阅读说明：本技术 一种高强压敏胶及其制备方法和应用 (High-strength pressure-sensitive adhesive and preparation method and application thereof ) 是由 刘强 蔺东顺 孙德权 杨国富 于 2021-10-12 设计创作，主要内容包括：本发明属于压敏胶制备及应用技术领域,公开了一种高强压敏胶及其制备方法和应用。该高强压敏胶中使用了石墨烯和木质素,石墨烯的纳米片层结构赋予了压敏胶优异的水汽阻隔性能和力学性能；含有酚羟基、羟基、羧基等基团的木质素进一步提高了压敏胶的力学性能,并且提高了压敏胶与金属基材在高温下的粘结力。因而所制备的高强压敏胶在高温下具有较好的耐水性能、粘结力以及防腐性能。该高强压敏胶的制备过程简单,节省人力,环保,安全性高。(The invention belongs to the technical field of preparation and application of pressure-sensitive adhesives, and discloses a high-strength pressure-sensitive adhesive and a preparation method and application thereof. Graphene and lignin are used in the high-strength pressure-sensitive adhesive, and the nano-sheet structure of the graphene endows the pressure-sensitive adhesive with excellent water vapor barrier property and mechanical property; the lignin containing phenolic hydroxyl, carboxyl and other groups further improves the mechanical property of the pressure-sensitive adhesive and improves the adhesive force of the pressure-sensitive adhesive and the metal substrate at high temperature. Therefore, the prepared high-strength pressure-sensitive adhesive has better water resistance, adhesive force and corrosion resistance at high temperature. The high-strength pressure-sensitive adhesive is simple in preparation process, labor-saving, environment-friendly and high in safety.)

1. The high-strength pressure-sensitive adhesive is characterized by being prepared from the following raw materials in parts by mass:

10-25 parts of butyl rubber, 35-55 parts of polyisobutylene, 15-25 parts of tackifying resin, 0.5-10 parts of graphene, 5-20 parts of lignin and 10-25 parts of filler.

2. The high-strength pressure-sensitive adhesive according to claim 1, which is prepared from the following raw materials in parts by mass:

12-22 parts of butyl rubber, 38-50 parts of polyisobutylene, 18-23 parts of tackifying resin, 3-8 parts of graphene, 8-15 parts of lignin and 15-22 parts of filler.

3. The high-strength pressure-sensitive adhesive according to claim 2, which is prepared from the following raw materials in parts by mass:

18 parts of butyl rubber, 45 parts of polyisobutylene, 20 parts of tackifying resin, 5 parts of graphene, 10 parts of lignin and 18 parts of filler.

4. A high-strength pressure-sensitive adhesive according to any one of claims 1 to 3, wherein the molecular weight of the polyisobutylene is a medium molecular weight polyisobutylene;

the molecular weight of the medium molecular weight polyisobutylene is 3-10 ten thousand.

5. A high-strength pressure-sensitive adhesive according to any one of claims 1 to 3, wherein the tackifying resin is one or more of terpene resin, hydrocarbon petroleum resin and hydrocarbon petroleum resin.

6. A high strength pressure sensitive adhesive according to any one of claims 1 to 3, wherein the filler is composed of talc and calcium carbonate;

the mass part ratio of the talcum powder to the calcium carbonate is 1-3: 1-2.

7. A high-strength pressure-sensitive adhesive according to any one of claims 1 to 3, wherein the graphene is graphene oxide.

8. A process for the preparation of a high strength pressure sensitive adhesive according to any of claims 1 to 3, comprising the steps of: and (3) selecting butyl rubber, polyisobutylene, tackifying resin, graphene, lignin and a filler according to a corresponding proportion, mixing, heating, discharging and obtaining a finished product.

9. The method as claimed in claim 8, wherein the heating temperature is 140-180 ℃.

10. The use of a high-strength pressure-sensitive adhesive according to any one of claims 1 to 3 or a high-strength pressure-sensitive adhesive obtained by the method according to any one of claims 8 to 9 in cold winding.

Technical Field

The invention belongs to the technical field of preparation and application of pressure-sensitive adhesives, and particularly relates to a high-strength pressure-sensitive adhesive and a preparation method and application thereof.

