CN106220994B

CN106220994B - A kind of high intensity PP-RCT anti-flaming tubular products and preparation method

Info

Publication number: CN106220994B
Application number: CN201610590127.2A
Authority: CN
Inventors: 刘志光
Original assignee: 刘志光
Current assignee: Shanghai Zhongsu Pipe Industry Co., Ltd.
Priority date: 2016-07-25
Filing date: 2016-07-25
Publication date: 2018-06-01
Anticipated expiration: 2036-07-25
Also published as: CN106220994A

Abstract

High intensity PP RCT anti-flaming tubular products, including at least three layers, it is respectively internal layer, middle level and outer layer from inside to outside, the internal layer contains antiseptic and composite flame-retardant agent, contain glass fibre and composite flame-retardant agent in the middle level, the outer layer contains composite flame-retardant agent, and the composite flame-retardant agent contains morpholinyl thiocarbamide, organic silicon compound containing phosphorus.

Description

A kind of high intensity PP-RCT anti-flaming tubular products and preparation method

Technical field

The present invention relates to PP composite materials, more particularly to a kind of high intensity PP-RCT anti-flaming tubular products.

Background technology

Polypropylene (PP) is a kind of thermoplastic as one of general-purpose plastics.Its raw material sources enriches, is cheap, And possess preferable comprehensive performance, such as excellent mechanicalness, preferable heat resistance, good electrical insulating property, flexural fatigue resistance, Chemical resistance and light weight, the features such as density is small, thus it is widely used in the industries such as household electrical appliances, automobile, building, weaving.But It is that polyacrylic limit oxygen index only has 17.4-18.5, poor flame retardant properties, caloric value is big when meeting fire burning, and burning velocity is fast, production Raw a large amount of molten drops, and with smoke phenomenon, easily propagating flame, fire easily occurs, brings the wound of life and property Damage, therefore its application field is just very restricted.

Polypropylene pipe has the characteristics of light-weight, service life is long, easily shifts and installs, as fire-fighting spraying tubing Existing application, Chinese patent CN202769084U disclose a kind of polypropylene fire-fighting spray line.The fire retardant species used at present Various, the realization of fire retardation can generally pass through following two approach：First, selection with high heat capacity, high-termal conductivity and Compound with higher gasification latent heat is as fire retardant.Its fire retardant mechanism is to reduce height by the heat absorption of fire retardant, heat conduction Molecular material from the rate of external world's heat absorption or by the gasification of substance take away partial heat so as to play cooling effect or The rate of heat transfer is reduced by forming layer of charcoal in polymer surface.In short, their fire retardation is to pass through resistance It is stagnant and delay the high temperature thermal decomposition of polymer and be achieved.Second is set about in terms of burning is inhibited, by adding in fire retardant Change the decomposition mechanism of polymer, reduce the generation of volatile hydrocarbon, and try to increase the growing amount of carbon residue；Or change Become gas-phase combustion mechanism, by the effect of additive, reduce the concentration of high-energy hydrogen-based free radical in flame, be changed into it low The free radical of energy, so as to block the cycling of combustion reaction.When fire retardant additive amount in polypropylene pipe is less, flame retardant effect It does not reach requirement, when fire retardant additive amount is more, and its mechanical property and processing performance can be reduced.

The content of the invention

In order to solve prior art problem, the present invention provides a kind of high intensity PP-RCT anti-flaming tubular products, including at least three layers, It is respectively internal layer, middle level and outer layer from inside to outside, the internal layer contains antiseptic and composite flame-retardant agent, and glass is contained in the middle level Fiber and composite flame-retardant agent, the outer layer contain composite flame-retardant agent, and the composite flame-retardant agent contains morpholinyl thiocarbamide, phosphorous organic Silicon compound.

In some embodiments, the weight ratio of the morpholinyl thiocarbamide and organic silicon compound containing phosphorus is (1-2)：5.

In some embodiments, the morpholinyl thiocarbamide is selected from 1- [3- (4- morpholinyls) propyl] thiocarbamide, 1- [2- (4- Morpholinyl) ethyl] thiocarbamide, 1- cyclohexyl -3- (2- morpholinyl ethyls) thiocarbamide, 1- (2- morpholinyl ethyls) -3- phenylthioureas, 1- One kind in [3- ethyoxyls -2- (4- morpholinyls) propyl] -3- ethyl thioureas.

In some embodiments, the organic silicon compound containing phosphorus is by including phosphinylidyne dichloro compound and amido organosilicon The raw material of compound is prepared.

In some embodiments, the phosphinylidyne dichloro compound contains aromatic rings.

In some embodiments, the phosphinylidyne dichloro compound is selected from 2- phthalimide-based ethyl dichloro phosphoric acid One kind in ester, phenoxy group phosphinylidyne dichloro, 3,5- 3,5-dimethylphenyl phosphinylidyne dichloros.

In some embodiments, the amido organosilicon compound contains at least one primary amino radical and at least one parahelium Base.

In some embodiments, the amido organosilicon compound is selected from three ethoxy of N- (6- Aminohexyls) amino methyl Base silane, (((2- amino-ethyls) amino) methyl) triethoxysilane, (aminoethylaminomethyl) phenethyl trimethoxy One kind in silane, N- (2- amino-ethyls)-N'- (3- (dimethoxymethylsilane base) propyl) -1,2- ethylenediamines.

In some embodiments, the high intensity PP-RCT Frpipes also contain auxiliary agent, the auxiliary agent be selected from antioxidant, At least one in antistatic agent, plasticizer, ultraviolet absorber, heat stabilizer, mould inhibitor, anti-termite agent, Ratproof agent, antifoggant Kind.

The present invention also provides a kind of high intensity PP-RCT anti-flaming tubular products as described above in air-conditioning duct system, fire-fighting spraying Application in system.

High intensity PP-RCT anti-flaming tubular products fire retardant additive amount provided by the invention is few, good flame retardation effect, and with outstanding Mechanical property.

Specific embodiment

Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of fields of the present invention The normally understood identical meaning of art personnel.When there is a conflict, the definition in this specification shall prevail.

Quality, concentration, temperature, time or other values or parameter are preferred with scope, preferred scope or a series of upper limits During the Range Representation that value and lower preferable values limit, this, which is appreciated that, specifically discloses by any range limit or preferred value All scopes that any pairing with any range lower limit or preferred value is formed, regardless of whether the scope separately discloses. For example, the scope of 1-50 is 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、 44th, 45,46,47,48,49 or 50 any number, number combinatorics on words or subrange and all between above-mentioned integer Fractional value, for example, 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8 and 1.9.It is specific to consider from scope on subrange Interior arbitrary endpoint starts " the nested subrange " of extension.For example, 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 50-10 on other direction.

