CN105733023A - Composite auxiliary agent for high density polyethylene overpressure resistant tubing, preparation method thereof, and resin raw material containing the composite auxiliary agent - Google Patents
Composite auxiliary agent for high density polyethylene overpressure resistant tubing, preparation method thereof, and resin raw material containing the composite auxiliary agent Download PDFInfo
- Publication number
- CN105733023A CN105733023A CN201410764954.XA CN201410764954A CN105733023A CN 105733023 A CN105733023 A CN 105733023A CN 201410764954 A CN201410764954 A CN 201410764954A CN 105733023 A CN105733023 A CN 105733023A
- Authority
- CN
- China
- Prior art keywords
- density polyethylene
- auxiliary agent
- high density
- hdpe
- pressure resistant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Rigid Pipes And Flexible Pipes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a composite auxiliary agent for a high density polyethylene overpressure resistant tubing. The composite auxiliary agent comprises 30-50 parts by weight of a long-term ageing resistant auxiliary agent , 10-30 parts by weight of a thermal stable auxiliary agent, and 10-30 parts by weight of a processing auxiliary agent, wherein the long-term ageing resistant auxiliary agent is at least one selected from a group consisting of hindered phenols antioxidants, amines antioxidants, and phosphorus antioxidants; the thermal stable auxiliary agent is at least one selected from metal soap stabilizers; and the processing auxiliary agent comprises at least a fluoroelastomer. The invention also provides a preparation method of the composite auxiliary agent, and a high density polyethylene overpressure resistant tubing resin raw material containing the composite auxiliary agent. The high density polyethylene overpressure resistant tubing resin raw material containing the composite auxiliary agent has excellent processing performance. The formed tubing has excellent environmental stress crack resistance, ageing resistance, and rigidity-toughness balance.
Description
Technical field
The present invention relates to high density polyethylene (HDPE) pressure resistant pipe material composite assistant and preparation method thereof and the high density polyethylene (HDPE) pressure resistant pipe material resin raw material containing this composite assistant.
Background technology
Polyvinyl piping materials has the performances such as prominent chemical resistance, lower temperature resistance, heat-resistant antifriction, welding characteristic are excellent, pollution transportation medium, long service life, manufacture mounting cost be not low, is widely used in the fields such as fuel gas transmission, water supply, blowdown, heat supply, petrochemical industry and telecommunications at present.
The exploitation of the polyvinyl piping materials history of existing more than 50 year so far, its development is generally divided into three phases.First stage starts from the 1950's, and this stage occurs in that first generation high density polyethylene (HDPE) (HighDensityPolyethylene, HDPE) pressure resistant pipe material, its poor-performing, is equivalent to PE63 and following grade.Second stage starts from phase late 1970s, this stage occurs in that the PE80 level special material for tube with higher long-term hydraulic pressure resistant intensity and anti-cracking performance in succession, owing to environmental stress crack resistance is excellent, this PE80 level special material for tube is widely applied in the polyvinyl piping materials manufacture of feedwater and gas transmission and distribution system.Phase III starts from late 1980s, and this stage occurs in that third generation PE special material for tube PE100, and this PE100 level pipe resin is with when 20 DEG C, and the minimum of tubing must intensity be 10MPa, and service life was feature more than 50 years.And, most PE100 level tubing have the feature of bimodal molecular weight distribution, wherein, low molecular weight part can effectively reduce resin melt viscosity at high shear rates, improve the mobility in materials processing, ensureing that material has high degree of crystallinity, high molecular weight moieties then can give the mechanical performance that tubing is good.
Such as, document " PE100 level pipe resin structure and performance study " (elastomer, 2012,22 (4): 57～60) reports the pressure resistant pipe material resin adopting autoclave slurry process to produce and properties thereof.Having been contrasted by the domestic material and import material with its similar nature, this pressure resistant pipe material resins act has gone out the performance advantage of uniqueness, but the problem not mentioning pressure resistant pipe material used additives aspect in the publication.
And for example, document " structure of PE100 special material for tube and rheological behaviour research " (plastics science and technology, 2011,39 (3): 64～66) result of study of the basic structure performance of three kinds of PE100 special material for tube JHMGC100S, YGH041 and P600, rheological behaviour and dynamic rheological behavior is reported in.In the document, the problem of technique adjustment direction aspect when autoclave method being produced to performance advantage and the tubular object extruding of PE100 special material for tube JHMGC100S has been summed up.But, wherein also without the problem of the auxiliary formula aspect mentioning pressure resistant pipe material PP Pipe Compound.
A kind of processing aid for polychloroethylene pipes and pipe fitting and use the poly (vinyl chloride) resin composition of this processing aid disclosed in CN102786622B.This processing aid adopts two sections of emulsion polymerization techniques to be prepared, and adopts disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate as emulsifying agent during emulsion polymerization.First paragraph monomer composition accounts for 50 weight % of monomer composition total amount, and second segment monomer composition accounts for 50 weight % of monomer composition total amount.Second segment monomer composition adopts the method for pre-emulsification dropping, and polymerization temperature controls, at 55～75 DEG C, to prepare copolymer emulsion, and emulsion is then through, after spray drying, preparing pressed powder product.Wherein, with first paragraph, second segment monomer composition gross weight for 100%, styrene is 70～85%, and acrylonitrile is 10～20%, and n-BMA is 0～10%.When adopting this processing aid, it is possible to significantly improve polychloroethylene pipes, the hardness of tubing products and heat-resistant stability.
A kind of Compound stabilizer for plastic pipe disclosed in CN102807687A, and preparation method thereof.This Compound stabilizer for plastic pipe consist of stearic acid 490～510 weight portion, Plumbum preparatium 120～130 weight portion, ash calcium 25～30 weight portion, acetic acid 1～2 weight portion, Tissuemat E 50～60 weight portion, tribasic lead sulfate 170～185 weight portion, ground calcium carbonate 350～360 weight portion, barium stearate 60～80 weight portion, dibasic lead stearate 10～20 weight portion and bisphenol-A 1～20 weight portion.This complex stabilizer is applicable to plastic pipe, has good stability, high lubricating effect, cost is low, lead tolerance is low advantage.
