CN111154416B - Radiation crosslinking polypropylene thermal shrinkage belt for submarine pipeline anticorrosion joint and preparation method thereof - Google Patents
Radiation crosslinking polypropylene thermal shrinkage belt for submarine pipeline anticorrosion joint and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
- C09J7/243—Ethylene or propylene polymers
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
- C09J2423/106—Presence of homo or copolymers of propene in the substrate
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- C09J2451/00—Presence of graft polymer
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Abstract
The invention provides a radiation crosslinking polypropylene heat-shrinkable belt for an anticorrosion node of a submarine pipeline and a preparation method thereof, wherein the radiation crosslinking polypropylene heat-shrinkable belt for the anticorrosion node of the submarine pipeline consists of a radiation crosslinking polypropylene base material and a polypropylene hot melt adhesive, and the polypropylene hot melt adhesive comprises the following components in parts by weight: 35 to 55 percent of maleic anhydride grafted random copolymerization polypropylene; 10-20% of maleic anhydride grafted block copolymerized polypropylene; 10-15% of maleic anhydride grafted metallocene polyethylene; 10-20% of polyolefin elastomer; 10 to 20 percent of tackifying resin; 5 to 10 percent of chlorinated polypropylene; 3 to 7 percent of amorphous alpha-olefin copolymer; 1% -3% of Graphene Oxide (GO). The radiation crosslinking polypropylene heat-shrinkable belt for the submarine pipeline anticorrosion joint provided by the invention has very high shear strength and peel strength at normal temperature and high temperature, has good hot water soaking resistance, and meets the performance requirements of the submarine pipeline under high temperature and seawater corrosion.
Description
Technical Field
The invention relates to the technical field of oil and gas pipeline corrosion prevention, in particular to a radiation cross-linked polypropylene heat-shrinkable tape for a submarine pipeline corrosion prevention node and a preparation method thereof.
Background
With the continuous progress of the offshore oil exploitation technology in China, the development of the offshore oil and gas field is gradually transferred from a shallow sea area to a deep sea area, and the transportation demand of oil and gas exploitation on the seabed is more and more. Pipeline transportation is one of the main methods for submarine oil and gas transportation, and has the characteristics of continuity, rapidness, safety and economy. The laying quality of marine pipelines such as submarine oil and gas gathering and transportation pipelines, main pipelines, auxiliary pressurizing platforms, main pipes connected with the pipelines and the platforms and the like is very important to the transportation efficiency, the safety and the service life, and the joint coating of submarine pipeline nodes is a key link.
Because the viscosity of crude oil is very high, in order to improve the pipeline transportation efficiency, the viscosity of the crude oil is generally reduced by adopting a method of increasing the operation temperature, the maximum operation temperature can reach more than 110 ℃, and the influence of various factors such as seawater corrosion, temperature loss, buoyancy and the like is considered, so that the corrosion prevention requirement of the submarine pipeline joint is higher than that of a land pipeline in terms of high-temperature lap joint shear strength and hot water soaking resistance. The thermal shrinkage belt is a belt-shaped material formed by compounding a base material and a hot melt adhesive, has the advantages of high construction efficiency and good anti-corrosion effect, and is the most common node anti-corrosion form of the submarine pipeline.
Because polypropylene is easy to degrade after irradiation, poor in fire resistance after irradiation crosslinking and serious in surface decomposition after fire is baked, the conventional domestic polypropylene heat-shrinkable tape base material is mainly polyethylene, and the high-temperature resistance and other physical properties of the base material are improved by adding a proper amount of polypropylene. However, the poor compatibility between polypropylene and polyethylene can cause the problems of non-sticking or low bonding strength between the polyethylene-based substrate and the polypropylene-based hot melt adhesive. Therefore, the polypropylene hot melt adhesive of the domestic polypropylene heat-shrinkable tape is mainly prepared from polyethylene grafting materials, and a small amount of polypropylene grafting materials are added, so that the highest high-temperature operation temperature of the domestic polypropylene heat-shrinkable tape can only reach 100 ℃, the high-temperature shear strength (about 0.5MPa at 100 ℃) and the high-temperature peeling strength (about 2N/mm at 100 ℃) of the adhesive are small, and the difference between the high-temperature shear strength and the high-temperature peeling strength is large compared with that of foreign products.