The present invention provides a kind of high intensity PP-RCT anti-flaming tubular products, including at least three layers, from inside to outside respectively internal layer, in Layer and outer layer, the internal layer contain antiseptic and composite flame-retardant agent, and glass fibre and composite flame-retardant agent are contained in the middle level, described Outer layer contains composite flame-retardant agent, and the composite flame-retardant agent contains morpholinyl thiocarbamide, organic silicon compound containing phosphorus.

PP-RCT

Polypropylene (PP) can be classified as homopolypropylene (PP-H) according to different polymerization process conditions, block copolymerization gathers Propylene (PP-B) and atactic copolymerized polypropene (PP-R), the polypropylene of tubing grade can be used to process tubing.PP-H has excellent Good rigid, but its low temperature impact properties is poor, it is brittle, it is mainly used in discharge of industrial wastes；PP-B has preferable soft Toughness, especially shock resistance is excellent at low temperature, is mainly used for drainage pipeline and discharge of industrial wastes pipeline, while is also used for low Pressure, the conveying of low temperature (less than 60 DEG C) hot and cold water, such as ground heating system.Gather compared with homopolypropylene (PP-H), block copolymerization For propylene (PP-B), PP-R has high intensity and toughness, and improves PP-H " low temperature cold brittleness ", and has at relatively high temperatures Good creep-resistant property, PP-RCT are beta crystal atactic copolymerized polypropenes, and heat resisting temperature and pressure-resistant is improved 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 gathers for type III Propylene, PP-RCT are IV type polypropylene.

High intensity PP-RCT anti-flaming tubular products of the present invention can also use PP-H, PP-B or PP-R.

High intensity PP-RCT anti-flaming tubular products of the present invention can also be the blend using PP-RCT and polyolefin.Institute The example for stating polyolefin includes but not limited to, the random copolymer of ethylene and propylene；The random copolymer of ethylene and butylene；Ethylene With the random copolymer of hexene；The random copolymer of ethylene and octene；The random copolymer of propylene and butylene；Propylene and hexene Random copolymer；The random copolymer of propylene and octene；The random copolymer of butylene and hexene；The random copolymerization of butylene and octene Object；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 With the random copolymer of 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 products are using the blend of PP-RCT and polyolefin, the weight of the polyolefin contains Amount accounts for less than the 20% of blend total weight.

High intensity PP-RCT anti-flaming tubular products of the present invention can also use other polyolefine materials or olefin copolymer Material, specific example include but not limited to：Polyethylene, polybutene, polypenthylene, polyhexene, polyoctenamer, poly- 4- methyl-1-pentenes 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, magnalium flame retardant, Sb system fire retardant, molybdenum system fire retardant.

Halogenated flame retardant is one of fire retardant of yield maximum on our times, and is wherein applied most with smelling flame retardant To be extensive.Organic halogenated flame retardant has the advantages that flame retarding efficiency is high, dosage is few, it is small, moderate that material property is influenced, Thus it is widely used in the flame-retardant system of polymer.Industrial bromide fire retardant mainly has following three classes：Additive flame Agent is fired, including deca-BDE, double (2,3- dioxane propyl) ether, the octabromodiphenyl ethers of tetrabromobisphenol A etc.；Reactive flame retardant, bag Include tetrabromobisphenol A, 2,4,6- tribromphenols etc.；Polymer electrolyte fire retardant, it is double including brominated Polystyrene, brominated epoxy, tetrabromo Phenol A carbonic acid ester oligomers etc..But halogenated flame retardant can generate substantial amounts of flue dust and corrosive gas in hot tearing and burning, no Only corrode equipment together, can also be detrimental to health and ecological environment.In addition, it can be produced in halogen flame retardant product recycling combustion process Raw a large amount of toxic gases, secondary pollution is caused to environment.As various countries limit the use of halogenated flame retardant, halogen system is fire-retardant The use scope of agent is less and less.

Phosphorus flame retardant mainly includes red phosphorus and microencapsulated powder oil halogenated phosphate, non-halogenated phosphate, ammonium phosphate, poly- Ammonium phosphate, microcosmic salt etc..Current phosphorus flame retardant significant portion is all to play flame retardant effect in solid phase, burn including inhibition, Acid-catalyzed dehydration completely cuts off air etc. into charcoal, formation surface barrier carbon membrane.Phosphorus flame retardant can improve the charring rate of material, especially right Those oxygen containing high molecular materials are very effective.But phosphorus flame retardant effect in oxygen-containing and nitrogenous polymer is especially bright It is aobvious, and lack the polymer of these elements, such as the flame retarding efficiency of phosphorus flame retardant can substantially reduce in polyolefins.In order to reach To suitable flame retarding efficiency, additive amount is greatly increased, influences whether other performance instead, such as processing performance and mechanical property.

Nitrogenated flame retardant is actually a kind of compound in triazine class, it includes melamine (MA) and its esters, such as uric acid Salt, phosphate, guanidine salt and dicyandiamide salt etc., they can be used alone, and can also be used as the component of mixed expanded type fire retardant. Triazine based flame retardant mainly by decomposition absorbs heat and generates non-flammable gases to dilute combustible or be covered in high polymer composite wood The surface of material and play fire retardation.Major advantage is colourless, Halogen, low toxicity, low cigarette, does not generate corrosive gas, is inexpensive, is anti- Ultraviolet light irradiation etc.；The drawback is that flame retarding efficiency is not good enough, 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 both at home and abroad is main at present There are GE companies of U.S. SFR-100 resins and the D.C.R.M series silicones powder modifiers of DOWCorning companies of the U.S..It is inorganic Present most study is montmorillonite in silicon-series five-retardant.In order to which montmorillonite is used to prepare flame-retardant polymer/inorganic matter nanometer Composite material, it is necessary to natural montmorillonite intercalator or modifying agent (being mostly quaternary ammonium salt) is modified, i.e., with the sun of organic quaternary ammonium salt With the exchangeable cations (mainly sodium ion) in cheating engaging layer ion-exchange reactions occurs for ion, is covered in organic group The surface of montmorillonite makes its surface property change, and is changed into lipophile by original hydrophily, while increases between interlayer Away from being conducive to monomer or polymer and enter.But silicon-series five-retardant additive amount is higher, applies and is influenced whether in polypropylene pipe Sweat soldering between tubing can cause the pressure-resistant hydraulic performance decline of seam crossing.

Using phosphorus, nitrogen as the fire retardant of ignition-proof element, it is generally halogen-free, thus is also not required to use for expansion type flame retardant system Antimony oxide makees fire retarding synergist.Expansion type flame retardant have it is good fire-retardant and suppression hood, when high polymer by heat-flash Or during burning, surface can generate one layer of uniform porous carbonaceous froth bed, the froth bed is heat-insulated, oxygen barrier, suppression cigarette can simultaneously prevent from producing Raw molten drop.Expansion type flame retardant will reach good flame retardant effect, and additive amount will reach 25%-30%, influence whether tubing Other performance.