Additionally, a kind of composite auxiliary agent for random copolymerized polypropylene pipe material adopting liquid phase noumenal method single loop reactors to be polymerized disclosed in CN101638500B.This composite assistant is made up of resisting ageing for long time auxiliary agent 10～40 weight portion, processing aid 10～30 weight portion, compound modifying agent 20～50 weight portion and weather resisting agent 10～30 weight portion.Wherein, resisting ageing for long time auxiliary agent is made up of lactone stabilizer, hindered phenol anti-oxidants and nontoxic amine antioxidants, processing aid is the mixture that a kind of or any proportioning in fluoroelastomer, low polymer is several, weather resisting agent is made up of UV absorbent, organic nickel stabilizer and hindered amines stabilizer, and compound modifying agent is to make alpha-crystal form be converted into the compound modifying agent of beta crystal, i.e. beta crystal-type nucleater.This composite assistant is the composite assistant that polypropylene pipe is special, is not suitable for polyvinyl piping materials, it is possible to make the processing characteristics of atactic copolymerized polypropene resin, mechanical property, environmental stress crack resistance and resisting ageing for long time significantly improve.
High density polyethylene (HDPE) pressure resistant pipe material resin has the advantages that melt flow rate (MFR) is low, density is high.Therefore, processing relative difficulty, it is easy to the problem such as cause the tube wall uneven distribution of tubing, sharkskin occurs in the outer wall of tubing, the inner surface of tubing is rough.Further, mostly it is used in the fields such as feedwater, fuel gas transmission due to this type of tubing, therefore in use needs to bear certain pressure and environmental aging, thus its security performance be it is also proposed very harsh requirement.For this kind of requirement, usually in the course of processing, add a certain amount of special compound additive, in order to improve the processing characteristics of high density polyethylene (HDPE) pressure resistant pipe material resin, to improve the appearance property of tubing article, and give the excellent environmental stress crack resistance of tubing and resistance to ag(e)ing, thus meeting the industry instructions for use to high density polyethylene (HDPE) pressure resistant pipe material.
Summary of the invention
The problem that invention to solve
In view of problem above, it is an object of the invention to provide a kind of composite assistant for existing high density polyethylene (HDPE) pressure resistant pipe material and preparation method thereof and the resin raw material containing this composite assistant.High density polyethylene (HDPE) pressure resistant pipe material resin raw material containing this composite assistant has the processing characteristics of excellence, and the tubing after shaping has the environmental stress crack resistance of excellence, resistance to ag(e)ing and rigidity-toughness balanced.
The method of solution problem
The first aspect of the invention is in that to provide a kind of high density polyethylene (HDPE) pressure resistant pipe material composite assistant, it is characterized in that, this composite assistant is made up of resisting ageing for long time auxiliary agent 30～50 weight portion, thermally-stabilised auxiliary agent 10～30 weight portion and processing aid 10～30 weight portion, wherein, resisting ageing for long time auxiliary agent selects at least one in the group of free hindered phenol anti-oxidants, amine antioxidants and phosphorus antioxidants composition, described thermally-stabilised auxiliary agent at least one in metal soap stabilizer, processing aid is made up of at least one fluoroelastomer.
In an embodiment of the invention, described resisting ageing for long time auxiliary agent is to be blended by hindered phenol anti-oxidants, amine antioxidants, phosphorus antioxidants 1:0.1～10:0.1～10 in mass ratio to form.
nullHigh density polyethylene (HDPE) pressure resistant pipe material composite assistant according to the first aspect of the invention，Wherein，Hindered phenol anti-oxidants choosing free 2,6-DI-tert-butylphenol compounds、2,6-di-t-butyl-4-ethyl-phenol、2,6-di-tert-butyl-4-methy phenol、2,6-di-t-butyl-4-normal-butyl phenol，2,6-di-t-butyl-alpha, alpha-dimethyl amino paracresol、2,4,6-tri-butyl-phenol、β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propanoic acid n-octadecane alcohol ester、Styrenated phenol、Butylated octylated phenol、2,2 '-methylene bis (4-methyl-6-tert-butylphenol)、4,4 '-methylene bis (2,6-DI-tert-butylphenol compounds)、Four (3-(3 ',5 '-di-t-butyl-4 '-hydroxy phenyl) propanoic acid) pentaerythritol ester、1,1,At least one in the group of 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane composition.
High density polyethylene (HDPE) pressure resistant pipe material composite assistant according to the first aspect of the invention, wherein, amine antioxidants selects at least one in the group of free N-phenyl-a-naphthylamine, N-Phenyl beta naphthylamine, N, N '-two-betanaphthyl p-phenylenediamine, acetaldol-alpha-naphthylamine, N-isopropyl-N '-diphenyl-para-phenylene diamine composition.
High density polyethylene (HDPE) pressure resistant pipe material composite assistant according to the first aspect of the invention, wherein, phosphorus antioxidants select free triphenyl phosphite, phosphorous acid diphenyl monooctyl ester, trisnonyl phenyl phosphite, diphosphorous acid tetramethylolmethane distearyl alcohol ester, phosphorous acid two lauryl, didecyl phosphite, three (2,4-di-t-butyl) phenyl-phosphite, phosphorous acid 4,4-bis-different fork bis-phenol (12-14) carbon Arrcostab composition group at least one.
High density polyethylene (HDPE) pressure resistant pipe material composite assistant according to the first aspect of the invention, wherein, metal soap thermal stabilizers selects at least one in the group of free calcium stearate, magnesium stearate, lithium stearate, zinc stearate, aluminium stearate, sodium stearate, calcium laurate, double stearic acid aluminium composition.
High density polyethylene (HDPE) pressure resistant pipe material composite assistant according to the first aspect of the invention, wherein, fluoroelastomer selects at least one in the group of free FX-5911, FX-5920, FX-5924, VitonFFGB, SOLEFPVDF composition.
