A polybutene copolymer modified 3PE adhesive composition and preparation method thereof

Abstract

A polybutene copolymer-modified 3PE adhesive composition and its preparation method relate to the field of external anti-corrosion technology for steel pipeline protection. Prior art pipeline anti-corrosion adhesives have disadvantages such as low bonding strength, thick bonding layer, strong odor, and environmental impact. The present invention comprises, by weight, 50-60 parts of poly-1-butene maleic anhydride copolymer, 25-29 parts of linear low-density polyethylene DNDA7144, 10-14 parts of high-density polyethylene DMD7006A, 4-8 parts of polyvinylpyrrolidone PVP K-90, 0.05-0.1 parts of antioxidant 1010, 0.05-0.1 parts of antioxidant 168, and 0.1-0.2 parts of lubricant. The resulting polybutene copolymer-modified 3PE adhesive composition has high bonding performance, low adhesive film thickness, low odor, and is environmentally friendly.

Description

Technical Field

[0001] The present invention relates to the technical field of external anti-corrosion for protecting steel pipelines, in particular to a polybutene copolymer-modified 3PE adhesive composition and a preparation method thereof. Background Art

[0002] Currently, the following types of external anti-corrosion coatings are commonly used for steel pipeline protection: petroleum asphalt coatings, epoxy coal tar coatings, epoxy powder coatings, coal tar enamel coatings, polyethylene adhesive tape coatings, polyethylene coatings, and 3PE coatings. 3PE coatings are highly regarded in the industry for their excellent physical and mechanical properties, good chemical resistance, extremely low water and oxygen permeability, low environmental pollution, long corrosion resistance, and high insulation performance. With the exploration and development of oil and gas, pipeline transportation has become the primary mode of oil and gas transportation. 3PE coatings are widely used on oil and gas pipelines both domestically and internationally, and are the preferred solution for external corrosion protection. 3PE external anti-corrosion technology is a composite structure consisting of an inner epoxy coating, an adhesive in the middle, and an outer polyethylene film. PE is a non-polar polymer with virtually no adhesion to steel, requiring adhesives to bond the interface. Currently, the main adhesives used in the industry are ethylene-acrylic acid copolymer (EAA) and PE graft systems. EAA is completely dependent on imports, is expensive and has unstable supply; there is more research on the use of PE grafting system in hot melt adhesives for aluminum-plastic composite pipes, but relatively less research on the use of PE grafting system in hot melt adhesives for steel-plastic composite pipes.

[0003] Chinese patent CN102634304A discloses a low-temperature, high-performance 3PE dry film adhesive and its preparation method. The product comprises 100 parts of a base resin, 5-10 parts of a plasticizer, 1-2 parts of a masterbatch, 1-3 parts of a polar monomer, 0.1-0.3 parts of a peroxide, 0.2-0.5 parts of an antioxidant, 0.1-0.3 parts of a polymerization inhibitor, 20-50 parts of a filler, and 5-40 parts of a tackifying resin. The base resin is a mixture of one or more of butyl rubber and ethylene-propylene rubber, a polyalphaolefin copolymer with a melt index of 100-300 g / 10 min, or an ethylene-vinyl acetate copolymer with a melt index of 100-400 g / 10 min and a vinyl acetate content of 20-30% by weight. The 3PE dry film adhesive provided by the present invention can be used for dry film installation and can achieve the same effect as wet film installation. It has good flexibility at extremely low temperatures and a low-temperature brittle temperature of less than -60°C.

[0004] Chinese patent CN 108264870 A discloses a universal adhesive for 2PE and 3PE corrosion protection, comprising the following ingredients: 30-35 parts of EVA, 28% VA content; 20-30 parts of EVA, 33% VA content; 3-5 parts of polysulfide rubber; 0.1-0.3 parts of cobalt neodecanoate; 0.6-0.9 parts of porcelain powder; 0.5-1 parts of polypropylene fiber; 2-6 parts of silicone resin; 0.2-0.4 parts of amine curing agent; and 0.8-1.5 parts of zirconate coupling agent.

[0005] The adhesives for pipeline anti-corrosion involved in the above two patents have disadvantages such as low bonding strength, thick bonding layer, strong odor, and environmental pollution. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a polybutene copolymer modified 3PE adhesive composition with strong adhesion, low odor and environmental friendliness and a preparation method thereof.