In boron flame retardant, it is most important that zinc borate.It is a kind of nontoxic, tasteless, odorless white powder, it has There is fire-retardant, suppression cigarette, into the multiple functions such as charcoal and anti-molten drop.Its fire retardant mechanism is by being covered in material surface after melting, rising To blocking oxygen and the shield effectiveness of volatile combustible gases, further aoxidizing and promoting into charcoal for layer of charcoal is prevented.As fire-retardant Synergist, the drawback is that lower than antimony oxide efficiency, but advantage is usual raw smoke and cost ratio antimony oxide is much lower is commonly used for pressing down Fumicants also can partly replace fire retarding synergist of the antimony oxide as halogenated flame retardant.In the presence of bromine class compound, generation Halogenation boron, zinc halide etc. can be very good to inhibit and capture free hydroxyl group, form condensed phase coating, prevent combustion reaction chain Occur, completely cut off polymer surface air, flame is prevented to burn away and suppression cigarette effect can be played.

Magnalium fire retardant is the Representative Cultivars of inorganic combustion inhibitor, generally is white, nontoxic powder.Magnalium fire retardant passes through Water is sloughed after heating so as to play fire retardation, it not only can be fire-retardant, but also can drop low-smoke, cheap, raw material It is easy to get, is subject to countries in the world most attention.The consumption figure of the annual magnalium flame retardant in the U.S. and Japan accounts for inorganic combustion inhibitor 80%, be mainly used for epoxy resin, unsaturated polyester resin, polyvinyl chloride, polyethylene, polypropylene, PBT and polystyrene and ABS resin, nylon etc. it is fire-retardant.Its anti-flammability is typically implemented in be used cooperatively with fire retardants such as halogen systems, plays synergist and suppression The effect of fumicants often can largely improve the flame retarding efficiency of other fire retardants and drop low-smoke.But magnalium is fire-retardant Main problem is that additive amount is big, it is necessary to be used cooperatively with halogenated flame retardant.

Sb system fire retardant is one of important inorganic combustion inhibitor, exclusive use cannot play very big fire retardation, when it and Halogen containing flame-retardant and used time, you can very big flame retardant synergism is generated, so as to greatly reduce halogen containing flame-retardant dosage, because This it be a kind of effective auxiliary flame retardant, its principal item is antimony oxide.Antimony oxide burning is to generate largely Black smoke, in order to improve the transparency, develop antimony organic, antimony pentoxide and antimony oxide and fluoboric acid in succession both at home and abroad at present The mixture of salt.

On molybdenum system fire retardant, the efficient molybdenum compound of external shiploads of merchandise is molybdenum trioxide and ammonium octamolybdate (AOM), next has calcium molybdate and zinc molybdate.In addition, the compound of molybdenum, lead, zinc compound also has application, this based flame retardant can use In hard polyvinyl chloride, semirigid PVC wire-insulating material and flexible PVC and ABS resin.

Composite flame-retardant agent of the present invention contains morpholinyl thiocarbamide, organic silicon compound containing phosphorus.

As the preparation method of organic silicon compound containing phosphorus of the present invention, step is：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, lasting stirring for 24 hours, then adds in water and hexamethyldisiloxane, reaction temperature is down to 70 DEG C, continues stirring for 24 hours, stops After reaction, vacuum distillation pumps solvent, then is washed with water and ether, after vacuum drying to get.

Inventor has found that composite flame-retardant agent provided by the invention is less in additive amount in the research process for completing the present invention When just with outstanding flame retardant effect, also can simultaneously improve the mechanical strength and processing performance of tubing.It is it has been recognised by the inventors that described Aromatic rings in organic silicon compound containing phosphorus can improve the flame retardant effect of system, after introducing rigid structure, the plane of formation Structure is easy to tightly packed, and molecule rotary motion is restricted, so as to improve the heat resistance of polymer and anti-flammability.It is phosphorous to have Phosphorus in organic silicon compound has dehydration at high temperature, and molecular dehydration is made to carbonize to form layer of charcoal.And organo-silicon compound increase The content of element silicon in layer of charcoal is added, has formed the silicon protective layer of charcoal, thermal stability is provided for the layer of charcoal of formation.Introduce phenyl ring The ability that organic silicon compound containing phosphorus forms layer of charcoal is improved, improves flame retardant effect.But phenyl ring can increase steric hindrance, Its processing performance is influenced whether in PP-RCT tubing, in addition, fire-retardant in the oxygen-containing or nitrogenous polymer of organic silicon compound containing phosphorus Effect is particularly evident, and flame retarding efficiency is without so high in the PP-RCT for lacking these elements.Inventor has found, adds in specific The morpholinyl thiocarbamide of content can not only improve flame retarding efficiency of the organic silicon compound containing phosphorus in PP-RCT tubing, also can The technology resistance of processing performance can be reduced after introducing phenyl ring by overcoming.Beta crystal belongs to hexagonal crystal system, be a kind of thermodynamic instability and The metastable crystal form of dynamics, PP-RCT are being heated and can changed into alpha-crystal form in deformation process, and the introducing of morpholinyl thiocarbamide can The beta crystal of PP-RCT is kept, the transformation of crystal form will not be generated and influence other performance.Inventor speculate itself the possible reason is Quinoline base thiocarbamide can improve compatibility, and catalysis carbon-forming fire retardation at high temperature to a certain degree, inhibit the oxidation of condensed phase Reaction.

In some embodiments, counted by 100 parts by weight of PP-RCT resins, the content of the composite flame-retardant agent is 0.1- 35 parts.

