CN106220994A - A kind of high intensity PP RCT anti-flaming tubular product and preparation method - Google Patents

A kind of high intensity PP RCT anti-flaming tubular product and preparation method Download PDF

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CN106220994A
CN106220994A CN201610590127.2A CN201610590127A CN106220994A CN 106220994 A CN106220994 A CN 106220994A CN 201610590127 A CN201610590127 A CN 201610590127A CN 106220994 A CN106220994 A CN 106220994A
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ester
acid
rct
high intensity
ethyl
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CN106220994B (en
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刘志光
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SHANGHAI ZHONGSU PIPE INDUSTRY Co Ltd
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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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • C08K5/405—Thioureas; Derivatives thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
    • F16L57/04—Protection of pipes or objects of similar shape against external or internal damage or wear against fire or other external sources of extreme heat
    • 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
    • F16L9/00—Rigid pipes
    • F16L9/12—Rigid pipes of plastics with or without reinforcement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
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Abstract

High intensity PP RCT anti-flaming tubular product, including at least three layers, it is respectively internal layer, middle level and outer layer from inside to outside, described internal layer contains antibacterial and composite flame-retardant agent, glass fibre and composite flame-retardant agent are contained in described middle level, described outer layer contains composite flame-retardant agent, and described composite flame-retardant agent contains morpholinyl thiourea, organic silicon compound containing phosphorus.

Description

A kind of high intensity PP-RCT anti-flaming tubular product and preparation method
Technical field
The present invention relates to PP composite, particularly to a kind of high intensity PP-RCT anti-flaming tubular product.
Background technology
Polypropylene (PP), as one of general-purpose plastics, is a kind of thermoplastic.It is its abundant raw material source, cheap, And have preferable combination property, as excellent mechanicalness, preferable thermostability, good electrical insulating property, flexural fatigue resistance, The feature such as chemical proofing and light weight, density are little, thus be widely used in household electrical appliances, automobile, build, the industry such as weaving.But Being that polyacrylic limited oxygen index only has 17.4-18.5, fire resistance is poor, and when meeting fire burning, caloric value is big, and burning velocity is fast, produces Raw a large amount of molten drops, and with phenomenon of being fuming, easily propagating flame, it is susceptible to fire, brings the wound of life and property Damaging, therefore its application is just very restricted.
Polypropylene pipe have lightweight, service life is long, easily transfer and the feature installed, as fire-fighting spraying tubing Having applied, Chinese patent CN202769084U discloses a kind of polypropylene fire-fighting spray line.Currently used fire retardant kind Various, the realization of its fire retardation typically can pass through following two approach: first, select to have high heat capacity, high-termal conductivity and There is the compound of higher gasification latent heat as fire retardant.Its fire retardant mechanism is to reduce height by the heat absorption of fire retardant, heat conduction The speed that molecular material absorbs heat from the external world, or take away partial heat by the gasification of material thus play cooling effect, or The speed of conduction of heat is reduced by forming layer of charcoal at polymer surface.In a word, their fire retardation is all by resistance Stagnant and delay the high temperature thermal decomposition of polymer to be achieved.Second is to set about in terms of suppression burning, by adding fire retardant Change the decomposition mechanism of polymer, reduce the generation of volatile hydrocarbon, and manage to increase the growing amount of carbon residue；Or change Changing the flow of QI-blood phase combustion mechanism, by the effect of additive, reduces the concentration of high-energy hydrogen-based free radical in flame so that it is be changed into low The free radical of energy, thus block the circulation of combustion reaction.When fire retardant addition in polypropylene pipe is less, flame retardant effect Do not reach requirement, when fire retardant addition is more, its mechanical property and processing characteristics can be reduced again.
Summary of the invention
In order to solve prior art problem, the present invention provides a kind of high intensity PP-RCT anti-flaming tubular product, including at least three layers, Being respectively internal layer, middle level and outer layer from inside to outside, described internal layer contains antibacterial and composite flame-retardant agent, and glass is contained in described middle level Fiber and composite flame-retardant agent, described outer layer contains composite flame-retardant agent, and described composite flame-retardant agent contains morpholinyl thiourea, phosphorous organic Silicon compound.
In some embodiments, the weight ratio of described morpholinyl thiourea and organic silicon compound containing phosphorus is (1-2): 5.
In some embodiments, described morpholinyl thiourea is selected from 1-[3-(4-morpholinyl) propyl group] thiourea, 1-[2-(4- Morpholinyl) ethyl] thiourea, 1-cyclohexyl-3-(2-morpholinyl ethyl) thiourea, 1-(2-morpholinyl ethyl)-3-phenylthiourea, 1- One in [3-ethyoxyl-2-(4-morpholinyl) propyl group]-3-ethyl thiourea.
In some embodiments, described organic silicon compound containing phosphorus is by comprising phosphinylidyne dichloro compound and amido organosilicon The raw material of compound prepares.
In some embodiments, described phosphinylidyne dichloro compound contains aromatic rings.
In some embodiments, described phosphinylidyne dichloro compound is selected from 2-phthalimide-based ethyl dichloro phosphoric acid One in ester, phenoxy group phosphinylidyne dichloro, 3,5-3,5-dimethylphenyl phosphinylidyne dichloro.
In some embodiments, described amido organosilicon compound contains at least one primary amino radical and at least one parahelium Base.
In some embodiments, described amido organosilicon compound is selected from N-(6-Aminohexyl) amino methyl three ethoxy Base silane, (((2-amino-ethyl) amino) methyl) triethoxysilane, (aminoethylaminomethyl) phenethyl trimethoxy One in silane, N-(2-amino-ethyl)-N'-(3-(dimethoxymethylsilane base) propyl group)-1,2-ethylenediamine.
In some embodiments, described high intensity PP-RCT Frpipe possibly together with auxiliary agent, described auxiliary agent selected from antioxidant, In antistatic additive, plasticizer, ultraviolet absorber, heat stabilizer, antifungus agent, anti-termite agent, Ratproof agent, antifoggant at least one Kind.
The present invention also provides for a kind of high intensity PP-RCT anti-flaming tubular product as above at air-conditioning duct system, fire-fighting spraying Application in system.
The high intensity PP-RCT anti-flaming tubular product fire retardant addition that the present invention provides is few, good flame retardation effect, and has outstanding Mechanical property.
Detailed description of the invention
Unless otherwise defined, all technology used herein and scientific terminology have skill common with art of the present invention The identical implication that art personnel are generally understood that.When there is contradiction, it is as the criterion with the definition in this specification.
Quality, concentration, temperature, time or other value or parameter are preferred with scope, preferred scope or a series of upper limit During the Range Representation that value and lower preferable values limit, this is appreciated that and specifically discloses by any range limit or preferred value All scopes that arbitrary pairing with any range lower limit or preferred value is formed, regardless of whether whether this scope separately discloses. Such as, the scope of 1-50 be understood to include selected from 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18, 19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、 44, any numeral, number combinatorics on words or the subrange and all between above-mentioned integer of 45,46,47,48,49 or 50 Fractional value, such as, 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8 and 1.9.About subrange, specifically consider from scope Interior any end points starts " the nested subrange " extended.Such as, the nested subrange of exemplary range 1-50 can include 1-10,1-20,1-30 and 1-40 on one direction, or 50-40,50-30,50-20 and the 50-10 on other direction.
The present invention provides a kind of high intensity PP-RCT anti-flaming tubular product, including at least three layers, the most respectively internal layer, in Layer and outer layer, described internal layer contains antibacterial and composite flame-retardant agent, and glass fibre and composite flame-retardant agent are contained in described middle level, described Outer layer contains composite flame-retardant agent, and described composite flame-retardant agent contains morpholinyl thiourea, organic silicon compound containing phosphorus.
PP-RCT
Polypropylene (PP) can be classified as HOPP (PP-H) according to different polymerization process conditions, block copolymerization gathers Propylene (PP-B) and atactic copolymerized polypropene (PP-R), the polypropylene of tubing level all can be used to process tubing.PP-H has excellent Good rigid, but its low temperature impact properties is poor, brittle, it is mainly used in discharge of industrial wastes；PP-B has the most soft Toughness, shock resistance is excellent the most at low temperatures, is mainly used in drainage pipeline and discharge of industrial wastes pipeline, is also used for low simultaneously Pressure, the conveying of low temperature (less than 60 DEG C) hot and cold water, such as ground heating system.Gather relative to HOPP (PP-H), block copolymerization For propylene (PP-B), PP-R has high intensity and toughness, improves again PP-H " low temperature cold fragility ", and has at relatively high temperatures Well creep-resistant property, PP-RCT is beta crystal atactic copolymerized polypropene, improves heat resisting temperature and pressure on the basis of PPR Intensity.Homopolymerization type PP-H is I type polypropylene, and block copolymerization type PP-B is II type polypropylene, and random copolymerization type PP-R is that type III is gathered Propylene, PP-RCT is IV type polypropylene.
High intensity PP-RCT anti-flaming tubular product of the present invention can also use PP-H, PP-B or PP-R.