The second aspect of the invention is in that the preparation method providing above-specified high density polythene pressure pipe material composite assistant, it is characterized in that, by resisting ageing for long time auxiliary agent 30～50 weight portion, thermally-stabilised auxiliary agent 10～30 weight portion, and processing aid 10～30 weight portion is mixed and stirred for after uniformly, extruding pelletization, thus forming granular composite assistant, wherein, resisting ageing for long time auxiliary agent selects free hindered phenol anti-oxidants, amine antioxidants, at least one in the group of phosphorus antioxidants composition, thermally-stabilised auxiliary agent at least one in metal soap stabilizer, processing aid is made up of at least one fluoroelastomer.
The third aspect of the invention is in that to provide a kind of resin raw material manufacturing high density polyethylene (HDPE) pressure resistant pipe material, it is characterized in that, this resin raw material high density polyethylene (HDPE) pressure resistant pipe material composite assistant involved by high density polyethylene (HDPE) pressure resistant pipe material base resin and the first aspect of the invention forms.
Resin raw material according to the third aspect of the present invention, wherein, relative to resin raw material total amount, the addition of high density polyethylene (HDPE) pressure resistant pipe material composite assistant is 0.1～1 weight %.One of the present invention preferred embodiment in, in described resin raw material, relative to resin raw material total amount, the addition of high density polyethylene (HDPE) pressure resistant pipe material composite assistant is 0.4～0.5 weight %.
The effect of invention
1) composite assistant of the high density polyethylene (HDPE) pressure resistant pipe material of the present invention can significantly improve the processing characteristics of resin raw material, obtained hdpe pipe has the environmental stress crack resistance of excellence, pressure performance, resisting ageing for long time, has the mechanical properties such as good rigidity-toughness balanced simultaneously.
2) after adding the composite assistant body of the present invention, the processing difficulties that the high density polyethylene (HDPE) manufactured through slurry process double; two still series connection (or in parallel) polymerization technique occurs can be significantly improved when tube extrusion, and tubing appearance poor can be improved, inwall has pointing object or rough, occur the problem of sharkskin etc. the mechanical characteristics such as the resistance to pressure of hdpe pipe to be produced harmful effect simultaneously.
Detailed description of the invention
In the present invention, hdpe pipe composite assistant (following, to be also referred to simply as " composite assistant ") is made up of resisting ageing for long time auxiliary agent 30～50 weight portion, thermally-stabilised auxiliary agent 10～30 weight portion and processing aid 10～30 weight portion.Wherein, resisting ageing for long time auxiliary agent selects at least one in the group of free hindered phenol anti-oxidants, amine antioxidants and phosphorus antioxidants composition, described thermally-stabilised auxiliary agent at least one in metal soap stabilizer, described processing aid is made up of at least one fluoroelastomer.
In an embodiment of the invention, resisting ageing for long time auxiliary agent is the compound system blended hindered phenol anti-oxidants, amine antioxidants, phosphorus antioxidants 1:0.1～10:0.1～10 in mass ratio, wherein, preferably hindered phenol anti-oxidants, amine antioxidants, phosphorus antioxidants are the scope of 1:0.2～5:0.2～5 in mass ratio, the more preferably scope of 1:0.5～2:0.5～2.
nullIn the present invention，Hindered phenol anti-oxidants choosing free 2,6-DI-tert-butylphenol compounds、2,6-di-t-butyl-4-ethyl-phenol、2,6-di-tert-butyl-4-methy phenol、2,6-di-t-butyl-4-normal-butyl phenol，2,6-di-t-butyl-alpha, alpha-dimethyl amino paracresol、2,4,6-tri-butyl-phenol、β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propanoic acid n-octadecane alcohol ester、Styrenated phenol、Butylated octylated phenol、2,2 '-methylene bis (4-methyl-6-tert-butylphenol)、4,4 '-methylene bis (2,6-DI-tert-butylphenol compounds)、Four (3-(3 ',5 '-di-t-butyl-4 '-hydroxy phenyl) propanoic acid) pentaerythritol ester、1,1,At least one in the group of 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane composition.
In the present invention, as amine antioxidants, it is possible to enumerate aromatic amine and derivant, amide-type age resistor, ketone amines antioxidants etc., these, it is preferred to the secondary diarylamine class antioxidants such as p-phenylenediamine.Amine antioxidants is good to the barrier propterty of oxygen, ozone, has discolouration and the nonstaining property of excellence, it is possible to be used in dark goods or the less demanding situation of color to goods.In an embodiment of the invention, amine antioxidants selects at least one in the group of free N-phenyl-a-naphthylamine, N-Phenyl beta naphthylamine, N, N '-two-betanaphthyl p-phenylenediamine, acetaldol-alpha-naphthylamine, N-isopropyl-N '-diphenyl-para-phenylene diamine composition.
Phosphite antioxidant can be obviously improved discolouration and the embrittlement characteristic of high density polyethylene (HDPE) pressure resistant pipe material with phenol antioxidant when sharing.In the present invention, phosphorus antioxidants select free triphenyl phosphite, phosphorous acid diphenyl monooctyl ester, trisnonyl phenyl phosphite, diphosphorous acid tetramethylolmethane distearyl alcohol ester, phosphorous acid two lauryl, didecyl phosphite, three (2,4-di-t-butyl) phenyl-phosphite, phosphorous acid 4,4-bis-different fork bis-phenol (12-14) carbon Arrcostab composition group at least one.
In the hdpe pipe composite assistant of the present invention, thermally-stabilised auxiliary agent is metal soap stabilizer, and this metal soap stabilizer is referred to as again plumper, halogen-absorber, is a class additive conventional in polyvinyl resin powder.In general, the activity of catalyst during in order to improve olefinic polymerization or copolymerization, polar comonomers, radical initiator and Ziegler catalyst etc. can be introduced in polymerization reaction system, the introducing of these materials can cause that acid product remains in polymerizate.Such as, when adopting Ziegler catalyst to manufacture olefin polymer, product would generally remain a small amount of (10-6 level) chlorine-containing compound.The existence of these chlorine-containing compounds can cause the corrosion of metal-working plant (such as, exsiccator, mold apparatus), also results in the deterioration of the physical properties such as the variable color of polymer product, embrittlement simultaneously.Now, the interpolation of thermally-stabilised auxiliary agent can improve the overall performance of polymer product.In the present invention, there is no particular limitation for the composite assistant of metal soap thermal stabilizers in forming with to(for) hdpe pipe, for example, it is possible at least one being chosen from the group being made up of calcium stearate, magnesium stearate, lithium stearate, zinc stearate, aluminium stearate, sodium stearate, calcium laurate, double stearic acid aluminium.