At present, the anticorrosion layer of the submarine pipeline mainly uses fusion bonding epoxy powder (FBE), double-layer fusion bonding epoxy powder (double-layer FBE), three-layer polyethylene (3PE), three-layer polypropylene (3PP) and a high-performance composite coating (HPCC). Before the 3PP coating technology is mature, the submarine pipeline mainly uses a 3PE coating, the high temperature resistance is poor, the highest operation temperature of the pipeline can only reach 80 ℃, and the highest operation temperature of the pipeline using the 3PP coating can reach more than 110 ℃, so that the hot melt adhesive used by the heat shrinkable belt can meet the requirements: firstly, the alloy can bear the high temperature of 110 ℃ for a long time without great attenuation of the performance; high-temperature shear strength (the shear strength at 110 ℃ is more than or equal to 1.0MPa) and high-temperature peel strength (the peel strength at 110 ℃ is more than or equal to 40N/mm); and thirdly, the coating can form good bonding with both the pipe body anticorrosive coating PP and the solvent-free epoxy primer. Because the 3PP coating is not widely applied in China, the research on the polypropylene heat-shrinkable tape for the joint patch is very little. At present, the domestic polypropylene thermal shrinkage tape can reach the highest operation temperature of only 100 ℃, and the shear strength at high temperature (100 ℃) is only about 0.5MPa, which can not meet the requirements of international standard ISO21809-3-2016, so that the domestic polypropylene thermal shrinkage tape is monopolized by foreign products in the field.
Chinese patent application No. CN201610726843.9 discloses a polypropylene hot melt adhesive, a preparation method thereof and a preparation method of a polypropylene heat shrinkable tape, but the highest applicable running temperature is 100 ℃, and the high-temperature shearing (100 ℃) is only 0.5 MPa.
Chinese patent application with application number CN201610370539.5 discloses a hot melt adhesive for a high-temperature radiation resistant cross-linked polypropylene heat-shrinkable tape, the heat-shrinkable tape and a preparation method thereof, but the highest operation temperature capable of being borne by the hot melt adhesive is 100 ℃, and the high-temperature shear (100 ℃) is only 0.5 MPa.
The invention does not solve the problem of small high-temperature lap joint shear strength of the polypropylene heat shrinkable tape, has a larger difference with foreign similar products, and influences the operation reliability and service life of the submarine pipeline.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a radiation crosslinking polypropylene thermal shrinkage tape for a submarine pipeline anticorrosion joint, which has high-temperature lap joint shear strength, high peeling strength with a 3PP pipeline anticorrosion layer and good hot water soaking resistance, and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the utility model provides a submarine pipeline anticorrosion node is with radiation cross-linking polypropylene pyrocondensation area, comprises radiation cross-linking polypropylene substrate and polypropylene hot melt adhesive, polypropylene hot melt adhesive component by weight includes:
35-55% of maleic anhydride grafted random copolymerization polypropylene (PPR-MAH);
10-20% of maleic anhydride grafted block copolymerized polypropylene (PPB-MAH);
10-15% of maleic anhydride grafted metallocene polyethylene (mPE-MAH);
10-20% of polyolefin elastomer (POE);
10 to 20 percent of tackifying resin;
5 to 10 percent of chlorinated polypropylene (CPP);
2 to 7 percent of amorphous alpha-olefin copolymer (APAO);
1% -3% of Graphene Oxide (GO);
0.5 to 1 percent of antioxidant;
0.5 to 1 percent of black master batch.
