CN101812200B - Alpha-crystal form homopolymerized polypropylene composition for water-heater inner containers and preparation method thereof - Google Patents
Alpha-crystal form homopolymerized polypropylene composition for water-heater inner containers and preparation method thereof Download PDFInfo
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Abstract
The invention provides a homopolymerized polypropylene composition for water-heater inner containers, which comprises the following components in portions by weight: (a) 100 portions of homopolymerized polypropylene; (b) 0.01-10 portions of thermal stabilizer; (c) 0.01-10 portions of processing aid; and (d) 0.01-10 portions of alpha-crystal form nucleating agent. The processing aid is selected from one or a plurality of low-molecular-weight ester compounds, metallic soap compounds, stearic acid-compounded ester compounds and amide compounds. The alpha-crystal form homopolymerized polypropylene material of the invention overcomes the defect of insufficient rigidity of the common homopolymerized polypropylene, and has the advantage of high heat distortion temperature; and the tensile strength is greater than or equal to 37 MPa, the bending modulus is greater than or equal to 1800 MPa, and the notch impact strength is greater than or equal to 5 kj/m<2>.
Description
Technical field
The present invention relates to a kind of water heater liner with alpha-crystal form homopolymerized polypropylene mixture and preparation method thereof, be specifically related to be used for civilian and industrial solar water heater and inner container of electric water heater mixture and preparation method thereof.
Background technology
Water-heater mainly contains two kinds of liner materials, stainless steel inner container and enamel inner containers in the market.Stainless steel inner container, manufacturing process is complicated: the various workpiece-heat-insulating layer foamings of shear-punching-drum-weld seam-weld, but it is corrosion-resistant, and resistance to acids and bases is poor, easily fouling, the easy oxidation corrosion of high temperature is met in the weld, finally cause radiator leak to scrap until whole water-heater. stainless material, its withstand voltage degree is little, leaks easily, it is poor to be incubated, and the life-span is short.Enamel inner container is blackening one deck inanimate matter bristol glaze and making on general steel plate, and cost is high, and complete processing requires high, is easy to generate bubble or pinprick in the production process, and enamel fragility is bigger simultaneously, and vibrations, collision are easy to generate fish-scaling effect.In addition, enamel can be gradually in hot water dissolving peel off, technical being called " boiling water weightlessness " phenomenon, this courage is health when intact. but much defective in quality. or year for a long time enamel comes off and can the polluted water corrosion leak. failure rate is very high.More than these factors, all can cause the general steel plate under the enamel coating to expose, form corrosion and leak.Above as can be seen two kinds of liner material manufacturing process complexity, with high costs, there is hidden danger of quality.Along with the expansion in sun power market and to the popularization of rural area direction, many solar energy production producer is all considering how to guarantee to reduce cost in the sun power performance, what this at first considered is exactly the selection and the manufacture craft aspect of sun power inner bag.
Since polypropylene comes out, with outstanding thermal characteristics and mechanical property in a lot of fields, as being widely used in injection moulding, film, the fiber production, this versatility and economy make polypropylene surpass polyvinyl chloride, polystyrene, become to be only second to poly second largest synthetic resins.Especially along with various crystalline polyacrylics have been realized business-like applying, make polypropylene that boundless prospect be arranged on engineering plastics and functional materials.Wherein, the alpha-crystal form nucleator is to use the most sophisticated nucleator in the polypropylene.
The alpha-crystal form nucleator has effectively solved the insufficient shortcoming of common homo-polypropylene rigidity, obviously improves the tensile strength and the modulus in flexure of polypropylene material, and improves the heat-drawn wire 10-15 degree of homo-polypropylene.This makes the nucleater modified homo-polypropylene of alpha-crystal form substitute traditional metal and ceramic water-heater inner bag becomes possibility.Adopt the water heater liner of alpha-crystal form homopolymerized polypropylene manufacturing to have the following advantages: 1. cost is low: relative stainless steel inner container and enamel inner container in the market, on the basis that guarantees the water-heater normal working performance, greatly reduce cost value, increased the more profit margin of water-heater.2. environmental protection: material is environment-friendly materials, and nontoxic, free from extraneous odour can not produce any side effect to people's health.3. seamless leakproof: adopt rotational moulding, blowing, injection moulding or extrude disposal molding, broken through other metal material designs and produced limitation, solved the perishable hidden danger of leaking of metal inner tube weld.Seamless, no solder joint, leakproof, good airproof performance.4. cleaning non-scaling: the polypropylene plastic properties has effectively stoped the formation of incrustation scale, and the water heater liner inwall that this material is made is uniform and smooth, and self does not produce static, is not easy to be etched.5. high temperature resistant: adopt the nucleater modified homo-polypropylene of alpha-crystal form through high temperature test can be anti-high temperature more than 100 ℃.6. good heat insulating: have heat preservation and insulation, increased substantially heat insulation effect, prolonged the duration of service of hot water, heat-insulating property is more effective.7. long service life: alpha-crystal form homopolymerized polypropylene has superior resistance to acids and bases, broad application temperature range.