In the present invention, fluoroelastomer is the processing aid of structure based on fluoropolymer, the processing fluidity of high-density polyethylene resin can be improved, and play lubrication to by the polyvinyl resin melt of mould, thus improving extrusion performance and the extrusion efficiency of melt.In the present invention, as fluoroelastomer, for instance, it is possible to it is chosen from least one in the group being made up of FX-5911, FX-5920, FX-5924, VitonFFGB, SOLEFPVDF.
In the present invention, method for preparing high density polyethylene (HDPE) pressure resistant pipe material composite assistant is not particularly limited, such as, can be resisting ageing for long time auxiliary agent 30～50 weight portion, thermally-stabilised auxiliary agent 10～30 weight portion and processing aid 10～30 weight portion are mixed and stirred for after uniformly, extruding pelletization, thus obtaining granular composite assistant.In an embodiment of the invention, when preparing high density polyethylene (HDPE) pressure resistant pipe material composite assistant, it is that resisting ageing for long time auxiliary agent 30～50 weight portion, thermally-stabilised auxiliary agent 10～30 weight portion and processing aid 10～30 weight portion are added in high speed mixing smelting machine, at room temperature stirring, mixing 5～20 minutes after, it is transferred to powder body extruder, extrude at the cold working temperature of 20 DEG C～50 DEG C, thus preparing granular composite assistant.
In the present invention, the resin raw material manufacturing high density polyethylene (HDPE) pressure resistant pipe material is made up of the high density polyethylene (HDPE) pressure resistant pipe material composite assistant of high density polyethylene (HDPE) pressure resistant pipe material base resin and the present invention.Wherein, relative to resin raw material total amount, the scope that addition is 0.1～1 weight % of the high density polyethylene (HDPE) pressure resistant pipe material composite assistant of the present invention, it is preferred to the scope of 0.3～0.6 weight %, the more preferably scope of 0.4～0.5 weight %.After the composite assistant of the present invention and high density polyethylene (HDPE) pressure resistant pipe material base resin are blended by certain Blend proportion, melting mixing is carried out the processing temperatures of 180 DEG C～250 DEG C, pelletize after plasticizing uniformly, extrusion molding in pipe extruder subsequently, can obtain high density polyethylene (HDPE) pressure resistant pipe material.
In the present invention, (following for high density polyethylene (HDPE) pressure resistant pipe material base resin, it is also referred to as " base resin ") it is not particularly limited, such as, Ziegler catalyst, philip catalyst or CGC/ borate ester catalyst can be adopted (namely, single-activity site catalyst by carrier loaded), manufacture high density polyethylene (HDPE) base resin by slurry process double; two still series connection (or in parallel) polymerization technique.In the present invention, as high density polyethylene (HDPE) base resin, it is preferred that manufacture with Ziegler catalyst, CGC/ borate ester catalyst, the copolymer by Alathon, vinyl monomer and other 'alpha '-olefin monomers or the copolymer blended rear high-density polyethylene resin formed by Alathon and vinyl monomer and other 'alpha '-olefin monomers.Wherein, copolymer as vinyl monomer Yu other 'alpha '-olefin monomers, it can be the copolymer of the 'alpha '-olefin monomers that carbon number is 3～20 of vinyl monomer and more than a kind, and 'alpha '-olefin monomers unit the overall content ratio of copolymer 0.5～2.0% scope, it is preferable that in the scope of 1.0～2.0%.The density of high-density polyethylene resin is by the impact of monomer component composition, with the molecular weight of resin uncorrelated.In the present invention, for the density of high-density polyethylene resin, there is no particular limitation, for instance, it is possible at 940Kg/m3～980Kg/m3Scope, it is preferred to 940Kg/m3～970Kg/m3Scope, more preferably 940Kg/m3～960Kg/m3Scope.
In the present invention, for the molecular weight of high density polyethylene (HDPE) pressure resistant pipe material base resin, there is no particular limitation, for instance, weight average molecular weight can 20,000～500, the scope of 000, it is preferable that weight average molecular weight 40,000～300, the scope of 000.The high density polyethylene (HDPE) with bimodal molecular weight distribution can be produced by double; two stills series connection (or in parallel) polymerization technique, wherein, lower molecular wt part makes polymerizate have high density characteristic, and high molecular weight moieties then makes polymerizate have bigger viscosity.Here, so-called high and low molecular weight is that the two kinds of compositions having in the high density polyethylene (HDPE) of bimodal molecular weight distribution are relative to each other, is not offered as absolute numerical range.And, the molecular weight of high-density polyethylene resin substantially with its melt index (MeltFlowRate, MFR) corresponding, generally, the melt strength of resin powder can be strengthened during the weight average molecular weight height of resin powder, and the tubing enabled to has more excellent toughness and environmental stress crack resistance, but higher molecular weight also can make process operation be deteriorated, and adds the higher pressure of man-hour requirement or temperature.In the present invention, melt index as high-density polyethylene resin powder, desirably 230 DEG C, 21.6Kg be the scope of 0.01g/10 minute～100g/10 minute when loading, preferably in 230 DEG C, 21.6Kg be the scope of 0.1g/10 minute～50g/10 minute when loading, it is preferred that 230 DEG C, 21.6Kg be the scope of 1g/10 minute～10g/10 minute when loading.By controlling the molecular weight of high-density polyethylene resin powder, it is possible to regulate the scope of its melt index such that it is able to significantly improve its process operation.
After high density polyethylene (HDPE) pressure resistant pipe material base resin adds the composite assistant of the present invention, can significantly improve the pipe resin processing difficulties that occurs and the tubing appearance poor shaped, inwall when extrusion have pointing object or rough, the problems such as sharkskin occur, the processing characteristics of high density polyethylene (HDPE) pressure resistant pipe material, pressure performance, resisting ageing for long time, environmental stress crack resistance and mechanical property can be made to significantly improve simultaneously.
