CN111484818A - Pipe end sealant for heat-insulating pipe and preparation method thereof - Google Patents

Pipe end sealant for heat-insulating pipe and preparation method thereof Download PDF

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Publication number
CN111484818A
CN111484818A CN202010354337.8A CN202010354337A CN111484818A CN 111484818 A CN111484818 A CN 111484818A CN 202010354337 A CN202010354337 A CN 202010354337A CN 111484818 A CN111484818 A CN 111484818A
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Prior art keywords
pipe
pipe end
ethylene
resin
weight
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CN111484818B (en
Inventor
杨军伟
韦良
陆伟
於维伟
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Jiangsu Dasheng Pyrocondensation Material Co ltd
Jiangsu Dasheng Thermal Shrinkage Protection Products Co ltd
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Jiangsu Dasheng Pyrocondensation Material Co ltd
Jiangsu Dasheng Thermal Shrinkage Protection Products Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04Homopolymers or copolymers of ethene
    • C09J123/08Copolymers of ethene
    • C09J123/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869Acids or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/14Gas barrier composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/18Applications used for pipes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention relates to a pipe end sealant for a heat-preservation pipe, which comprises the following components: 13-16% of butyl rubber, 30-42% of ethylene-acrylate-maleic anhydride terpolymer, 20-30% of ethylene-methyl acrylate copolymer, 7-10% of terpene resin, 11-15% of carbon five petroleum resin, 2-10% of calcium carbonate, 1-3% of antioxidant and 1-3% of carbon black. The hot-melt sealant disclosed by the invention specifically takes butyl rubber, ethylene-acrylate-maleic anhydride terpolymer and ethylene-methyl acrylate copolymer as main raw materials, and components such as tackifying resin, antioxidant and filler are added at the same time, so that the hot-melt sealant has the characteristic of high viscosity, the finished product does not flow and become brittle, and has better adhesion compared with an adhesive mainly based on polyacrylate homopolymer resin, and has better toughness compared with an adhesive mainly based on aromatic polyester resin, and is less prone to becoming brittle and hard.

Description

Pipe end sealant for heat-insulating pipe and preparation method thereof
Technical Field
The invention relates to the field of sealants, in particular to a pipe end sealant for a heat-preservation pipe.
Background
The heat insulation pipe is a short-term heat insulation pipeline, is commonly used for conveying liquid, gas and other media, and is an important component in pipeline construction projects such as petroleum, chemical engineering, aerospace, military, central heating, municipal administration and the like. The insulating tube is suitable for conveying various media in the range of-50 ℃ to 150 ℃.
The heat preservation pipe is divided into three layers from inside to outside. A first layer: the working steel pipe layer is generally seamless steel pipe, spiral steel pipe and straight seam steel pipe. A second layer: the polyurethane heat-insulating layer is formed by injecting rigid polyurethane foam stock solution into a cavity formed between the steel pipe and the outer protective layer at one time by using a high-pressure foaming machine. And a third layer: high density polyethylene protective layer: the black or yellow polyethylene plastic pipe with a certain wall thickness is prefabricated, and has the functions of protecting the polyurethane heat-insulating layer from being damaged by mechanical hard objects, and preventing corrosion and water.
In order to facilitate subsequent construction, the two ends of the heat-insulating pipe are not protected by heat-insulating layers, exposed parts are generally protected by adopting a fusion bonding epoxy powder (FBE) coating and a high-density polyethylene (HDPE) material, and the FBE coating has excellent bonding protection performance on the steel pipe but has poor bonding performance on the HDPE material. In order to improve the protection effect of the part, an adhesive material with good bonding property, good sealing effect and good temperature resistance to FBE and HDPE needs to be developed.
Disclosure of Invention
The invention aims to solve the problem of sealing protection at two ends of a heat-insulating pipe, provides a sealant for the heat-insulating pipe, particularly provides a hot melt adhesive for sealing protection at two ends of the heat-insulating pipe, and also aims to provide a preparation method of the hot melt adhesive. The sealant prepared by the invention has good bonding performance on FBE and HDPE at the end part of the heat-insulating pipe, good sealing effect and good temperature resistance.
The invention provides a pipe end sealant for a heat-insulating pipe, which mainly comprises the following components in percentage by weight:
13 to 16 percent of butyl rubber
30-42% of ethylene-acrylate-maleic anhydride terpolymer
20-30% of ethylene-methyl acrylate copolymer
18-25% of tackifying resin.