But solar water heater liner internal temperature under sky solarization situation is very high, generally can reach about 150 ℃.Common alpha-crystal form polypropylene (comprising alpha-crystal form homopolymerized polypropylene) can not satisfy empty requirement of shining usually.
Chinese patent CN 101358012A discloses a kind of water heater liner polypropylene composite, and its formula system is polypropylene and nucleator two components.But this polypropylene composite does not satisfy all requirements of solar water heater, for example empty the solarization.
Therefore, be badly in need of being used to prepare the liner material of water-heater (particularly solar water heater) in this area.
Summary of the invention
The object of the present invention is to provide a kind of particularly material of solar water heater liner of water-heater that is used for, it has high temperature resistant (can satisfy empty requirement of shining usually), corrosion-resistant, water-fast dirt, high strength, hygienic advantages.
The homopolymerization polypropylene composition that one aspect of the present invention provides a kind of water heater liner to use, described composition comprises following component:
(a) homo-polypropylene of 100 weight parts;
(b) in the homo-polypropylene of 100 weight parts, 0.01-10 weight part, better 0.1-5 weight part, better 0.2-3 weight part, the preferably thermo-stabilizer of 0.3-2 weight part;
(c) in the homo-polypropylene of 100 weight parts, 0.01-10 weight part, better 0.05-5 weight part, better 0.1-2 weight part, the processing aid of best 0.5-1 weight part, described processing aid is selected from one or more in lower molecular weight ester cpds, metallic soap compound, stearic acid complex ester compound and the amide compound;
(d) in the homo-polypropylene of 100 weight parts, 0.01-10 weight part, better 0.01-8 weight part, better 0.02-5 weight part, preferably the alpha-crystal form nucleator of 0.03-4 weight part.
In a preferred embodiment of the present invention, described thermo-stabilizer is selected from the mixture of phenolic compound, amine compound, bi-ester of phosphite, acryl functional group and monothioester or a kind of or its mixture in the calixarene; Preferably, described phenolic compound is selected from alkyl list phenol, alkyl bis-phenol, sulfuration bis-phenol, triaizine compounds, hindered phenol compound, half hindered phenol compound, benzoic ether hindered phenol and combination thereof; Preferably, described phenolic compound comprises hindered phenol 1010, hindered phenol 1076, hindered phenol 330, hindered phenol 168, dihydroxyphenyl propane, bisphenol-c, 2,6 ditertiary butyl p cresol, 1,3,5-trimethylammonium-2,4,6-three (3,5-tertiary butyl-4-hydroxy benzyl) benzene, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) Three methyl Benzene and 2,2 '-methylene bis (4-ethyl-6-tert.-butyl phenol) and combination thereof; Preferably, described amine compound is selected from naphthylamines, pentanoic, Ursol D, quinoline and combination thereof; Preferably, described amine compound is selected from diphenyl-para-phenylene diamine, diphenyl-para-phenylene diamine, 4-hydroxy-dodecanoic acid anilide and 4-hydroxyl octadecanoic acid anilide and combination thereof; Preferably, described bi-ester of phosphite is selected from triphenyl phosphite, phosphorous acid hexichol one monooctyl ester, phosphorous acid hexichol ester in one last of the ten Heavenly stems, tricresyl phosphite (nonyl phenyl ester), the hot diphenyl ester of phosphorous acid and combination thereof; Preferably, the mixture of described acryl functional group and monothioester is a Tyox B; Preferably, described calixarene be selected from cup (a 4) aromatic hydrocarbons, cup (6) aromatic hydrocarbons, cup (8) aromatic hydrocarbons, to tertiary butyl cup (4) aromatic hydrocarbons, to tertiary butyl cup (6) aromatic hydrocarbons with to tertiary butyl cup (8) aromatic hydrocarbons and combination thereof.
In a preferred embodiment of the present invention, described lower molecular weight ester cpds comprises the lower molecular weight stearate, as list, two or three stearic acid alkyl esters; Preferably, described lower molecular weight ester cpds comprises methyl stearate, Stearic ethyl stearate, stearic acid propyl ester, butyl stearate, glyceryl monostearate, three stearic acid triglyceride level and combinations thereof; Preferably, described metallic soap compound comprises carboxylate salt, as lead salt, barium salt, cadmium salt, zinc salt and/or the calcium salt of carboxylic acid; Preferably, described metallic soap compound is selected from lead stearate, 2-ethyl acetic acid lead, lead salicylate, tribasic lead stearate, Dythal, tribasic Malaysia lead plumbate, barium stearate, orange osmanthus acid barium, ricinoleate acid barium, cadmium stearate, cadmium recinoleate, calcium stearate, calcium ricinoleate, Zinic stearas, Magnesium Stearate and combination thereof; Preferably, described stearic acid complex ester compound comprises polyvalent alcohol list or many stearates; Preferably, described stearic acid complex ester compound is selected from three Polyglycerine Stearinsaeures, Polyglycerine monostearate, sorbitol monostearate, ethylene glycol monostearate, polyethylene glycol mono stearate,, two Polyglycerine Stearinsaeures, trimerization Stearic diglyceride, Polyglycerine SUNSOFT Q-182S, sorbyl alcohol SUNSOFT Q-182S, Unister E 275, polyglycol distearate, sorbitol anhydride SUNSOFT Q-182S, dimerization Stearic diglyceride and combination thereof; Preferably, described amide compound comprises carboxylic acid amide, as amine hydroxybenzene, stearic amide, ethylene bis stearic acid amide, ricinoleate acid acid amides, orange osmanthus acid acid amides, salicylamide, ethanamide, propionic acid amide, Palmiticacid acid amides and combination thereof.