Preferably, the radiation crosslinking polypropylene thermal shrinkage belt for the submarine pipeline anticorrosion node comprises a radiation crosslinking polypropylene substrate and a polypropylene hot melt adhesive, wherein the polypropylene hot melt adhesive comprises the following components in parts by weight:
40-50% of maleic anhydride grafted random copolymerization polypropylene (PPR-MAH);
12 to 15 percent of maleic anhydride grafted block copolymerization polypropylene (PPB-MAH);
12-15% of maleic anhydride grafted metallocene polyethylene (mPE-MAH);
12 to 15 percent of polyolefin elastomer (POE);
10 to 15 percent of tackifying resin;
6 to 8 percent of chlorinated polypropylene (CPP);
3 to 6 percent of amorphous alpha-olefin copolymer (APAO);
1.5% -2.5% of Graphene Oxide (GO);
0.5 to 0.6 percent of antioxidant;
0.5 to 0.6 percent of black master batch.
Further preferably, the radiation cross-linked polypropylene thermal shrinkage belt for the submarine pipeline anticorrosion node is composed of a radiation cross-linked polypropylene substrate and a polypropylene hot melt adhesive, wherein the polypropylene hot melt adhesive comprises the following components in parts by weight:
40% of maleic anhydride grafted random copolymer polypropylene (PPR-MAH);
12% of maleic anhydride grafted block copolymerized polypropylene (PPB-MAH);
12% of maleic anhydride grafted metallocene polyethylene (mPE-MAH);
polyolefin elastomer (POE) 12%;
10% of tackifying resin;
chlorinated polypropylene (CPP) 8%;
amorphous alpha-olefin copolymer (APAO) 3%;
2% of Graphene Oxide (GO);
0.5 percent of antioxidant;
0.5 percent of black master batch.
The grafting rate of the maleic anhydride grafted random copolymerization polypropylene is 0.6-1.2%, the melt flow index of the selected random copolymerization polypropylene is 5-15 g/10min, and the melting point is 140-150 ℃.
The grafting rate of the maleic anhydride grafted block copolymer polypropylene is 0.8-1.2%, the melt flow index of the selected block copolymer polypropylene is 5-15 g/10min, and the melting point is 160-170 ℃.
The grafting rate of the maleic anhydride grafted metallocene polyethylene is 0.6-1.0%, the melt flow index of the selected metallocene polyethylene is 3-10 g/10min, and the melting point is 110-120 ℃.
The polyolefin elastomer is at least one of POE5101, POE8450, POE8480 and POE8540 of exxonmobil, the melt flow index is 1.0-10 g/10min, and the melting point is 95-105 ℃.
The tackifying resin is at least one of hydrogenated petroleum resin with C5, terpene T-120 or copolymerized petroleum resin with C5/C9, and the ring-and-ball softening point of the resin is 120-140 ℃.
The chlorinated polypropylene is chlorinated copolymer polypropylene, the chlorine content is 25-35%, and the viscosity is 300-800 mPa.
The ring-and-ball softening point of the amorphous alpha-olefin copolymer (APAO) is 140-160 ℃, and the penetration (100g/25 ℃/5s) is 20-40 dmm.
The Graphene Oxide (GO) is 250-350 nm in diameter and 0.8-1.2 nm in thickness.
The antioxidant is at least one of antioxidant 1010, antioxidant 1076 or antioxidant SKY-1035.
On the other hand, the invention also discloses a preparation method of the radiation crosslinking polypropylene heat-shrinkable belt for the submarine pipeline anticorrosion joint, which comprises the following steps:
the method comprises the following steps: weighing the raw materials of the polypropylene hot melt adhesive according to the formula, and adding the raw materials into a mixer for mixing;
step two: feeding the uniformly mixed polypropylene hot melt adhesive raw material into a feed opening of a double-screw extruder through a hopper, and melting and extruding;
step three: and coating the extruded polypropylene hot melt adhesive on a radiation crosslinking polypropylene substrate, and cooling and pressing to obtain the radiation crosslinking polypropylene heat-shrinkable belt for the submarine pipeline anticorrosion joint.