Background

Pipelines are used in a wide range of applications, for example, in the transportation of fluids such as oil, gas, water, etc. The material of the pipeline is generally steel, and the problem of corrosion is inevitable in the use process of the pipeline. At present, the main solution is to arrange polyethylene (3PE) with a three-layer structure on the wall of a main pipeline, and perform corrosion prevention and joint coating on the welded junction on site, which is very important for ensuring the integrity of corrosion resistance.

The cold winding belt is a hot-melt material based on asphalt, and the glue layer of the cold winding belt has excellent low-temperature bonding performance due to the use of the asphalt and can be used for corrosion prevention and joint coating of pipelines. However, the conventional cold-winding belt material uses a large amount of asphalt, and has structural and performance defects, mainly including insufficient water resistance at high temperature, poor mechanical properties, easy deformation and flowing, poor adhesion with metal pipelines at high temperature and the like.

Disclosure of Invention

In order to solve the problems in the prior art, the invention aims to provide a high-strength pressure-sensitive adhesive and a preparation method and application thereof.

The technical scheme adopted by the invention is as follows: the high-strength pressure-sensitive adhesive is mainly prepared from the following raw materials in parts by mass:

10-25 parts of butyl rubber, 35-55 parts of polyisobutylene, 15-25 parts of tackifying resin, 0.5-10 parts of graphene, 5-20 parts of lignin and 10-25 parts of filler.

Butyl rubber, a type of synthetic rubber, is synthesized from isobutylene and a small amount of isoprene. Are generally used for manufacturing tires. In the field of building waterproofing, butyl rubber has been widely used to replace asphalt with an environmental protection name. The air tightness is good. It is also resistant to heat, ozone, aging, chemicals, shock absorption, and electrical insulation. Has good resistance to sunlight and ozone, and can be exposed to animal or vegetable oil or oxidizable chemical. The inner tube of various tyres, the air-tight layer of tubeless tyre and various sealing washers are made up, and used as lining, pipeline and conveyer belt of container for corrosive liquid in chemical industry and as water-proof material in agriculture. The dispersion speed of gas in the polymer is related to the thermal activity of polymer molecules, and the lateral methyl groups in the molecular chain of the butyl rubber are densely arranged, so that the thermal activity of the polymer molecules is limited, and the air permeability is low and the air tightness is good. The butyl rubber vulcanized rubber has excellent heat resistance and invariability, the sulfur vulcanized butyl rubber can be used in the air for a long time at 100 ℃ or slightly low temperature, and the operating temperature of the resin vulcanized butyl rubber can reach 150-200 ℃. The thermal oxidative aging of the butyl rubber belongs to a degradation type, and the aging tendency is softening. The butyl rubber has short double bonds in the molecular structure and larger dispersion density of side chain methyl groups, thereby having excellent characteristics of receiving vibration and impact energy, and the rebound characteristics of the butyl rubber are not more than 20 percent within a wide temperature limit (minus 30 ℃ to minus 50 ℃), which clearly shows that the butyl rubber has better mechanical function receiving performance than other rubbers. The damping properties of butyl rubber at high deformation speeds are inherent to the polyisobutylene segment and to a large extent are not affected by the application temperature, the degree of unsaturation, the vulcanization profile and the formulation changes. Therefore, butyl rubber is the ideal sound insulation and vibration reduction data.

Preferably, the high-strength pressure-sensitive adhesive is mainly prepared from the following raw materials in parts by mass:

12-22 parts of butyl rubber, 38-50 parts of polyisobutylene, 18-23 parts of tackifying resin, 3-8 parts of graphene, 8-15 parts of lignin and 15-22 parts of filler.

Preferably, the high-strength pressure-sensitive adhesive is mainly prepared from the following raw materials in parts by mass:

18 parts of butyl rubber, 45 parts of polyisobutylene, 20 parts of tackifying resin, 5 parts of graphene, 10 parts of lignin and 18 parts of filler.

Preferably, the molecular weight of the polyisobutylene is a medium molecular weight polyisobutylene;

the molecular weight of the medium molecular weight polyisobutylene is 3-10 ten thousand.