In a preferred embodiment of the present invention, described α-nucleator comprises inorganic α-nucleator, organic α-nucleator and polymer-type α-nucleator; Preferably, described inorganic α-nucleator comprises talcum powder, silicon-dioxide, mica and combination thereof; Preferably, described organic α-nucleator comprises aryl orthophosphate, sorbyl alcohol type compound, carboxylic metallic salt, dehydrogenation abietic acid and salt, branching amide compound and combination thereof; Preferably, described polymer-type α-nucleator comprises polyvinyl naphthenic hydrocarbon, for example polyvinyl tetramethylene, polyvinyl eyclohexane, polyvinyl pentamethylene, polyvinyl-2-methylcyclohexane, poly 3 methyl butene 1 and combination thereof.
In a preferred embodiment of the present invention, described α-nucleator is selected from talcum powder, silicon-dioxide, phenylformic acid soap, sorbyl alcohol, aryl orthophosphate, carboxylic metallic salt, dehydroabietic acid, dehydroabietic acid soap, one or more of branching acid amides and polyvinyl naphthenic hydrocarbon etc.
The alpha-crystal form homopolymerized polypropylene material that the present invention also provides a kind of water heater liner to use, described material is made by homopolymerization polypropylene composition of the present invention, and described composition comprises following component:
(a) homo-polypropylene of 100 weight parts;
(b) in the homo-polypropylene of 100 weight parts, 0.01-10 weight part, better 0.1-5 weight part, better 0.2-3 weight part, the preferably thermo-stabilizer of 0.3-2 weight part;
(c) in the homo-polypropylene of 100 weight parts, 0.01-10 weight part, better 0.05-5 weight part, better 0.1-2 weight part, the processing aid of best 0.5-1 weight part, described processing aid is selected from one or more in lower molecular weight ester cpds, metallic soap compound, stearic acid complex ester compound and the amide compound;
(d) in the homo-polypropylene of 100 weight parts, 0.01-10 weight part, better 0.01-8 weight part, better 0.02-5 weight part, preferably the alpha-crystal form nucleator of 0.03-4 weight part.
The present invention also provides a kind of method for preparing the alpha-crystal form homopolymerized polypropylene material that water heater liner uses, and described method comprises: with forcing machine with homopolymerization polypropylene composition extruding pelletization of the present invention.
The inner bag that the present invention also provides a kind of water-heater to use, described inner bag is made by alpha-crystal form polypropylene material of the present invention.
The invention provides the purposes of a kind of composition in the preparation water heater liner, described composition comprises following component:
(a) homo-polypropylene of 100 weight parts;
(b) in the homo-polypropylene of 100 weight parts, 0.01-10 weight part, better 0.1-5 weight part, better 0.2-3 weight part, the preferably thermo-stabilizer of 0.3-2 weight part;
(c) in the homo-polypropylene of 100 weight parts, 0.01-10 weight part, better 0.05-5 weight part, better 0.1-2 weight part, the processing aid of best 0.5-1 weight part, described processing aid is selected from one or more in lower molecular weight ester cpds, metallic soap compound, stearic acid complex ester compound and the amide compound;
(d) in the homo-polypropylene of 100 weight parts, 0.01-10 weight part, better 0.01-8 weight part, better 0.02-5 weight part, preferably the alpha-crystal form nucleator of 0.03-4 weight part.
The present invention provides a kind of water-heater on the other hand, and described water-heater comprises the inner bag that water-heater of the present invention is used.
Alpha-crystal form homopolymerized polypropylene material of the present invention has solved the insufficient shortcoming of common homo-polypropylene rigidity, heat-drawn wire height, tensile strength 〉=37MPa, modulus in flexure 〉=1800MPa, notched Izod impact strength 〉=5KJ/m
2Adopt the water heater liner of this material preparation to have excellent internal surface glossiness, excellent electric insulating, high temperature resistant, water-fast dirt, high strength, wholesomeness and resistance to pressure, compare with ceramic liner with metal and have with short production cycle and the low advantage of tooling cost.