Preferably, the mixture is added into a mixer for mixing in the first step, the stirring speed is 300r/min, and the mixing time is 45-60 min;
preferably, the second step enters a double-screw extruder for melting and extruding, and the temperature of the barrel of the extruder is set as follows:
a first region: 100 ± 10 ℃, second zone: 120 plus or minus 10 ℃; a third zone: 140 plus or minus 10 ℃; a fourth area: 160 +/-10 ℃; a fifth area: 180 plus or minus 10 ℃; a sixth zone: 200 plus or minus 10 ℃; a seventh region: 200 plus or minus 10 ℃; the eighth area is 200 +/-10 ℃;
the extruder die temperature was set as:
a first region: 200 plus or minus 10 ℃; a second region: 200 plus or minus 10 ℃; a third zone: 200 plus or minus 10 ℃;
preferably, in the third step, the thickness of the radiation crosslinking polypropylene base material is 1.2mm, the thickness of the polypropylene hot melt adhesive is 1.5mm, and the total thickness of the radiation crosslinking polypropylene heat-shrinkable tape for the submarine pipeline anticorrosion joint is 2.7 m.
Compared with the prior art, the radiation cross-linked polypropylene thermal shrinkage belt for the submarine pipeline anticorrosion node has the following gain effects:
(1) has high shear strength at normal temperature and high temperature (110 ℃), and the shear strength at 110 ℃ is more than 1.0 MPa.
The content of the polypropylene grafting material and the chlorinated polypropylene in the formula of the polypropylene hot melt adhesive provided by the invention exceeds 50%, the content of the polyethylene grafting material and the polyolefin elastomer is only about 30%, the ring-and-ball softening point of the tackifying resin is above 120 ℃, the melting point of the polypropylene is 140-170 ℃, the high-temperature shear strength of the polypropylene hot melt adhesive is ensured, and the high-temperature shear strength is more than 1.0MPa at 110 ℃. The radiation crosslinking polypropylene heat-shrinkable belt for the submarine pipeline anticorrosion joint provided by the invention adopts crosslinking polypropylene as a base material, and has good compatibility with the polypropylene hot melt adhesive.
(2) The high-strength anticorrosive coating 3LPP has high peel strength at high temperature (110 ℃), and the peel strength at 110 ℃ is more than 4N/mm.
The polypropylene hot melt adhesive polypropylene grafting material developed by the invention has high content and the melting point is above 140 ℃, so that the peeling strength of the heat shrinkable belt at 110 ℃ is higher than that of the existing polypropylene heat shrinkable belt. The high-temperature peel strength of the existing polypropylene heat-shrinkable belt to the pipe body anticorrosive layer 3LPP is only 2N/mm at 100 ℃, the radiation crosslinking polypropylene heat-shrinkable belt for the submarine pipeline anticorrosive node provided by the invention has high-temperature peel strength to the pipe body anticorrosive layer 3LPP, the temperature of 110 ℃ is more than 4N/mm, and the radiation crosslinking polypropylene heat-shrinkable belt can meet the standard requirement of ISO 21809-3.
(3) The hot water soaking resistance is excellent. A small amount of amorphous alpha-olefin copolymer (APAO) and Graphene Oxide (GO) are added into the polypropylene hot melt adhesive provided by the invention, and the APAO is used as an upgraded product of random polypropylene (APP), has very good compatibility with polypropylene, and simultaneously has excellent high and low temperature performances and water resistance, so that the polypropylene hot melt adhesive has very good high-temperature hot water soaking resistance. GO is a novel sheet-shaped reinforcing material, a perfect reinforcing network can be constructed in a hot melt adhesive system by using a small amount of GO, and meanwhile, the sheet-shaped structure of GO has a separation effect on heat, so that the shear strength, the peel strength and the hot water soaking resistance of the hot melt adhesive are improved.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are merely exemplary and not exhaustive for the technical effects of the invention.
