CN104311982A - Room-temperature silane self-crosslinking POE hose and preparation method thereof - Google Patents
Room-temperature silane self-crosslinking POE hose and preparation method thereof Download PDFInfo
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- CN104311982A CN104311982A CN201410544566.0A CN201410544566A CN104311982A CN 104311982 A CN104311982 A CN 104311982A CN 201410544566 A CN201410544566 A CN 201410544566A CN 104311982 A CN104311982 A CN 104311982A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92609—Dimensions
- B29C2948/92619—Diameter or circumference
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised 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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- 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
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- 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
Abstract
The invention discloses a room-temperature silane self-crosslinking POE hose and a preparation method thereof, belonging to the technical field of macromolecule tube preparation. The room-temperature silane self-crosslinking POE hose comprises the following components in parts by weight: 80-95 parts of POE resin, 1-3 parts of a vinyl unsaturated silane crosslinking agent, 0.05-0.9 part of an organic peroxide initiator, 5-10 parts of benzenesulfonic acid catalyst master batch, 0.1-0.5 part of a processing additive, 4-10 parts of self water production master batch and 0.2-0.4 part of a composite antioxidant. As the above components of the limited parts by weight are adopted, and moreover the benzenesulfonic acid catalyst master batch and the self water production master batch are respectively self-made mixed materials, the POE hose can be prepared by using a two-step method; and without thermal treatment, the POE hose is very good in forming property, softness, thermal resistance and low cost, and can be widely used in the fields such as conveying systems of chemical fluid, cold/hot water and the like.
Description
Technical field
The invention belongs to polymer pipe fitting preparing technical field, be specifically related to a kind of room temperature silane self-crosslinking POE flexible pipe and preparation method thereof being applicable to carry cold/hot-fluid flexible pipe.
Background technology
:along with the development of society and the progress of science and technology, such as, among all trades and professions such as macromolecular material is widely used in each suitable application area of people gradually, the delivery system of automobile, household electrical appliances, gas and liquid.Have a large amount in variety for the tubing of fluid conveying in present existing market, such as polyvinyl piping materials (high density polyethylene(HDPE), linear low density polyethylene, Low Density Polyethylene), polychloroethylene pipes, rubber tubing (EPDM, natural rubber etc.) etc.But in the middle of the flexible pipe of conveyance fluid or gas, substantially by polyvinyl chloride, Low Density Polyethylene, the starting material preparations such as natural rubber and other elastomerics.This kind of flexible pipe also exists various defect, and such as resistance toheat does not reach requirement, wholesomeness can not satisfy the demands, weathering resistance is poor.In order to address these problems, many scientific workers conduct extensive research and develop.China national patent of invention CN 102432943 A discloses the preparation method of a kind of elastic composition, elastomeric hose and elastomeric hose.The composition that elastomeric hose is formed by elastomer resin multipolymer, vinyl silanes, organo-peroxide, catalyzer, phenolic antioxidant and silicone lubricating grease, and as raw material, be extruded into tubing after mixing according to a certain percentage, then obtain elastomeric hose goods through hydrolytic crosslinking reaction.This invention provides a kind of preparation method of elastomeric hose, by carrying out single stage method reactive extrusion molding and cross-linking modified technique to elastomerics, significantly improve the thermotolerance of elastomeric hose, corrosion-resistant, resisting environmental stress and cracking intensity, chemical fluid conveying and Building Cooling water system can be widely used in.Although but this patent improves the thermotolerance of elastomeric hose, corrosion-resistant, resisting environmental stress and cracking intensity by silane grafting and crosslinking, need just can reach relevant performance by poach.Simultaneously because POE elastomerics causes into free radical than being easier to by peroxide initiator comparatively speaking, so very easily producing the side reaction of C-C coupling in the process extruding pipe, causing the quality of flexible pipe uneven and have impact on the withstand voltage properties of flexible pipe.In addition, because catalyzer and silane are mixed together in resin, very easily cause silane in the hydrolysis of the extruding pipe period of the day from 11 p.m. to 1 a.m, cause