CN109679533A - A kind of adhering resin and method suitable for aramid fiber reinforced composite pipe - Google Patents

A kind of adhering resin and method suitable for aramid fiber reinforced composite pipe Download PDF

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Publication number
CN109679533A
CN109679533A CN201811587360.0A CN201811587360A CN109679533A CN 109679533 A CN109679533 A CN 109679533A CN 201811587360 A CN201811587360 A CN 201811587360A CN 109679533 A CN109679533 A CN 109679533A
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CN
China
Prior art keywords
adhering resin
aramid fiber
fiber reinforced
reinforced composite
composite pipe
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201811587360.0A
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Chinese (zh)
Inventor
孙晓光
欧阳贵
程泰山
肖传富
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SHANGHAI BANGZHONG NEW MATERIAL CO Ltd
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SHANGHAI BANGZHONG NEW MATERIAL CO Ltd
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Priority to CN201811587360.0A priority Critical patent/CN109679533A/en
Publication of CN109679533A publication Critical patent/CN109679533A/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives 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
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives 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
    • C09J123/10—Homopolymers or copolymers of propene
    • C09J123/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a kind of adhering resin and method suitable for aramid fiber reinforced composite pipe, adhering resin is following raw material components and parts by weight: 30-45 parts of linear low density polyethylene (LLDPE), 20-60 parts of copolymer polypropylene, 10-25 parts of ethylene-vinyl acetate copolymer, 5-20 parts of compatilizer, -5 parts of silica 1,0.5-2 parts of stabilizer；Method includes: 1) according to parts by weight, linear low density polyethylene, copolymer polypropylene, ethylene-vinyl acetate copolymer, compatilizer, silica, stabilizer to be weighed and mixed；2) well-mixed raw material is added to progress high temperature mixing in double screw extruder, and extruding pelletization, technological temperature is set as 180-220 DEG C, and screw speed is that 300-380 turns/min；The present invention provides a kind of adhesive properties, and good, bonding aramid fiber enhancing compound pipeline complex pipeline is not easy the adhering resin and method suitable for aramid fiber reinforced composite pipe for delamination, segregation phenomenon occur.