As required, the composite assistant of the present invention can also coordinate with other additives known and adds in high density polyethylene (HDPE) pressure resistant pipe material base resin, thus playing collaborative modifying function.As these known additives, for instance, it is possible to it is antiblocking agent, antistatic additive, lubricant, weather resisting agent, light stabilizer, UV absorbent, inorganic or organic filler, organic peroxide, nertralizer etc..In the present invention, for antiblocking agent, there is no particular limitation, specifically, it is possible to enumerates the inoganic solids powder etc. such as Talcum, silicon oxide, kaolinite.As antistatic additive, it is not particularly limited, for example, it is possible to enumerate the nonionic antistatic additive such as alkyl sulphate type anionic antistatic agents, Quaternary Cation Antistatic Agent, polyoxyethylene sorbitan monostearate, betaines both sexes antistatic additive etc..As lubricant, also without special restriction, for example, it is possible to enumerate the fat hydrocarbon lubricants such as ethylenebis stearamide, butyl stearate, Tissuemat E, hard paraffin, higher fatty acids lubricant, aliphatic amide series lubricant agent, fatty acid ester type emollients etc..In the present invention, for weather resisting agent, there is no particular limitation, specifically, it is possible to enumerates resorcin compound, salicylate compounds, benzotriazole compound, benzophenone compounds, hindered amine compound etc..As light stabilizer, for instance, it is possible to enumerate but be not limited to hindered amine compound, benzotriazole compound, compound in triazine class, benzophenone compounds, benzoic acid salt compounds etc..As UV absorbent, for instance, it is possible to enumerate but be not limited to benzotriazole compound, compound in triazine class, benzophenone compounds etc..As inorganic filler, there is no particular limitation in the present invention, specifically, it is possible to enumerate the inorganic fillers such as threadiness, microgranular, lamellar and the silicon oxide of hollow, quartz powder, bead, calcium silicates, kieselguhr, ferrum oxide, titanium oxide, aluminium silicate, aluminium oxide, magnesium carbonate, silicon nitride, boron nitride.As organic filler, in the present invention also without special restriction, specifically, it is possible to enumerate the powder body of starch, producing starch, wooden slurry, chitin/chitosan class, Exocarpium cocois (Cocos nucifera L), bamboo matter powder body, bark powder body, kenaf etc..As organic peroxide, for instance, it is possible to enumerate but be not limited to diacyl peroxide class, peroxidating ketone, hydroperoxide kind, dialkyl peroxide class, ketal peroxide class, peroxy acid alkyl esters and peroxycarbonic acid esters etc..As nertralizer, there is no particular limitation in the present invention, for instance, it is possible to enumerate various Metallic stearates, hydrotalcite etc..
Hereinafter, the present invention is described further in conjunction with the embodiments.Without polylogia, the present invention is also not restricted by the embodiments.Further, in the scope without departing from general idea of the present invention, change, deformation or change etc. that these embodiments are done belong in scope of the invention.
Hereinafter, embodiment 1～6 is an illustration for the preparation of the composite assistant of the present invention, and comparative example 1 is an illustration for the preparation of the polythene pressure pipe material composite assistant of prior art.
Embodiment 1
By 100g tetra-(3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propanoic acid) pentaerythritol ester is (namely, Bis-phenolic antioxidants 1010), 80g tri-(2,4-di-t-butyl) phenyl-phosphite (trade (brand) name: Mark2112), 60g calcium stearate, 6g fluoroelastomer VitonFFGB (E.I.Du Pont Company's system) join in mixer, after mixing 5 minutes under room temperature, send into powder body extruder, force extrusion under room temperature, obtain granular composite assistant (GC-1).
Embodiment 2
By 100g tetra-(3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propanoic acid) pentaerythritol ester, 100g tri-(2,4-di-t-butyl) phenyl-phosphite, 60g calcium stearate, 7g fluoroelastomer VitonFFGB (E.I.Du Pont Company's system) join in mixer, after mixing 10 minutes under room temperature, send into powder body extruder, force extrusion under room temperature, obtain granular composite assistant (GC-2).
Embodiment 3
By 100g tetra-(3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propanoic acid) pentaerythritol ester, 120g tri-(2,4-di-t-butyl) phenyl-phosphite, 60g calcium stearate, 8 grams of fluoroelastomer VitonFFGB (E.I.Du Pont Company's system) join in mixer, after mixing 20 minutes under room temperature, send into powder body extruder, force extrusion under room temperature, obtain granular composite assistant (GC-3).
Embodiment 4
By 100g tetra-(3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propanoic acid) pentaerythritol ester, 100g tri-(2,4-di-t-butyl) phenyl-phosphite, 60g metal soap stabilizer (wherein, calcium stearate and zinc stearate are respectively 30 grams), 6g fluoroelastomer VitonFFGB (E.I.Du Pont Company's system) join in mixer, after mixing 5 minutes under room temperature, send into powder body extruder, force extrusion under room temperature, obtain granular composite assistant (GC-4).
Embodiment 5
By 100g tetra-(3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propanoic acid) pentaerythritol ester, 100g tri-(2,4-di-t-butyl) phenyl-phosphite, 80g metal soap stabilizer (wherein, calcium stearate and zinc stearate are respectively 40 grams), 7g fluoroelastomer VitonFFGB (E.I.Du Pont Company's system) join in mixer, after mixing 10 minutes under room temperature, send into powder body extruder, force extrusion under room temperature, obtain granular composite assistant (GC-5).
Embodiment 6
By 100g tetra-(3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propanoic acid) pentaerythritol ester, 100g tri-(2,4-di-t-butyl) phenyl-phosphite, 100g metal soap stabilizer (wherein, calcium stearate and zinc stearate are respectively 50 grams), 8g fluoroelastomer VitonFFGB (E.I.Du Pont Company's system) join in mixer, after mixing 20 minutes under room temperature, send into powder body extruder, force extrusion under room temperature, obtain granular composite assistant (GC-6).