Auxiliary agent

PP-RCT tubing has oxidative degradation certain sensibility, and a small amount of oxygen is with regard to that can make the performances such as its intensity, appearance It changes.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- cumenes, bis- tertiary fourths of 2,6- Base phenol, 2,6- di-t-butyl -4- ethyl -phenols, 2,6 di tert butyl 4 methyl phenol, 2,6- di-t-butyl -4- normal-butyls Phenol, 4 hydroxymethyl 2,6 di t butyl phenol, butylhydroxy anisole, 2- (1- methylcyclohexyls) -4,6- dimethyl benzenes Phenol, 2,4 dimethyl 6 tert butyl phenol, 2 methyl 4,6 dinonyl phenol, 2,6- di-t-butyls-alpha, alpha-dimethyl amino-to first Double (the octylsulfo) -1,3,5- three of phenol, 2,4,6- tri-butyl-phenols, 6- (4- hydroxyl -3,5- di-tert-butyls amido) -2,4- Double (4- hydroxyl -3,5- di-t-butyls the phenoxy group) -2- n-octylthio -1,3,5- triazines of piperazine, 4,6-, β-(3,5- di-t-butyls - 4- hydroxy phenyls) methyl propionate, the β-positive octadecanol ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, styrol benzene Phenol, 4,4 '-dihydroxybiphenyl, butylated octylated phenol, butylated stytrene cresols, 2,2 '-methylene bis (4- methyl -6- Tert-butyl phenol), 2,2 '-methylene bis (4- ethyl -6- tert-butyl phenols), 2,2 '-methylene bis (4- methyl -6- cyclohexyl benzenes Phenol), 4,4 '-methylene bis(2,6-di-butyl phenol), 2,2 '-methylene bis (6- α-methylbenzyls paracresol), 4,4 '-isopropylidene Bis-phenol, 4,4 '-fourth fork double (3 methy 6 tert butyl phenols), 1,1- double (4- hydroxy benzenes) hexamethylene, 2,2 '-methylene bis (4- first Base -6- (Alpha-Methyl cyclohexyl) phenol), 1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, 1, 1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane, four (3- (3 ' 5 '-di-t-butyl -4 '-hydroxy phenyl) propionic acid) Pentaerythritol ester, 4,4 '-thiobis (6- tertiary butyl -3- methylphenols), 4,4 '-thiobis (2- methyl-6-tert-butylphenols), 2,2 '-thiobis (4- methyl-6-tert-butylphenols), hexylene glycol double (β-(3,5- di-tert-butyl-hydroxy phenyls) propionic ester), 2,2 '-thiobis (3 ,-(3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate), N, N '-hexamethylene it is double (3,5- di-t-butyls- 4- hydroxyls hydrocinnamamide), 1,3,5- tri- (4- tertiary butyl-3- hydroxyl-2,6- dimethyl benzyls) 1,3,5-triazine-2,4,6- (1H, 3H, 5H)-triketone, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) guanamine, 4,6- (1H, 3H, 5H) triketone, Isocyanuric acid three [β-(3,5- di-tert-butyl-hydroxy phenyls) propionyloxy ethyl ester], double [double (3 '-tertiary butyls -4 '-hydroxyl of 3,3- Base phenyl) butyric acid] glycol ester, 1,1 '-thiobis (beta naphthal), double (3,5- di-tert-butyl-4-hydroxyl benzyls) thioethers, 2,5- Di-tert-butyl hydroquinone, 2,5 di tert amyl hydroquinone, 3,5- di-tert-butyl-4-hydroxyl benzyls di(2-ethylhexyl)phosphate (18) ester, Double -3- (3- tertiary butyl-4-hydroxy -5- the first of 3,5- di-tert-butyl-4-hydroxyl benzyls diethyl phosphate, octylatcd phenol, triethylene glycol 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-α-naphthylamines, N- phenyl-β-naphthylamines, fourth Aldehyde-alpha-naphthylamine, DPPD N,N' diphenyl p phenylene diamine, N- isopropyls-N '-diphenyl-para-phenylene diamine, N, N '-two-betanaphthyl are to benzene two Amine, N, N '-bis- (1,4- dimethyl amyl groups) p-phenylenediamine, N, N '-bis- (1- ethyl -3- methyl amyls) p-phenylenediamine, N- hexamethylenes Base-N '-diphenyl-para-phenylene diamine, N, N '-bis- (1- methylheptyls) p-phenylenediamine, N- (1,3- dimethylbutyls)-N '-phenyl are to benzene Diamines, N- phenyl-N '-octyl group p-phenylenediamine, 6- ethyoxyl -2,2,4- trimethyl -1,2- dihyaroquinolines, 2,2,4- front threes Base -1,2- dihyaroquinolines condensate, 6- dodecyl -2,2,4- trimethyl -1,2- dihyaroquinolines, N- (methacryls Base oxo -2- hydroxypropyls)-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 It is phenylenediamine, N, N '-dimethyl-N, N '-two (1- methyl-propyls) p-phenylenediamine, right, right '-dioctyl diphenylamine, 4,4 '-bis- (α- Methylbenzyl)-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, three (nonyl benzene of phosphorous acid Ester), three different monooctyl ester of phosphorous acid, triisodecyl phosphite ester, phosphorous acid benzene diisodecyl ester, trilauryl trithiophosphite, phosphorous Sour three lauryls, phosphorous acid three (octadecyl ester), diphosphorous acid pentaerythrite diisodecyl ester, diphosphorous acid pentaerythrite distearyl alcohol Ester, 4,4 '-fourth fork double (phosphorous acid (3- methyl-6-tert butyl phenyl) two (tridecyl) esters), isooctyl diphenyl phosphite, Asias Phosphoric acid benzene di-isooctyl, octyl diphenyl phosphite, diphenyl isophthalate, 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 nonyls of four esters, triethyl phosphite, tributyl phosphite, triisopropyl phosphite, three monooctyl ester of phosphorous acid, phosphorous acid-benzene Benzene) ester, phosphorous acid hexichol nonyl phenyl ester, phosphorous acid three (2- chloroethenes) ester, phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, phosphorous Sour bisphenol-A ester, phosphorous acid three (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 '-thio two butyric acid two (18) ester, thio-2 acid bay octadecyl ester, thio-2 acid two (13) ester, Thio-2 acid two (14) ester.

Antioxidant can also be other type antioxidants, and specific example includes but not limited to：2-mercaptobenzimidazole, 2- Mercapto methyl benzimidazole, zinc salt of 2 mercaptobenzimidazole, N- salicylidenes-N '-salicylyl hydrazine, 1,2- are double (2- (2-hydroxybenzoyl)s) Hydrazine, N, N '-two hydrazides of diacetyl adipyl base, 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, thioacetic acid pentyl ester.

