, 0.3 portion of antioxidant, 0.5 portion of ultraviolet initiator and 3 to 10 portions of phenylboronic acid ester dynamic cross-linking agent,
the content of styrene in the SBS thermoplastic elastomer is 28-31%;
the antioxidant is prepared by mixing tetra [ [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris [2, 4-di-tert-butylphenyl ] phosphite ester according to the mass ratio of 3: 1;
the ultraviolet initiator is 2, 2-dimethoxy-2-phenylacetophenone;
the phenylboronic acid ester dynamic cross-linking agent is a white solid and is a product of 1, 4-phenylboronic acid and 1-thioglycerol, wherein the molar ratio of the 1, 4-phenylboronic acid to the 1-thioglycerol is 1: 2;
the SBS hot-melt pressure-sensitive adhesive is a white sheet, the shear tensile strength is higher than 2.55MPa, and the shear failure temperature is higher than 70 ℃; the shear tensile strength and the shear failure temperature recovery rate of the re-bonded SBS hot-melt pressure-sensitive adhesive are both higher than 90%;
the re-bonding is to re-bond 2 stainless steel sheets with SBS hot-melt pressure-sensitive adhesive after 2 sheets of used SBS hot-melt pressure-sensitive adhesive are bonded, and after the stainless steel sheets are cut and stretched to lose efficacy, the 2 sheets of waste stainless steel sheets with SBS hot-melt pressure-sensitive adhesive are re-bonded on a flat plate vulcanizing machine, wherein the bonding temperature is 180 ℃, the pressure is 3MPa, and the bonding time is 20 min.
2. The process for the preparation of a dynamically crosslinked SBS hot-melt pressure sensitive adhesive as claimed in claim 1, which comprises the following operating steps:
(1) preparation of phenylboronic acid ester dynamic cross-linking agent
Dissolving 1, 4-phenyl diboronic acid and 1-thioglycerol in 15 times of tetrahydrofuran by mass, wherein the molar ratio of the 1, 4-phenyl diboronic acid to the 1-thioglycerol is 1: 2; adding anhydrous magnesium sulfate, wherein the mass ratio of the anhydrous magnesium sulfate to the tetrahydrofuran is 1: 4; reacting for 24 hours under the condition of nitrogen protection and 30 ℃, filtering to obtain a liquid mixture, and performing rotary evaporation to remove 80% of tetrahydrofuran to obtain a concentrated phenylboronic acid ester dynamic cross-linking agent solution; washing and precipitating for three times by using n-hexane with the mass being 50 times that of the active component to obtain a phenylboronic acid ester dynamic cross-linking agent, wherein the phenylboronic acid ester dynamic cross-linking agent is a white solid;
(2) preparation of the mixture
Taking 100 parts of SBS thermoplastic elastomer, 0.3 part of antioxidant, 0.5 part of ultraviolet initiator and 3-10 parts of phenylboronic acid ester dynamic cross-linking agent according to the formula; firstly, coating a roll with SBS thermoplastic elastomer, then adding an antioxidant, an ultraviolet light initiator and a phenylboronic acid ester dynamic cross-linking agent in sequence for mixing to obtain a mixture;
(3) preparation of dynamically crosslinked SBS hot-melt pressure-sensitive adhesive
Pouring the mixture into a mold with the volume of 100mm multiplied by 1mm, and forming on a flat vulcanizing machine, wherein the mold temperature is 180 ℃, the pressure is 5MPa, and the hot pressing time is 20-30 min; irradiating the molded sample under a low-pressure mercury lamp in a closed environment; obtaining the dynamically crosslinked SBS hot-melt pressure-sensitive adhesive.
3. The method of claim 2, wherein: in the step (2), the temperature of a front roller and the temperature of a rear roller of the open mill are both 160 ℃, and the mixing time is 30-40 min.
4. The method of claim 2, wherein: in the step (3), the molding conditions are as follows: the temperature of the die is 180 ℃, the pressure is 5MPa, and the hot pressing time is 20-30 min; irradiation conditions of a low-pressure mercury lamp: the power of the low-pressure mercury lamp is 48W, the distance between the low-pressure mercury lamp and the surface of the sample is 10 cm, and the irradiation time is 20-30 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437778A (en) * | 2019-09-20 | 2019-11-12 | 淄博鲁华泓锦新材料股份有限公司 | Adhesive tape hot-fusible pressure-sensitive adhesive and preparation method thereof |
| CN112480556A (en) * | 2019-12-25 | 2021-03-12 | 新亚特电缆股份有限公司 | Dynamically crosslinked halogen-free flame-retardant cable material and preparation method thereof |
| CN112812331A (en) * | 2021-01-12 | 2021-05-18 | 华南理工大学 | Heterogeneous cross-linked rubber, preparation method and recovery method |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437778A (en) * | 2019-09-20 | 2019-11-12 | 淄博鲁华泓锦新材料股份有限公司 | Adhesive tape hot-fusible pressure-sensitive adhesive and preparation method thereof |
| CN112480556A (en) * | 2019-12-25 | 2021-03-12 | 新亚特电缆股份有限公司 | Dynamically crosslinked halogen-free flame-retardant cable material and preparation method thereof |
| CN112812331A (en) * | 2021-01-12 | 2021-05-18 | 华南理工大学 | Heterogeneous cross-linked rubber, preparation method and recovery method |
Non-Patent Citations (1)
| Title |
|---|
| Yi Chen et al..Covalently Cross-Linked Elastomers with Self-Healing and Malleable Abilities Enabled by Boronic Ester Bonds.《ACS Applied Materials & Interfaces》.2018,第10卷(第28期), * |
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