High intensity PP-RCT anti-flaming tubular product of the present invention can also is that employing PP-RCT and polyolefinic blend.Institute State polyolefinic example to include but not limited to, ethylene and the random copolymer of propylene；Ethylene and the random copolymer of butylene；Ethylene Random copolymer with hexene；Ethylene and the random copolymer of octene；Propylene and the random copolymer of butylene；Propylene and hexene Random copolymer；Propylene and the random copolymer of octene；Butylene and the random copolymer of hexene；Butylene and the random copolymerization of octene Thing；The random copolymer of ethylene, propylene and butylene；The random copolymer of ethylene, propylene and hexene；Ethylene, propylene and octene Random copolymer；The random copolymer of ethylene, butylene and hexene；The random copolymer of ethylene, butylene and octene；Propylene, butylene Random copolymer with hexene；The random copolymer of propylene, butylene and octene；The random copolymer of butylene, hexene and octene.
When high intensity PP-RCT anti-flaming tubular product uses PP-RCT and polyolefinic blend, described polyolefinic weight contains Amount accounts for less than the 20% of blend gross weight.
High intensity PP-RCT anti-flaming tubular product of the present invention can also use other polyolefine material or olefin copolymer Material, its instantiation includes but not limited to: polyethylene, polybutene, polypenthylene, polyhexene, polyoctenamer, poly-4-methyl-1-pentene Alkene, ethylene-butene copolymer, ethylene-hexene co-polymers, ethylene-octene copolymer, butylene-hexene copolymer, butylene-octene Copolymer, Ethylene/Butylene-hexene copolymer, Ethylene/Butylene-octene copolymer, butylene-hexene-octene copolymer.
Composite flame-retardant agent
Existing fire retardant has halogenated flame retardant, phosphorus flame retardant, nitrogenated flame retardant, silicon-series five-retardant, expansion type flame-retarding Agent, boron flame retardant, high purity alumina-magnesia fire retardant, Sb system fire retardant, molybdenum flame retardant.
Halogenated flame retardant is one of fire retardant that on our times, yield is maximum, and wherein to smell flame retardant application For extensively.Organic halogenated flame retardant, has that flame retarding efficiency is high, consumption is few, the advantage little, moderate on material property impact, Thus be widely used in the flame-retardant system of polymer.Industrial bromide fire retardant mainly has following three classes: additive flame Combustion agent, including deca-BDE, double (2,3-dioxane propyl group) ether, the octabromodiphenyl ether etc. of tetrabromobisphenol A；Reactive flame retardant, bag Include tetrabromobisphenol A, 2,4,6-tribromphenol etc.；Polymer electrolyte fire retardant, including brominated Polystyrene, brominated epoxy, tetrabromo pair Phenol A carbonic ester oligomer etc..But halogenated flame retardant can produce substantial amounts of flue dust and corrosive gas, no when hot tearing and burning Only corrode equipment together, also can be detrimental to health and ecological environment.Can produce additionally, halogen flame retardant goods reclaim in combustion process Raw a large amount of toxic gas, cause secondary pollution to environment.Along with the use of halogenated flame retardant is limited by various countries, halogen system is fire-retardant The range of agent is more and more less.
Phosphorus flame retardant mainly includes red phosphorus and microencapsulated powder oil halogenated phosphate, non-halogenated phosphate ester, ammonium phosphate, gathers Ammonium phosphate, microcosmic salt etc..Current phosphorus flame retardant significant portion is all to play flame retardant effect in solid phase, burn including suppression, Acid-catalyzed dehydration becomes charcoal, forms surface barrier carbon membrane isolation air etc..Phosphorus flame retardant can improve the charring rate of material, the most right Those oxygen containing macromolecular materials are the most effective.But phosphorus flame retardant effect in oxygen-containing and nitrogenous polymer is the brightest Aobvious, and lack the polymer of these elements, such as in TPO, the flame retarding efficiency of phosphorus flame retardant can be substantially reduced.In order to reach To suitable flame retarding efficiency, addition to be greatly increased, influence whether other performance on the contrary, such as processing characteristics and mechanical property.
Nitrogenated flame retardant is actually a class compound in triazine class, and it includes tripolycyanamide (MA) and its esters, such as uric acid Salt, phosphate, guanidinesalt and dicyandiamide salt etc., they can be used alone, it is possible to the component as mixed expanded type fire retardant uses. Triazines fire retardant is mainly absorbed heat by decomposition and generates non-flammable gases and with dilution combustible or covers at high polymer composite wood Material surface and play fire retardation.Major advantage is colourless, Halogen, low toxicity, low cigarette, do not produce corrosive gas, inexpensive, anti- Ultraviolet irradiation etc.；Its shortcoming is that flame retarding efficiency is not good enough, and the compatibility is poor, makes to be increased by flame retardant viscosity.
Silicon-series five-retardant is divided into organosilicon and inorganic silicon fire retardant, and the silicon-series five-retardant of commercialization the most is main There is the D.C.R.M series silicones powder modifier of GE company of U.S. SFR-100 resin and DOWCorning company of the U.S..Inorganic In silicon-series five-retardant, present most study is montmorillonite.In order to montmorillonite being used for prepare flame-retardant polymer/inorganic matter nanometer Composite, it is necessary to by modified, i.e. with the sun of organic quaternary ammonium salt to natural montmorillonite intercalator or modifying agent (mostly being quaternary ammonium salt) There is ion-exchange reactions with the exchangeable cations (mainly sodium ion) in cheating engaging layer in ion, makes organic group be covered in The surface of montmorillonite, makes its surface property change, original hydrophilic is changed into lipophile, increases between interlayer simultaneously Away from, beneficially monomer or polymer enters.But silicon-series five-retardant addition is higher, applies and influences whether in polypropylene pipe Sweat soldering between tubing, can make the pressure hydraulic performance decline of seam crossing.
The expansion type flame retardant system fire retardant with phosphorus, nitrogen as ignition-proof element, it is typically without halogen, thus is also not required to use Fire retarding synergist made by antimony oxide.Expansion type flame retardant has good fire-retardant and presses down hood, when high polymer by heat-flash Or burning time, surface can generate one layer of uniform porous carbonaceous froth bed, this froth bed is heat insulation, oxygen barrier, press down cigarette and can prevent produce Raw molten drop.Expansion type flame retardant to reach good flame retardant effect, its addition 25%-30% to be reached, and influences whether tubing Other performance.
In boron flame retardant, it is most important that Firebrake ZB.It is a kind of nontoxic, tasteless, white powder of odorless, its tool Have fire-retardant, press down cigarette, become the several functions such as charcoal and anti-molten drop.Its fire retardant mechanism is to be covered afterwards at material surface by melted, rises To the shield effectiveness of blocking oxygen Yu volatile combustible gases, prevent aoxidizing further and promoting into charcoal of layer of charcoal.As fire-retardant Synergist, its shortcoming is lower than stibium oxide efficiency, but advantage be generally give birth to smoke and cost than stibium oxide much lower being commonly used for press down Fumicants, it is possible to part replaces antimony oxide as the fire retarding synergist of halogenated flame retardant.In the presence of bromine compounds, generate Halogenation boron, zinc halide etc. can well suppress and capture free hydroxyl group, form condensed phase cover layer, stop combustion reaction chain Occur, completely cut off polymer surface air, stop flame to burn away and can play and press down cigarette effect.
Magnalium fire retardant is the Representative Cultivars of inorganic combustion inhibitor, generally is white, nontoxic powder.Magnalium fire retardant warp Sloughing water after heating thus play fire retardation, it is possible not only to fire-retardant, and can drop low-smoke, cheap, raw material It is easy to get, by countries in the world most attention.The consumption figure of the U.S. and Japan annual high purity alumina-magnesia fire retardant accounts for inorganic combustion inhibitor 80%, be mainly used in epoxy resin, unsaturated polyester resin, polrvinyl chloride, polyethylene, polypropylene, PBT and polystyrene and ABS resin, nylon etc. fire-retardant.Its anti-flammability be typically implemented in the fire retardant such as halogen system with the use of, play synergist and press down The effect of fumicants, often can largely improve flame retarding efficiency and the fall low-smoke of other fire retardant.But magnalium is fire-retardant Main problem is that addition is big, need and halogenated flame retardant with the use of.
Sb system fire retardant is one of important inorganic combustion inhibitor, is used alone and can not play the biggest fire retardation, when it and Halogen containing flame-retardant used time, the biggest flame retardant synergism can be produced, such that it is able to greatly reduce halogen containing flame-retardant consumption, because of This it be a kind of effective auxiliary flame retardant, its principal item is antimony oxide.Antimony oxide burning is to produce in a large number Black smoke, in order to improve the transparency, in succession develop antimony organic, antimony pentoxide and stibium oxide and fluoboric acid both at home and abroad at present The mixture of salt.
About molybdenum flame retardant, the most efficient molybdenum compound of shiploads of merchandise is molybdenum trioxide and ammonium octamolybdate (AOM), next has calcium molybdate and zinc molybdate.It addition, the compound of molybdenum, lead, zinc compound also has application, this based flame retardant can be used In PVC-U, semirigid PVC wire-insulating material and flexible PVC and ABS resin.