As the example of antistatic agent, include but not limited to：Stearamidopropyl dimethyl-beta-hydroxyethyl ammonium nitrate, (3- dodecanamide propyls) trimethyl ammonium Methylsulfate salt, double (the 2- hydroxyethyls)-N- (3 '-dodecyloxies -2 '-hydroxyl of N, N- Base propyl) first ammonium Methylsulfate salt, N- (3- dodecyloxy -2- hydroxypropyls) ethanolamine, trihydroxyethyl methyl ammonium sulfuric acid first Ester salt, stearamidopropyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate, alkyl phosphate diethanolamine salt, double (the 2- hydroxyls of N, N- Base ethyl) alkylamine, N, N- cetyl ethyl morpholine ethyl-sulfates salt, octadecyldimethyl ethoxy quaternary ammonium nitrate, HZ-1 antistatic agents, HKD-300, HKD-311, HBT-5 type antistatic agent, ECH types antistatic agent, 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, glutaric 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, epoxy analog derivative, 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：Repefral, O-phthalic Diethyl phthalate, dipropyl phthalate, n-butyl phthalate, diisobutyl phthalate, phthalic acid fourth The just own ester of monooctyl ester, diamyl phthalate, phthalic acid two, phthalic acid two (2- ethyls fourth) ester, phthalic acid Dicyclohexyl maleate, phthalic acid two (methyl cyclohexane) ester, the positive fourth cyclohexyl of phthalic acid, dibutyl phthalate (DHP), adjacent benzene Dioctyl phthalate two (2- ethyl hexyls) ester, di-n-octyl phthalate, diisooctyl phthalate, phthalic acid di-secondary are pungent Ester, dinonyl phthalate, diisononyl phthalate, diisooctyl phthalate, didecyl phthalate, neighbour Phthalic acid fourth last of the ten Heavenly stems ester, n-octyl-n-decyl phthalate, iso-octyl isodecyl phthalate ester, the 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 ester, 13 ester of the phthalic acid last of the ten Heavenly stems, 14 ester of phthalic acid fourth, capryl octyl phthalate, phthalic acid Diphenyl ester, dibenzyl phthalate, BBP(Butyl Benzyl Phthalate, octyl phthalate, two (methoxyl group of phthalic acid 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-alkanols mixed ester, phthalic acid C7~C9 alcohol mixed ester, phthalic acid C7~C10 alcohol mixed ester, phthalic acid C8~C10 n-alkanols 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 hexyls) ester, tetrahydrophthalic acid di-n-octyl, Tetrahydrophthalic acid diisodecyl ester, tetrahydrophthalic acid C7~C10 Arrcostabs, two (2- of hexahydro-phthalic acid Ethyl hexyl) ester, phthalic acid dibenzyl must alcohol ester, phthalic acid dihydro rosin alcohol ester, Santicizer 213,218A, 267,679,885, Loxiol W100, W101, W300S, plasticizer DGPO, plasticizer BD.

As the example of glutaric acid ester plasticizer, include but not limited to：Dioctyl Glutaricate, didecyl glutarate, penta Diacid diisodecyl ester, two fourth 2-ethoxyethyl acetate of glutaric acid, two fourth oxygen ethoxy ethyl ester of glutaric acid.

As the example of adipic acid ester plasticizer, include but not limited to：Di-n-butyl Adipate, two isobutyl of adipic acid Ester, di-n-hexyl adipate, dioctyl adipate, diisooctyl adipate, dinonyl adipate, diisononyl adipate, oneself The positive butyl benzyl of diacid diisodecyl ester, adipic acid, octyl adipate, two fourth 2-ethoxyethyl acetate of adipic acid, (the butoxy ethoxy of adipic acid two Base second) ester, adipic acid two (610 alkyl) ester, adipic acid C7~C9 linear esters, n-octyl n-decyl adipate (NODA), adipic acid be different pungent different 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 just oneself Ester, azelaic acid two (2- ethyls fourth) ester, azelaic acid two (2- ethyl hexyls) ester, diisooctyl azelate, the thio two (2- of azelaic acid of 4- Ethyl hexyl) ester, two fourth 2-ethoxyethyl acetate of azelaic acid, dibenzyl azelate, dicyclohexyl azelate.

As the example of sebacic acid ester plasticizer, include but not limited to：Dimethyl sebacate, n-butyl sebacate, Diisopropyl sebacate, dioctyl sebacate, Plexol 201, decanedioic acid di-sec-octyl, di-n-nonyl sebacate, decanedioic acid Two (butoxy second) esters, decanedioic acid two (Butoxyethoxy second) ester, dibenzyl sebacate, two C7 of decanedioic acid~C9 alcohol esters, 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 Sour dimethylbenzene diphenyl ester, isodecyl diphenyl phosphate, tricresyl phosphate (butoxy second) ester, phosphoric acid tri-isopropyl benzene ester, tricresyl phosphate (2- chlorine Second) ester, tricresyl phosphate (dichloro the third) ester, mono phosphoric acid ester neighbour 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, glycerin monostearate, Stearic acid 2- butoxyethyls, butyl acetoxystearate, monostearate 1,2- propylene glycol esters, (acetoxyl group is hard for glycerine three Resin acid) ester, distearyl acid diethylene glycol (DEG) 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- propylene glycol esters, mono laurate Glyceride, mono laurate diethylene glycol (DEG) 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, three positive fourth fat of acetyl tributyl citrate, acetyl trihexyl citrate, acetyl tributyl citrate three (2- ethyl hexyls) Ester, acetyl tributyl citrate three (the just 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 Sour tetrahydrofuran methyl esters, methoxyethyl oleate, oleic acid 2- fourths 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 hexyls) 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 just pungent positive last of the ten Heavenly stems) ester, diisooctyl manoisodecyl trimellitate, tri n hexyl trimellitate, Santicizer 79TM、TX-85。

As the example of epoxy analog derivative plasticizer, include but not limited to：Epoxidized soybean oil, epoxy Linseed oil, 4, 5- epoxies diisodecyl tetrahydrophthalate, 4,5- epoxies tetrahydrophthalic acid two (2- ethyl hexyls) ester, epoxystearic acid Butyl ester, epoxystearic acid 2- ethylhexyls, the different monooctyl ester of epoxystearic acid, epoxidized tall oil acid 2- ethylhexyls, epoxidized soybean oil Sour 2- ethylhexyls, epoxidized methyl acetorieinoleate, epoxy pupal fat acid butyl ester, epoxyfuoic-oleic, epoxidation glycerine three Acid esters, epoxy chlorinated paraffin, epoxy chloroparaffin, epoxy cotton seed oil, epoxyoleic acid last of the ten Heavenly stems ester, 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, triethylene glycol hexichol Formic acid esters, triethylene glycol two (2 Ethylbutanoic acid) ester, triethylene glycol two (2 ethyl hexanoic acid) ester, triethylene glycol dieaprylate, triethylene glycol two (C7-9 carboxylates), tetraethylene glycol two (2 ethyl hexanoic acid) ester, diethylene glycol dipelargonate, triethylene glycol dipelargonate, the triethylene glycol pungent last of the ten Heavenly stems Acid esters, triethylene glycol diheptylate, tetraethylene glycol diheptanoate, ethylene diacetate, triethylene glycol diacetate, 59 acid glycerides, C5~C9 fatty acid mixeds 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 It is formic acid glyceride, dipropylene glycol dibenzoate, propylene glycol dibenzoate, trimethylolethane trimethacrylate benzoic ether, sweet Oily monoacetate, glyceryl diacetate, triacetin, glycerin tributyrate, glycerol ether acetate, glycerin tripropionate, Pentaerythritol fatty ester, pentaerythritol tetrabenzoate, four caprylatecaprate of pentaerythrite, (C5~C9 is mixed pentaerythrite four Close aliphatic ester), bipentaerythrite support adipic acid six (C5~C9 mixed aliphatic esters).

As the example of maleic acid ester plasticizer, include but not limited to：N-butyl maleate, (the 2- second of maleic acid two Base oneself) ester, dimethyl maleate, diethyl maleate.