Example 1 radiation cross-linked polypropylene heat-shrinkable tape for submarine pipeline anticorrosion joint
A radiation cross-linked polypropylene thermal shrinkage belt for an anticorrosion node of a submarine pipeline is composed of a radiation cross-linked polypropylene substrate and a polypropylene hot melt adhesive, wherein the components of the polypropylene hot melt adhesive are shown in Table 1 by weight;
a preparation method of a radiation cross-linked polypropylene heat-shrinkable belt for an anticorrosion node of a submarine pipeline comprises the following steps:
the method comprises the following steps: weighing the polypropylene hot melt adhesive raw materials according to the formula, adding the raw materials into a mixer for mixing, wherein the stirring speed is 300r/min, and the mixing time is 45 min;
step two: the evenly mixed polypropylene hot melt adhesive raw material enters a feed opening of a double-screw extruder through a hopper for melting and extruding,
extruder barrel temperature settings were:
a first region: 100 ± 10 ℃, second zone: 120 plus or minus 10 ℃; a third zone: 140 plus or minus 10 ℃; a fourth area: 160 +/-10 ℃; a fifth area: 180 plus or minus 10 ℃; a sixth zone: 200 plus or minus 10 ℃; a seventh region: 200 plus or minus 10 ℃; the eighth area is 200 +/-10 ℃;
the extruder die temperature was set as:
a first region: 200 plus or minus 10 ℃; a second region: 200 plus or minus 10 ℃; a third zone: 200 plus or minus 10 ℃;
step three: coating the extruded polypropylene hot melt adhesive on a radiation cross-linked polypropylene substrate, wherein the thickness of the radiation cross-linked polypropylene substrate is 1.2mm, the thickness of the polypropylene hot melt adhesive is 1.5mm, the total thickness of the radiation cross-linked polypropylene heat-shrinkable tape for the submarine pipeline anticorrosion joint is 2.7m, and cooling and pressing are carried out to obtain the radiation cross-linked polypropylene heat-shrinkable tape for the submarine pipeline anticorrosion joint.
Examples 2 to 5
A radiation crosslinking polypropylene thermal shrinkage tape for an anticorrosion node of a submarine pipeline is composed of a radiation crosslinking polypropylene base material and a polypropylene hot melt adhesive, wherein the components of the polypropylene hot melt adhesive are shown in the table 1 in terms of weight, and the preparation method is the same as that in the embodiment 1.
Comparative example 1
A radiation cross-linked polypropylene thermal shrinkage belt for an anticorrosion node of a submarine pipeline is composed of a radiation cross-linked polypropylene substrate and a polypropylene hot melt adhesive, wherein the components of the polypropylene hot melt adhesive are shown in Table 1 by weight;
the preparation method comprises the following steps:
the procedure was as in example 1;
step two: the evenly mixed polypropylene hot melt adhesive raw material enters a feed opening of a double-screw extruder through a hopper for melting and extruding,
extruder barrel temperature settings were:
a first region: 100 ± 10 ℃, second zone: 120 plus or minus 10 ℃; a third zone: 140 plus or minus 10 ℃; a fourth area: 160 +/-10 ℃; a fifth area: 160 +/-10 ℃; a sixth zone: 180 plus or minus 10 ℃; a seventh region: 180 plus or minus 10 ℃; the eighth area is 180 +/-10 ℃;
the extruder die temperature was set as:
a first region: 180 plus or minus 10 ℃; a second region: 180 plus or minus 10 ℃; a third zone: 180 plus or minus 10 ℃;
the third step is the same as example 1.
Comparative examples 2 to 3
A radiation cross-linked polypropylene thermal shrinkage belt for an anticorrosion node of a submarine pipeline is composed of a radiation cross-linked polypropylene substrate and a polypropylene hot melt adhesive, wherein the components of the polypropylene hot melt adhesive are shown in the table 1 in terms of weight, and the preparation method is the same as the comparative example 1.