Comparative example 1
By Tissuemat E 2000g, 100g composite antioxidant, 700g metal soap stabilizer (wherein, calcium stearate is 200g, zinc stearate is 500g), 100gFX-5920 (the extraordinary fluoropolymer additive of Minnesota Mining and Manufacturing Company) join in mixer, after mixing 20 minutes under room temperature, send in cone-type mixer, force extrusion under room temperature, obtain granular composite assistant (DB-1).
Hereinafter, manufacture example 1～6 and be an illustration for having blended the manufacture of the high density polyethylene (HDPE) pressure resistant pipe material resin raw material of the composite assistant GC-1～GC-6 of the present invention and the performance evaluation after forming tubular product.Manufacture comparative example 1 and be an illustration for having blended the manufacture of the high density polyethylene (HDPE) pressure resistant pipe material resin raw material of the composite assistant DB-1 of comparative example 1 and the performance evaluation after forming tubular product.
Manufacture example 1
By 300gGC-1 and 50Kg high density polyethylene (HDPE) pressure resistant pipe material base resin (when 5Kg loads, MFR is at the PE100 level pipe resin powder of the bimodal molecular weight distribution of 0.2～0.4g/10 minute) use high speed mixing smelting machine mix homogeneously, with double screw extruder at 200 DEG C of extruding pelletizations, shape at 210 DEG C of crowded pipes with single screw rod pipe extruder.After forming tubular product, inside and outside wall is smooth, even tube wall.Further, the oxidation induction period of tubing was more than 120 minutes, and yield strength is 24.1MPa, and impact strength is 55.1KJ/m2.Table 1 illustrates independent base resin and in base resin, has blended the Performance comparision of pipe resin of GC-1.
Manufacture example 2
By 250gGC-2 and 50Kg high density polyethylene (HDPE) pressure resistant pipe material base resin (when 5Kg loads, MFR is at the PE100 level pipe resin powder of the bimodal molecular weight distribution of 0.2～0.4g/10 minute) use high speed mixing smelting machine mix homogeneously, with double screw extruder at 200 DEG C of extruding pelletizations, shape at 210 DEG C of crowded pipes with single screw rod pipe extruder.After forming tubular product, inside and outside wall is smooth, even tube wall.Further, the oxidation induction period of tubing was more than 120 minutes, and yield strength is 25.2MPa, and impact strength is 54.2KJ/m2.Table 1 illustrates independent base resin and in base resin, has blended the Performance comparision of pipe resin of GC-2.
Manufacture example 3
By 200gGC-3 and 50Kg high density polyethylene (HDPE) pressure resistant pipe material base resin (when 5Kg loads, MFR is at the PE100 level pipe resin powder of the bimodal molecular weight distribution of 0.2～0.4g/10 minute) use high speed mixing smelting machine mix homogeneously, with double screw extruder at 200 DEG C of extruding pelletizations, shape at 210 DEG C of crowded pipes with single screw rod pipe extruder.After forming tubular product, inside and outside wall is smooth, even tube wall.Further, the oxidation induction period of tubing was more than 120 minutes, and yield strength is 25.3MPa, and impact strength is 53.4KJ/m2.Table 1 illustrates independent base resin and in base resin, has blended the Performance comparision of pipe resin of GC-3.
Manufacture example 4
By 300gGC-4 and 50Kg high density polyethylene (HDPE) pressure resistant pipe material base resin (when 5Kg loads, MFR is at the PE100 level pipe resin powder of the bimodal molecular weight distribution of 0.2～0.4g/10 minute) use high speed mixing smelting machine mix homogeneously, with double screw extruder at 200 DEG C of extruding pelletizations, shape at 210 DEG C of crowded pipes with single screw rod pipe extruder.After forming tubular product, inside and outside wall is smooth, even tube wall.Further, the oxidation induction period of tubing was more than 120 minutes, and yield strength is 24.8MPa, and impact strength is 55.7KJ/m2.Table 1 illustrates independent base resin and in base resin, has blended the Performance comparision of pipe resin of GC-4.
Manufacture example 5
By 250gGC-5 and 50Kg high density polyethylene (HDPE) pressure resistant pipe material base resin (when 5Kg loads, MFR is at the PE100 level pipe resin powder of the bimodal molecular weight distribution of 0.2～0.4g/10 minute) use high speed mixing smelting machine mix homogeneously, with double screw extruder at 200 DEG C of extruding pelletizations, shape at 210 DEG C of crowded pipes with single screw rod pipe extruder.After forming tubular product, inside and outside wall is smooth, even tube wall.Further, the oxidation induction period of tubing was more than 120 minutes, and yield strength is 25.9MPa, and impact strength is 53.4KJ/m2.Table 1 illustrates independent base resin and in base resin, has blended the Performance comparision of pipe resin of GC-5.
Manufacture example 6
By 200gGC-6 and 50Kg high density polyethylene (HDPE) pressure resistant pipe material base resin (when 5Kg loads, MFR is at the PE100 level pipe resin powder of the bimodal molecular weight distribution of 0.2～0.4g/10 minute) use high speed mixing smelting machine mix homogeneously, with double screw extruder at 200 DEG C of extruding pelletizations, shape at 210 DEG C of crowded pipes with single screw rod pipe extruder.After tube forming, inside and outside wall is smooth, even tube wall.Further, the oxidation induction period of tubing was more than 120 minutes, and yield strength is 24.3MPa, and impact strength is 55.4KJ/m2.Table 1 illustrates independent base resin and in base resin, has blended the Performance comparision of pipe resin of GC-6.
Manufacture comparative example 1
By 200gDB-1 and 50Kg high density polyethylene (HDPE) pressure resistant pipe material base resin (when 5Kg loads, MFR is at the PE100 level pipe resin powder of the bimodal molecular weight distribution of 0.2～0.4g/10 minute) use high speed mixing smelting machine mix homogeneously, with double screw extruder at 200 DEG C of extruding pelletizations, shape at 210 DEG C of crowded pipes with single screw rod pipe extruder.After tube forming, inside and outside wall is smooth, even tube wall.Further, the oxidation induction period of tubing is 35 minutes, and yield strength is 24.0MPa, and impact strength is not for rupture.Table 1 illustrates independent base resin and in base resin, has blended the Performance comparision of pipe resin of DB-1.