The medium molecular weight polyisobutylene is selected, so that the initial viscosity of the finally obtained pressure-sensitive adhesive product is adjusted, and the pressure-sensitive adhesive product has stronger pressure-sensitive performance.

Polyisobutylene, (PIB) is a polymer made from the ongoing polymerization of isobutylene, and can have molecular weights ranging from hundreds to millions. It is a typical saturated linear polymer. The molecular chain main body does not contain double bonds, no long-chain branch exists, the structural unit is- (CH2-C (CH3)2) -, asymmetric carbon atoms do not exist, and the structural units are connected in a head-to-tail regular sequence. The method is mainly applied to many fields such as petroleum additives, adhesives and the like. Used for manufacturing pressure sensitive adhesives and sealants. It can also be used as thickener, and can be used in combination with other materials to improve adhesion, flexibility, aging resistance, air tightness and electrical insulation. But also for the manufacture of wire and cable, plasticizers, etc. Chewing gum base of gum. Colorless to pale yellow viscous liquid or rubbery semisolid with elasticity (soft gel for low molecular weight and tough and elastic for high molecular weight). All are tasteless, odorless or slightly peculiar in odor. The average molecular weight is 20-8700 ten thousand. Is soluble in benzene and diisobutylene, is soluble in polyvinyl acetate, wax and other polar solvents, and is insoluble in water, alcohol and other polar solvents. The chewing gum has excellent softness at low temperature and certain plasticity at high temperature, so as to make up for the defects of polyvinyl acetate such as over-hardness at cold, over-softening at hot days and over-softening at mouth temperature. Has good light resistance, heat resistance and oxidation resistance.

Preferably, the tackifying resin is one or more of terpene resin, carbon five petroleum resin and carbon acanthopanax hydrocarbon petroleum resin.

The tackifying resin is a hydrocarbon petroleum resin, and is most preferred.

Terpene resin, some thermoplastic block copolymer, have light color, low odor, high hardness, high adhesion, good oxidation resistance and thermal stability, good compatibility and solubility, especially EVA SIS series, SBS series, etc. have good compatibility and weather resistance and tackifying effect. The product is widely applied to the aspects of adhesives, double-sided tapes, solvent-based glues, book binding plates, color packages, rubberized fabrics, olefin rubberized fabrics, kraft paper card rubberized fabrics, tape labels, woodworking adhesives, pressure-sensitive adhesives, thermosol, sealants, paints, printing inks and other polymer modifiers and the like. Terpene resins are excellent tackifiers for some thermoplastic block copolymers, such as styrene-butadiene rubber (SBR), phenylacetic acid-isoprene-styrene (SIS), and styrene (SBS), which resins have excellent color stability properties. It is a new type of excellent tackifier with tackifying performance superior to that of rosin, modified rosin, petroleum resin, etc. Terpene resins are yellow, transparent, brittle, thermoplastic solids. The paint has the performances of no toxicity, no odor, radiation resistance, crystallization and the like, and is stable to oxygen, heat and light; the coating has good compatibility with various synthetic substances; resistance to dilute acid and alkali; strong viscosity increasing property and electric insulation property, and is insoluble in water and ethanol. The terpene resin is polymerized from a mixture of terpenes, also known as polyterpene resin, chemical formula (C10H16) n, average molecular weight 650-. It is an excellent tackifier, and has the excellent performances of strong bonding force, good ageing resistance, high cohesion, heat resistance, light resistance, acid resistance, alkali resistance, odor resistance, no toxicity and the like, and the adhesive is characterized in that: hot melt adhesive, pressure sensitive adhesive, all-purpose adhesive, sealing adhesive, glue, and the like; in the aspect of coating: template paint, interior and exterior wall latex paint, fire-proof latex paint, building coating and the like; the rubber field is as follows: natural rubber, synthetic rubber, latex, raw rubber, liquid rubber, powdered rubber, and the like; the textile leather field: printing adhesives, fabric sticking hot melt adhesives, lining cloth processing hot melt adhesives, carpet back glue hot melt adhesives and the like; packaging materials: packaging glues, packaging adhesives, food packaging adhesives, beverage packaging adhesives, cigarette package glues, and the like; ink material: paper printing inks, packaging box printing inks, solvent-based inks, resin-based inks, and the like.