As a preferable technical scheme, the tackifying resin is terpene resin and carbon penta petroleum resin. The content of the terpene resin is preferably 7-10% by weight, and the content of the carbon penta petroleum resin is preferably 11-15% by weight. In other embodiments provided herein, the terpene resin is more preferably present in an amount of 8-9%, and the carbon pentapetroleum resin is more preferably present in an amount of 11-13%. More preferably, the softening point of the carbon five petroleum resin is 110-130 ℃. The softening point of the terpene resin is 110-120 ℃. Among them, the softening point can be obtained by testing GB/T15332-1994.
As a preferable technical scheme, the pipe end sealant for the heat-preservation pipe further comprises 3-13% of filler in percentage by weight. More preferably, the filler is calcium carbonate and carbon black. In other embodiments provided by the present invention, the pipe end sealant for the thermal insulation pipe comprises 2-10% of calcium carbonate and 1-3% of carbon black.
As a preferred technical scheme, the pipe end sealant for the heat preservation pipe further comprises 1-3% of an antioxidant in percentage by weight, preferably, the antioxidant is pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), and the addition of the components can improve the oxidation resistance and the heat resistance stability of the sealant.
The invention has no limitation on the selection of raw material sources and can be obtained from the market.
The manufacturing process of the pipe end sealant for the heat-preservation pipe comprises the following steps:
step 1: preparing materials: weighing the raw materials according to the weight ratio;
step 2: banburying: banburying butyl rubber, terpene resin and calcium carbonate in an internal mixer for 30-40min at the temperature of 130-;
and step 3: kneading: kneading the internally mixed raw materials and other raw materials in a kneader for 120-150min at the kneading temperature of 120-150 ℃;
and 4, step 4: molding: and tabletting and forming to obtain the pipe end sealant for the heat-preservation pipe.
The technical performance of the pipe end sealant for the heat-preservation pipe prepared by the invention is shown in the following table 1:
table 1:
color appearance Black color
Smell(s) No peculiar smell during working
Embrittlement resistance at-50 DEG C By passing
Flowability at 150 ℃ Does not flow down
Adhesive strength >100N/cm
The hot-melt sealant disclosed by the invention specifically takes butyl rubber, an ethylene-acrylate-maleic anhydride terpolymer (EMH) and an ethylene-methyl acrylate copolymer (EMA) as main raw materials, and is added with tackifying resin, an antioxidant, a filler and other components, so that the hot-melt sealant has the characteristic of high viscosity, a finished product does not flow and is not brittle, and compared with a binder which uses polyacrylate homopolymer resin or silicone resin as a main component in the prior art, the hot-melt sealant has better adhesion, and compared with a binder which uses aromatic polyester resin as a main component in the prior art, the hot-melt sealant has better toughness and is less brittle and hard.
On the basis of selecting proper raw materials, the invention further tests and screens the usage amount of the raw materials, determines the optimal usage proportion, further improves the bonding property and the temperature resistance of the prepared product, and obtains the hot melt adhesive with good bonding property, good sealing effect, good temperature resistance, simple production process and convenient use. Meanwhile, the invention also provides a preparation process of the sealant.
The beneficial technical effects of the invention are as follows:
1. the pipe end sealant for the heat-insulating pipe has high bonding strength (more than 100N/cm), greatly improves the temperature resistance of hot melt adhesive products, has wide working temperature range, and can completely meet the requirements of sealing protection and use conditions of the heat-insulating pipe. Has good continuous adhesion and higher mechanical strength. Very suitable for the treatment of FBE coatings and HDPE surfaces on pipes.
2. The invention has simple process and low energy consumption, and has good economic benefit and industrial production prospect.
3. The invention has the advantages of wide material source, convenient processing, quick production process, high productivity, simple construction, no solvent in the product, no pollution to the environment, and excellent aging resistance and air tightness.
4. The product of the invention has long shelf life and service life, and excellent oil resistance, water resistance, acid resistance, alkali resistance and salt solution performance.