the Quality Down of flexible pipe.Therefore the flexible pipe mixture that this patent obtains is a Unstable Systems, the non-constant of long-term storage performance.Chinese invention patent CN 1438262 A has openly invented a kind of organosilane crosslinked polyolefin elastic-body composition.This composition adopts LLDPE(or ULDPE) and paraffin oil replacement EPDM, replace phenolic resin vulcanization system by Silane Grafted system.The elastomer modulus variable range of preparation is very large, can meet the needs of different purposes.But in this patent be resin based on PP or ULDPE, adopt paraffin oil as softening agent, and the elastic composition obtained.Although this elastic composition modulus is adjustable, in life-time service process, paraffin oil can be separated out, thus causes elastomeric pliability to reduce, degradation.In addition, in the formula of this patent, employ water as one of composition, it is crosslinked that this composition very easily makes silane that early stage occurs, and cause elastomerics processing characteristics to decline.The crosslinked thermoset olefin elastomer that Chinese invention patent CN 101842432 A discloses a kind of crosslinkable thermoplastic polyolefin elastomer and obtains from it.Although the elastomerics of this patent preparation has the compression set value of 30-65%, the elongation at break of more than 8 and the ratio of compression set value, and the shore A hardness value of less than 90.But this patent system Preparation Method is complicated, and cost is higher.Chinese invention patent CN 102504287 A has openly invented a kind of Silane Grafted and warm water crosslinking natural rubber composition and preparation method thereof.This patent adopts one-step method silanes grafting and warm water crosslinking technology to prepare natural rubber composition, and said composition can be used for the production of hot water seal goods.By selecting composite graft crosslinking agent, adding a kind of compound polymerization inhibitor and being cross-linked too early to prevent grafted natural rubber, with organic tin compound for catalyzer, adopt Banbury mixer to achieve natural rubber silane fusion-grafting.Silane Grafted natural rubber makes Silane Grafted natural rubber be cross-linked by warm water soaking or boiling, obtains the natural rubber composition that a kind of novel silane is crosslinked, and its hot water seal product flexibility of operation prepared is strong, excellent product performance.What this patent adopted is the Silane Grafted prepared of Banbury mixer preparation technology and crosslinked natural rubber, complicated process of preparation.This patent have employed organic tin catalyzer simultaneously, is not suitable for the flexible pipe preparing the cold/hot liquid of conveying.Chinese invention patent CN 103951869 A discloses crosslinked with silicane POE/EAA blend and preparation method thereof.This patent have employed two-step approach preparation technology, and employing is warm water crosslinking technique, and manufacturing cost is high.
Chinese invention patent CN 102140196 A discloses a kind of room temperature self-crosslinked polyethylene insulation material, primarily of normal linear polyvinyl resin, EVA resin, silane coupling agent, Graft Processing auxiliary agent, self-crosslinking promotor, antioxidant and PE lubricant composition.Only need after above each raw material mix, successively through extruding, water-cooled, granulation, air-dry, namely can be made into.Because this invention adds self-crosslinking promotor, after cable is produced at ambient temperature, can self-assembling formation cross-linking process.So invention decreases the process that two step method crosslinked cable produces rear poach, reach the good result of cross linked insulation.Although this invention does not specifically provide the kind of self-crosslinking promotor, its theoretical starting point is carried out from promotion crosslinked with silicane angle obviously, does not consider that the water that silane hydrolyzate uses carrys out source problem.Chinese invention patent CN 1900130 A discloses a kind of method of preparing silane crosslinked polyethylene by room temperature crosslinking.Have employed product aqua in this patent silane hydrolyzate is provided and is cross-linked, but the catalyzer adopted is the organotin catalysts that Catalysis Rate and efficiency are lower.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of room temperature silane self-crosslinking POE flexible pipe and preparation method thereof being applicable to carry cold/hot-fluid flexible pipe.
Described a kind of room temperature silane self-crosslinking POE flexible pipe, is characterized in that the component comprising following parts by weight:
POE resin 80-95 part, vinyl unsaturated silane linking agent 1-3 part, organic peroxide evocating agent 0.05-0.9 part, Phenylsulfonic acid class catalyst masterbatch 5-10 part, processing aid 0.1-0.5 part, self-produced jellyfish material 4-10 part, composite antioxidant 0.2-0.4 part.