Carbon five petroleum resin, C5petroleum resin, also known as carbon five petroleum resin, is a tackifying resin. As a tackifying resin, the carbon five petroleum resin plays an important role, and has the characteristics of good fluidity and capability of improving the wettability of a main material in an adhesive system. Good viscosity and outstanding initial viscosity. Excellent aging resistance. The cohesion strength and the peel strength are optimally balanced. The color was light. Transparent, low odor and low volatile matter. The carbon five petroleum resin has the characteristics of excellent tackifying property in the field of tire rubber. Can play softening and reinforcing roles in the processing process, and improve the extensibility and the anti-stripping property. The raw viscosity is obviously improved, but the vulcanization time and the physical properties after vulcanization are not influenced. Adhesion to processing machinery is avoided. Helping the filler material to be evenly distributed.

The hydrocarbon petroleum resin is produced by using the carbon five fraction cracked by ethylene device as raw material and through the processes of pretreatment, polymerization, hydrogenation, refining, etc. The adhesive is water white, has good tackifying property, compatibility, thermal stability and light stability, can improve the adhesive property of the adhesive, and better solves the problems of smell, chroma, stability and the like of petroleum resin. The product indexes such as softening point, color, bromine number and the like can be adjusted according to the needs of users to produce products with different brands, thus greatly widening the application field of petroleum resin. The product application is as follows: the product is an indispensable tackifying component for a plurality of adhesives, such as hot melt adhesives, welding type road sign paints and pressure-sensitive adhesives. Can replace terpene resin and rosin resin and be widely applied to the industries of structure and decoration, automobile assembly, tires, commodity packaging, book binding, sanitary products (sanitary towels, baby diapers and the like), shoe manufacturing and the like in the building industry. The product is also used in the fields of geological exploration, well drilling, rubber, plastics, textiles, printed matters, optical recording materials and the like.

Preferably, the filler consists of talc and calcium carbonate;

the mass part ratio of the talcum powder to the calcium carbonate is 1-3: 1-2.

Preferably, the graphene is graphene oxide.

The graphene oxide is selected, and has the advantages of wide source, easy acquisition and strong dispersibility.

Graphene oxide (graphene oxide) is an oxide of graphene, and has a brown-yellow color, and common products in the market are in a powder form, a flake form and a solution form. After oxidation, the oxygen-containing functional groups on the graphene are increased, so that the graphene is more active than graphene in property, and the properties of the graphene can be improved through various reactions with the oxygen-containing functional groups. The graphene oxide sheet is a product obtained by chemically oxidizing and stripping graphite powder, and the graphene oxide is a single atomic layer and can be expanded to tens of microns in transverse dimension at any time. Thus, its structure spans the typical dimensions of general chemistry and material science. Graphene oxide can be considered a non-traditional soft material with properties of polymers, colloids, films, and amphiphilic molecules. Graphene oxide has long been considered as a hydrophilic substance because of its superior dispersibility in water, but related experimental results show that graphene oxide is actually amphiphilic, exhibiting a distribution of hydrophilic to hydrophobic properties from the edge to the center of a graphene sheet. Therefore, the graphene oxide may exist at an interface as a surfactant and reduce energy between interfaces. Its hydrophilicity is widely recognized. Graphene oxide is a novel carbon material with excellent performance, and has a high specific surface area and rich functional groups on the surface. The graphene oxide composite materials including polymer composite materials and inorganic composite materials have a wide application field, so that the surface modification of graphene oxide becomes another important research point. The Shanghai application physical research of Chinese academy of sciences discovers that the application of graphene oxide in the PCR technology can obviously improve the specificity, sensitivity and amplification yield of PCR, can eliminate primer dimers formed in amplification, has a wide optimization interval, and can be widely applied to DNA templates with various concentrations and complexity. Compared with other carbon nano materials applied to the PCR technology, the graphene oxide has more excellent comprehensive effect on the optimization of PCR.