Description

A kind of adhering resin and method suitable for aramid fiber reinforced composite pipe
Technical field
The present invention relates to pipe material field more particularly to a kind of adhering resins and side suitable for aramid fiber reinforced composite pipe Method.
Background technique
Aramid fiber is a kind of organic polymer fiber, its intensity height, good toughness, modulus are high, density is small, corrosion-resistant, hot steady Qualitative good, tensile strength is up to 2800N/mm2, elongation at break 3.8%, aerial decomposition temperature be up to 400 DEG C with On.The compound pipe diameter manufactured with aramid fiber can theoretically produce random length product from 50-250mm.According further to not With the demand of occasion, specific requirement can be had reached by increasing and decreasing the number of plies of aramid fiber.
Aramid fiber reinforced composite pipe is mainly used as oil-gas transportation, city gas net engineering, shallow sea oil-gas pipeline etc. at present, it With light weight, intensity height, endurance, anticorrosive, flexible, more extensive requirement can satisfy.However, this production The production of product is concentrated mainly on foreign countries, and the key constraints of the such product of domestic production are in aramid fiber and the compound mistake of tubing Compound sticking in journey, once the adhering resin selected cannot reach enough adhesive strengths, the aramid fiber enhancing produced Compound pipeline complex pipeline be easy to appear delamination, segregation phenomenon in use, seriously affect the quality of product.
In conclusion the adhesive property of the adhering resin for aramid fiber reinforced composite pipe of the prior art is bad.
Summary of the invention
In view of the above technical problems, that the present invention provides a kind of adhesive properties is good, the multiple tube of bonding aramid fiber enhancing Road is not easy delamination, the adhering resin of segregation phenomenon and method occur.
One aspect of the present invention provides a kind of adhering resin suitable for aramid fiber reinforced composite pipe, described viscous Connecing resin is following raw material components and parts by weight:
Preferably, the melt flow rate (MFR) of the linear low density polyethylene is 1.0-8.0g/10min, and melting temperature is Between 115-125 DEG C.
Preferably, the melt flow rate (MFR) of the copolymer polypropylene is 2.8-10.0g/10min, density 0.90- 0.92g/cm3。
Preferably, the melt flow rate (MFR) of the ethylene-vinyl acetate copolymer is 2.0-6.0g/10min, wherein vinegar The content of vinyl acetate is 18%-42%.
Preferably, the melt flow rate (MFR) of the compatilizer is 2.0-7.0g/10min, and the grafting rate of maleic anhydride is 0.4-1.0%.
Preferably, the surface area of the silica is 180-200m2/ g, partial size are 4-4.5 μm, density 45-95g/ L。
Preferably, the stabilizer is antioxidant, coupling agent, age resister, antistatic agent, one in heat stabilizer Kind or multiple combinations.
The second aspect of the invention provides a kind of preparation method of adhering resin, comprising the following steps:
1) according to parts by weight, by linear low density polyethylene, copolymer polypropylene, ethylene-vinyl acetate copolymer, phase Hold agent, silica, stabilizer mixing；
2) well-mixed raw material is added to progress high temperature mixing in double screw extruder, and extruding pelletization, process warm Degree is 180-220 DEG C, and screw speed is that 300-380 turns/min.
The third aspect of the invention provides application of the adhering resin in aramid fiber reinforced composite pipe bonding.
The principle that adhering resin of the invention can be realized adhesive property enhancing specifically includes that
1, in system of the invention, linear low density polyethylene, copolymer polypropylene, ethylene-vinyl acetate mutual association Same-action significantly increases the adhesive property of adhering resin；In addition, compatilizer selects maleic anhydride grafting ratio for 0.4-1%, it is Since the combination of the compatilizer and linear low density polyethylene, copolymer polypropylene, ethylene-vinyl acetate of this grafting rate reaches most Good state, to keep the amalgamation of whole system more preferable.
2, adhering resin of the invention can be such that adhesive property is remarkably reinforced after silica is added, and analysis reason may be Since silica enhances the intensity of adhering resin, to promote adhesive property.In addition, silica surface area is 180- 200m2/ g, partial size are 4-4.5 μm, density 45-95g/L, these three index comprehensives influence, and silica can be made entire It is uniformly dispersed in system, stablizes the performance of final products.
Compared with prior art, technical solution of the present invention has the advantage that aramid fiber enhancing provided by the invention Compound effective adhering resin is mainly adjusted in product formula and ratio, the boundary between Lai Gaishan adhering resin and aramid fiber Face bonding, final optimization pass selection achieve the purpose that improve adhering resin adhesive property；The product produced is viscous on the market The adhesive property for connecing resin compares, and can reach processing performance and stablize, adhesive strength is high, and cementability is lasting, and is applicable in In the production of a variety of production equipments, it is made to be widely used in the compound pipeline complex pipeline of aramid fiber enhancing.
Specific embodiment
The technical effect of design of the invention, specific structure and generation will be described further below, with fully Solve the purpose of the present invention, feature and effect.
Embodiment 1
Adhering resin used in the present embodiment is following components and parts by weight:
In the present embodiment, the melt flow rate (MFR) of linear low density polyethylene is 7.0g/10min, and melting temperature is 120 DEG C Between.
In the present embodiment, the melt flow rate (MFR) of copolymer polypropylene is 8.0g/10min, density 0.92g/cm3。
In the present embodiment, the melt flow rate (MFR) of ethylene-vinyl acetate copolymer is 5.0g/10min, wherein acetic acid second The content of enester component is 32%.
In the present embodiment, compatilizer is maleic anhydride grafted polyethylene, melt flow rate (MFR) 5.0g/10min, maleic acid The grafting rate of acid anhydride is 1.0%.
In the present embodiment, the surface area of silica is 200m2/ g, partial size are 4.5 μm, density 70g/L.
In the present embodiment, stabilizer is antioxidant BASF 1010.
Adhering resin is prepared in accordance with the following steps:
1, according to the parts by weight of regulation, linear low density polyethylene, copolymer polypropylene, ethylene-vinyl acetate is total Polymers, compatilizer, silica, stabilizer are weighed, and are mixed the above component with high-speed mixer；
2, well-mixed raw material is added to progress high temperature mixing in double screw extruder, and extruding pelletization, process warm Degree is set as 180-220 DEG C, and screw speed is that 300-380 turns/min.
Embodiment 2
Adhering resin used in the present embodiment is following components and parts by weight:
In the present embodiment, the melt flow rate (MFR) of linear low density polyethylene is 5.0g/10min, and melting temperature is 120 DEG C Between.
In the present embodiment, the melt flow rate (MFR) of copolymer polypropylene is 9.0g/10min, density 0.90g/cm3。
In the present embodiment, the melt flow rate (MFR) of ethylene-vinyl acetate copolymer is 5.0g/10min, wherein acetic acid second The content of enester component is 42%.
In the present embodiment, compatilizer is maleic anhydride grafted polyethylene, melt flow rate (MFR) 2.0g/10min, maleic acid The grafting rate of acid anhydride is 1.0%.
In the present embodiment, the surface area of silica is 200m2/ g, partial size are 4.5 μm, density 80g/L.
In the present embodiment, stabilizer be antioxidant BASF 1010.
Adhering resin is prepared in accordance with the following steps:
1, according to the parts by weight of regulation, linear low density polyethylene, copolymer polypropylene, ethylene-vinyl acetate is total Polymers, compatilizer, silica, stabilizer are weighed, and are mixed the above component with high-speed mixer；
2, well-mixed raw material is added to progress high temperature mixing in double screw extruder, and extruding pelletization, process warm Degree is set as 180-220 DEG C, and screw speed is that 300-380 turns/min.
Embodiment 3
Adhering resin used in the present embodiment is following components and parts by weight:
In the present embodiment, the melt flow rate (MFR) of linear low density polyethylene is 8.0g/10min, and melting temperature is 125 DEG C Between.
In the present embodiment, the melt flow rate (MFR) range of copolymer polypropylene is 10.0g/10min, density 0.92g/cm3。
In the present embodiment, the melt flow rate (MFR) range of ethylene-vinyl acetate copolymer is 6.0g/10min, wherein vinegar The content of vinyl acetate component is 42%.
In the present embodiment, compatilizer is maleic anhydride grafted polyethylene, melt flow rate (MFR) 7.0g/10min, maleic acid The grafting rate of acid anhydride is 1.0%.
In the present embodiment, the surface area of silica is 200m2/ g, partial size are 4.5 μm, density 85g/L.
In the present embodiment, stabilizer is antioxidant BASF 1010.
Adhering resin is prepared in accordance with the following steps:
1, according to the parts by weight of regulation, linear low density polyethylene, copolymer polypropylene, ethylene-vinyl acetate is total Polymers, compatilizer, silica, stabilizer are weighed, and are mixed the above component with high-speed mixer；
2, well-mixed raw material is added to progress high temperature mixing in double screw extruder, and extruding pelletization, process warm Degree is set as 180-220 DEG C, and screw speed is that 300-380 turns/min.
Embodiment 4
Adhering resin used in the present embodiment is following components and parts by weight:
In the present embodiment, the melt flow rate (MFR) of linear low density polyethylene is 1.0g/10min, and melting temperature is 115 DEG C Between.
In the present embodiment, the melt flow rate (MFR) range of copolymer polypropylene is 2.8g/10min, density 0.92g/cm3。
In the present embodiment, the melt flow rate (MFR) range of ethylene-vinyl acetate copolymer is 6.0g/10min, wherein vinegar The content of vinyl acetate component is 20%.
In the present embodiment, compatilizer is maleic anhydride grafted polyethylene, melt flow rate (MFR) 2.0g/10min, maleic acid The grafting rate of acid anhydride is 0.4%.
In the present embodiment, the surface area of silica is 180m2/ g, partial size are 4 μm, density 60g/L.
In the present embodiment, stabilizer is antioxidant BASF 1010.
Adhering resin is prepared in accordance with the following steps:
3, according to the parts by weight of regulation, linear low density polyethylene, copolymer polypropylene, ethylene-vinyl acetate is total Polymers, compatilizer, silica, stabilizer are weighed, and are mixed the above component with high-speed mixer；
Well-mixed raw material is added to progress high temperature mixing in double screw extruder, and extruding pelletization, technological temperature It is set as 180-220 DEG C, screw speed is that 300-380 turns/min.
Embodiment 5
Adhering resin in embodiment 1-4 is tested as follows:
1) according to GB/T2791 sample preparation specification, " adhering resin-aramid fiber fibre is produced using the adhering resin of embodiment 1-4 The removing batten of dimension band ",
2) peel strength of test bars, unit N/25mm, result are to be as follows:
As can be seen from the above table, the peel strength of adhering resin of the invention bonding aramid fiber band is 213-270N/ 25mm。
The present embodiment also uses 3 kinds of adhering resins of commercial type to carry out above-mentioned experiment, as a result are as follows: peel strength 120- 150N/25mm。
In conclusion the adhesive strength of the aramid fiber reinforced composite pipe adhering resin of embodiment 1-4 has a distinct increment, it can The problem of very good solution aramid fiber reinforced composite pipe quality of production, improve the service performance of multiple tube.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Technical solution, all should be within the scope of protection determined by the claims.

Claims (9)

1. a kind of adhering resin suitable for aramid fiber reinforced composite pipe, which is characterized in that the adhering resin is following original Expect component and parts by weight:
2. being suitable for the adhering resin of aramid fiber reinforced composite pipe as described in claim 1, which is characterized in that described linear The melt flow rate (MFR) of low density polyethylene (LDPE) is 1.0-8.0g/10min, and melting temperature is between 115-125 DEG C.
3. being suitable for the adhering resin of aramid fiber reinforced composite pipe as described in claim 1, which is characterized in that the copolymerization Polyacrylic melt flow rate (MFR) is 2.8-10.0g/10min, density 0.90-0.92g/cm3。
4. being suitable for the adhering resin of aramid fiber reinforced composite pipe as described in claim 1, which is characterized in that the second Alkene-vinyl acetate co-polymer melt flow rate (MFR) is 2.0-6.0g/10min, and wherein the content of vinylacetate is 18%- 42%.
5. being suitable for the adhering resin of aramid fiber reinforced composite pipe as described in claim 1, which is characterized in that described compatible The melt flow rate (MFR) of agent is 2.0-7.0g/10min, and the grafting rate of maleic anhydride is 0.4-1.0%.
6. being suitable for the adhering resin of aramid fiber reinforced composite pipe as described in claim 1, which is characterized in that the dioxy The surface area of SiClx is 180-200m2/ g, partial size are 4-4.5 μm, density 45-95g/L.
7. being suitable for the adhering resin and method of aramid fiber reinforced composite pipe as described in claim 1, which is characterized in that institute The stabilizer stated is one of antioxidant, coupling agent, age resister, antistatic agent, heat stabilizer or multiple combinations.
8. a kind of preparation method of the adhering resin as described in claim 1-7 any one, comprising the following steps:
1) according to parts by weight, by linear low density polyethylene, copolymer polypropylene, ethylene-vinyl acetate copolymer, compatible Agent, silica, stabilizer mixing；
2) well-mixed raw material is added to progress high temperature mixing in double screw extruder, and extruding pelletization, technological temperature are 180-220 DEG C, screw speed is that 300-380 turns/min.
9. a kind of adhering resin as described in claim 1-7 any one answering in aramid fiber reinforced composite pipe bonding With.
CN201811587360.0A 2018-12-25 2018-12-25 A kind of adhering resin and method suitable for aramid fiber reinforced composite pipe Withdrawn CN109679533A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811587360.0A CN109679533A (en) 2018-12-25 2018-12-25 A kind of adhering resin and method suitable for aramid fiber reinforced composite pipe

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811587360.0A CN109679533A (en) 2018-12-25 2018-12-25 A kind of adhering resin and method suitable for aramid fiber reinforced composite pipe

Publications (1)

Publication Number Publication Date
CN109679533A true CN109679533A (en) 2019-04-26

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CN201811587360.0A Withdrawn CN109679533A (en) 2018-12-25 2018-12-25 A kind of adhering resin and method suitable for aramid fiber reinforced composite pipe

Country Status (1)

Country Link
CN (1) CN109679533A (en)

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