Composite flame-retardant agent of the present invention contains morpholinyl thiourea, organic silicon compound containing phosphorus.
In some embodiments, the weight ratio of described morpholinyl thiourea and organic silicon compound containing phosphorus is (1-2): 5.
In some embodiments, described morpholinyl thiourea is selected from 1-[3-(4-morpholinyl) propyl group] thiourea, 1-[2-(4- Morpholinyl) ethyl] thiourea, 1-cyclohexyl-3-(2-morpholinyl ethyl) thiourea, 1-(2-morpholinyl ethyl)-3-phenylthiourea, 1- One in [3-ethyoxyl-2-(4-morpholinyl) propyl group]-3-ethyl thiourea.
In some embodiments, described organic silicon compound containing phosphorus is by comprising phosphinylidyne dichloro compound and amido organosilicon The raw material of compound prepares.
As the preparation method of organic silicon compound containing phosphorus of the present invention, the steps include: under nitrogen protection, by phosphorus Acyl dichloro compound and amido organosilicon compound mix in acetonitrile, add triethylamine as catalyst, are heated to 110 DEG C, continuously stirred 24h, it is subsequently adding water and hexamethyl disiloxane, reaction temperature is down to 70 DEG C, continue stirring 24h, stop After reaction, decompression distillation pumps solvent, then washs with water and ether, after vacuum drying, to obtain final product.
In some embodiments, described phosphinylidyne dichloro compound contains aromatic rings.
In some embodiments, described phosphinylidyne dichloro compound is selected from 2-phthalimide-based ethyl dichloro phosphoric acid One in ester, phenoxy group phosphinylidyne dichloro, 3,5-3,5-dimethylphenyl phosphinylidyne dichloro.
In some embodiments, described amido organosilicon compound contains at least one primary amino radical and at least one parahelium Base.
In some embodiments, described amido organosilicon compound is selected from N-(6-Aminohexyl) amino methyl three ethoxy Base silane, (((2-amino-ethyl) amino) methyl) triethoxysilane, (aminoethylaminomethyl) phenethyl trimethoxy One in silane, N-(2-amino-ethyl)-N'-(3-(dimethoxymethylsilane base) propyl group)-1,2-ethylenediamine.
Inventor finds in the research process complete the present invention, and the composite flame-retardant agent that the present invention provides is less at addition Time just can have outstanding flame retardant effect, also can improve mechanical strength and the processing characteristics of tubing simultaneously.It has been recognised by the inventors that it is described Aromatic rings in organic silicon compound containing phosphorus can improve the flame retardant effect of system, after introducing rigid structure, and its plane formed Structure is prone to tightly packed, and molecule rotary motion is restricted, it is thus possible to improve thermostability and the anti-flammability of polymer.Phosphorous have Phosphorus in organic silicon compound at high temperature has dehydration, makes molecular dehydration carbonization form layer of charcoal.And organo-silicon compound increase Add the content of element silicon in layer of charcoal, formed the silicon protective layer of charcoal, provide thermal stability for the layer of charcoal formed.Introduce phenyl ring also Improve organic silicon compound containing phosphorus and form the ability of layer of charcoal, improve flame retardant effect.But phenyl ring can increase sterically hindered, PP-RCT tubing influences whether its processing characteristics, additionally, fire-retardant in the oxygen-containing or nitrogenous polymer of organic silicon compound containing phosphorus Effect is obvious especially, and flame retarding efficiency is the highest in the PP-RCT lack these elements.Inventor finds, adds specific The morpholinyl thiourea of content, can not only improve organic silicon compound containing phosphorus flame retarding efficiency in PP-RCT tubing, it is also possible to Overcome the technology resistance that can reduce processing characteristics after introducing phenyl ring.Beta crystal belongs to hexagonal crystal system, be a kind of thermodynamic instability and The metastable crystal formation of kinetics, PP-RCT can change into alpha-crystal form in heating and deformation process, and the introducing of morpholinyl thiourea can Keep the beta crystal of PP-RCT, the transformation of crystal formation will not be produced and affect other performance.Inventor speculate its possible reason is that right Quinoline base thiourea can to a certain degree improve the compatibility, and at high temperature catalysis carbon-forming fire retardation, the oxidation of suppression condensed phase Reaction.
In some embodiments, being in terms of 100 weight portions by PP-RCT resin, the content of described composite flame-retardant agent is 0.1- 35 parts.
Auxiliary agent
In some embodiments, described high intensity PP-RCT Frpipe possibly together with auxiliary agent, described auxiliary agent selected from antioxidant, In antistatic additive, plasticizer, ultraviolet absorber, heat stabilizer, antifungus agent, anti-termite agent, Ratproof agent, antifoggant at least one Kind.
PP-RCT tubing has certain sensitivity to oxidative degradation, and a small amount of oxygen just can make its performance such as intensity, outward appearance Change.Antioxidant can be divided into phenolic antioxidant, amine antioxidants, phosphite ester kind antioxidant, containing sulphur ester antioxidant.
As the example of phenolic antioxidant, include but not limited to: 1-hydroxy-3-methyl-4-cumene, 2, the tertiary fourth of 6-bis- Base phenol, 2,6-di-t-butyl-4-ethyl-phenol, 2,6 di tert butyl 4 methyl phenol, 2,6-di-t-butyl-4-normal-butyl Phenol, 4 hydroxymethyl 2,6 di t butyl phenol, butylhydroxy anisole, 2-(1-methylcyclohexyl)-4,6-dimethyl benzene Phenol, 2,4 dimethyl 6 tert butyl phenol, 2 methyl 4,6 dinonyl phenol, 2,6-di-t-butyl-alpha, alpha-dimethyl amino-to first Double (the octylsulfo)-1,3,5-three of phenol, 2,4,6-tri-butyl-phenol, 6-(4-hydroxyl-3,5-di-tert-butyl amido)-2,4- Double (4-hydroxyl-3,5-di-t-butyl the phenoxy group)-2-n-octylthio-1,3,5-triazine of piperazine, 4,6-, β-(3,5-di-t-butyl- 4-hydroxy phenyl) methyl propionate, β-(4 hydroxyl 3,5 di-tert-butyl-phenyl) propanoic acid positive octadecanol ester, styrol benzene Phenol, 4,4 '-dihydroxybiphenyl, butylated octylated phenol, butylated stytrene cresol, 2,2 '-methylene bis (4-methyl-6- Tert-butyl phenol), 2,2 '-methylene bis (4-ethyl-6-tert-butyl phenol), 2,2 '-methylene bis (4-methyl-6-cyclohexyl benzene Phenol), 4,4 '-methylene bis(2,6-di-butyl phenol), 2,2 '-methylene bis (6-α-methylbenzyl paracresol), 4,4 '-isopropylidene Bis-phenol, 4,4 '-fourth fork double (3 methy 6 tert butyl phenol), 1,1-double (4-hydroxy benzenes) hexamethylene, 2,2 '-methylene bis (4-first Base-6-(Alpha-Methyl cyclohexyl) phenol), 1,3,5-trimethyl-2,4,6-three (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1, 1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, four (3-(3 ' 5 '-di-t-butyl-4 '-hydroxy phenyl) propanoic acid) Pentaerythritol ester, 4,4 '-thiobis (the 6-tert-butyl group-3-methylphenol), 4,4 '-thiobis (2-methyl-6-tert-butylphenol), 2,2 '-thiobis (4-methyl-6-tert-butylphenol), hexanediol double (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester), 2,2 '-thiobis (3 ,-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate), N, N '-hexamethylene double (3,5-di-t-butyl- 4-hydroxy benzenes propionic acid amide .), 1,3,5-tri-(the 4-tert-butyl group-3-hydroxyl-2,6-dimethyl benzyl) 1,3,5 triazine-2,4,6- (1H, 3H, 5H)-triketone, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) triketone, Isocyanuric acid three [β-(3,5-di-tert-butyl-hydroxy phenyl) propionyloxy ethyl ester], double [double (3 '-tert-butyl group-4 '-hydroxyl of 3,3- Base phenyl) butanoic acid] glycol ester, 1,1 '-thiobis (beta naphthal), double (3,5-di-tert-butyl-4-hydroxyl benzyl) thioether, 2,5- Di-tert-butyl hydroquinone, 2,5 di tert amyl hydroquinone, 3,5-di-tert-butyl-4-hydroxyl benzyl di(2-ethylhexyl)phosphate (18) ester, Double-3-(3-tertiary butyl-4-hydroxy-5-the first of 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphate, octylatcd phenol, 2,2'-ethylenedioxybis(ethanol). Base phenyl) propionic ester, hydroquinone dibenzyl ether, " Ethyl " Antioxidant 728, " Ethyl " Antioxidant 733, “Ethyl”Antioxidant 735、Cyanox 96、Cyanox 53、Cyanox LF、Cyanox 1735、Antioxidant Q-328、Santonox、Antioxidant MBP-5P、MBP-5T、TBM-6P、TBM-6T、Irganox 1890、MD-1024、 Seenox M-100、M-200、M-220、Vanox GT、SKT、Escoflex A122、A123、Sumilizer MPO、 Sumilizer-NW、Sumilizer CS-4、Sumilizer CS-42、Santowhite MK、Nonox-HO、Nonox-EX、 Nonox-EXN, Nonox-EXP, Nonox-WMP, Nonox-WSO, Antioxidant KSM, KSM-EM-33%, TSP, DS, DS/F、NKF、Naugawhite、Naugawhite 434、Naugawhite 431、Naugawhite Powder。