A preparation method of a high-strength pressure-sensitive adhesive comprises the following steps: and (3) selecting butyl rubber, polyisobutylene, tackifying resin, graphene, lignin and a filler according to a corresponding proportion, mixing, heating, discharging and obtaining a finished product.

Preferably, the heating temperature is 140-180 ℃ during the heating treatment.

The above-mentioned setting of the temperature for the heat treatment is because if the temperature is too low, the pressure-sensitive adhesive is too adhesive to be mixed; too high, it is liable to cause oxidative degradation.

The application of the high-strength pressure-sensitive adhesive disclosed in any one of claims 1 to 3 or the high-strength pressure-sensitive adhesive prepared by the preparation method disclosed in any one of claims 8 to 9 in cold winding of a tape.

The invention has the beneficial effects that:

the invention provides a high-strength pressure-sensitive adhesive, which uses graphene and lignin, wherein the nano-sheet structure of the graphene endows the pressure-sensitive adhesive with excellent water vapor barrier property and mechanical property; the lignin containing phenolic hydroxyl, carboxyl and other groups further improves the mechanical property of the pressure-sensitive adhesive and improves the adhesive force of the pressure-sensitive adhesive and the metal substrate at high temperature. Therefore, the prepared high-strength pressure-sensitive adhesive has better water resistance, adhesive force and corrosion resistance at high temperature.

The high-strength pressure-sensitive adhesive is simple in preparation process, labor-saving, environment-friendly and high in safety.

Detailed Description

The present invention is further illustrated below with reference to specific examples. It will be appreciated by those skilled in the art that the following examples, which are set forth to illustrate the present invention, are intended to be part of the present invention, but not to be construed as limiting the scope of the present invention. The reagents used are all conventional products which are commercially available.

Example 1:

a preparation method of a high-strength pressure-sensitive adhesive comprises the following steps: according to the corresponding proportion, 100 g of butyl rubber, 350 g of polyisobutylene (with the molecular weight of 3-10 ten thousand), 150 g of tackifying resin, 0.5 g of graphene, 50 g of lignin and 100 g of filler (60 g of talcum powder and 40 g of calcium carbonate) are selected and mixed, heated to 140 ℃, processed, discharged and finished products are obtained.

Example 2:

a preparation method of a high-strength pressure-sensitive adhesive comprises the following steps: according to the corresponding proportion, 250 g of butyl rubber, 550 g of polyisobutylene (with the molecular weight of 3-10 ten thousand), 250 g of tackifying resin, 10 g of graphene, 200 g of lignin and 250 g of filler (150 g of talcum powder and 100 g of calcium carbonate) are selected and mixed, heated to 180 ℃ for treatment, and discharged to obtain a finished product.

Example 3:

a preparation method of a high-strength pressure-sensitive adhesive comprises the following steps: according to the corresponding proportion, 120 g of butyl rubber, 380 g of polyisobutylene (with the molecular weight of 3-10 ten thousand), 180 g of tackifying resin, 3 g of graphene, 80 g of lignin and 150 g of filler (90 g of talcum powder and 60 g of calcium carbonate) are selected and mixed, heated to 140 ℃, discharged and the finished product is obtained.

Example 4:

a preparation method of a high-strength pressure-sensitive adhesive comprises the following steps: according to the corresponding proportion, 220 g of butyl rubber, 500 g of polyisobutylene (with the molecular weight of 3-10 ten thousand), 230 g of tackifying resin, 8 g of graphene, 150 g of lignin and 220 g of filler (110 g of talcum powder and 110 g of calcium carbonate) are selected and mixed, heated to 180 ℃ for treatment, and discharged to obtain a finished product.

Example 5:

a preparation method of a high-strength pressure-sensitive adhesive comprises the following steps: selecting 180 g of butyl rubber, 450 g of polyisobutylene (with the molecular weight of 3-10 ten thousand), 200 g of tackifying resin, 5 g of graphene, 100 g of lignin and 180 g of filler (90 g of talcum powder and 90 g of calcium carbonate) according to corresponding proportion, mixing, heating at 140 ℃, discharging, and obtaining a finished product.