Further, table 2 has illustrated the performance test results of the forming tube manufacturing example 1～6 and manufacture comparative example 1.
As shown in Table 1, the composite assistant of the present invention can be obviously improved the processing characteristics of high density polyethylene (HDPE) pressure resistant pipe material resin, antioxygenic property and the mechanical property that autoclave slurry process produces.Further, after having blended the composite assistant of the present invention, the oxidation induction period of tubing has exceeded 120 minutes, impact strength is more than 50KJ/m2.Further, as shown in Table 2, the hydrostatic index of tubing of the φ 32mm × 3mm tubing shaped with the pipe resin raw material of the composite assistant having blended the present invention has reached Standard.
By above example 1～6 and comparative example 1 it can be seen that compared with existing composite assistant DB-1, the composition of the composite assistant of the present invention is more simple, and the consumption of constituent is also more reasonable.And, from table 1,2, after having blended the composite assistant of the present invention, the various physical property of pipe resin are more rational, and the pipe performance such as the processing characteristics of the forming tube front and back change of melt index (specific targets be) and longitudinal welds becomes more excellent.Therefore, after base resin blends the composite assistant of the present invention, can solve the problem that the processing difficulties that the high density polyethylene (HDPE) pressure resistant pipe material resin manufactured through autoclave slurry process occurs when extrusion molding, and appearance poor after forming tubular product, inwall have pointing object or rough, the problems such as sharkskin occur, and, high density polyethylene (HDPE) pressure resistant pipe material can be made to have the antioxygenic property of excellence, mechanical property, environmental stress crack resistance and pressure performance, and disclosure satisfy that the current requirement to PE100 level pressure resistant pipe material.
Claims (11)
1. a high density polyethylene (HDPE) pressure resistant pipe material composite assistant, it is characterised in that
This composite assistant is made up of resisting ageing for long time auxiliary agent 30～50 weight portion, thermally-stabilised auxiliary agent 10～30 weight portion and processing aid 10～30 weight portion, wherein,
Described resisting ageing for long time auxiliary agent selects at least one in the group of free hindered phenol anti-oxidants, amine antioxidants and phosphorus antioxidants composition,
Described thermally-stabilised auxiliary agent at least one in metal soap stabilizer,
Described processing aid is made up of at least one fluoroelastomer.
2. high density polyethylene (HDPE) pressure resistant pipe material composite assistant as claimed in claim 1, wherein, described resisting ageing for long time auxiliary agent is to be blended by hindered phenol anti-oxidants, amine antioxidants, phosphorus antioxidants 1:0.1～10:0.1～10 in mass ratio to form.
3. high density polyethylene (HDPE) pressure resistant pipe material composite assistant as claimed in claim 1 or 2, wherein,
nullDescribed hindered phenol anti-oxidants choosing free 2,6-DI-tert-butylphenol compounds、2,6-di-t-butyl-4-ethyl-phenol、2,6-di-tert-butyl-4-methy phenol、2,6-di-t-butyl-4-normal-butyl phenol，2,6-di-t-butyl-alpha, alpha-dimethyl amino paracresol、2,4,6-tri-butyl-phenol、β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propanoic acid n-octadecane alcohol ester、Styrenated phenol、Butylated octylated phenol、2,2 '-methylene bis (4-methyl-6-tert-butylphenol)、4,4 '-methylene bis (2,6-DI-tert-butylphenol compounds)、Four (3-(3 ',5 '-di-t-butyl-4 '-hydroxy phenyl) propanoic acid) pentaerythritol ester、1,1,At least one in the group of 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane composition.
4. high density polyethylene (HDPE) pressure resistant pipe material composite assistant as claimed in claim 1 or 2, wherein,
Described amine antioxidants selects at least one in the group of free N-phenyl-a-naphthylamine, N-Phenyl beta naphthylamine, N, N '-two-betanaphthyl p-phenylenediamine, acetaldol-alpha-naphthylamine, N-isopropyl-N '-diphenyl-para-phenylene diamine composition.
5. high density polyethylene (HDPE) pressure resistant pipe material composite assistant as claimed in claim 1 or 2, wherein,
Described phosphorus antioxidants select free triphenyl phosphite, phosphorous acid diphenyl monooctyl ester, trisnonyl phenyl phosphite, diphosphorous acid tetramethylolmethane distearyl alcohol ester, phosphorous acid two lauryl, didecyl phosphite, three (2,4-di-t-butyl) phenyl-phosphite, phosphorous acid 4,4-bis-different fork bis-phenol (12-14) carbon Arrcostab composition group at least one.
6. high density polyethylene (HDPE) pressure resistant pipe material composite assistant as claimed in claim 1, wherein,
Described metal soap thermal stabilizers selects at least one in the group of free calcium stearate, magnesium stearate, lithium stearate, zinc stearate, aluminium stearate, sodium stearate, calcium laurate, double stearic acid aluminium composition.
7. high density polyethylene (HDPE) pressure resistant pipe material composite assistant as claimed in claim 1, wherein,
Described fluoroelastomer selects at least one in the group of free FX-5911, FX-5920, FX-5924, VitonFFGB, SOLEFPVDF composition.
8. a preparation method for high density polyethylene (HDPE) pressure resistant pipe material composite assistant, it is the method preparing the high density polyethylene (HDPE) pressure resistant pipe material composite assistant described in claim 1, it is characterised in that
Resisting ageing for long time auxiliary agent 30～50 weight portion, thermally-stabilised auxiliary agent 10～30 weight portion and processing aid 10～30 weight portion are mixed and stirred for after uniformly, extruding pelletization, thus forming granular composite assistant, wherein,
Described resisting ageing for long time auxiliary agent selects at least one in the group of free hindered phenol anti-oxidants, amine antioxidants, phosphorus antioxidants composition,
Described thermally-stabilised auxiliary agent at least one in metal soap stabilizer,
Described processing aid is made up of at least one fluoroelastomer.
9. the resin raw material manufacturing high density polyethylene (HDPE) pressure resistant pipe material, it is characterised in that
Described resin raw material high density polyethylene (HDPE) pressure resistant pipe material composite assistant described in any one in high density polyethylene (HDPE) pressure resistant pipe material base resin and claim 1～7 forms.