As the example of amine antioxidants, include but not limited to: alcohol between N-phenyl-a-naphthylamine, N-Phenyl beta naphthylamine, fourth Aldehyde-alpha-naphthylamine, DPPD N,N' diphenyl p phenylene diamine, N-isopropyl-N '-diphenyl-para-phenylene diamine, N, N '-two-betanaphthyl are to benzene two Amine, N, N '-bis-(1,4-dimethyl amyl group) p-phenylenediamine, N, N '-bis-(1-ethyl-3-methyl amyl) p-phenylenediamine, N-hexamethylene Base-N '-diphenyl-para-phenylene diamine, N, N '-bis-(1-methylheptyl) p-phenylenediamine, N-(1,3-dimethylbutyl)-N '-phenyl are to benzene Diamidogen, N-phenyl-N '-octyl group p-phenylenediamine, 6-ethyoxyl-2,2,4-trimethyl-1,2-dihyaroquinoline, 2,2,4-front three Base-1,2-dihyaroquinoline polymer, 6-dodecyl-2,2,4-trimethyl-1,2-dihyaroquinoline, N-(methacryl Base oxo-2-hydroxypropyl)-N '-diphenyl-para-phenylene diamine, N-cyclohexyl-P-nethoxyaniline, right, right '-dimethoxy hexichol Amine, p-(p-tolylsulfonyl-amido) diphenylamines, double-(propyloxy phenyl fork)-4,4 '-diphenylamines, N, N '-diphenyl second two Amine, N, N '-di-o-tolyl-ethylene-diamine, N,N' diphenyl propylenediamine, p-isopropoxydiphenylamine, N, N '-di-sec-butyl pair Phenylenediamine, N, N '-dimethyl-N, N '-two (1-methyl-propyl) p-phenylenediamine, right, right '-dioctyl diphenylamine, 4,4 '-bis-(α- Methyl-benzyl)-diphenylamines, Antioxidant 445, Goodrite 3120, Goodrite 3140, Irganox LD-62, Wingstay 29。
As the example of phosphite ester kind antioxidant, include but not limited to: triphenyl phosphite, tricresyl phosphite (nonyl benzene Ester), the different monooctyl ester of tricresyl phosphite, triisodecyl phosphite ester, phosphorous acid benzene two isodecyl ester, trilauryl trithiophosphite, phosphorous Acid three lauryls, tricresyl phosphite (octadecyl ester), diphosphorous acid tetramethylolmethane two isodecyl ester, diphosphorous acid tetramethylolmethane distearyl alcohol Ester, 4,4 '-fourth fork double (phosphorous acid (3-methyl-6-tert butyl phenyl) two (tridecyl) ester), isooctyl diphenyl phosphite, Asia Phosphoric acid benzene di-isooctyl, octyl diphenyl phosphite, phosphorous acid hexichol isodecyl ester, dioctyl phosphite, phosphorous acid dilauryl, Asia Double 13 esters of dimethyl phosphate, dioleyl phosphite, didecyl phosphite, dibutyl phosphite, phosphorous acid, phosphorous acid double ten Double (the nonyl of four esters, NSC 5284, tributyl phosphite, triisopropyl phosphite, tricresyl phosphite monooctyl ester, phosphorous acid-benzene Benzene) ester, phosphorous acid hexichol nonyl phenyl ester, tricresyl phosphite (2-chloroethene) ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, phosphorous Acid bisphenol-A ester, tricresyl phosphite (single nonyl benzene and dinonyl benzene mixed ester), Mark 329, Mark 1500, Mark C, Wytox 345、Wytox 438、Wytox X-540。
As the example containing sulphur ester antioxidant, include but not limited to: dilauryl thiodipropionate, thio-2 acid two Stearic alcohol ester, β, β '-sulfur generation two butanoic acid two (18) esters, thio-2 acid Laurel octadecyl ester, thio-2 acid two (13) ester, Thio-2 acid two (14) ester.
Antioxidant can also is that other type antioxidants, and its instantiation includes but not limited to: 2-mercaptobenzimidazole, 2- Mercapto methyl benzimidazole, zinc salt of 2 mercaptobenzimidazole, N-salicylidene-N '-salicylyl hydrazine, 1,2-are double (2-(2-hydroxybenzoyl)) Hydrazine, N, N '-diacetyl adipyl two hydrazides, Naugard XL-1, Irganox MD 1024, Eastman inhibitor OABH、Sandostab P-EPQ、Mark 260、HCA、Perkanox PC-19、Mark AO-23、Mark AO-412S、Mark CDA 1, Mark CDA-6, Nonox CNS, Seenox 412S, TGA pentyl ester.
As the example of antistatic additive, include but not limited to: stearamidopropyl dimethyl-beta-hydroxyethyl ammonium nitrate, (3-dodecanamide propyl) trimethyl ammonium Methylsulfate salt, double (2-hydroxyethyl)-N-(3 '-dodecyloxy-2 '-hydroxyl of N, N- Base propyl group) first ammonium Methylsulfate salt, N-(3-dodecyloxy-2-hydroxypropyl) ethanolamine, trihydroxyethyl ammonium methyl sulphuric acid first Ester salt, stearamidopropyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate, alkyl phosphate diethanolamine salt, double (the 2-hydroxyl of N, N- Base ethyl) alkylamine, N, N-cetyl ethyl morpholine ethyl-sulfate salt, octadecyldimethyl ethoxy quaternary ammonium nitrate, HZ-1 antistatic additive, HKD-300, HKD-311, HBT-5 type antistatic additive, ECH type antistatic additive, Antistat 68, Drewplast 017, Drewplast 032, Drewplast 051, Atmos 150, Armostat 310,410, Armostat 375,450,475,575, Antistatic agent 273C, 273E, Lubrol PE, Lubrol PEX, Lubrol PX, Nopcostate HS、Lankrostat LDN、Lankrostat LD、TB-109。
Plasticizer include phthalate, 1,3-propanedicarboxylic acid esters, adipic acid esters, Azelaic Acid esters, sebacic acid ester, Phosphoric acid ester, stearic acid esters, lauric acid esters, citric acid ester type, oleic acid esters, trimellitic acid esters, epoxies derivant, Sulfonic acid, polyol derivative, maleic acid esters, fumaric acid esters, itaconic acid esters.
As the example of phthalic ester plasticizer, include but not limited to: dimethyl phthalate, O-phthalic Diethyl phthalate, dipropyl phthalate, n-butyl phthalate, diisobutyl phthalate, phthalic acid fourth Monooctyl ester, diamyl phthalate, the most own ester of phthalic acid two, phthalic acid two (2-ethyl fourth) ester, phthalic acid Dicyclohexyl maleate, phthalic acid two (methyl cyclohexane) ester, phthalic acid positive fourth cyclohexyl, dibutyl phthalate (DHP), adjacent benzene Dioctyl phthalate two (2-ethyl hexyl) ester, dinoctyl phthalate, diisooctyl phthalate, phthalic acid di-secondary are pungent Ester, dinonyl phthalate, diisononyl phthalate, diisooctyl phthalate, didecyl phthalate, neighbour Phthalic acid fourth ester in the last of the ten Heavenly stems, n-octyl-n-decyl phthalate, iso-octyl isodecyl phthalate ester, phthalic acid ethylhexyl last of the ten Heavenly stems Ester, phthalic acid two (11) ester, phthalic acid two (12) ester, phthalic acid two (13) ester, phthalic acid Pungent 13 esters, phthalic acid ester in the last of the ten Heavenly stems 13, phthalic acid fourth 14 ester, capryl octyl phthalate, phthalic acid Diphenyl ester, dibenzyl phthalate, BBP(Butyl Benzyl Phthalate, OBP, phthalic acid two (methoxyl group Second) ester, phthalic acid two (ethyoxyl second) ester, phthalic acid two (butoxy second) ester, methyl phthalyl Acetoacetic ester, ethyl phthalyl acetoacetic ester, butyl phthalyl acid butyl ester, phthalic acid C6～ C10 n-alkanol mixed ester, phthalic acid C7～C9 alcohol mixed ester, phthalic acid C7～C10 alcohol mixed ester, phthalic acid C8～C10 n-alkanol mixed ester, phthalic acid C9～C11 alcohol mixed ester, phthalic acid C7～C11 alcohol mixed ester, adjacent benzene Dioctyl phthalate two (C8～C13) ester, tetrahydrophthalic acid two (2-ethyl hexyl) ester, tetrahydrophthalic acid di-n-octyl, Tetrahydrophthalic acid two isodecyl ester, tetrahydrophthalic acid C7～C10 Arrcostab, hexahydro-phthalic acid two (2- Ethyl hexyl) ester, phthalic acid dibenzyl must alcohol ester, phthalic acid dihydro Colophonium alcohol ester, Santicizer 213,218A, 267,679,885, Loxiol W100, W101, W300S, plasticizer DGPO, plasticizer BD.