Example 6:

a preparation method of a high-strength pressure-sensitive adhesive comprises the following steps: selecting 180 g of butyl rubber, 450 g of polyisobutylene (with the molecular weight of 3-10 ten thousand), 200 g of tackifying resin, 5 g of graphene, 100 g of lignin and 180 g of filler (108 g of talcum powder and 72 g of calcium carbonate) according to corresponding proportion, mixing, heating at 180 ℃, processing, discharging and obtaining a finished product.

Example 7:

a preparation method of a high-strength pressure-sensitive adhesive comprises the following steps: according to the corresponding proportion, 150 g of butyl rubber, 400 g of polyisobutylene (with the molecular weight of 3-10 ten thousand), 200 g of tackifying resin, 5 g of graphene and 200 g of filler (100 g of talcum powder and 100 g of calcium carbonate) are selected and mixed, heated to 180 ℃, and discharged to obtain a finished product.

Example 8:

a preparation method of a high-strength pressure-sensitive adhesive comprises the following steps: according to the corresponding proportion, 150 g of butyl rubber, 350 g of polyisobutylene (with the molecular weight of 3-10 ten thousand), 200 g of tackifying resin, 10 g of graphene and 200 g of filler (100 g of talcum powder and 100 g of calcium carbonate) are selected and mixed, heated to 180 ℃, and discharged to obtain a finished product.

Example 9:

a preparation method of a high-strength pressure-sensitive adhesive comprises the following steps: according to the corresponding proportion, 150 g of butyl rubber, 350 g of polyisobutylene (with the molecular weight of 3-10 ten thousand), 200 g of tackifying resin, 100 g of lignin and 200 g of filler (100 g of talcum powder and 100 g of calcium carbonate) are selected and mixed, heated to 180 ℃, and discharged to obtain a finished product.

Example 10:

a preparation method of a high-strength pressure-sensitive adhesive comprises the following steps: according to the corresponding proportion, 150 g of butyl rubber, 250 g of polyisobutylene (with the molecular weight of 3-10 ten thousand), 200 g of tackifying resin, 10 g of graphene, 100 g of lignin and 200 g of filler (100 g of talcum powder and 100 g of calcium carbonate) are selected and mixed, heated to 180 ℃, processed, discharged and the finished product is obtained.

In all the embodiments, in the preparation method of the high-strength pressure-sensitive adhesive, when all the raw materials are mixed, a kneader can be used for processing, and the equipment for mixing is not limited to the equipment, and all the equipment capable of realizing a uniform mixing state belong to the protection scope of the present invention.

Meanwhile, as for the heating mode in the preparation process, a gradual heating mode is suggested, which is more beneficial to the preparation of each raw material and the thoroughness of the modification effect.

Examples of the experiments

Experimental groups: the above examples 7 to 10 were selected as experimental examples.

Control group: comparative example the following raw materials were mixed and prepared according to the methods of examples 7-10 to obtain the final product of comparative example.

Now, according to the test of GB/T23257-2017 standard, the shear strength under normal temperature and high temperature conditions and the peel strength under normal temperature and high temperature conditions of the high-strength pressure-sensitive cold winding tape obtained by the comparative example and the examples 7-10 are shown in the following table 1:

TABLE 1 high-strength pressure-sensitive cold-wound strip Performance test results

And (4) conclusion: from the data results, it can be seen that the ordinary pressure-sensitive cold-wound tape has drooling and dripping at high temperature. After graphene modification, the high-temperature resistance of the pressure-sensitive adhesive is obviously improved, the pressure-sensitive adhesive does not flow at high temperature, and the peel strength and the shear strength are firstly obviously improved. After the lignin is continuously added for modification, the peel strength at high temperature is further improved.

The present invention is not limited to the above alternative embodiments, and any other products in various forms can be obtained by the present invention, and the present invention is within the protection scope of the present invention. The above embodiments should not be construed as limiting the scope of the present invention, and it will be understood by those skilled in the art that modifications may be made to the technical solutions described in the above embodiments, or equivalent substitutions may be made to some or all of the technical features thereof, without departing from the scope of the present invention, and at the same time, such modifications or substitutions may not make the essence of the corresponding technical solutions depart from the scope of the embodiments of the present invention.