As the example of fumaric acid esters plasticizer, include but not limited to：Di n butyl fumarate, (the 2- second of fumaric acid two 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 hexyls) ester.

Plasticizer can also be other types of plasticizer, and specific example includes but not limited to：Acetylricinoleate alkyd first Ester, acetylricinoleate alcohol acid butyl ester, single monoricinoleate, single ricinoleic acid diethylene glycol (DEG) ester, glycerine 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, isobutyl palmitate, isopropyl myristate, n-butyl myristate, myristic acid palm Isopropyl propionate, sucrose octa-acetate, sucrose acetate isobutyrate, sucrose benzoate, tall oil acid methyl esters, tall oil acid are different pungent Ester, methyl abietate, hydrogenated methyl rosinate, hydroabietyl alcohol, poly alpha methylstyrene resin, (the 2- ethyls of pyromellitic acid four Oneself) ester, four n-octyl of pyromellitic acid, 2,2,4- trimethyl -1,3- pentanediol diisobutyrates, oleoyl nitrile, two fourth of tartaric acid Ester, 2- ketone group -1,7,7- trimethylnorcamphanes, M-phthalic acid two (2- ethylhexyls), diisooctyl isophthalate, to benzene Dioctyl phthalate two (2- ethyl hexyls) ester, A.G.S acid two (2- ethyl hexyls) ester, Monoplex S-38, S-90E, Kodaflex 135, 10 °, TS, Reomol DV35, DV49, MI, Reomol RIG, MN of Nevillac, MD, NB-10, polyadipate 1,2-PD Ester, poly- decanedioic acid -1,2- propylene glycol esters, poly adipate succinic acid ester.

Ultraviolet absorber includes salicylic acid esters, benzophenone, benzotriazole, triazines, group-substituted acrylonitrile, grass Amides, organic nickel complex class, hindered amines.

As salicylic acid esters, specific example includes but not limited to：Phenyl salicylate, p-octylphenyl salicylate, water Poplar acid is to tertiary butyl phenyl ester, double acid double phenol A ester.

As benzophenone, specific example includes but not limited to：2,4 dihydroxyl benzophenone, 2- hydroxyl -4- first Oxygroup benzophenone, 2,2 '-dihydroxy -4- methoxy benzophenones, 2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenone, Sodium salt, the 2- hydroxyl -4- methoxyl groups -2 '-carboxyl hexichol first of 2,2 '-dihydroxy -4,4 '-dimethoxy -5- diphenylsulfone ketones Ketone, 2- hydroxyl -4- methoxyl group -5- diphenylsulfone ketones trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2- hydroxyls -4- Octadecane epoxide benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2- hydroxyl -4- dodecyloxy benzophenones, 2,2 ' - Dihydroxy -4- oxy-octyl benzophenones, 2- hydroxyl -5- chlorobenzophenones, 2- hydroxyl -4- methoxyl groups -4 '-chloro hexichol first Ketone, 2- hydroxyl -4- methoxyl groups -2 ', 4 '-dichloro benzophenone, 2- hydroxyl -4- behzyloxybenzophenones, 2- hydroxyl -4- [2 '-hydroxyls Base -3 '-(methacryloxypropoxy)] benzophenone, 2- hydroxyls -4- (2 '-hydroxyl -3 '-acryloxy propoxyl group) Benzophenone, 1,3- double (3 '-hydroxyl -4 '-benzoyl phenoxy group) propyl alcohol -2,2- hydroxyl -4- ethoxyl phenenyls 17 (alkane) Ketone, Uvinul 490, Permyl B-100, Mark 1535, Mark LA-51.

As benzotriazole, specific example 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 '-hydroxyls -3 '-tertiary butyl -5 '-methylbenzene Base) -5- chlorinated benzotriazoles, 2- (2 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) -5 chlorinated benzotriazoles, 2- (2 '-hydroxyl - 4 '-n-octyl phenyl) benzotriazole, 2- (2 '-hydroxyl -3 ', 5 '-diamyl phenyl) benzotriazole, 2- (2 '-hydroxyl -5 ' - T-octyl phenyl) benzotriazole, Tinuvin PS, Mark 446.

As benzoates, specific example includes but not limited to：Resorcinol monobenzoate, bis- tertiary fourths of 3,5- Base -4-HBA 2,4- 6- di-tert-butyl phenyl esters, the positive hexadecyl ester of 3,5- di-tert-butyl-4-hydroxybenzoic acids.

As organic nickel complex class, specific example 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 oxygroup) nickel-n-butylamine complex compound, 2,2- thiobis (4- t-octyls Phenol oxygroup) nickel -2 ethyl hexylamine complex compound, 2,2 '-thiobis (4- t-octyl phenol oxygroup) nickel, N, two thio ammonia of N- di-n-butyls 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, specific example includes but not limited to：Double (2,2,6,6- tetramethyl -4- the piperidines of decanedioic acid Ester), three (1,2,2,6,6- pentamethvls base) phosphite esters, 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 be other types, include but not limited to：2-cyano -3,3-diphenyl ethyl acrylate, 2- cyano -3,3- diphenylacrylate 2- ethylhexyls, 2,4,6- tri- (2 '-hydroxyl -4 '-n-butoxyphenyl) -1,3,5- three Piperazine, hexamethylphosphoramide, 2,4- dibenzoyl resorcinols, N- (2- ethylphenyls)-N '-(2- ethyoxyl -5- tertiary butyls Phenyl) oxamide, 2- ethyls -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, compound Stabilizer.

As the example of basic lead salt heat stabilizer, include but not limited to：Dibasic lead stearate, tribasic sulfuric acid Lead, Dythal, dibasic lead phosphite, tribasic Malaysia lead plumbate, basic lead carbonate, 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 compound, Chloro phthalein lead silicate, alkali formula sulfo group lead phosphite compound, alkali formula chlorine lead silicate-lead sulfate compound, 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 Sour magnesium, lithium stearate, zinc stearate, aluminum stearate, double stearic acid aluminium, lead stearate, strontium stearate, cobaltous octadecanate, stearic acid Stannous, odium stearate, barium laurate, calcium laurate, zinc laurate, cadmium laurate, barium ricinoleate, ricinoleic acid calcium, castor-oil plant 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 Tin, lauric acid dibutyitin maleate, maleic acid dioctyltin, Bis(lauroyloxy)dioctyltin, double (thio Glycolic acid is different pungent Ester) dioctyltin, lauryl mercaptan dibutyl tin, double (the thio different monooctyl ester of Glycolic acid) dibutyl tin β-mercaptopropionic acid dibutyl Tin, double (single-ethylhexyl maleate) di-n-butyl tins, double (butyl maleate) dibutyl tins, double (pungent fat of maleic acid list) two are just pungent It is Ji Xi, double (butyl maleate) dioctyltins, poly- tin glycol dilaurate, poly- tin glycol lauric acid-maleate, poly- Tin 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 sulphur Double (beta-amino butenoic acid) esters of urea, 1,4- butanediols, thio-diethylene glycol double (beta-amino butenoic acid) ester, pentaerythrite, sorbs Sugar alcohol, Synpron 1034, Synpron 1027.