Table 1 examples 1 to 5 and comparative examples 1 to 2 each component raw material formulation (%)
The radiation cross-linked polypropylene heat-shrinkable tapes for the anticorrosion joints of the submarine pipelines obtained in the examples 1-5 and the comparative examples 1-2 are respectively subjected to lap joint shear strength test at normal temperature/high temperature, peel strength at normal temperature/high temperature and 3LPP and hot water immersion resistance test, wherein the lap joint shear strength test at normal temperature/high temperature is in reference to the standard EN 12068 cathode protection, organic coating, adhesive tape and shrinkage material which are used for protecting the external corrosion of buried or underwater steel pipelines together with cathode protection, and the peel strength at normal temperature/high temperature and 3LPP and hot water immersion resistance test is in reference to the standard ISO21809-3 buried or underwater pipeline transportation system used in the external coating of the petroleum and natural gas industry-part 3: spot seam coating ", test results are as follows:
TABLE 2 test results of lap joint strength at Normal temperature/high temperature and 3LPP peel strength
TABLE 3 Hot Water immersion resistance test results
As can be seen from the test results in tables 2 and 3, the polypropylene hot melt adhesive in the radiation cross-linked polypropylene heat-shrinkable tapes for the anti-corrosion nodes of the submarine pipelines in examples 1 to 5 provided by the invention has a higher polypropylene content, and has good compatibility with the radiation cross-linked polypropylene base material and 3LPP, and the normal temperature/high temperature lap shear strength and the normal temperature/high temperature peel strength thereof are obviously higher than those of comparative example 1 and comparative example 3, in which the normal temperature/high temperature lap shear strength of example 1 is respectively improved by 83%/97% compared with that of comparative example 1, improved by 100%/109% compared with that of comparative example 3, and the normal temperature/high temperature peel strength is respectively improved by 18%/74% compared with that of comparative example 1, and improved by 32%/93% compared with that of comparative example 3. In the embodiments 1-5, a small amount of amorphous α -olefin copolymer (APAO) and Graphene Oxide (GO) are added to the polypropylene hot melt adhesive, and APAO has very good compatibility with polypropylene, and also has excellent high and low temperature properties and water resistance; GO is a sheet-shaped reinforcing material, a complete reinforcing network can be constructed in a hot melt adhesive system with a small amount of GO, and the sheet-shaped structure of GO has a barrier effect on heat, so that the polypropylene hot melt adhesive has very good high-temperature hot water soaking resistance, wherein the high-temperature hot water soaking resistance of the embodiment 1 is improved by 34% and 39% respectively compared with that of a comparative example 2 and a comparative example 3 which are not added with APAO and GO.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (9)
1. The utility model provides a submarine pipeline anticorrosion node is with radiation cross-linking polypropylene pyrocondensation area comprises radiation cross-linking polypropylene substrate and polypropylene hot melt adhesive, its characterized in that, polypropylene hot melt adhesive component by weight includes:
35-40% of maleic anhydride grafted random copolymer polypropylene (PPR-MAH);
10-16% of maleic anhydride grafted block copolymer polypropylene (PPB-MAH);
10% -14% of maleic anhydride grafted metallocene polyethylene (mPE-MAH);
10% -20% of polyolefin elastomer (POE);
10% -20% of tackifying resin;
5% -10% of chlorinated polypropylene (CPP);
3% -7% of amorphous alpha-olefin copolymer (APAO);
1% -3% of Graphene Oxide (GO);
0.5% -1% of antioxidant;
0.5-1% of black master batch.
2. The utility model provides a submarine pipeline anticorrosion node is with radiation cross-linking polypropylene pyrocondensation area comprises radiation cross-linking polypropylene substrate and polypropylene hot melt adhesive, its characterized in that, polypropylene hot melt adhesive component by weight includes:
40% of maleic anhydride grafted random copolymer polypropylene (PPR-MAH);
12% of maleic anhydride grafted block copolymerized polypropylene (PPB-MAH);
12% of maleic anhydride grafted metallocene polyethylene (mPE-MAH);
polyolefin elastomer (POE) 12%;
10% of tackifying resin;
chlorinated polypropylene (CPP) 8%;
amorphous alpha-olefin copolymer (APAO) 3%;
2% of Graphene Oxide (GO);
0.5 percent of antioxidant;
0.5 percent of black master batch.
3. The radiation crosslinked polypropylene heat-shrinkable tape for the corrosion prevention node of the submarine pipeline according to any one of claims 1 to 2, wherein:
the grafting rate of the maleic anhydride grafted random copolymerization polypropylene is 0.6-1.2%, the melt flow index of the selected random copolymerization polypropylene is 5-15 g/10min, and the melting point is 140-150 ℃;
the grafting rate of the maleic anhydride grafted block copolymer polypropylene is 0.8-1.2%, the melt flow index of the selected block copolymer polypropylene is 5-15 g/10min, and the melting point is 160-170 ℃;
the grafting rate of the maleic anhydride grafted metallocene polyethylene is 0.6-1.0%, the melt flow index of the selected metallocene polyethylene is 3-10 g/10min, and the melting point is 110-120 ℃.