Embodiment
" scope " disclosed herein is with the form of the lower limit and the upper limit.Can be respectively one or more lower limits and one or more upper limit.Given range limits by a selected lower limit and a upper limit.The border that the selected lower limit and the upper limit define special scope.All can carry out restricted portion by this way and comprise with capable of being combined, and promptly any lower limit can be combined to form a scope with any upper limit.For example, listed the scope of 60-120 and 80-110, be interpreted as that the scope of 60-110 and 80-120 also reckons with at special parameter.In addition, if if the minimum extent value of listing 1 and 2 and listed maximum range value 3,4 and 5, then Xia Mian scope could all reckon with: 1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless have other the explanation, each components contents scope of composition with and preferable range between can be combined to form new technical scheme mutually.
In the present invention, unless other explanations are arranged, the technical characterictic of each technical scheme can be combined to form new technical scheme mutually.For concise and to the point purpose, the applicant has omitted the specific descriptions of these combinations in specification sheets, but can think that the open scope of this specification sheets has specifically comprised these technical schemes that obtain by combination.
In the present invention, unless other explanations are arranged, the multicomponent mixture of described each element of " its combination " expression, for example two kinds, three kinds, four kinds and up to the multicomponent mixture of maximum possible.
In the present invention, unless other explanations are arranged, all " parts " and percentage ratio (%) all refer to weight percentage.
In the present invention, unless other explanations are arranged, the percentage ratio sum of each component is 100% in all compositions.
In the present invention, unless other explanations are arranged, numerical range " a-b " expression a represents that to the breviary of any real number combination between the b wherein a and b are real numbers.For example the whole real numbers between " 0-5 " have all been listed in numerical range " 0-5 " expression herein, and " 0-5 " just the breviary of these combinations of values represents.
In the present invention, unless other explanations are arranged, integer numerical range " a-b " expression a represents that to the breviary of the combination of the arbitrary integer between the b wherein a and b are integers.For example integer numerical range " 1-N " expression 1,2 ... N, wherein N is an integer.
Mention all documents (comprising patent disclosure text and non-patent publication us) in this manual and all be inserted in this in full by reference, as the part of this specification sheets.For the purpose of concise and to the point, this specification sheets no longer is described the full text of above-mentioned document, but does not represent that the content of above-mentioned document is not open in this manual.
If do not spell out, then used term " a kind of " is meant " at least a " among the present invention.
In the present invention, unless other explanations are arranged, described " alkyl " expression C1-C8 alkyl, for example C1-C6 alkyl, C1-C4 alkyl better are methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl and octyl group.
In the present invention, unless other explanations are arranged, described " aryl " expression C6-C20 aryl, for example C6-C12 aryl, C6-C10 aryl better are phenyl etc.
In the present invention, unless other explanations are arranged, described " water-heater " comprise electric water heater, solar water heater etc. commonly used be used to add the hot water auto levelizer.
In the present invention, unless other explanations are arranged, described " inner bag " expression is used in the water-heater storing and otherwise makes water rest on any device of water-heater, for example water tank or the like.
In the present invention, unless other explanations are arranged, described " lower molecular weight " generally represents molecular weight less than 1000, better less than 800, better less than 500, preferably less than 300.Preferably, described " lower molecular weight " expression 10-1000, better 20-800, better 30-500, the preferably molecular weight of 50-300.
The homopolymerization polypropylene composition that one aspect of the present invention provides a kind of water heater liner to use, described composition comprises following component:
(a) homo-polypropylene of 100 weight parts;
(b) in the homo-polypropylene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the homo-polypropylene of 100 weight parts, the processing aid of 0.01-10 weight part, described processing aid are selected from one or more in lower molecular weight ester cpds, metallic soap compound, stearic acid complex ester compound and the amide compound;
(d) in the homo-polypropylene of 100 weight parts, the alpha-crystal form nucleator of 0.01-10 weight part.
In the present invention, described homo-polypropylene is conventional, and it can be a polypropylene commonly used arbitrarily in this area.In a preferred embodiment of the present invention, described homo-polypropylene is the homo-polypropylene of melt flow rate (MFR) at 0.01-100g/10min.In another preferred embodiment of the present invention, described homo-polypropylene comprises PP B1101 (available from platformization), PP H710 (available from Korea S SK), PP T30S (available from the Lanzhou petrochemical industry), PPS700 (available from raising sub-petrochemical industry), PP S900 (available from the Lanzhou petrochemical industry), PP YPJ3860 (available from raising sub-petrochemical industry).
In the present invention, described thermo-stabilizer is conventional, and it can be a thermo-stabilizer commonly used in this area.In a preferred embodiment of the present invention, described thermo-stabilizer is selected from the mixture of phenolic compound, amine compound, bi-ester of phosphite, acryl functional group and monothioester or a kind of or its mixture in the calixarene.