Described a kind of room temperature silane self-crosslinking POE flexible pipe, is characterized in that the component comprising following parts by weight:
POE resin
80-85 part, vinyl unsaturated silane linking agent 1-1.5 part, organic peroxide evocating agent 0.1-0.5 part, Phenylsulfonic acid class catalyst masterbatch 5-7 part, processing aid 0.2-0.4 part, self-produced jellyfish material
4-7 part, composite antioxidant 0.2-0.4 part.
Described a kind of room temperature silane self-crosslinking POE flexible pipe, it is characterized in that described vinyl unsaturated silane linking agent is one in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl front three Ethoxysilane or several middle mixture, described processing aid is the DZH2001 of Shanghai Ze Hui Chemical Industry Science Co., Ltd.
Described a kind of room temperature silane self-crosslinking POE flexible pipe, it is characterized in that described organic peroxide evocating agent is one or more mixtures in dibenzoyl peroxide, dicumyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, the tertiary fourth fat of isopropyl peroxide carbonic acid, be preferably dibenzoyl peroxide and dicumyl peroxide, wherein dibenzoyl peroxide is referred to as BPO, dicumyl peroxide referred to as DCP, below replaces full name with being called for short.
Described a kind of room temperature silane self-crosslinking POE flexible pipe, it is characterized in that described Phenylsulfonic acid class catalyst masterbatch is made up of the component of following parts by weight: POE resin 100 parts, Phenylsulfonic acid class catalyzer 2 parts, antioxidant 1010 0.2 part, irgasfos 168 0.2 part, by above-mentioned each component after homogenizer mixing, be catalyst masterbatch by single screw extrusion machine granulation, prilling temperature is 100-180 DEG C.
Described a kind of room temperature silane self-crosslinking POE flexible pipe, is characterized in that described Phenylsulfonic acid class catalyzer is Witco 1298 Soft Acid, cetyl benzenesulfonic acid or two kinds of mixtures.
Described a kind of room temperature silane self-crosslinking POE flexible pipe, it is characterized in that described self-produced jellyfish material is made up of the component of following parts by weight: POE resin 100 parts, stearic acid 2 parts, 5 parts, zinc oxide, antioxidant 1010 0.2 part, irgasfos 168 0.2 part, said components is after homogenizer mixing, be self-produced jellyfish material by single screw extrusion machine granulation, prilling temperature is 80-130 DEG C.
Described a kind of room temperature silane self-crosslinking POE flexible pipe, is characterized in that described zinc oxide order number is 4000-6000 order.
Described a kind of room temperature silane self-crosslinking POE flexible pipe, is characterized in that described composite antioxidant be weight ratio is the antioxidant 1010 of 1:1 and the composition of irgasfos 168.
The preparation method of described room temperature silane self-crosslinking POE flexible pipe, is characterized in that comprising the steps:
1) POE resin, vinyl unsaturated silane linking agent, organic peroxide evocating agent and composite antioxidant are put into airtight kneader, mix 0.5-1 hour at 60-90 DEG C after, then it is for subsequent use to add Phenylsulfonic acid class catalyst masterbatch, processing aid and self-produced jellyfish material remix 10-20 minute blowing;
2) compound step 1) obtained is extruded through twin screw extruder and is obtained silane self-crosslinking POE flexible pipe, the transportation section temperature 80-100 DEG C of forcing machine, frit reaction section temperature 130-180 DEG C, die temperature 160-170 DEG C, extruder screw length-to-diameter ratio L/D=44-52:1.
By adopting above-mentioned technology, beneficial effect of the present invention is as follows: it passes through with POE resin, vinyl unsaturated silane linking agent, organic peroxide evocating agent, Phenylsulfonic acid class catalyst masterbatch, processing aid, self-produced jellyfish material, composite antioxidant is raw material, and the formula adopting the present invention to limit, and Phenylsulfonic acid class catalyst masterbatch and self-produced jellyfish material are respectively homemade compound, POE flexible pipe is obtained by two-step approach, this POE flexible pipe requires no thermal treatment, namely extraordinary formability is had, flexibility, good thermotolerance and low cost, chemical fluid can be widely used in, the fields such as the delivery system of cold and hot water.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited in this:
Phenylsulfonic acid class catalyst masterbatch of the present invention is made up of the component of following parts by weight: POE resin 100 parts, Phenylsulfonic acid class catalyzer 2 parts, antioxidant 1010 0.2 part, irgasfos 168 0.2 part, by above-mentioned each component after homogenizer mixing, be catalyst masterbatch by single screw extrusion machine granulation, prilling temperature is 100-180 DEG C, and wherein Phenylsulfonic acid class catalyzer is Witco 1298 Soft Acid, cetyl benzenesulfonic acid or two kinds of mixtures.
Self-produced jellyfish material of the present invention is made up of the component of following parts by weight: POE resin 100 parts, stearic acid 2 parts, 5 parts, zinc oxide, antioxidant 1010 0.2 part, irgasfos 168 0.2 part, said components is after homogenizer mixing, be self-produced jellyfish material by single screw extrusion machine granulation, prilling temperature is 80-130 DEG C, and wherein zinc oxide order number is 4000-6000 order.
embodiment 1: the preparation of room temperature silane self-crosslinking POE flexible pipe
1) parts by weight of each component of composition are as follows: POE resin 90 parts; Vinyltriethoxysilane 2 parts; BPO 0.5 part; Catalyst masterbatch (Witco 1298 Soft Acid) 5 parts; 5 parts, self-produced jellyfish material; Processing aid 0.2 part, antioxidant 1010 0.2 part; Irgasfos 168 0.2 part;
2) preparation process: POE resin, vinyltriethoxysilane, BPO initiator, antioxidant 1010 and irgasfos 168 are put into airtight kneader by the first step, at 70 DEG C, mix after 0.5 hour, then add catalyst masterbatch (Witco 1298 Soft Acid), self-produced jellyfish material, processing aid remix 15 minutes blowings are for subsequent use; Second step by the composition that mixes through twin screw (length-to-diameter ratio L/D=48:1) forcing machine extruding pipe material.The processing condition of forcing machine: transportation section temperature 100 DEG C, frit reaction section temperature 180 DEG C, die temperature 170 DEG C.
In this embodiment, described vinyl unsaturated silane linking agent vinyltriethoxysilane, vinyltrimethoxy silane, one in vinyl front three Ethoxysilane or several middle mixture replace vinyltriethoxysilane, described organic peroxide evocating agent dibenzoyl peroxide, dicumyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, one or more mixtures in the tertiary fourth fat of isopropyl peroxide carbonic acid replace BPO, all can obtain same technique effect, and the processing aid described in this embodiment is the DZH2001 of Shanghai Ze Hui Chemical Industry Science Co., Ltd, lower same.
embodiment 2: the preparation of room temperature silane self-crosslinking POE flexible pipe
1) parts by weight of each component of composition are as follows: POE resin 80 parts; Vinyl front three Ethoxysilane 1 part; The peroxidation trimethylacetic acid tert-butyl ester 0.05 part; Catalyst masterbatch (Witco 1298 Soft Acid) 10 parts; 7 parts, self-produced jellyfish material; Processing aid 0.5 part, antioxidant 1010 0.2; Irgasfos 168 0.2.
Preparation process: POE resin, vinyl front three Ethoxysilane, the peroxidation trimethylacetic acid tert-butyl ester, antioxidant 1010 and irgasfos 168 are put into airtight kneader by the first step, at 70 DEG C, mix after 0.5 hour, then add catalyst masterbatch (Witco 1298 Soft Acid), self-produced jellyfish material, processing aid remix 15 minutes blowings are for subsequent use; Second step by the composition that mixes through twin screw (length-to-diameter ratio L/D=48:1) forcing machine extruding pipe material.The processing condition of forcing machine: transportation section temperature 80 DEG C, frit reaction section temperature 130 DEG C, die temperature 160 DEG C.
embodiment 3: the preparation of room temperature silane self-crosslinking POE flexible pipe
1) parts by weight of each component of composition are as follows: POE resin 90 parts; Vinyltrimethoxy silane 2 parts; The peroxidation trimethylacetic acid tert-butyl ester 0.5 part; Catalyst masterbatch (cetyl benzenesulfonic acid) 5 parts; 5 parts, self-produced jellyfish material; Processing aid 0.2 part, antioxidant 1010 0.1 part; Irgasfos 168 0.1 part.
Preparation process: POE resin, vinyltrimethoxy silane, peroxidation trimethylacetic acid tert-butyl ester initiator, antioxidant 1010 and irgasfos 168 are put into airtight kneader by the first step, at 70 DEG C, mix after 0.5 hour, add catalyst masterbatch (cetyl benzenesulfonic acid), self-produced jellyfish material, processing aid remix 15 minutes blowings again, for subsequent use; Second step by the composition that mixes through twin screw (length-to-diameter ratio L/D=48:1) forcing machine extruding pipe material.The processing condition of forcing machine: transportation section temperature 90 DEG C, frit reaction section temperature 140 DEG C, die temperature 160 DEG C.
embodiment 4: the preparation of room temperature silane self-crosslinking POE flexible pipe
1) parts by weight of each component of composition are as follows: POE resin 80 parts; The vinyltrimethoxy silane of 1:1 and 2 parts, vinyltriethoxysilane mixture; DCP 0.5 part; Catalyst masterbatch (Witco 1298 Soft Acid and cetyl benzenesulfonic acid) 5 parts; 5 parts, self-produced jellyfish material; Processing aid 0.2 part, antioxidant 1010 0.2 part; Irgasfos 168 0.2 part.
Preparation process: POE resin, vinyltrimethoxy silane and vinyltriethoxysilane mixture, DCP initiator, antioxidant 1010 and irgasfos 168 are put into airtight kneader by the first step, at 70 DEG C, mix after 0.5 hour, add catalyst masterbatch, self-produced jellyfish material, processing aid remix 15 minutes blowings again, for subsequent use; Second step by the composition that mixes through twin screw (length-to-diameter ratio L/D=48:1) forcing machine extruding pipe material.The processing condition of forcing machine: transportation section temperature 85 DEG C, frit reaction section temperature 135 DEG C, die temperature 170 DEG C.
embodiment 5: the preparation of room temperature silane self-crosslinking POE flexible pipe
1) parts by weight of each component of composition are as follows: POE resin 80 parts; Vinyltriethoxysilane 2 parts; DCP 0.5 part; Catalyst masterbatch (Witco 1298 Soft Acid) 10 parts; 8 parts, self-produced jellyfish material; Processing aid 0.2 part, antioxidant 1010 0.2 part; Irgasfos 168 0.2 part.
Preparation process: POE resin, vinyltriethoxysilane, DCP initiator, antioxidant 1010 and irgasfos 168 are put into airtight kneader by the first step, at 70 DEG C, mix after 0.5 hour, add catalyst masterbatch, self-produced jellyfish material, processing aid remix 15 minutes blowings again, for subsequent use, second step by the composition that mixes through twin screw (length-to-diameter ratio L/D=48:1) forcing machine extruding pipe material.The processing condition of forcing machine: transportation section temperature 88 DEG C, frit reaction section temperature 170 DEG C, die temperature 170 DEG C.
embodiment 6: the preparation of room temperature silane self-crosslinking POE flexible pipe
1) parts by weight of each component of composition are as follows: POE resin 80 parts; Vinyltriethoxysilane 2 parts; BPO 0.5 part; Catalyst masterbatch (Witco 1298 Soft Acid) 10 parts; 8 parts, self-produced jellyfish material; Processing aid 0.2 part, antioxidant 1010 0.2 part; Irgasfos 168 0.2 part.