As the example of compound stabilizer, include but not limited to：Liquid organic calcium zinc complexes, the organic barium zinc of liquid are compound The organic barium cadmium zinc complexes of object, liquid, the organic barium cadmium compound of liquid, the organic barium lead compound of liquid, phosphorous acid Ca Zn composite Object, 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 mould inhibitor, include but not limited to：Pentachlorophenol, sodium pentachlorophenol, lauric ester of pentachlorophenol, water Poplar anilid, copper 8-quinolinolate, double (tri-n-butyl tin) oxides, double (tributyl tin) sulfide, tributyl tin acetate, Tributyltin chloride, tributyl-tin fumarate, tributyl tin fluoride, N- (trichloromethylthio) phthalimide, N- (three Chloromethyl is thio) -4- cyclohexene -1,2- dicarboximides, 5,6- dichloro benzoxazole quinolines ketone, N- (fluorine dichloromethyl is thio) be adjacent Phthalimide, N, N- dimethyl-N '-phenyl (fluorine dichloromethyl is thio) sulfonamide, 2,2 '-dihydroxy -5,5 '-dichloro- The double phenoxy group arsines of diphenyl methane, 2- (4- thiazolyls) benzimidazole, p-chloro-m-xylol, 10,10 '-oxo, 2- methoxies Base carbonylamino benzo imidazoles, Preventol K1, hexahydro -1,3,5- triethyl groups triazine, sodium-o-phenyl phenolate, 2- hydroxyls connection Benzene, 3,4 ', 5- tribromosalicylanilides, Antimycoticum A, Hyamine, Preventol OC 3014, Corobex, ASC-4、Cubide。

As the example of anti-termite agent, include but not limited to：1,4,5,6,7,8,8- heptachlors -3a, 4,7,7a tetrahydrochysene -4,7- Methanoindene, 2,3,4,5,6,7,8,8- eight chloro- 2,3,3a, 4,7,7a- hexahydro -4,7- methanoindene, 1,2,3,4,10,10- chlordenes - Two methylene naphthalenes of 6,7- epoxies -1,4,4a, 5,6,7,8,8a- octahydro -1,4-5,8-, 1,2,3,4,10,10- chlordenes -1,4,4a, 5, 8,8a- hexahydros -1,4 (interior) -5,8- (outer)-two methylene naphthalene, right, the chloro- 2- phenyl benzene of right '-dichloro-diphenyl-trichloro-ethane, 4- 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- oxocyclohexyls) -2- hydroxyl second Base] glutarimide, tributyl tin acetate.

As the example of antifoggant, include but not limited to：Monoolein, glyceryl monoricinoleate, D-sorbite It is acid anhydride monoleate, Span-20, sorbitan monopalmitate, sorbitan monostearate, poly- Ethylene oxide (20) glyceryl monostearate, polyethylene oxide (5) glyceryl monostearate, polyethylene oxide (20) D-sorbite Acid anhydride monoleate, polyethylene oxide (5) Monoolein, polyethylene oxide (9) monoleate, polyethylene oxide (20) glycerine Monoleate, Drewplast 100, Mark 630, Drewplast 084, glycerin monostearate.

Antiseptic

The antiseptic is selected from silver-series antibacterial agent, titanium series antibacterial agent, organic polymer salt antiseptic, imidazoles antibacterial At least one of agent, organic antibacterial agent containing arsenic, organic metal class antiseptic, pyridines antiseptic and phenolic antiseptic.

It is other

High intensity PP-RCT anti-flaming tubular products of the present invention with outer lining or can be lined with metal pipe material, specific example bag It includes but is not limited to aluminium alloy lining PPR pipe, aluminium lining PPR pipe, liner copper PPR pipe, inner liner stainless steel PPR pipe.

The preparation of tubing

High intensity PP-RCT anti-flaming tubular products of the present invention squeeze out to obtain using laminated multi-layer co-extrusion technology.Internal layer hopper For the PP-RCT particles containing antiseptic and fire retardant, middle level hopper is the PP-RCT particles containing fire retardant and glass fibre, Outer layer hopper is the PP-RCT particles containing fire retardant, and high intensity PP-RCT Frpipes are obtained by being plasticized co-extrusion, wherein, it is 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 a kind of high intensity PP-RCT anti-flaming tubular products as described 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- morpholinyls) propyl] thiocarbamide, regent biochemical technology Co., Ltd of Shenzhen, No. CAS：111538- 46-6

C1 organic silicon compound containing phosphorus

It is prepared by the raw material comprising phenoxy group phosphinylidyne dichloro and N- (6- Aminohexyls) amino methyl triethoxysilane It arrives.

Preparation method is：Under nitrogen protection, by 0.05mol phenoxy group phosphinylidyne dichloros and 0.1mol N- (6- amino oneself Base) amino methyl triethoxysilane mixes in 250mL acetonitriles, adds 0.11mol triethylamines, be heated to 110 DEG C, continues Stirring for 24 hours, then adds in 5mL water and 0.05g hexamethyldisilanes, reaction temperature is down to 70 DEG C, continues stirring for 24 hours, stops After reaction, vacuum distillation pumps solvent, then is washed successively using 20mL water and 20mL ether, after vacuum drying to get.

C2 organic silicon compound containing phosphorus

By being prepared comprising phenoxy group phosphinylidyne dichloro and 4- ammobutyltriethoxysilane raw materials.

Preparation method is：Under nitrogen protection, by 0.05mol phenoxy group phosphinylidyne dichloros and 0.1mol 4- aminobutyls three Ethoxysilane mixes in 250mL acetonitriles, adds 0.11mol triethylamines, is heated to 110 DEG C, lasting to stir for 24 hours, then 5mL water and 0.05g hexamethyldisilanes are added in, reaction temperature is down to 70 DEG C, continues stirring for 24 hours, after stopping reaction, decompression is steamed Evaporate and pump solvent, then washed successively using 20mL water and 20mL ether, after vacuum drying to get.