4. The radiation crosslinked polypropylene heat-shrinkable tape for the corrosion prevention node of the submarine pipeline according to any one of claims 1 to 2, wherein:
the polyolefin elastomer is at least one of POE5101, POE8450, POE8480 and POE8540 of exxonmobil, the melt flow index is 1.0-10 g/10min, and the melting point is 95-105 ℃.
5. The radiation crosslinked polypropylene heat-shrinkable tape for the corrosion prevention node of the submarine pipeline according to any one of claims 1 to 2, wherein:
the tackifying resin is at least one of hydrogenated petroleum resin with C5, terpene T-120 or copolymerized petroleum resin with C5/C9, and the ring-and-ball softening point of the resin is 120-140 ℃.
6. The radiation crosslinked polypropylene heat-shrinkable tape for the corrosion prevention node of the submarine pipeline according to any one of claims 1 to 2, wherein:
the chlorinated polypropylene is chlorinated copolymer polypropylene, the chlorine content is 25-35%, and the viscosity is 300-800 mPa & s.
7. The radiation crosslinked polypropylene heat-shrinkable tape for the corrosion prevention node of the submarine pipeline according to any one of claims 1 to 2, wherein:
the ring-and-ball softening point of the amorphous alpha-olefin copolymer (APAO) is 140-160 ℃, and the penetration under the condition of 100g/25 ℃/5s is 20-40 dmm;
the Graphene Oxide (GO) has a diameter of 250-350 nm and a thickness of 0.8-1.2 nm;
the antioxidant is at least one of antioxidant 1010, antioxidant 1076 or antioxidant SKY-1035.
8. A method for preparing a radiation crosslinked polypropylene heat-shrinkable belt for an anti-corrosion node of a submarine pipeline according to any one of claims 1-2, which comprises the following steps: the method comprises the following steps:
the method comprises the following steps: weighing the raw materials of the polypropylene hot melt adhesive according to the formula, and adding the raw materials into a mixer for mixing;
step two: feeding the uniformly mixed polypropylene hot melt adhesive raw material into a feed opening of a double-screw extruder through a hopper, and melting and extruding;
step three: and coating the extruded polypropylene hot melt adhesive on a radiation crosslinking polypropylene substrate, and cooling and pressing to obtain the radiation crosslinking polypropylene heat-shrinkable belt for the submarine pipeline anticorrosion joint.
9. The preparation method of the radiation crosslinking polypropylene heat-shrinkable belt for the submarine pipeline anticorrosion joint according to claim 8, wherein the preparation method comprises the following steps:
adding the mixture into a mixer for mixing in the first step, wherein the stirring speed is 300r/min, and the mixing time is 45-60 min;
and in the second step, the mixture enters a double-screw extruder for melting and extruding, and the temperature of a machine barrel of the extruder is set as follows:
a first region: 100 ± 10 ℃, second zone: 120 plus or minus 10 ℃; a third zone: 140 plus or minus 10 ℃; a fourth area: 160 +/-10 ℃; a fifth area: 180 plus or minus 10 ℃; a sixth zone: 200 plus or minus 10 ℃; a seventh region: 200 plus or minus 10 ℃; the eighth area is 200 +/-10 ℃;
the extruder die temperature was set as:
a first region: 200 plus or minus 10 ℃; a second region: 200 plus or minus 10 ℃; a third zone: 200 plus or minus 10 ℃;
in the third step, the thickness of the radiation crosslinking polypropylene base material is 1.2mm, the thickness of the polypropylene hot melt adhesive is 1.5mm, and the total thickness of the radiation crosslinking polypropylene heat-shrinkable tape for the submarine pipeline anticorrosion joint is 2.7 mm.
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| CN106010391B (en) * | 2016-05-27 | 2017-11-03 | 长园长通新材料股份有限公司 | A kind of high temperature resistant radiating crosslinked polypropylene pyrocondensation belt PUR, pyrocondensation belt and preparation method thereof |
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