Detailed Description
The invention is further described with reference to specific examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The preparation methods in the following examples and comparative examples were: weighing the raw materials according to the raw material ratio, banburying the butyl rubber, the terpene resin and the calcium carbonate in an internal mixer for 35min at the banburying temperature of 140 ℃, kneading all the raw materials in a kneader for 135min at the kneading temperature of 135 ℃, and tabletting for forming to obtain the finished product.
Example 1
The pipe end sealant for the thermal insulation pipe comprises the following components in percentage by weight:
butyl rubber 15%
Ethylene-acrylate-maleic anhydride terpolymer (EMH) 35%
Ethylene-methyl acrylate copolymer (EMA) 20%
Terpene resin 9%
14 percent of carbon five petroleum resin
Calcium carbonate 5%
1 percent of antioxidant
1% of carbon black
The antioxidant is pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).
Example 2
The pipe end sealant for the thermal insulation pipe comprises the following components in percentage by weight:
butyl rubber 16%
Ethylene-acrylate-maleic anhydride terpolymer (EMH) 30%
Ethylene-methyl acrylate copolymer (EMA) 25%
Terpene resin 10%
15 percent of carbon five petroleum resin
2 percent of calcium carbonate
1 percent of antioxidant
1% of carbon black
The antioxidant is pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).
Example 3
The pipe end sealant for the thermal insulation pipe comprises the following components in percentage by weight:
butyl rubber 13%
Ethylene-acrylate-maleic anhydride terpolymer (EMH) 42%
Ethylene-methyl acrylate copolymer (EMA) 20%
Terpene resin 7%
11 percent of carbon five petroleum resin
3 percent of calcium carbonate
Antioxidant 2%
2 percent of carbon black
The antioxidant is pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).
Example 4
The pipe end sealant for the thermal insulation pipe comprises the following components in percentage by weight:
butyl rubber 14%
Ethylene-acrylate-maleic anhydride terpolymer (EMH) 30%
Ethylene-methyl acrylate copolymer (EMA) 30%
Terpene resin 8%
13 percent of carbon five petroleum resin
2 percent of calcium carbonate
Antioxidant 2%
1% of carbon black
The antioxidant is pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).
Example 5
The pipe end sealant for the thermal insulation pipe comprises the following components in percentage by weight:
butyl rubber 16%
Ethylene-acrylate-maleic anhydride terpolymer (EMH) 31%
Ethylene-methyl acrylate copolymer (EMA) 23%
Terpene resin 7%
11 percent of carbon five petroleum resin
Calcium carbonate 10%
1 percent of antioxidant
1% of carbon black
The antioxidant is pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).
Comparative example 1
The pipe end sealant for the thermal insulation pipe comprises the following components in percentage by weight:
12 percent of butyl rubber
Ethylene-acrylate-maleic anhydride terpolymer (EMH) 29%
Ethylene-methyl acrylate copolymer (EMA) 19%
Terpene resin 11%
Carbon five petroleum resin 10%
15 percent of calcium carbonate
Antioxidant 2%
2 percent of carbon black
The antioxidant is pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).
Comparative example 2
The pipe end sealant for the thermal insulation pipe comprises the following components in percentage by weight:
butyl rubber 17%
Ethylene-acrylate-maleic anhydride terpolymer (EMH) 27%
Ethylene-methyl acrylate copolymer (EMA) 16%
Terpene resin 11%
16 percent of carbon five petroleum resin
11 percent of calcium carbonate
1 percent of antioxidant
1% of carbon black
The antioxidant is pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).
The sealants prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to performance tests, and the results are shown in table 2:
table 2:
Figure 22244DEST_PATH_IMAGE001
and (4) conclusion: from examples 1 to 5, it can be seen that, in a proper proportion range, the main raw materials such as butyl rubber, EMH, EMA and the like, and the components such as tackifying resin, antioxidant, filler and the like are configured, so that the product has high normal-temperature bonding strength, and the tolerance of the product to high temperature and low temperature is enhanced to a certain extent. The results of comparative examples 1-2 show that reducing the amount of butyl rubber, EMH, EMA results in a product that is brittle at low temperatures, has reduced viscosity at high temperatures, and reduces product performance. The excessive proportion of the butyl rubber, the EMH and the EMA can reduce the content of the auxiliary agent, reduce the bonding strength, deteriorate the durability, be easily corroded by acid and alkali, and cause the phenomena of peeling and the like. Therefore, the selection of the proper dosage ratio is important for the pipe end sealant for the heat preservation pipe.