[0007] The technical solution adopted by the present invention to solve the technical problem is: a polybutene copolymer-modified 3PE adhesive composition, characterized in that: the composition comprises, by weight, 50-60 parts of poly-1-butene maleic anhydride copolymer, 25-29 parts of linear low-density polyethylene DNDA7144, 10-14 parts of high-density polyethylene DMD7006A, 4-8 parts of polyvinylpyrrolidone PVP K-90, 0.05-0.1 parts of antioxidant 1010, 0.05-0.1 parts of antioxidant 168, and 0.1-0.2 parts of lubricant.

[0008] The poly(1-butene-maleic anhydride) copolymer, antioxidant 1010 and antioxidant 168 form a good synergistic stabilizing effect. At the same time, polyvinyl pyrrolidone has excellent physiological inertness, film-forming properties and adhesion. The addition of polyvinyl pyrrolidone PVP K-90 has a good synergistic effect with the poly(1-butene-maleic anhydride) copolymer, effectively improving the adhesion performance of the adhesive. Compared with traditional adhesives, the peel strength of the adhesive of the present invention with epoxy resin and PE is 1 to 2 times higher. When 3PE anti-corrosion extrusion is performed on steel pipes, the thickness of the adhesive film layer can be effectively reduced, the amount of adhesive used can be reduced, and the extrusion speed of the anti-corrosion pipe can be effectively increased. Compared with traditional PE maleic anhydride co-extruded grafts, the odor of the composition during extrusion granulation and application of the adhesive to the anti-corrosion pipe extrusion is extremely low, which is convenient for workers to operate and is environmentally friendly.

[0009] Preferably, the molecular weight of the poly-1-butene maleic anhydride copolymer is 45,000 to 55,000.

[0010] Preferably, the poly-1-butene maleic anhydride copolymer has a molecular weight of 50,000.

[0011] The preferred molecular weight can form the best coordination effect with polyvinyl pyrrolidone and the above antioxidant, so that the adhesive composition obtains the best bonding performance and reduces the amount of adhesive used.

[0012] Preferably, the amount of the linear low-density polyethylene DNDA7144 is 26 to 28 parts by weight.

[0013] Preferably, the amount of the high-density polyethylene DMD7006A is 11 to 13 parts by weight.

[0014] Preferably, the amount of polyvinyl pyrrolidone (PVP) K-90 is 5 to 7 parts by weight. Polyvinyl pyrrolidone is an auxiliary adhesive, and the preferred amount can form a good coordination effect with the poly (1-butene maleic anhydride) copolymer to improve the adhesive effect.

[0015] Preferably, the antioxidant 1010 is pentaerythritol tetrakis[methyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) ester], and the amount used is 0.05-0.1 parts by weight.

[0016] Preferably, the amount of the antioxidant 168 is 0.05 to 0.1 parts by weight.

[0017] The antioxidant 168 is tris(2,4-di-tert-butylphenyl) phosphite.

[0018] Preferably, the lubricant is stearic acid with a molecular weight of 3000-5000, and the amount used is 0.1-0.2 parts by weight. More preferably, the molecular weight of the lubricant is 4000.

[0019] A method for preparing a polybutene copolymer-modified 3PE adhesive composition is characterized by: weighing raw materials in proportion and adding them to a high-speed mixer, mixing at 700-1400 rpm for 4-6 minutes, discharging and cooling, and granulating in a twin-screw extruder, wherein the base temperatures of the granulator zones from zone 1 to the die are, in order, 100°C, 130°C, 140°C, 150°C, 160°C, 170°C, 170°C, and 160°C.

[0020] Compared with existing technologies, the present invention has the following advantages: the poly(1-butene-maleic anhydride) copolymer and polyvinylpyrrolidone exhibit a synergistic effect, significantly improving the adhesive's bonding properties. This effectively reduces adhesive film thickness and adhesive usage during 3PE anti-corrosion extrusion of steel pipes, significantly increasing the extrusion speed of the anti-corrosion pipes. The polyvinylpyrrolidone provided by the present invention exhibits excellent physiological inertness, resulting in extremely low odor during extrusion granulation of the composition and application of the adhesive in anti-corrosion pipe extrusion, facilitating operator operation and being environmentally friendly. DETAILED DESCRIPTION

[0021] The present invention will be further described below with reference to the embodiments.

[0022] In the following examples, the preparation method of the polybutene copolymer modified 3PE adhesive composition adopts:

[0023] The Examples and Comparative Examples were weighed according to the recipes and poured into a high-speed mixer. Stirring was started (at a speed of 700-1400 rpm). After mixing for 4-6 minutes, the mixture was discharged and cooled. The mixed materials were granulated in a twin-screw extruder. The granulation parameters were set as shown in Table 1.

[0024] Table 1 Granulation parameters

[0025] .

[0026] The linear low-density polyethylene DNDA7144 is produced by Sinopec Maoming Branch, and the high-density polyethylene DMD7006A is produced by Sinopec Qilu Branch. Example

[0027] The formula components of the polybutene copolymer modified 3PE adhesive composition in each embodiment are shown in Table 2 below.

[0028] Table 2 Example formulations

[0029] .

[0030] Comparative Example

[0031] The formula components of the polybutene copolymer modified 3PE adhesive composition in each comparative example are shown in Table 3 below.

[0032] Table 3 Comparative Example Formula

[0033] .

[0034] Performance Testing

[0035] The performance of the polybutene copolymer-modified 3PE adhesive compositions prepared by the method for preparing a polybutene copolymer-modified 3PE adhesive composition according to the above examples and comparative examples was tested. The performance test results of Examples 1 to 5 are shown in Table 4 below.

[0036] Table 4 Test results of the embodiment

[0037] .

[0038] The performance test results of Comparative Examples 1 to 5 are shown in Table 5 below.

[0039] Table 5 Comparative Example Test Results

[0040] .

[0041] As shown in the Examples and Comparative Examples, poly(1-butene-maleic anhydride) copolymer and poly(vinyl pyrrolidone) exhibit a strong synergistic effect, significantly improving the adhesive's bonding properties. With increasing poly(vinyl pyrrolidone) dosage, the adhesive's bonding strength continues to improve, reaching a peak at 6 parts. The addition of poly(vinyl pyrrolidone) also effectively enhances the adhesive's fluidity, effectively reducing the adhesive film thickness and adhesive dosage during 3PE anti-corrosion extrusion of steel pipes, thereby increasing the extrusion speed of the anti-corrosion pipe. Compared to PE maleic anhydride extrusion graft copolymers, adhesives prepared using poly(1-butene-maleic anhydride) copolymer exhibit significantly improved bonding properties, low odor, and environmental friendliness.

[0042] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any other manner. Any person skilled in the art may utilize the above-disclosed technical content to modify or modify the present invention into equivalent embodiments. However, any simple modifications, equivalent variations, and modifications to the above embodiments that do not depart from the technical content of the present invention and are based on the technical essence of the present invention remain within the scope of protection of the present invention.

Claims

1. A polybutene copolymer-modified 3PE adhesive composition, characterized in that: The invention comprises, by weight, 50 to 60 parts of poly-1-butene maleic anhydride copolymer, 25 to 29 parts of linear low-density polyethylene DNDA7144, 10 to 14 parts of high-density polyethylene DMD7006A, 4 to 8 parts of polyvinyl pyrrolidone PVP K-90, 0.05 to 0.1 parts of antioxidant 1010, 0.05 to 0.1 parts of antioxidant 168, and 0.1 to 0.2 parts of lubricant.

2. The polybutene copolymer-modified 3PE adhesive composition according to claim 1, wherein: The molecular weight of the poly 1-butene maleic anhydride copolymer is 45,000 to 55,000.

3. The polybutene copolymer-modified 3PE adhesive composition according to claim 1, wherein: The molecular weight of the poly 1-butene maleic anhydride copolymer is 50,000.

4. The polybutene copolymer-modified 3PE adhesive composition according to claim 1, wherein: The amount of the linear low-density polyethylene DNDA7144 is 26 to 28 parts by weight.

5. The polybutene copolymer-modified 3PE adhesive composition according to claim 1, wherein: The amount of the high-density polyethylene DMD7006A is 11 to 13 parts by weight.

6. The polybutene copolymer-modified 3PE adhesive composition according to claim 1, wherein: The antioxidant 1010 is pentaerythritol tetrakis[methyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) ester], and the amount used is 0.05-0.1 parts by weight.

7. The polybutene copolymer-modified 3PE adhesive composition according to claim 6, wherein: The amount of the antioxidant 168 is 0.05-0.1 parts by weight.

8. The polybutene copolymer-modified 3PE adhesive composition according to claim 6, wherein: The lubricant is stearic acid with a molecular weight of 3000-5000, and the usage amount is 0.1-0.2 parts by weight.

9. The method for preparing a polybutene copolymer-modified 3PE adhesive composition according to any one of claims 1 to 8, characterized in that: The raw materials were weighed in proportion and added into a high-speed mixer. After mixing at 700-1400 rpm for 4-6 minutes, the materials were discharged, cooled, and granulated in a twin-screw extruder. The basic temperatures of the zones from zone 1 to the die of the granulator were 100°C, 130°C, 140°C, 150°C, 160°C, 170°C, 170°C, and 160°C, respectively.