10. resin raw material as claimed in claim 9, wherein, relative to described resin raw material total amount, the addition of described high density polyethylene (HDPE) pressure resistant pipe material composite assistant is 0.1～1 weight %.
11. resin raw material as claimed in claim 10, wherein, relative to described resin raw material total amount, the addition of described high density polyethylene (HDPE) pressure resistant pipe material composite assistant is 0.4～0.5 weight %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764954.XA CN105733023B (en) | 2014-12-11 | 2014-12-11 | High density polyethylene (HDPE) pressure resistant pipe material composite assistant and preparation method thereof and the resin raw material containing the composite assistant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764954.XA CN105733023B (en) | 2014-12-11 | 2014-12-11 | High density polyethylene (HDPE) pressure resistant pipe material composite assistant and preparation method thereof and the resin raw material containing the composite assistant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105733023A true CN105733023A (en) | 2016-07-06 |
| CN105733023B CN105733023B (en) | 2018-08-10 |
Family
ID=56241314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410764954.XA Active CN105733023B (en) | 2014-12-11 | 2014-12-11 | High density polyethylene (HDPE) pressure resistant pipe material composite assistant and preparation method thereof and the resin raw material containing the composite assistant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105733023B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610531A (en) * | 2016-12-09 | 2018-10-02 | 中国石油天然气股份有限公司 | Polyvinyl piping materials composite assistant packet and preparation method thereof |
| CN109092375A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The free radical stabilizer of hexamethylene direct oxidation adipic acid |
| CN110100777A (en) * | 2019-03-25 | 2019-08-09 | 广东南风王科技有限公司 | A kind of cordless super strong type cultivation frame |
| CN112898663A (en) * | 2021-01-25 | 2021-06-04 | 孙牡花 | PE composite material and preparation method thereof |
| CN113881151A (en) * | 2020-07-02 | 2022-01-04 | 中国石油天然气股份有限公司 | Special polybutylene resin composition for cold and hot water pipes and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102449059A (en) * | 2009-05-29 | 2012-05-09 | 美利肯公司 | Polymer compositions, articles made from such compositions, and methods for molding such compositions |
| CN103524861A (en) * | 2012-07-05 | 2014-01-22 | 中国石油化工股份有限公司 | High-temperature and high-pressure resistant polyethylene composition as well as preparation method thereof |
-
2014
- 2014-12-11 CN CN201410764954.XA patent/CN105733023B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102449059A (en) * | 2009-05-29 | 2012-05-09 | 美利肯公司 | Polymer compositions, articles made from such compositions, and methods for molding such compositions |
| CN103524861A (en) * | 2012-07-05 | 2014-01-22 | 中国石油化工股份有限公司 | High-temperature and high-pressure resistant polyethylene composition as well as preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610531A (en) * | 2016-12-09 | 2018-10-02 | 中国石油天然气股份有限公司 | Polyvinyl piping materials composite assistant packet and preparation method thereof |
| CN109092375A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The free radical stabilizer of hexamethylene direct oxidation adipic acid |
| CN109092375B (en) * | 2017-06-21 | 2021-06-22 | 中国石油化工股份有限公司 | Free radical stabilizer for preparing adipic acid by direct oxidation of cyclohexane |
| CN110100777A (en) * | 2019-03-25 | 2019-08-09 | 广东南风王科技有限公司 | A kind of cordless super strong type cultivation frame |
| CN113881151A (en) * | 2020-07-02 | 2022-01-04 | 中国石油天然气股份有限公司 | Special polybutylene resin composition for cold and hot water pipes and preparation method thereof |
| CN112898663A (en) * | 2021-01-25 | 2021-06-04 | 孙牡花 | PE composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105733023B (en) | 2018-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105733023A (en) | Composite auxiliary agent for high density polyethylene overpressure resistant tubing, preparation method thereof, and resin raw material containing the composite auxiliary agent | |
| CN102863711B (en) | Heat-resisting PVC high impact-resisting tubular product and preparation method thereof | |
| CN100595229C (en) | Polyethylene color masterbatch and preparing method thereof | |
| CN103571039B (en) | High melting means polypropene composition and preparation method thereof | |
| CN102382344B (en) | Composition for preparing polyethylene pipe with superhigh molecular weight and preparation method thereof | |
| CN103524861B (en) | A kind of pressure polyethylene composition high temperature resistant, high | |
| CN109306109A (en) | A kind of thermoplasticity cross-linking polyethylene materials, preparation method and applications | |
| JP4749725B2 (en) | Polyethylene resin material and hollow molded body using the same | |
| CN102617914A (en) | Polyethylene cable duct | |
| CN104837919A (en) | Heat aging resistant ethylene vinly acetate copolymer composition and process for producing same | |
| CN103382274B (en) | A kind of block copolymerization polypropylene composite additive | |
| CN111607162B (en) | Marine plastic pipe and preparation method thereof | |
| CN103421236A (en) | Polypropylene composition and polypropylene blown film | |
| CN112210146A (en) | Low-sag carbon black master batch and preparation method thereof | |
| CN102295799B (en) | Polyethylene resin composition for pipe | |
| CN103923422A (en) | CPVC with advantages of corrosion resistance and high temperature resistance used for industry and its preparation method | |
| CN102276891A (en) | Polyolefin resin composition for tubing | |
| CN104497393A (en) | Anticorrosive modified polyethylene pipeline and preparation method thereof | |
| MXPA04011608A (en) | Thermoplastic formulations for manufacturing fluid pipes and accessories for home and industrial use, and process for the same. | |
| CN103172937A (en) | Special material for silicane grafted PPR (polypropylene random) pipe and preparation method thereof | |
| CN105237861B (en) | A kind of polyethylene composition of rigidity-toughness balanced | |
| CN106317546A (en) | High-density polyethylene resin for large hollow containers | |
| CN111040307A (en) | Polypropylene corrugated pipe composite material and preparation method of composite polypropylene corrugated pipe | |
| CN108047573B (en) | Special material for PPR (polypropylene random) pipe and preparation method thereof | |
| CN110511517A (en) | A kind of antistatic Teflon special material for tube and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |