CN105419043A - Polyolefin powder for corrosion resistance of marine pipelines - Google Patents

Polyolefin powder for corrosion resistance of marine pipelines Download PDF

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Publication number
CN105419043A
CN105419043A CN201510843062.3A CN201510843062A CN105419043A CN 105419043 A CN105419043 A CN 105419043A CN 201510843062 A CN201510843062 A CN 201510843062A CN 105419043 A CN105419043 A CN 105419043A
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China
Prior art keywords
polyolefin
polyolefin powder
powder
submarine pipeline
added
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CN201510843062.3A
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Chinese (zh)
Inventor
周宏宇
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HANGZHOU HAOGANG TECHNOLOGY Co Ltd
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HANGZHOU HAOGANG TECHNOLOGY Co Ltd
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Priority to CN201510843062.3A priority Critical patent/CN105419043A/en
Publication of CN105419043A publication Critical patent/CN105419043A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246Intercrosslinking of at least two polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/08Copolymers of ethene
    • 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
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/062HDPE
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00Crosslinking
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00Crosslinking
    • C08L2312/08Crosslinking by silane

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides polyolefin powder for corrosion resistance of marine pipelines. The polyolefin powder is prepared through the following method which includes the steps that a cross-linking agent, namely dibutyl maleic acid ester, is added into a polyolefin matrix, peroxide is then added as an initiating agent, an organic tin derivative serves as a catalyst, a silane coupling agent is added and subjected to hydrolytic condensation with polyolefin to form cross bonds for melt blending, a product obtained after mixing is melted, cross linking occurs in the melting process, the product obtained after melting is subjected to extruding granulation through a screw extruder, and polyolefin granules are obtained; the prepared polyolefin granules are ground into powder through a mechanical method grinding technology, and the polyolefin powder is obtained. Dibutyl maleic acid ester serves as the cross-linking agent, a proper quantity of silane coupling agent is used for increasing the interface bonding force of metal peroxide and polyvinyl, and thus the tensile strength and the elastic modulus of the polyolefin powder are effectively improved.

Description

A kind of for submarine pipeline rot-resistant polyolefin powder
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of for submarine pipeline rot-resistant polyolefin powder.
Background technology
Polyethylene is non-polar polymer, belong to low-surface energy substance, that generally acknowledged difficulty glues material, it is neither good glue paste, neither be good by sticky material, when after a small amount of polar monomer maleic acid ester of grafting on its macromolecular chain, it becomes the substrate surface of polar polymer simultaneously containing band lone pair electron and can increase, if this grafts had both been added by the polar adsorption power of sticky material as tackiness agent, also can form dative bond with materials such as metals simultaneously, greatly improve cohesive force.In addition polycthylene grafted thing increases due to polarity, improves the blended characteristic of homopolarity material, expands polyolefine purposes.
But crosslinking technology domestic at present only can meet the tensile strength to the highest 7.5MPa of carbon steel, and percentage of grafting is lower, consumption is excessive, average Graft Adhesive application percentage is in the powder in 30% (initiator amount 2%) left and right, elongation at break is lower than 300%, cost is high, poor performance, and preservative effect is more difficult to ensure.
Summary of the invention
The object of this invention is to provide one for submarine pipeline rot-resistant polyolefin powder, to overcome the deficiencies in the prior art, reach tensile strength and Young's modulus that polyolefin powder material is effectively provided, strengthen the object of preservative effect.
For achieving the above object, the present invention takes following technical proposals to realize:
A kind of for submarine pipeline rot-resistant polyolefin powder, described polyolefin powder adopts following methods preparation:
The two butyl maleic acid ester of linking agent is added in polyolefin substrate, add superoxide again as initiator, organic tin derivates is catalyzer, and add silane coupling agent and polyolefine material generation hydrolytic condensation and form cross-link bond and carry out melt blending, obtain carrying out melting after mixing, occur crosslinked in melting process, by screw extrusion press extruding pelletization after melting completes, obtain polyolefine material grain;
Obtained polyolefine material grain carries out abrasive dust with mechanical process milling process, obtains polyolefin powder.
Further, described polyolefin substrate is polyethylene or polyethylene and polyacrylic mixture.Wherein polyethylene is one in high density polyethylene(HDPE), Low Density Polyethylene, linear low density polyethylene or mixture.Linear low density polyethylene is preferably in the present invention.
Further, described superoxide is dicumyl peroxide (DCP), and the consumption of dicumyl peroxide is polyolefin-based body weight is 0.1-1%.
Preferably, the consumption of described dicumyl peroxide is polyolefin-based body weight is 0.25%.
Further, the consumption of described pair of butyl maleic acid ester is the 0.5-4% of polyolefin-based body weight.
Further, described organic tin derivates is dibutyl tin or stannous octoate, and the consumption of organic tin derivates is the 0.04-0.5% of polyolefin-based body weight.
Further, described silane coupling agent is vinylsiloxane, and the consumption of vinylsiloxane is the 0.4-1.3% of polyolefin-based body weight.
Further, can also be added with antibacterial matrices in described polyolefin powder, addition is the 0.4-1.3% of polyolefin-based body weight.Obtained polyethylene powders is applicable to the more environment of microorganism.
Further, rubber and plastic alloy can also be added with in described polyolefin powder.Add the compounded modified poly ethylene master batch of rubber and plastic alloy sulfuration, effectively improve impact resistance, be applicable to the area application etc. that dust storm is larger.
Compared with prior art, the present invention has the following advantages:
The present invention adopts two butyl maleic acid ester as linking agent, and increases metal hydroxides and polyolefinic interface binding power with appropriate silane coupling agent, effectively raises tensile strength and the Young's modulus of polyolefin powder material.
The two butyl maleic acid ester of linking agent of the present invention is added in polyolefine, after adding silane coupling agent simultaneously, occur crosslinked in melting process, and then introduce crosslinked polyethylene in product, significantly improve the stability of product form, creep resistant and environmental stress cracking.Structurally all different from thermoplastics, thermosetting resin and vulcanized rubber after peroxide crosslinking, it has three dimensional structure not but to be be cross-linked completely, therefore in performance, have the feature of three concurrently, namely there is the performance such as thermoplastically and excellent hardness, toughness and stress crack resistant simultaneously.
Further, polyolefin powder of the present invention is under the condition of DCP initiation, organic tin derivates catalysis, vinylsiloxane and polyolefine material generation hydrolytic condensation are formed cross-link bond, crosslinked polyethylene is merged in polyolefin powder product, thus substantially increase stability and the resistance to corrosion of product, can be used for the steel pipe under oceanic climate condition and acid rain weather condition and traffic facilities.
Further, the present invention's research obtains DCP consumption when being less than 1%, and shock strength can be made to improve 25% ~ 50% than general polyethylene, and when particularly DCP consumption is 0.25%, shock strength can improve 48%.With the increase of DCP consumption, heat-drawn wire improves, and can be used for the heat-resisting pipeline carrying class.
Further, polyolefin substrate is that in polyethylene and polypropylene (PP) mixture system, polyethylene has obvious toughening effect to PP.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail.
Embodiment 1
Raw material will be taken by following weight percentage:
Dicumyl peroxide 0.1%, two butyl maleic acid ester 0.5%, dibutyl tin 0.04%, vinylsiloxane 0.4%, LLDPE 15%, surplus is high density polyethylene(HDPE).
The two butyl maleic acid ester of linking agent is added in LLDPE, add superoxide again as initiator, organic tin derivates is catalyzer, and add silane coupling agent and polyolefine material generation hydrolytic condensation and form cross-link bond and carry out melt blending, add high density polyethylene(HDPE) again and carry out melting, occur crosslinked in melting process, by screw extrusion press extruding pelletization after melting completes, obtain polyolefine material grain;
Obtained polyolefine material grain carries out abrasive dust with mechanical process milling process, obtains polyolefin powder.
Embodiment 2:
Raw material will be taken by following weight percentage:
Dicumyl peroxide 0.25%, two butyl maleic acid ester 2%, dibutyl tin 0.1%, vinylsiloxane 0.9%, LLDPE 20%, surplus is high density polyethylene(HDPE).
The two butyl maleic acid ester of linking agent is added in LLDPE, add superoxide again as initiator, organic tin derivates is catalyzer, and add silane coupling agent and polyolefine material generation hydrolytic condensation and form cross-link bond and carry out melt blending, add high density polyethylene(HDPE) again and carry out melting, occur crosslinked in melting process, by screw extrusion press extruding pelletization after melting completes, obtain polyolefine material grain;
Obtained polyolefine material grain carries out abrasive dust with mechanical process milling process, obtains polyolefin powder.
Embodiment 3:
Raw material will be taken by following weight percentage:
Dicumyl peroxide 1%, two butyl maleic acid ester 4%, dibutyl tin 0.5%, vinylsiloxane 1.3%, LLDPE 25%, surplus is high density polyethylene(HDPE).
The two butyl maleic acid ester of linking agent is added in LLDPE, add superoxide again as initiator, organic tin derivates is catalyzer, and add silane coupling agent and polyolefine material generation hydrolytic condensation and form cross-link bond and carry out melt blending, add high density polyethylene(HDPE) again and carry out melting, occur crosslinked in melting process, by screw extrusion press extruding pelletization after melting completes, obtain polyolefine material grain;
Obtained polyolefine material grain carries out abrasive dust with mechanical process milling process, obtains polyolefin powder.
Embodiment 4
Raw material will be taken by following weight percentage:
Dicumyl peroxide 0.25%, two butyl maleic acid ester 2%, dibutyl tin 0.1%, vinylsiloxane 0.9%, LLDPE 20%, antibacterial matrices (Chinese Academy of Sciences's purchase) 1%, surplus is high density polyethylene(HDPE).
The two butyl maleic acid ester of linking agent is added in LLDPE, add superoxide again as initiator, organic tin derivates is catalyzer, and add silane coupling agent and polyolefine material generation hydrolytic condensation and form cross-link bond and carry out melt blending, add high density polyethylene(HDPE) again and carry out melting, occur crosslinked in melting process, by screw extrusion press extruding pelletization after melting completes, obtain polyolefine material grain;
Obtained polyolefine material grain carries out abrasive dust with mechanical process milling process, obtains polyolefin powder.
Although the present invention with preferred embodiment openly as above; but it is not for limiting the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; what can utilize above-mentioned announcement makes possible variation and amendment for submarine pipeline rot-resistant polyolefin powder and technology contents to technical solution of the present invention; therefore; every content not departing from technical solution of the present invention; according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all belong to the protection domain of technical solution of the present invention.

Claims (9)

1. for a submarine pipeline rot-resistant polyolefin powder, it is characterized in that, described polyolefin powder adopts following methods preparation:
The two butyl maleic acid ester of linking agent is added in polyolefin substrate, add superoxide again as initiator, organic tin derivates is catalyzer, and add silane coupling agent and polyolefine material generation hydrolytic condensation and form cross-link bond and carry out melt blending, obtain carrying out melting after mixing, occur crosslinked in melting process, by screw extrusion press extruding pelletization after melting completes, obtain polyolefine material grain;
Obtained polyolefine material grain carries out abrasive dust with mechanical process milling process, obtains polyolefin powder.
2. according to claim 1ly it is characterized in that for submarine pipeline rot-resistant polyolefin powder, described polyolefin substrate is polyethylene or polyethylene and polyacrylic mixture.
3. according to claim 1ly it is characterized in that for submarine pipeline rot-resistant polyolefin powder, described superoxide is dicumyl peroxide, and the consumption of dicumyl peroxide is polyolefin-based body weight is 0.1-1%.
4. according to claim 3ly it is characterized in that for submarine pipeline rot-resistant polyolefin powder, the consumption of described dicumyl peroxide is polyolefin-based body weight is 0.25%.
5. according to claim 1ly it is characterized in that for submarine pipeline rot-resistant polyolefin powder, the consumption of described pair of butyl maleic acid ester is the 0.5-4% of polyolefin-based body weight.
6. according to claim 1ly it is characterized in that for submarine pipeline rot-resistant polyolefin powder, described organic tin derivates is dibutyl tin or stannous octoate, and the consumption of organic tin derivates is the 0.04-0.5% of polyolefin-based body weight.
7. according to claim 1ly it is characterized in that for submarine pipeline rot-resistant polyolefin powder, described silane coupling agent is vinylsiloxane, and the consumption of vinylsiloxane is the 0.4-1.3% of polyolefin-based body weight.
8. according to claim 1ly to it is characterized in that for submarine pipeline rot-resistant polyolefin powder, in described polyolefin powder, be also added with antibacterial matrices.
9. according to claim 1ly to it is characterized in that for submarine pipeline rot-resistant polyolefin powder, in described polyolefin powder, be also added with rubber and plastic alloy.
CN201510843062.3A 2015-11-26 2015-11-26 Polyolefin powder for corrosion resistance of marine pipelines Pending CN105419043A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113913054A (en) * 2020-07-10 2022-01-11 国家能源投资集团有限责任公司 Crosslinkable polyethylene composition, crosslinkable polyethylene blend and composite article

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101585214A (en) * 2009-06-18 2009-11-25 上海交通大学 Method for preparing crosslinkable polyethylene cable material
CN103102499A (en) * 2013-02-05 2013-05-15 常熟市中联光电新材料有限责任公司 Preparation method of environment-friendly one-step process organosilane crosslinked polyethylene cable material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101585214A (en) * 2009-06-18 2009-11-25 上海交通大学 Method for preparing crosslinkable polyethylene cable material
CN103102499A (en) * 2013-02-05 2013-05-15 常熟市中联光电新材料有限责任公司 Preparation method of environment-friendly one-step process organosilane crosslinked polyethylene cable material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
汪多仁 等 主编: "《精细化工品实用生产技术手册:增塑剂化学品生产配方和合成工艺》", 31 August 1999, 科学技术文献出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113913054A (en) * 2020-07-10 2022-01-11 国家能源投资集团有限责任公司 Crosslinkable polyethylene composition, crosslinkable polyethylene blend and composite article

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