Preparation process: POE resin, vinyltriethoxysilane, BPO initiator, antioxidant 1010 and irgasfos 168 are put into airtight kneader by the first step, at 70 DEG C, mix after 0.5 hour, add catalyst masterbatch, self-produced jellyfish material, processing aid remix 15 minutes blowings again, for subsequent use, the composition that the first step mixes by second step is through twin screw (length-to-diameter ratio L/D=48:1) forcing machine extruding pipe material.The processing condition of forcing machine: transportation section temperature 90 DEG C, frit reaction section temperature 150 DEG C, die temperature 160 DEG C.
embodiment 7: the preparation of room temperature silane self-crosslinking POE flexible pipe
1) parts by weight of each component of composition are as follows: POE resin 85 parts; Vinyl front three Ethoxysilane 1.5 parts; DCP 0.5 part; Catalyst masterbatch (cetyl benzenesulfonic acid) 7 parts; 10 parts, self-produced jellyfish material; Processing aid 0.5 part, antioxidant 1010 0.2 part; Irgasfos 168 0.2 part.
Preparation process: POE resin, vinyl front three Ethoxysilane, DCP initiator, antioxidant 1010 and irgasfos 168 are put into airtight kneader by the first step, at 70 DEG C, mix after 0.5 hour, add catalyst masterbatch (cetyl benzenesulfonic acid), self-produced jellyfish material, processing aid remix 15 minutes blowings again, for subsequent use, the composition that the first step mixes by second step is through twin screw (length-to-diameter ratio L/D=48:1) forcing machine extruding pipe material.The processing condition of forcing machine: transportation section temperature 90 DEG C, frit reaction section temperature 160 DEG C, die temperature 170 DEG C.
embodiment 8: the preparation of room temperature silane self-crosslinking POE flexible pipe
1) parts by weight of each component of composition are as follows: POE resin 85 parts; Vinyltrimethoxy silane 1.5 parts; BPO 0.5 part; Catalyst masterbatch (Witco 1298 Soft Acid) 7 parts; 10 parts, self-produced jellyfish material; Processing aid 0.5 part, antioxidant 1010 0.2 part; Irgasfos 168 0.2 part.
Preparation process: POE resin, vinyltrimethoxy silane, BPO initiator, antioxidant 1010 and irgasfos 168 are put into airtight kneader by the first step, at 60 DEG C, mix after 1 hour, add catalyst masterbatch, self-produced jellyfish material, processing aid remix 15 minutes blowings again, for subsequent use, the composition that the first step mixes by second step is through twin screw (length-to-diameter ratio L/D=48:1) forcing machine extruding pipe material.The processing condition of forcing machine: transportation section temperature 95 DEG C, frit reaction section temperature 140 DEG C, die temperature 170 DEG C.
embodiment 9: the preparation of room temperature silane self-crosslinking POE flexible pipe
1) parts by weight of each component of composition are as follows: POE resin 85 parts; Vinyltrimethoxy silane 1.5 parts; BPO 0.5 part; Catalyst masterbatch (Witco 1298 Soft Acid) 7 parts; 7 parts, self-produced jellyfish material; Processing aid 0.4 part, antioxidant 1010 0.2 part; Irgasfos 168 0.1 part.
Preparation process: POE resin, vinyl unsaturated silane linking agent, BPO initiator, antioxidant 1010 and irgasfos 168 are put into airtight kneader by the first step, at 90 DEG C, mix after 1 hour, add catalyst masterbatch, self-produced jellyfish material, processing aid remix 10 minutes blowings again, for subsequent use; Second step by the composition that mixes through twin screw (length-to-diameter ratio L/D=44:1) forcing machine extruding pipe material.The processing condition of forcing machine: transportation section temperature 90 DEG C, frit reaction section temperature 180 DEG C, die temperature 170 DEG C.
the POE flexible pipe embodiment of the present invention obtained is tested by GB (GB/T 531.1, GB/T 18474, GB/T 8804.3, GB/T 15560) with the performance such as Shore A hardness, gel content, tensile strength, elongation at break, hydrostaticpressure of the common PE X flexible pipe (comparative example) used in the market, and test result is in table 1:
The performance index of table 1 comparative example and embodiment POE flexible pipe
As can be seen from Table 1, common tubing is compared, the POE flexible pipe that the present invention obtains, common good of its Performance Ratio, such as Shore A hardness, gel content, tensile strength, elongation at break and hydrostaticpressure are all better than the tubing that prior art obtains, and can be widely used in the field such as delivery system of chemical fluid, cold and hot water.
Claims (10)
1. a room temperature silane self-crosslinking POE flexible pipe, is characterized in that the component comprising following parts by weight:
POE resin 80-95 part, vinyl unsaturated silane linking agent 1-3 part, organic peroxide evocating agent 0.05-0.9 part, Phenylsulfonic acid class catalyst masterbatch 5-10 part, processing aid 0.1-0.5 part, self-produced jellyfish material 4-10 part, composite antioxidant 0.2-0.4 part.
2. a kind of room temperature silane self-crosslinking POE flexible pipe according to claim 1, is characterized in that the component comprising following parts by weight:
POE resin 80-85 part, vinyl unsaturated silane linking agent 1-1.5 part, organic peroxide evocating agent 0.1-0.5 part, Phenylsulfonic acid class catalyst masterbatch 5-7 part, processing aid 0.2-0.4 part, self-produced jellyfish material 4-7 part, composite antioxidant 0.2-0.4 part.
3. a kind of room temperature silane self-crosslinking POE flexible pipe according to claim 1, is characterized in that described vinyl unsaturated silane linking agent is one in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl front three Ethoxysilane or several middle mixture.
4. a kind of room temperature silane self-crosslinking POE flexible pipe according to claim 1, it is characterized in that described organic peroxide evocating agent is one or more mixtures in dibenzoyl peroxide, dicumyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, the tertiary fourth fat of isopropyl peroxide carbonic acid, be preferably dibenzoyl peroxide and dicumyl peroxide.
5. a kind of room temperature silane self-crosslinking POE flexible pipe according to claim 1, it is characterized in that described Phenylsulfonic acid class catalyst masterbatch is made up of the component of following parts by weight: POE resin 100 parts, Phenylsulfonic acid class catalyzer 2 parts, antioxidant 1010 0.2 part, irgasfos 168 0.2 part, by above-mentioned each component after homogenizer mixing, be catalyst masterbatch by single screw extrusion machine granulation, prilling temperature is 100-180 DEG C.
6. a kind of room temperature silane self-crosslinking POE flexible pipe according to claim 1, is characterized in that described Phenylsulfonic acid class catalyzer is Witco 1298 Soft Acid, cetyl benzenesulfonic acid or two kinds of mixtures.
7. a kind of room temperature silane self-crosslinking POE flexible pipe according to claim 1, it is characterized in that described self-produced jellyfish material is made up of the component of following parts by weight: POE resin 100 parts, stearic acid 2 parts, 5 parts, zinc oxide, antioxidant 1010 0.2 part, irgasfos 168 0.2 part, said components is after homogenizer mixing, be self-produced jellyfish material by single screw extrusion machine granulation, prilling temperature is 80-130 DEG C.
8. a kind of room temperature silane self-crosslinking POE flexible pipe according to claim 1, is characterized in that described zinc oxide order number is 4000-6000 order.
9. a kind of room temperature silane self-crosslinking POE flexible pipe according to claim 1, is characterized in that described composite antioxidant be weight ratio is the antioxidant 1010 of 1:1 and the composition of irgasfos 168.
10. a preparation method for room temperature silane self-crosslinking POE flexible pipe according to claim 1, is characterized in that comprising the steps:
1) POE resin, vinyl unsaturated silane linking agent, organic peroxide evocating agent and composite antioxidant are put into airtight kneader, mix 0.5-1 hour at 60-90 DEG C after, then it is for subsequent use to add Phenylsulfonic acid class catalyst masterbatch, processing aid and self-produced jellyfish material remix 10-20 minute blowing;
2) compound step 1) obtained is extruded through twin screw extruder and is obtained silane self-crosslinking POE flexible pipe, the transportation section temperature 80-100 DEG C of forcing machine, frit reaction section temperature 130-180 DEG C, die temperature 160-170 DEG C, extruder screw length-to-diameter ratio L/D=44-52:1.
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