As the example of 1,3-propanedicarboxylic acid ester plasticizer, include but not limited to: Dioctyl Glutaricate, didecyl glutarate, penta Diacid two isodecyl ester, 1,3-propanedicarboxylic acid two fourth 2-ethoxyethyl acetate, 1,3-propanedicarboxylic acid two fourth oxygen ethoxy ethyl ester.
As the example of adipic acid ester plasticizer, include but not limited to: Di-n-butyl Adipate, adipic acid two isobutyl Ester, di-n-hexyl adipate, dioctyl adipate, Adipol 10A, dinonyl adipate, diisononyl adipate, oneself Diacid two isodecyl ester, the positive butyl benzyl of adipic acid, BOA, adipic acid two fourth 2-ethoxyethyl acetate, adipic acid two (butoxy ethoxy Base second) ester, adipic acid two (610 alkyl) ester, adipic acid C7～C9 linear ester, n-octyl n-decyl adipate (NODA), adipic acid be different pungent different The last of the ten Heavenly stems ester, adipic acid two (methyl cyclohexane) ester, adipic acid two (diethylene glycol monobutyl ether) ester.
As the example of Azelaic Acid ester plasticizer, include but not limited to: diisobutyl azelate, Azelaic Acid two are just own Ester, Azelaic Acid two (2-ethyl fourth) ester, Azelaic Acid two (2-ethyl hexyl) ester, diisooctyl azelate, 4-sulfur are for Azelaic Acid two (2- Ethyl hexyl) ester, Azelaic Acid two fourth 2-ethoxyethyl acetate, dibenzyl azelate, dicyclohexyl azelate.
As the example of sebacic acid ester plasticizer, include but not limited to: dimethyl sebacate, n-butyl sebacate, Dermol DIPS, di-n-octyl sebacate, Plexol 201, decanedioic acid di-sec-octyl, di-n-nonyl sebacate, decanedioic acid Two (butoxy second) ester, decanedioic acid two (Butoxyethoxy second) ester, dibenzyl sebacate, decanedioic acid two C7～C9 alcohol ester, the last of the ten Heavenly stems Diethyl adipate, dihexyl sebacate, butyl benzyl sebacate.
As the example of phosphate plasticizer, include but not limited to: triethyl phosphate, tributyl phosphate, phosphide three are pungent Ester, diphenyl 2 ethylhexyl phosphate, triphenyl phosphate, phosphate toluene diphenyl ester, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, phosphorus Acid dimethylbenzene diphenyl ester, isodecyl diphenyl phosphate, tricresyl phosphate (butoxy second) ester, tricresyl phosphate isopropyl phenyl ester, tricresyl phosphate (2-chlorine Second) ester, tricresyl phosphate (dichloro third) ester, mono phosphoric acid ester neighbour's biphenyl diphenyl phosphate, di(2-ethylhexyl)phosphate (adjacent biphenyl) monophenyl, Phosflex 200, 300、Santicizer 145。
As the example of stearic acid ester plasticizer, include but not limited to: n-butyl stearate, glyceryl monostearate, Stearic acid 2-butoxyethyl, butyl acetoxystearate, monostearate 1,2-propylene glycol ester, (acetoxyl group is hard for glycerol three Fat acid) ester, distearyl acid diethylene glycol ester, methyl pentachlorostearate, stearic acid methoxy ethyl ester.
As the example of lauric acid ester plasticizer, include but not limited to: mono laurate 1,2-PD ester, mono laurate Glyceride, mono laurate diethylene glycol ester, lauric acid fourth 2-ethoxyethyl acetate, Polyethylene Glycol (400) dilaurate.
As the example of citric acid ester plasticizer, include but not limited to: triethyl citrate, tri-n-butyl citrate, Acetyl triethyl citrate, the positive fourth fat of acetyl tributyl citrate three, ATHC, acetyl tributyl citrate three (2-ethyl hexyl) Ester, acetyl tributyl citrate three (the most pungent positive last of the ten Heavenly stems) ester.
As the example of oleic acid ester plasticizer, include but not limited to: methyl oleate, n propyl oleate, butyl oleate, oil Acid oxolane methyl ester, methoxyethyl oleate, oleic acid 2-fourth 2-ethoxyethyl acetate, glyceryl monooleate, single diglycol oleate.
As the example of trimellitic acid esters plasticizer, include but not limited to: tri trimellitate (2-ethyl hexyl) ester, inclined benzene Three sour three n-octyls, triisooctyl trimellitate, triisodecyl trimellitate, the secondary monooctyl ester of tri trimellitate, tri trimellitate are different Nonyl ester, tri trimellitate (the most pungent positive last of the ten Heavenly stems) ester, diisooctyl manoisodecyl trimellitate, tri n hexyl trimellitate, Santicizer 79TM、TX-85。
As the example of epoxies derivant plasticizer, include but not limited to: epoxy soybean oil, epoxy Semen Lini oil, 4, 5-epoxy diisodecyl tetrahydrophthalate, 4,5-epoxy tetrahydrophthalic acid two (2-ethyl hexyl) ester, epoxystearic acid Butyl ester, epoxystearic acid 2-Octyl Nitrite, the different monooctyl ester of epoxystearic acid, epoxidized tall oil acid 2-Octyl Nitrite, epoxy soybean oil Acid 2-Octyl Nitrite, epoxidized methyl acetorieinoleate, epoxy pupa oil acid butyl ester, epoxyfuoic-oleic, epoxidation glycerol three Acid esters, epoxy chlorinated paraffin, epoxy chloroparaffin, epoxy cotton seed oil, epoxyoleic acid ester in the last of the ten Heavenly stems, Monoplex S-70, Flexol GPE.
As the example of sulfonic acid plasticizer, include but not limited to: benzene sulfonyl butylamine, neighbour, para toluene sulfonamide, N- Ethyl-neighbour, p-methylphenyl sulphonylamine, N-cyclohexyl-p-methylphenyl sulphonylamine, phenyl alkylsulf.
As the example of polyol derivative plasticizer, include but not limited to: diethylene glycol dibenzoate, 2,2'-ethylenedioxybis(ethanol). hexichol Formic acid esters, 2,2'-ethylenedioxybis(ethanol). two (2 Ethylbutanoic acid) ester, 2,2'-ethylenedioxybis(ethanol). two (2 ethyl hexanoic acid) ester, triethylene glycol dieaprylate, 2,2'-ethylenedioxybis(ethanol). two (C7-9 carboxylate), tetraethylene glycol (TEG) two (2 ethyl hexanoic acid) ester, diethylene glycol dipelargonate, triethylene glycol dipelargonate, 2,2'-ethylenedioxybis(ethanol). pungent last of the ten Heavenly stems Acid esters, triethylene glycol diheptylate, tetraethylene glycol diheptanoate, ethylene diacetate, 2,2'-ethylenedioxybis(ethanol). diacetate, 59 acid glycerides, C5～C9 fatty acid mixed glycol ester, Polyethylene Glycol, Polyethylene Glycol (200) dibenzoate, Polyethylene Glycol (600) hexichol first Acid esters, diglycol benzoate and dipropylene glycol benzoate mixture (1:1), neopentyl glycol dibenzoate, triphen Formic acid glyceride, dipropylene glycol dibenzoate, propylene glycol dibenzoate, trimethylolethane trimethacrylate benzoate, sweet Oil monoacetate, glyceryl diacetate, triacetin, glycerin tributyrate, glycerol ether acetate, glycerin tripropionate, (C5～C9 mixes for pentaerythritol fatty ester, pentaerythritol tetrabenzoate, tetramethylolmethane four caprylatecaprate, tetramethylolmethane four Close fatty acid ester), Bis(pentaerythritol) support adipic acid six (C5～C9 mixed aliphatic ester).
As the example of maleic acid ester plasticizer, include but not limited to: n-butyl maleate, maleic acid two (2-second Base oneself) ester, dimethyl maleate, ethyl maleate..
As the example of fumaric acid esters plasticizer, include but not limited to: di n butyl fumarate, fumaric acid two (2-second Base oneself) ester, diisooctyl fumarate.
As the example of itaconic acid ester plasticizer, include but not limited to: itaconic acid list formic acid, monobutyl itaconate, clothing Health dimethyl phthalate, diethyl itaconate, dibutyl itaconate, itaconic acid two (2-ethyl hexyl) ester.
Plasticizer can also be other type of plasticizer, and its instantiation includes but not limited to: acetylricinoleate alkyd first Ester, acetylricinoleate alcohol acid butyl ester, single monoricinoleate, single ricinoleic acid diethylene glycol ester, glycerol three (acetylricinoleate alkyd) Ester, methyl ricinoleate, ricinoleic acid butyl ester, single propylene glycol ricinoleate, acetylricinoleate alkyd methoxy ethyl ester, ricinoleic acid Methoxy ethyl ester, isopropyl palmitate, iso-octyl palmitate, isopropyl myristate, n-butyl myristate, myristic acid Petiolus Trachycarpi Isopropyl propionate, sucrose octa-acetate, sucrose acetate isobutyrate, sucrose benzoate, tall oil acid methyl ester, tall oil acid are different pungent Ester, Abalyn., hydrogenated methyl rosinate, hydroabietyl alcohol, poly alpha methylstyrene resin, PMA four (2-ethyl Oneself) ester, PMA four n-octyl, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, oleoyl nitrile, tartaric acid two fourth Ester, 2-ketone group-1,7,7-trimethylnorcamphane, M-phthalic acid two (2-Octyl Nitrite), diisooctyl isophthalate, to benzene Dioctyl phthalate two (2-ethyl hexyl) ester, A.G.S acid two (2-ethyl hexyl) ester, Monoplex S-38, S-90E, Kodaflex 135, Nevillac 10 °, TS, Reomol DV35, DV49, MI, Reomol RIG, MN, MD, NB-10, polyadipate 1,2-PD Ester, poly-decanedioic acid-1,2-propylene glycol ester, poly adipate succinic acid ester.
Ultraviolet absorber includes salicylic acid esters, benzophenone, benzotriazole, triazines, group-substituted acrylonitrile, grass Amide-type, organic nickel complexation species, hindered amines.
As salicylic acid esters, its instantiation includes but not limited to: phenyl salicylate, p-octylphenyl salicylate, water Poplar acid is to tert-butyl group phenyl ester, double acid double phenol A ester.
As benzophenone, its instantiation includes but not limited to: 2,4-DihydroxyBenzophenone, 2-hydroxyl-4-first Epoxide benzophenone, 2,2 '-dihydroxy-4-methoxy benzophenone, 2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone, 2,2 '-dihydroxy-4,4 '-sodium salt of dimethoxy-5-diphenylsulfone ketone, 2-hydroxyl-4-methoxyl group-2 '-carboxyl hexichol first Ketone, 2-hydroxyl-4-methoxyl group-5-diphenylsulfone ketone trihydrate, Octabenzone, 2-hydroxyl-4- Octadecane epoxide benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2-hydroxyl-4-dodecyloxy benzophenones, 2,2 '- Dihydroxy-4-oxy-octyl benzophenone, 2-hydroxyl-5-chlorobenzophenone, 2-hydroxyl-4-methoxyl group-4 '-chloro hexichol first Ketone, 2-hydroxyl-4-methoxyl group-2 ', 4 '-dichloro benzophenone, 2-hydroxyl-4-behzyloxybenzophenone, 2-hydroxyl-4-[2 '-hydroxyl Base-3 '-(methacryloxypropoxy)] benzophenone, 2-hydroxyl-4-(2 '-hydroxyl-3 '-acryloxy propoxyl group) Benzophenone, 1,3-double (3 '-hydroxyl-4 '-benzoyl phenoxy group) propanol-2,2-hydroxyl-4-ethoxyl phenenyl 17 (alkane) Ketone, Uvinul 490, Permyl B-100, Mark 1535, Mark LA-51.
As benzotriazole, its instantiation includes but not limited to: 2-(2 '-hydroxyl-3 ', 5 '-dihydroxy tert-butyl benzene Base) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-tert-butyl group-5 '-methylbenzene Base)-5-chlorinated benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5 chlorinated benzotriazoles, 2-(2 '-hydroxyl- 4 '-n-octyloxy phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-diamyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '- T-octyl phenyl) benzotriazole, Tinuvin PS, Mark 446.
As benzoates, its instantiation includes but not limited to: resorcinol monobenzoate, 3, the tertiary fourth of 5-bis- Base-4-HBA 2,4-6-di-tert-butyl phenyl ester, the positive hexadecyl ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid.
As organic nickel complexation species, its instantiation includes but not limited to: double (3,5-di-tert-butyl-4-hydroxyl benzyls Phosphonic acids mono ethyl ester) nickel, 2,2 '-thiobis (4-t-octyl phenol epoxide) nickel-n-butylamine complex, 2,2-thiobis (4-t-octyl Phenol epoxide) nickel-2 ethyl hexylamine complex, 2,2 '-thiobis (4-t-octyl phenol epoxide) nickel, N, N-di-n-butyl dithio ammonia Base nickel formate, nickel dimethyldithiocarbamate, dioctyl aminodithioformic acid nickel, Mark 1306A, Mark 1306B, UV Chek AM-205, Sanduvor NPU, 10%Nickel Hex-Cem.
As hindered amines, its instantiation includes but not limited to: double (2,2,6, the 6-tetramethyl-4-piperidines of decanedioic acid Ester), three (1,2,2,6,6-pentamethvl base) phosphite ester, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine, Mark LA-57、Mark LA-62、Mark LA-63、Mark LA-67、Mark LA-68、Tinuvin 144、Tinuvin 622、 Chimassorb 944、Good-Rite UV-3034、Hostavin N 20、Cyasorb UV 3230。
Ultraviolet absorber can also is that other type, includes but not limited to: 2-cyano-3,3-diphenyl ethyl acrylate, 2-cyano group-3,3-diphenylacrylate 2-Octyl Nitrite, 2,4,6-tri-(2 '-hydroxyl-4 '-n-butoxyphenyl)-1,3,5-three Piperazine, HMPA, 2,4-dibenzoyl resorcinols, N-(2-ethylphenyl)-N '-(2-ethyoxyl-5-tert-butyl group Phenyl) oxamide, 2-ethyl-2 '-ethyoxyl oxanilide, Vanstay L, UV Chek-541A, Cyasorb UV 2126。
Heat stabilizer includes base lead salt class, metal soap, organic tin, organic compound and polyalcohols, is combined Stabilizer.
As the example of basic lead salt heat stabilizer, include but not limited to: dibasic lead stearate, tribasic sulphuric acid Lead, Dythal, dibasic lead phosphite, tribasic Malaysia lead plumbate, C.I. 77597, basic lead sulphate, alkali Formula lead sulfite, lead silicate, co-precipitation basic lead silicate-lead sulfate, co-precipitation lead orthosilicate-silica gel, chlorine lead silicate complex, Chloro phthalein lead silicate, alkali formula sulfo group lead phosphite complex, alkali formula chlorine lead silicate-lead sulfate complex, alkali formula thioesters lead-neighbour's benzene Diformazan lead plumbate, four alkali fumaric acid lead, lead salicylate.
As the example of metal soap stabilizer, include but not limited to: calcium stearate, barium stearate, cadmium stearate, tristearin Acid magnesium, lithium stearate, zinc stearate, aluminium stearate, double stearic acid aluminium, lead stearate, Strontium bis(stearate), cobaltous octadecanate, stearic acid Stannous, sodium stearate, barium laurate, calcium laurate, Dodecanoic acid, zinc salt, cadmium laurate, barium ricinoleate, ricinoleic acid calcium, Semen Ricini Alkyd cadmium, ricinoleic acid strontium, 2 ethyl hexanoic acid zinc, 2 ethyl hexanoic acid lead, cadmium 2-ethylhexoate, 2 ethyl hexanoic acid barium.
As the example of organic tin stabilizer, include but not limited to: dibutyitin maleate, di lauric dibutyl Stannum, lauric acid dibutyitin maleate, maleic acid dioctyltin, Bis(lauroyloxy)dioctyltin, double (sulfur is different pungent for glycolic acid Ester) dioctyltin, lauryl mercaptan dibutyl tin, double (sulfur is for the different monooctyl ester of glycolic acid) dibutyl tin β-mercaptopropionic acid dibutyl Stannum, double (single-ethylhexyl maleate) di-n-butyl tin, double (butyl maleate) dibutyl tin, double (pungent fat of maleic acid list) two are the most pungent Ji Xi, double (butyl maleate) dioctyltin, poly-stannum glycol dilaurate, poly-stannum glycol lauric acid-maleate, poly- Stannum glycol ether-ether, aggretion type organotin mercaptide compound, TM-387, TM-692.
As organic compound and the example of polyalcohols stabilizer, include but not limited to: 2-phenylindone, diphenyl sulfur Double (beta-amino butenoic acid) ester of urea, 1,4-butanediol, thio-diethylene glycol double (beta-amino butenoic acid) ester, tetramethylolmethane, Pyrusussuriensis Sugar alcohol, Synpron 1034, Synpron 1027.
As the example of complex stabilizer, include but not limited to: liquid organic calcium zinc complexes, the organic barium zinc of liquid are compound Thing, liquid organic barium cadmium zinc complexes, liquid organic barium cadmium complex, liquid organic barium lead complex, phosphorous acid Ca Zn composite Thing, co-precipitation barium laurate cadmium, co-precipitation barium myristate cadmium, modified calcium stannous zinc complexes, dustless complex lead salt, rare earth are multiple Close stabilizer.
As the example of antifungus agent, include but not limited to: pentachlorophenol, sodium pentachlorophenol, lauric ester of pentachlorophenol, water Poplar anilid, copper 8-quinolinolate, double (tri-n-butyl tin) oxide, double (tributyl tin) sulfide, tributyl tin acetate, Tributyltin chloride, tributyl-tin fumarate, tributyl tin fluoride, N-(trichloromethylthio) phthalimide, N-(three Chloromethyl sulfur generation)-4-cyclohexene-1,2-dicarboximide, 5,6-dichloro benzo oxazoline ketone, N-(fluorine dichloromethyl sulfur generation) be adjacent Phthalimide, N, N-dimethyl-N '-phenyl (fluorine dichloromethyl sulfur generation) sulfonamide, 2,2 '-dihydroxy-5,5 '-dichloro- Diphenyl methane, 2-(4-thiazolyl) benzimidazole, PCMX, 10,10 '-oxo double phenoxy group arsine, 2-methoxy Base carbonylamino benzo imidazoles, Preventol K1, hexahydro-1,3,5-triethyl group triazine, o-Phenylphenol Sodium salt tetrahydrate, 2-hydroxyl join Benzene, 3,4 ', 5-tribromsalan, Antimycoticum A, Hyamine, Preventol OC 3014, Corobex, ASC-4、Cubide。
As the example of anti-termite agent, include but not limited to: Isosorbide-5-Nitrae, 5,6,7,8,8-heptachlor-3a, 4,7,7a tetrahydrochysene-4,7- Methanoindene, the chloro-2,3,3a of 2,3,4,5,6,7,8,8-eight, 4,7,7a-hexahydro-4,7-methanoindene, 1,2,3,4,10,10-chlordene- 6,7-epoxy-1,4,4a, 5,6,7,8,8a-octahydro-1,4-5,8-two methylene naphthalene, 1,2,3,4,10,10-chlordene-1,4,4a, 5, 8,8a-hexahydro-1,4 (interior)-5,8-(outward)-two methylene naphthalene, right, right '-dichloro-diphenyl-trichloro-ethane, 4-chloro-2-phenyl benzene Phenol, Termite Repellent LK-1212, Termite Repellent-K.
As the example of Ratproof agent, include but not limited to: 3-[2-(3,5-dimethyl-2-oxocyclohexyl)-2-hydroxyl second Base] glutarimide, tributyl tin acetate.
As the example of antifoggant, include but not limited to: glycerin mono-fatty acid ester, glyceryl monoricinoleate, Sorbitol Acid anhydride monoleate, Span-20, sorbitan monopalmitate, sorbitan monostearate, poly- Oxirane (20) glyceryl monostearate, poly(ethylene oxide) (5) glyceryl monostearate, poly(ethylene oxide) (20) Sorbitol Acid anhydride monoleate, poly(ethylene oxide) (5) glycerin mono-fatty acid ester, poly(ethylene oxide) (9) monoleate, poly(ethylene oxide) (20) glycerol Monoleate, Drewplast 100, Mark 630, Drewplast 084, glyceryl monostearate.
Antibacterial
Described antibacterial is antibacterial selected from silver-series antibacterial agent, titanium series antibacterial agent, organic polymer salt antibacterial, imidazoles Agent, containing in arsenic organic antibacterial agent, organic metal class antibacterial, pyridines antibacterial and phenolic antiseptic at least one.
Other
High intensity PP-RCT anti-flaming tubular product of the present invention can be with outer lining or be lined with metal pipe material, its instantiation bag Include but be not limited to aluminium alloy lining PPR pipe, aluminum lining PPR pipe, liner copper PPR pipe, inner liner stainless steel PPR pipe.
The preparation of tubing
High intensity PP-RCT anti-flaming tubular product of the present invention uses laminated multi-layer co-extrusion technology extrusion to obtain.Internal layer hopper For the PP-RCT granule containing antibacterial and fire retardant, middle level hopper is the PP-RCT granule containing fire retardant and glass fibre, Outer layer hopper is the PP-RCT granule containing fire retardant, obtains high intensity PP-RCT Frpipe through plasticizing co-extrusion, wherein, interior Layer, middle level, the thickness of outer layer can be arbitrary proportions, and the present invention does not do any restriction.
The present invention also provides for a kind of high intensity PP-RCT anti-flaming tubular product as above in central air-conditioning pipe system, fire-fighting With the application in fire-fighting spraying pipeline system.
Embodiment
A PP-RCT, Borealis RA7050
B 1-[3-(4-morpholinyl) propyl group] thiourea, regent biochemical technology company limited of Shenzhen, No. CAS: 111538- 46-6
C1 organic silicon compound containing phosphorus
It is prepared into by the raw material comprising phenoxy group phosphinylidyne dichloro and N-(6-Aminohexyl) amino methyl triethoxysilane Arrive.
Preparation method is: under nitrogen protection, by 0.05mol phenoxy group phosphinylidyne dichloro and 0.1mol N-(6-amino oneself Base) amino methyl triethoxysilane mixes in 250mL acetonitrile, adds 0.11mol triethylamine, be heated to 110 DEG C, continues Stirring 24h, is subsequently adding 5mL water and 0.05g hexamethyldisilane, reaction temperature is down to 70 DEG C, continues stirring 24h, stops After reaction, decompression distillation pumps solvent, then uses 20mL water and the washing of 20mL ether successively, after vacuum drying, to obtain final product.
C2 organic silicon compound containing phosphorus
By comprising phenoxy group phosphinylidyne dichloro and 4-ammobutyltriethoxysilane raw material prepares.
Preparation method is: under nitrogen protection, by 0.05mol phenoxy group phosphinylidyne dichloro and 0.1mol 4-aminobutyl three Ethoxysilane mixes in 250mL acetonitrile, adds 0.11mol triethylamine, is heated to 110 DEG C, continuously stirred 24h, then Adding 5mL water and 0.05g hexamethyldisilane, reaction temperature is down to 70 DEG C, continue stirring 24h, after stopped reaction, decompression is steamed Evaporate and pump solvent, then use 20mL water and the washing of 20mL ether successively, after vacuum drying, to obtain final product.
Acetonitrile, Yongfeng, Taizhou plain Chemical Co., Ltd., No. CAS: 75-05-8
Triethylamine, Zhejiang Bo Laite Science and Technology Ltd., No. CAS: 121-44-8
Hexamethyldisilane, Zhejiang Bo Laite Science and Technology Ltd., No. CAS: 1450-14-2
Phenoxy group phosphinylidyne dichloro, Changzhou Watson Fine Chemical Co., Ltd., No. CAS: 770-12-7
N-(6-Aminohexyl) amino methyl triethoxysilane, Shanghai Ji Laide new material Science and Technology Ltd., CAS Number: 15129-36-9
4-ammobutyltriethoxysilane, Shanghai Shi Yang Chemical Co., Ltd., No. CAS: 3069-30-5
The weight ratio of D1 B and C1 is the mixture of 1.5:5
The weight ratio of D2 B and C1 is the mixture of 0.1:5
The weight ratio of D3 B and C1 is the mixture of 5:5
The weight ratio of D4 B and C2 is the mixture of 1.5:5
E1 silver ion antimicrobial agent, BASF IRGAGUARD B6000
E2 Tissuemat E, Honeywell AC-6
E3 glass fibre, Tai'an white jade glass fiber composite material company limited
Embodiment 1
The internal layer hopper of embodiment 1-9 and comparative example 1-6 is the PP-RCT granule containing antibacterial and composite flame-retardant agent, former Material proportioning is the most identical, and in parts by weight, its concrete proportioning raw materials is as shown in table 1.
Table 1
A D1 D2 D3 D4 B C1 E1 E2
Example 1 100 0.1 10 2
Example 2 100 0.5 10 2
Example 3 100 1 10 2
Example 4 100 5 10 2
Example 5 100 10 10 2
Example 6 100 15 10 2
Example 7 100 20 10 2
Example 8 100 30 10 2
Example 9 100 35 10 2
To 1 100 30 10 2
To 2 100 30 10 2
To 3 100 30 10 2
To 4 100 30 10 2
To 5 100 30 10 2
To 6 100 10 2
The middle level hopper of embodiment 1-9 and comparative example 1-6 is the PP-RCT granule containing glass fibre and composite flame-retardant agent, In parts by weight, its concrete proportioning raw materials is as shown in table 2.
Table 2
A D1 D2 D3 D4 B C1 E3
Example 1 100 0.1 10
Example 2 100 0.5 10
Example 3 100 1 10
Example 4 100 5 10
Example 5 100 10 10
Example 6 100 15 10
Example 7 100 20 10
Example 8 100 30 10
Example 9 100 35 10
To 1 100 30 10
To 2 100 30 10
To 3 100 30 10
To 4 100 30 10
To 5 100 30 10
To 6 100 10
The outer layer hopper of embodiment 1-9 and comparative example 1-6 is the PP-RCT granule containing composite flame-retardant agent, with weight portion Meter, its concrete proportioning raw materials is as shown in table 3.
Table 3
A D1 D2 D3 D4 B C1 E2
Example 1 100 0.1 2
Example 2 100 0.5 2
Example 3 100 1 2
Example 4 100 5 2
Example 5 100 10 2
Example 6 100 15 2
Example 7 100 20 2
Example 8 100 30 2
Example 9 100 35 2
To 1 100 30 2
To 2 100 30 2
To 3 100 30 2
To 4 100 30 2
To 5 100 30 2
To 6 100 2
The preparation method of embodiment 1-9 and comparative example 1-6 is:
The raw material interpolation of table 1, table 2, table 3 pressed respectively by material in internal layer, middle level, outer layer hopper, uses extruder pelletize, Prilling temperature: feeding section 160 DEG C, 190 DEG C, compression section, metering section 200 DEG C, head 200 DEG C, mouth die 210 DEG C；It is then passed through plasticizing Co-extrusion obtains.Wherein, internal layer, middle level, the thickness of outer layer are 1:1:1.
Performance evaluation
1. limited oxygen index test
Sample is carried out according to the method for GB/T 2406-2008 defined.Length of flame 10mm, 30 seconds durations of ignition, sentences According to: burning length 50mm, i.e. igniting 30 seconds, sample can't burn, although can burn in other words, but burning length is not enough 40mm, then explanation oxygen concentration is on the low side, in addition it is also necessary to heighten.If can light sample in 30 seconds, and the burning length of sample surpasses Cross 40mm, then it represents that oxygen concentration is high, needs to turn down.So, until finding a critical oxygen concentration, refer to as limit oxygen Number, unit %.
2. vertical combustion test
Test according to UL94-2009 standard, according to sample burning times, if whether molten drop and molten drop can ignite Absorbent cotton overall merit sample flame retardant effect immediately below sample, is fixed on 30.5cm above the thick absorbent cotton of 0.6cm by sample Local.By burning things which may cause a fire disaster continuous action 10 seconds below sample, according to the time removed after burning things which may cause a fire disaster to sample self-gravitation, by test result It is divided into tri-fire-retardant ranks of FV-0, FV-1, FV-2.FV-0: burning time is less than 10 seconds, and do not ignite absorbent cotton；FV-1, burning Time is less than 30 seconds, and do not ignite absorbent cotton；FV-2, is less than 30 seconds burning time, and ignite absorbent cotton.
3. tensile property test
Carry out tension test according to GB/T 1040-2006, measure hot strength, unit MP.
4. impact property test
The impact strength of sample, unit kJ/m is measured according to GB/T 1834-20082。
Test result is shown in Table 4.
Table 4
Limited oxygen index % Vertical combustion grade Hot strength MP Impact strength kJ/m2
Example 1 23.2 FV-1 23.8 5.5
Example 2 24.6 FV-1 25.7 6.3
Example 3 27.4 FV-1 26.6 6.9
Example 4 30.8 FV-0 27.2 7.8
Example 5 31 FV-0 30.5 8.2
Example 6 31.1 FV-0 30.3 8.5
Example 7 31 FV-0 30.1 8.8
Example 8 31.1 FV-0 30.2 9
Example 9 31.2 FV-0 30.1 9.1
To 1 23.5 FV-2 18.9 6.5
To 2 24.2 FV-2 19.3 6.8
To 3 19.5 FV-2 17.8 6.1
To 4 18.5 FV-2 16.1 5.6
To 5 19.2 FV-2 17.4 6.2
To 6 18.1 FV-2 15.8 5.3
As can be seen from Table 4, the high intensity PP-RCT anti-flaming tubular product fire retardant addition that the present invention provides is few, fire-retardant effect The best, and there is outstanding mechanical property.The above, the only present invention preferably specific embodiment, but the protection of the present invention Scope is not limited thereto, and any those familiar with the art is in the range of the invention discloses, according to the present invention Technical scheme and inventive concept equivalent or change in addition, broadly fall into protection scope of the present invention.

Claims (10)

1. a high intensity PP-RCT anti-flaming tubular product, it is characterised in that including at least three layers, the most respectively internal layer, in Layer and outer layer, described internal layer contains antibacterial and composite flame-retardant agent, and glass fibre and composite flame-retardant agent are contained in described middle level, described Outer layer contains composite flame-retardant agent, and described composite flame-retardant agent contains morpholinyl thiourea, organic silicon compound containing phosphorus.
2. high intensity PP-RCT anti-flaming tubular product as claimed in claim 1, it is characterised in that described morpholinyl thiourea and phosphorous have The weight ratio of organic silicon compound is (1-2): 5.
3. high intensity PP-RCT anti-flaming tubular product as claimed in claim 1, it is characterised in that described morpholinyl thiourea is selected from 1- [3-(4-morpholinyl) propyl group] thiourea, 1-[2-(4-morpholinyl) ethyl] thiourea, 1-cyclohexyl-3-(2-morpholinyl ethyl) sulfur In urea, 1-(2-morpholinyl ethyl)-3-phenylthiourea, 1-[3-ethyoxyl-2-(4-morpholinyl) propyl group]-3-ethyl thiourea one Kind.
4. high intensity PP-RCT anti-flaming tubular product as claimed in claim 1, it is characterised in that described organic silicon compound containing phosphorus by The raw material comprising phosphinylidyne dichloro compound and amido organosilicon compound prepares.
5. high intensity PP-RCT anti-flaming tubular product as claimed in claim 4, it is characterised in that described phosphinylidyne dichloro compound contains Aromatic rings.
6. high intensity PP-RCT anti-flaming tubular product as claimed in claim 4, it is characterised in that described phosphinylidyne dichloro compound is selected from In 2-phthalimide-based ethyl either dichlorophosphate, phenoxy group phosphinylidyne dichloro, 3,5-3,5-dimethylphenyl phosphinylidyne dichloro one Kind.
7. high intensity PP-RCT anti-flaming tubular product as claimed in claim 4, it is characterised in that described amido organosilicon compound contains There are at least one primary amino radical and at least one secondary amino group.
8. high intensity PP-RCT anti-flaming tubular product as claimed in claim 4, it is characterised in that described amido organosilicon compound selects From N-(6-Aminohexyl) amino methyl triethoxysilane, (((2-amino-ethyl) amino) methyl) triethoxysilane, (ammonia Base ethylaminomethyl) phenethyl trimethoxy silane, N-(2-amino-ethyl)-N'-(3-(dimethoxymethylsilane base) third Base) one in-1,2-ethylenediamine.
9. high intensity PP-RCT anti-flaming tubular product as claimed in claim 1, it is characterised in that described high intensity PP-RCT Frpipe Possibly together with auxiliary agent, described auxiliary agent is selected from antioxidant, antistatic additive, plasticizer, ultraviolet absorber, heat stabilizer, antifungus agent, prevents in vain At least one in ant agent, Ratproof agent, antifoggant.
10. the high intensity PP-RCT anti-flaming tubular product as described in claim any one of claim 1-9 is at central air-conditioning pipe Application in system, fire-fighting and fire-fighting spraying pipeline system.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107189197A (en) * 2017-05-24 2017-09-22 上海中塑管业有限公司 The fire-retardant comprehensive colliery carries tubing of pipeline gallery of high-strength insulating
CN109291525A (en) * 2018-09-25 2019-02-01 上海伟星新型建材有限公司 The polypropylene random copolymer composite tube and preparation method of fiber reinforcement beta crystal
CN110435071A (en) * 2019-08-05 2019-11-12 周红艳 A kind of making material and production method of environmental protection penholder
CN110938258A (en) * 2019-11-28 2020-03-31 爱康企业集团(上海)有限公司 Flame-retardant antibacterial fresh air pipe and preparation method thereof
CN111730941A (en) * 2020-06-08 2020-10-02 安徽兴中新材料股份有限公司 Flame-retardant PE film and preparation method thereof

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CN102286171A (en) * 2011-06-21 2011-12-21 公安部四川消防研究所 Blow molding type halogen-free flame-retardant polypropylene material
CN105605339A (en) * 2016-03-16 2016-05-25 刘志光 High-strength antibacterial oxygen-resistant PP-RCT composite pipe

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Publication number Priority date Publication date Assignee Title
CN102286171A (en) * 2011-06-21 2011-12-21 公安部四川消防研究所 Blow molding type halogen-free flame-retardant polypropylene material
CN105605339A (en) * 2016-03-16 2016-05-25 刘志光 High-strength antibacterial oxygen-resistant PP-RCT composite pipe

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107189197A (en) * 2017-05-24 2017-09-22 上海中塑管业有限公司 The fire-retardant comprehensive colliery carries tubing of pipeline gallery of high-strength insulating
CN109291525A (en) * 2018-09-25 2019-02-01 上海伟星新型建材有限公司 The polypropylene random copolymer composite tube and preparation method of fiber reinforcement beta crystal
CN110435071A (en) * 2019-08-05 2019-11-12 周红艳 A kind of making material and production method of environmental protection penholder
CN110938258A (en) * 2019-11-28 2020-03-31 爱康企业集团(上海)有限公司 Flame-retardant antibacterial fresh air pipe and preparation method thereof
CN111730941A (en) * 2020-06-08 2020-10-02 安徽兴中新材料股份有限公司 Flame-retardant PE film and preparation method thereof

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