Acetonitrile, Taizhou plain Yongfeng Chemical Co., Ltd., No. CAS：75-05-8

Triethylamine, Zhejiang Bo Laite Science and Technology Ltd.s, No. CAS：121-44-8

Hexamethyldisilane, Zhejiang Bo Laite Science and Technology Ltd.s, No. CAS：1450-14-2

Phenoxy group phosphinylidyne dichloro, Changzhou Watson Fine Chemical Co., Ltd., No. CAS：770-12-7

N- (6- Aminohexyls) amino methyl triethoxysilane, Shanghai Ji Laide new materials Science and Technology Ltd., CAS Number：15129-36-9

4- ammobutyltriethoxysilanes, Shanghai Shi Yang Chemical Co., Ltd.s, No. CAS：3069-30-5

The weight ratio of D1 B and C1 are 1.5：5 mixture

The weight ratio of D2 B and C1 are 0.1：5 mixture

The weight ratio of D3 B and C1 are 5：5 mixture

The weight ratio of D4 B and C2 are 1.5：5 mixture

E1 silver ion antimicrobial agents, BASF IRGAGUARD B6000

E2 polyethylene waxes, Honeywell AC-6

E3 glass fibres, Tai'an white jade glass fiber composite material Co., Ltd

Embodiment 1

The internal layer hopper of embodiment 1-9 and comparative example 1-6 is the PP-RCT particles containing antiseptic and composite flame-retardant agent, former Material proportioning all same, in parts by weight, specific raw material proportioning 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 particles containing glass fibre and composite flame-retardant agent, In parts by weight, specific raw material proportioning 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 particles containing composite flame-retardant agent, with parts by weight Meter, specific raw material proportioning are 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：

Material in internal layer, middle level, outer layer hopper is granulated respectively by the raw material addition of table 1, table 2, table 3 using extruder, Prilling temperature：160 DEG C of feeding section, 190 DEG C of compression section, 200 DEG C of metering section, 200 DEG C of head, 210 DEG C of mouth mold；Then by plasticizing Co-extrusion obtains.Wherein, internal layer, middle level, the thickness of outer layer are 1：1：1.

Performance evaluation

1. limit oxygen index is tested

Sample is carried out according to the method for GB/T 2406-2008 defineds.Length of flame 10mm, sentences 30 seconds durations of ignition According to：Burning length 50mm lights a fire 30 seconds, sample can't burn, although can burn in other words, burning length deficiency 40mm then illustrates that oxygen concentration is relatively low, it is also necessary to heighten.If sample can be lighted in 30 seconds, and the burning length of sample surpasses Cross 40mm, then it represents that oxygen concentration is high, it is necessary to turn down.In this way, until finding a critical oxygen concentration, refer to as limit oxygen Number, unit %.

2. vertical burn test

It is tested according to UL94-2009 standards, according to sample burning times, if whether molten drop and molten drop can ignite Sample is fixed on 30.5cm above the absorbent cotton of 0.6cm thickness by absorbent cotton overall merit sample flame retardant effect immediately below sample Place.By burning things which may cause a fire disaster continuous action 10 seconds below the sample, according to time that sample self-gravitation is arrived after burning things which may cause a fire disaster is removed, by test result It is divided into tri- fire-retardant ranks of FV-0, FV-1, FV-2.FV-0：Burning time is no more than 10 seconds, and do not ignite absorbent cotton；FV-1, burning Time is no more than 30 seconds, and do not ignite absorbent cotton；FV-2, burning time are no more than 30 seconds, and ignite absorbent cotton.

3. tensile property is tested

Tension test is carried out according to GB/T 1040-2006, measures tensile strength, unit MP.

4. impact property is tested

According to the impact strength of GB/T 1834-2008 determination samples, unit kJ/m²。

Test result is listed in Table 4 below.

Table 4

	Limit oxygen index %	Vertical combustion grade	Tensile 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, high intensity PP-RCT anti-flaming tubular products fire retardant additive amount provided by the invention is few, fire-retardant effect Fruit is good, and with outstanding mechanical property.The above, the only preferable specific embodiment of the present invention, but the protection of the present invention Scope is not limited thereto, and any one skilled in the art is the invention discloses in the range of, according to the present invention Technical solution and inventive concept be subject to equivalent substitution or change, belong to protection scope of the present invention.

Claims

1. a kind of high intensity PP-RCT anti-flaming tubular products, which is characterized in that including at least three layers, from inside to outside respectively internal layer, in Layer and outer layer, the internal layer contain antiseptic and composite flame-retardant agent, and glass fibre and composite flame-retardant agent are contained in the middle level, described Outer layer contains composite flame-retardant agent, and the composite flame-retardant agent contains morpholinyl thiocarbamide, organic silicon compound containing phosphorus, the morpholinyl sulphur The weight ratio of urea and organic silicon compound containing phosphorus is (1-2)：5, the organic silicon compound containing phosphorus is by including phosphinylidyne gold dichloride Object and the raw material of amido organosilicon compound are prepared, and are counted by 100 parts by weight of PP-RCT resins, the composite flame-retardant agent Content is 5-35 parts.

2. high intensity PP-RCT anti-flaming tubular products as described in claim 1, which is characterized in that the morpholinyl thiocarbamide is selected from 1- [3- (4- morpholinyls) propyl] thiocarbamide, 1- [2- (4- morpholinyls) ethyl] thiocarbamide, 1- cyclohexyl -3- (2- morpholinyl ethyls) sulphur One in urea, 1- (2- morpholinyl ethyls) -3- phenylthioureas, 1- [3- ethyoxyls -2- (4- morpholinyls) propyl] -3- ethyl thioureas Kind.

3. high intensity PP-RCT anti-flaming tubular products as described in claim 1, which is characterized in that the phosphinylidyne dichloro compound contains Aromatic rings.

4. high intensity PP-RCT anti-flaming tubular products as described in claim 1, which is characterized in that the phosphinylidyne dichloro compound is selected from One in 2- phthalimide-based ethyls either dichlorophosphate, phenoxy group phosphinylidyne dichloro, 3,5- 3,5-dimethylphenyl phosphinylidyne dichloros Kind.

5. high intensity PP-RCT anti-flaming tubular products as described in claim 1, which is characterized in that the amido organosilicon compound contains There are at least one primary amino radical and at least one secondary amino group.

6. high intensity PP-RCT anti-flaming tubular products as described in claim 1, which is characterized in that the amido organosilicon compound choosing From N- (6- Aminohexyls) amino methyl triethoxysilane, (((2- amino-ethyls) amino) methyl) triethoxysilane, (ammonia Base ethylaminomethyl) phenethyl trimethoxy silane, N- (2- amino-ethyls)-N'- (3- (dimethoxymethylsilane base) third Base) one kind in -1,2- ethylenediamines.

7. high intensity PP-RCT anti-flaming tubular products as described in claim 1, which is characterized in that the high intensity PP-RCT Frpipes Also contain auxiliary agent, the auxiliary agent is selected from antioxidant, antistatic agent, plasticizer, ultraviolet absorber, heat stabilizer, mould inhibitor, anti-white At least one of ant agent, Ratproof agent, antifoggant.

8. the high intensity PP-RCT anti-flaming tubular products as described in any one of claim 1-7 claim are in central air-conditioning pipe system Application in system, fire-fighting and fire-fighting spraying pipeline system.