The sealants of examples 1 and 3, as well as a commercially available polyacrylate sealant and a commercially available silicone sealant were used to perform a performance test comparison in accordance with GB/T23257, a tensile tester was used at a test speed of about 10mm/min, an anticorrosive structure was set in accordance with FBE, sealant and HDPE, and a sealant coating thickness of about 250 μm was obtained, and the results are shown in Table 3.
Table 3:
Figure 283592DEST_PATH_IMAGE002
the experimental results in table 3 show that the pipe end sealant for the heat-insulating pipe of the invention has more excellent bonding performance for FBE and HDPE compared with the common polyacrylate sealant and silicone sealant sold in the market, and can meet the requirements of sealing protection and use conditions of the heat-insulating pipe.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (9)

1. The pipe end sealant for the heat-preservation pipe is characterized by comprising the following components in parts by weight: the composite material comprises the following components in percentage by weight:
13 to 16 percent of butyl rubber
30-42% of ethylene-acrylate-maleic anhydride terpolymer
20-30% of ethylene-methyl acrylate copolymer
18-25% of tackifying resin.
2. The pipe end sealant for an insulated pipe according to claim 1, wherein: the tackifying resin is terpene resin and carbon five petroleum resin, and the terpene resin accounts for 7-10% by weight, and the carbon five petroleum resin accounts for 11-15% by weight.
3. The pipe end sealant for an insulated pipe according to claim 1, wherein: the composite material also comprises 3-13% of filler by weight percentage, wherein the filler is calcium carbonate and carbon black.
4. The pipe end sealant for an insulated pipe according to claim 3, wherein: the sealant comprises 2-10% of calcium carbonate and 1-3% of carbon black in percentage by weight.
5. The pipe end sealant for heat preservation pipes as claimed in claim 1, further comprising 1-3% by weight of an antioxidant which is pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).
6. The pipe end sealant for an insulated pipe according to claim 2, wherein: the softening point of the carbon five petroleum resin is 110-130 ℃.
7. The pipe end sealant for an insulated pipe according to claim 2, wherein: the softening point of the terpene resin is 110-120 ℃.
8. The pipe end sealant for an insulated pipe according to claim 1, wherein: the composite material comprises the following components in percentage by weight:
butyl rubber 13%
Ethylene-acrylate-maleic anhydride terpolymer (EMH) 42%
Ethylene-methyl acrylate copolymer (EMA) 20%
Terpene resin 7%
11 percent of carbon five petroleum resin
3 percent of calcium carbonate
Antioxidant 2%
2% of carbon black.
9. The method for preparing the pipe end sealant for the heat preservation pipe as claimed in claim 8, wherein: the method comprises the following steps:
step 1: preparing materials: weighing the raw materials according to the weight ratio;
step 2: banburying: banburying butyl rubber, terpene resin and calcium carbonate in an internal mixer for 30-40min at the temperature of 130-;
and step 3: kneading: kneading the internally mixed raw materials and other raw materials in a kneader for 120-150min at the kneading temperature of 120-150 ℃;
and 4, step 4: molding: and tabletting and forming to obtain the pipe end sealant for the heat-preservation pipe.
CN202010354337.8A 2020-04-29 2020-04-29 Pipe end sealant for heat-insulating pipe and preparation method thereof Active CN111484818B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4127545A (en) * 1976-05-24 1978-11-28 Cities Service Company Hot melt crosslinked butyl sealant
CN104479592A (en) * 2014-12-15 2015-04-01 江苏达胜热缩材料有限公司 Low-temperature 2PE hot melt adhesive and preparation method thereof
CN110028915A (en) * 2019-04-26 2019-07-19 江苏达胜热缩防护用品有限公司 A kind of Pipeline joint anticorrosion low form 3PE dry film hot melt adhesive and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4127545A (en) * 1976-05-24 1978-11-28 Cities Service Company Hot melt crosslinked butyl sealant
CN104479592A (en) * 2014-12-15 2015-04-01 江苏达胜热缩材料有限公司 Low-temperature 2PE hot melt adhesive and preparation method thereof
CN110028915A (en) * 2019-04-26 2019-07-19 江苏达胜热缩防护用品有限公司 A kind of Pipeline joint anticorrosion low form 3PE dry film hot melt adhesive and preparation method thereof

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