In the present invention, phenolic compound as thermo-stabilizer is conventional in the art, and it can be such as but not limited to alkyl list phenol, alkyl bis-phenol, sulfuration bis-phenol, triaizine compounds, hindered phenol compound, half hindered phenol compound, benzoic ether hindered phenol and combination thereof etc.In the art, Chang Yong phenolic compound comprises hindered phenol 1010, hindered phenol 1076, hindered phenol 330, dihydroxyphenyl propane, bisphenol-c, 2,6 ditertiary butyl p cresol, 1,3,5-trimethylammonium-2,4,6-three (3,5-tertiary butyl-4-hydroxy benzyl) benzene, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) Three methyl Benzene and 2,2 '-methylene bis (4-ethyl-6-tert.-butyl phenol) and combination thereof.In a preferred embodiment of the present invention, described phenolic compound is selected from Irganox 1010 (available from vapour Bagong department).
In the present invention, be conventional as the amine compound of thermo-stabilizer, it can be such as but not limited to naphthylamines, pentanoic, Ursol D, quinoline and combination thereof.In a preferred embodiment of the present invention, described amine compound is selected from diphenyl-para-phenylene diamine, diphenyl-para-phenylene diamine, 4-hydroxy-dodecanoic acid anilide and 4-hydroxyl octadecanoic acid anilide and combination thereof.In a preferred embodiment of the present invention, described amine compound is selected from NC-GX45 (available from the Guangzhou promise company of speeding).
In the present invention, bi-ester of phosphite as thermo-stabilizer is conventional, and it can be such as but not limited to triphenyl phosphite, three (2.4-di-tert-butyl-phenyl) phosphorous acid ester, phosphorous acid hexichol one monooctyl ester, phosphorous acid hexichol ester in one last of the ten Heavenly stems, tricresyl phosphite (nonyl phenyl ester), the hot diphenyl ester of phosphorous acid and combination thereof.In a preferred embodiment of the present invention, described bi-ester of phosphite is selected from 627A (available from Compton Co.,Ltd).
In the present invention; as the acryl functional group of thermo-stabilizer and the mixture of monothioester is conventional, and it can be such as but not limited to Tyox B, the two stearyl alcohol esters of thio-2 acid, two 14 esters of thio-2 acid, the two tridecanol esters of thio-2 acid and combination thereof.In a preferred embodiment of the present invention, the mixture of described acryl functional group and monothioester is selected from DLTDP (available from Albemarle Corporation).
In the present invention, be conventional as the calixarene of thermo-stabilizer, it can be such as but not limited to cup (n) aromatic hydrocarbons, and wherein n is 1 to 10 positive integer, for example cup (4) aromatic hydrocarbons, cup (6) aromatic hydrocarbons and glass (8) aromatic hydrocarbons.Described calixarene also can be the derivative of above-mentioned cup (n) aromatic hydrocarbons, as to tertiary butyl cup (n) aromatic hydrocarbons, for example to tertiary butyl cup (4) aromatic hydrocarbons, to tertiary butyl cup (6) aromatic hydrocarbons with to tertiary butyl cup (8) aromatic hydrocarbons.In a preferred embodiment of the present invention, described calixarene is selected from tertiary butyl cup (8) aromatic hydrocarbons (available from lark prestige company).
In homopolymerization polypropylene composition of the present invention, the consumption of described thermo-stabilizer is generally the 0.01-10 weight part, better 0.1-5 weight part, and better 0.2-3 weight part, best 0.3-2 weight part is in the homo-polypropylene of 100 weight parts.
In the present invention, the lower molecular weight ester cpds that is used as described processing aid is conventional, and it can be such as but not limited to the lower molecular weight stearate, as list, two or three stearic acid alkyl esters.In a preferred embodiment of the present invention, described lower molecular weight ester cpds comprises methyl stearate, Stearic ethyl stearate, stearic acid propyl ester, butyl stearate, glyceryl monostearate, three stearic acid triglyceride level and combinations thereof.In another example of the present invention, described lower molecular weight ester cpds is selected from glyceryl monostearate (available from vapour Bagong department).
In the present invention, the metallic soap compound that is used as described processing aid is conventional, and it can be such as but not limited to carboxylate salt, as lead salt, barium salt, cadmium salt, zinc salt and/or the calcium salt of carboxylic acid.In a preferred embodiment of the present invention, described metallic soap compound is selected from lead stearate, 2-ethyl acetic acid lead, lead salicylate, tribasic lead stearate, Dythal, tribasic Malaysia lead plumbate, barium stearate, orange osmanthus acid barium, ricinoleate acid barium, cadmium stearate, cadmium recinoleate, calcium stearate, calcium ricinoleate, Zinic stearas, Magnesium Stearate and combination thereof.In another preferred embodiment of the present invention, described metallic soap compound is selected from Zinic stearas (available from Shandong friend and auxiliary agent company limited).
In the present invention, the stearic acid complex ester compound that is used as described processing aid is conventional, and it can be such as but not limited to polyvalent alcohol list or many stearates.In a preferred embodiment of the present invention, described stearic acid complex ester compound is selected from three Polyglycerine Stearinsaeures, Polyglycerine monostearate, sorbitol monostearate, ethylene glycol monostearate, polyethylene glycol mono stearate,, two Polyglycerine Stearinsaeures, trimerization Stearic diglyceride, Polyglycerine SUNSOFT Q-182S, sorbyl alcohol SUNSOFT Q-182S, Unister E 275, polyglycol distearate, sorbitol anhydride SUNSOFT Q-182S, dimerization Stearic diglyceride and combination thereof.In another preferred embodiment of the present invention, described stearic acid complex ester compound is selected from three Polyglycerine Stearinsaeures (available from the logical food ingredients company limited in sky, Zhengzhou).
In the present invention, amide compound as described processing aid is conventional, it can be such as but not limited to carboxylic acid amide, as amine hydroxybenzene, stearic amide, ethylene bis stearic acid amide, ricinoleate acid acid amides, orange osmanthus acid acid amides, salicylamide, ethanamide, propionic acid amide, Palmiticacid acid amides and combination thereof.In a preferred embodiment of the present invention, described amide compound is selected from amine hydroxybenzene (available from Lu Bo chemical company).
In homopolymerization polypropylene composition of the present invention, the consumption of described processing aid is generally the 0.01-10 weight part, better 0.05-5 weight part, and better 0.1-2 weight part, best 0.5-1 weight part is in the homo-polypropylene of 100 weight parts.
In the present invention, described α-nucleator is conventional, and which α-nucleator those of ordinary skill in the art can direct derivation goes out in conjunction with its expertise again according to description of the invention and can be used for the present invention.Usually, be used for being divided into inorganic α-nucleator, organic α-nucleator and polymer-type α-nucleator the α-nucleator of polypropylene (as homo-polypropylene).Usually, inorganic α-nucleator comprises talcum powder, silicon-dioxide, mica and combination thereof.Usually, organic α-nucleator comprises aryl orthophosphate, sorbyl alcohol type compound, carboxylic metallic salt, dehydrogenation abietic acid and salt, branching amide compound and combination thereof.Usually, described polymer-type α-nucleator comprises polyvinyl naphthenic hydrocarbon, for example polyvinyl tetramethylene, polyvinyl eyclohexane, polyvinyl pentamethylene, polyvinyl-2-methylcyclohexane, poly 3 methyl butene 1 and combination thereof.
In the present invention, aryl orthophosphate as α-nucleator mainly includes but not limited to two (2, the 4-di-tert-butyl-phenyl) sodium phosphates, [2,2 methylene radical-two (4,6-di-n-butyl phenol) sodium phosphate], [methylene-bis (2, the 4-di-tert-butyl-phenyl) aluminum phosphate] and composition thereof.
In the present invention, mainly include but not limited to Millad3905, Millad3940, the Millad3988 of Milliken Corp. as the sorbyl alcohol type compound of α-nucleator; The TM-1 of Shanxi chemical institute, TM-2, TM-6; The SKY2-5988 of Songzi City, Hubei South Sea chemical industry company limited; And the ZG3 and the combination thereof of a Yantai Chu synthetic chemistry company limited.
In the present invention, the carboxylic metallic salt as α-nucleator mainly includes but not limited to the p-tert-butyl benzoic acid oxyaluminum; The sodium of phenylformic acid, hexanodioic acid, diphenyl acetic acid, sebacic acid, phthalic acid, iron, aluminium, titanium salt and combination thereof.
In the present invention, mainly include but not limited to sylvic acid and an alkali metal salt thereof, for example available from KM-1300, the KM-1500 of Japan waste river company and KM-1600 etc. as the dehydrogenation abietic acid and the salt thereof of α-nucleator.
In the present invention, the branching amide compound as α-nucleator mainly includes but not limited to 1,3,5-three t-butyl carboxamide base benzene etc.
In a preferred embodiment of the present invention, described α-nucleator is selected from talcum powder, silicon-dioxide, phenylformic acid soap, sorbyl alcohol, aryl orthophosphate, carboxylic metallic salt, dehydroabietic acid, dehydroabietic acid soap, one or more of branching acid amides and polyvinyl naphthenic hydrocarbon etc.
In homopolymerization polypropylene composition of the present invention, the consumption of described α-nucleator is generally the 0.01-10 weight part, better 0.01-8 weight part, and better 0.02-5 weight part, best 0.03-4 weight part is in the homo-polypropylene of 100 weight parts.
In the present invention, polymer composition of the present invention can also comprise other additives that usually use this area, for example antioxidant, static inhibitor, whipping agent, lubricant, impact modifier, softening agent, tinting material and weighting agent.
In the present invention, antioxidant can be any antioxidant that usually use this area.In according to a preferred embodiment of the invention, antioxidant is selected from following material: butylation toluene (BHT), phenyl-B-naphthylamines, alkyl paraquinones, thioether, salol, sulfydryl thioether, sulfo--propionic ester, organo phosphorous compounds, dithio sulphonate, amidate, hydrazine class, aromatic amine compound and their combination.
In the present invention, static inhibitor can be any static inhibitor that usually use this area.In according to a preferred embodiment of the invention, static inhibitor is selected from following compound: quaternary ammonium salt, ethoxylated amine, aliphatic ester and sulfonation paraffin and their combination.
In the present invention, whipping agent can be the normally used any whipping agent in this area.In according to a preferred embodiment of the invention, whipping agent is selected from following material: nitrogen, carbonic acid gas, air, butane, pentane, sherwood oil, methyl chlorofluoride, azobisformamide ABFA, the two isobutyl esters of azo and their combination.
In the present invention, lubricant can be the normally used any lubricant in this area.In a preferred embodiment of the invention, lubricant is selected from aliphatic ester class (for example, the direactive glyceride of lipid acid) and their combination.
In the present invention, softening agent can be the normally used any plasticizer in this area.In a preferred embodiment of the invention, softening agent is selected from following material: terephthalate, phthalic ester, aliphatic dibasic esters, phosphoric acid ester, clorafin and their combination.
In the present invention, weighting agent can be any weighting agent, but is preferably selected from following material: lime carbonate, the glass fibre with circle and non-circular cross sections, sheet glass, granulated glass sphere, carbon fiber, talcum powder, mica, wollastonite, calcined clay, kaolin, diatomite, sal epsom, Magnesium Silicate q-agent, barium sulfate, titanium dioxide, aluminium carbonate sodium, barium ferrite, potassium titanate and their mixture.
Glass fibre with non-circular cross sections is meant the glass fibre with following cross section, and described cross section has the major axis of long slant range in the vertical vertical and cross section taken in correspondence with glass fibre.Non-circular cross sections has in the cross section taken in correspondence perpendicular to the minor axis of long slant range on the direction of major axis.The non-circular cross sections of fiber can have multiple shape, comprises cocoon shape (8 font), rectangle, ellipse, subtriangular, Polygons and rectangle.It should be appreciated by those skilled in the art that cross section can have other shapes.The ratio of the length of major axis and the length of minor axis is preferably between about 1.5: 1 and about 6: 1.This ratio more preferably between about 2: 1 and 5: 1, yet more preferably between about 3: 1 to about 4: 1.Suitable glass fibre has disclosed in EP 0190001 and EP 0196194.
The alpha-crystal form homopolymerized polypropylene material that the present invention provides a kind of water heater liner to use on the other hand, described material is made by homopolymerization polypropylene composition of the present invention, and described composition comprises following component:
(a) homo-polypropylene of 100 weight parts;
(b) in the homo-polypropylene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the homo-polypropylene of 100 weight parts, the processing aid of 0.01-10 weight part, described processing aid are selected from one or more in lower molecular weight ester cpds, metallic soap compound, stearic acid complex ester compound and the amide compound;
(d) in the homo-polypropylene of 100 weight parts, the alpha-crystal form nucleator of 0.01-10 weight part.
The present invention provides a kind of method for preparing the alpha-crystal form homopolymerized polypropylene material that water heater liner uses on the other hand, and described method comprises: with forcing machine with homopolymerization polypropylene composition extruding pelletization of the present invention.
In a preferred embodiment of the present invention, described water heater liner is as follows with the preparation method of polypropylene material:
Is that melting mixing is disperseed in 40: 1 the twin screw extruder with homo-polypropylene of the present invention, thermo-stabilizer, processing aid, alpha-crystal form nucleator in length-to-diameter ratio, and extruding pelletization finally obtains product.
In the present invention, available other materials also can be with described homo-polypropylene, thermo-stabilizer, processing aid, alpha-crystal form nucleator extruding pelletization in the homopolymerization polypropylene composition of the present invention.
The inner bag that the present invention also provides a kind of water-heater to use, described inner bag is made by alpha-crystal form polypropylene material of the present invention.
Usually, the technology for preparing described inner bag includes but not limited to rotational moulding, blowing and working method such as extrudes.
The present invention also provides the purposes of a kind of composition in the preparation water heater liner, and described composition comprises following component:
(a) homo-polypropylene of 100 weight parts;
(b) in the homo-polypropylene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the homo-polypropylene of 100 weight parts, the processing aid of 0.01-10 weight part, described processing aid are selected from one or more in lower molecular weight ester cpds, metallic soap compound, stearic acid complex ester compound and the amide compound;
(d) in the homo-polypropylene of 100 weight parts, the alpha-crystal form nucleator of 0.01-10 weight part.
Product of the present invention, solved the insufficient shortcoming of common homo-polypropylene rigidity, tensile strength 〉=37MPa, modulus in flexure 〉=1800MPa, notched Izod impact strength 〉=5KJ/m2, adopt the water heater liner of this material preparation to have excellent internal surface glossiness, excellent electric insulating and resistance to pressure, compare with ceramic liner with metal and have with short production cycle and the low advantage of tooling cost.
Further illustrate the present invention below in conjunction with embodiment.Should be appreciated that following embodiment only is used for illustration purpose, is not limited to the present invention.
Embodiment
Embodiment 1
With 100 kilograms of homo-polypropylene PP B1101 (platformization), 0.5 kilogram of thermo-stabilizer Irganox 1010 (CIBA company), 0.5 kilogram of Irganox 168 (CIBA company), 0.5 the kilogram processing aid EBS (chemical industry is won in the Shandong), 0.01 kilogram two (3,4-dimethyl benzal) sorbyl alcohol (DMDBS) (Beijing University's Fine Chemical Works) is that melting mixing is disperseed in 40: 1 the twin screw extruder in length-to-diameter ratio, extrusion temperature is 200 ℃, extruding pelletization finally obtains the homo-polypropylene material.
Above-mentioned homo-polypropylene material has solved the insufficient shortcoming of common homo-polypropylene rigidity, tensile strength 〉=37MPa, modulus in flexure 〉=1800MPa, notched Izod impact strength 〉=5KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ℃ | ISO75/1-93 | 118 |
| Tensile strength | MPa | ISO527/2-93 | 38 |
| Elongation at break | ％ | ISO527/2-93 | 50 |
| Flexural strength | MPa | ISO178-93 | 56 |
| Modulus in flexure | MPa | ISO178-93 | 1850 |
| Notched Izod impact strength | KJ/m 2 | ISO180-93 | 5.6 |
Adopt extruding-out process to be processed into water heater liner embodiment 1 gained material, be processed into solar water heater then.This solar water heater voltage-withstand test, the empty solarization are tested and the full water test, and test result is as follows:
Voltage withstand class: 2.0MPa (wall thickness 5mm).
Full water shines not have in 38 days and leaks and metamorphism, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.
Low-temperature test 8 days, daytime temperature 0-2 ℃, night-5 are to 2 ℃, and nothing is leaked.
Freezer test 7 days, outside temperature-20 ℃ does not have distortion, leaks.
The empty solarization do not have the distortion flawless in 6 days, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.During empty the solarization, survey the inner bag temperature, the part reaches 145 ℃ of high temperature.
Embodiment 2
With 100 kilograms of homo-polypropylene PP S700 (raising sub-petrochemical industry), 0.5 kilogram of thermo-stabilizer Irganox1010 (CIBA company), 0.5 kilogram of Irganox 168 (CIBA company), 0.5 kilogram processing aid EBS (chemical industry win in the Shandong), 0.2 kilogram of polyvinyl pentamethylene (Shanghai traditional Chinese medicines) are melting mixing dispersion in 40: 1 the twin screw extruder in length-to-diameter ratio, extrusion temperature is 200 ℃, extruding pelletization finally obtains the homo-polypropylene material.
Above-mentioned homo-polypropylene material has solved the insufficient shortcoming of common homo-polypropylene rigidity, tensile strength 〉=37MPa, modulus in flexure 〉=1800MPa, notched Izod impact strength 〉=5KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ℃ | ISO75/1-93 | 117 |
| Tensile strength | MPa | ISO527/2-93 | 39 |
| Elongation at break | ％ | ISO527/2-93 | 70 |
| Flexural strength | MPa | ISO178-93 | 58 |
| Modulus in flexure | MPa | ISO178-93 | 2000 |
| Notched Izod impact strength | KJ/m 2 | ISO180-93 | 6.2 |
Adopt roll moulding shaping technology to be processed into water heater liner embodiment 2 gained materials, be processed into solar water heater then.This solar water heater is carried out voltage-withstand test, empty solarization test and full water test, and test result is as follows:
Voltage withstand class: 2.0MPa (wall thickness 5mm).
Full water shines not have in 38 days and leaks and metamorphism, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.
Low-temperature test 8 days, daytime temperature 0-2 ℃, night-5 are to 2 ℃, and nothing is leaked.
Freezer test 7 days, outside temperature-20 ℃ does not have distortion, leaks.
The empty solarization do not have the distortion flawless in 6 days, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.During empty the solarization, survey the inner bag temperature, the part reaches 147 ℃ of high temperature.
Embodiment 3
With 100 kilograms of homo-polypropylene PP H710 (Korea S SK), 0.35 kilogram of thermo-stabilizer Irganox1010 (CIBA company), 0.35 kilogram of Irganox 168 (CIBA company), 0.2 the kilogram processing aid Zinic stearas (Shandong friend and auxiliary agent), 1.1 kilogram 1,3,5-three t-butyl carboxamide base benzene (Shanghai traditional Chinese medicines) are that melting mixing is disperseed in 40: 1 the twin screw extruder in length-to-diameter ratio, extrusion temperature is 200 ℃, extruding pelletization finally obtains the homo-polypropylene material.
Above-mentioned homo-polypropylene material has solved the insufficient shortcoming of common homo-polypropylene rigidity, tensile strength 〉=37MPa, modulus in flexure 〉=1800MPa, notched Izod impact strength 〉=5KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ℃ | ISO75/1-93 | 118 |
| Tensile strength | MPa | ISO527/2-93 | 38 |
| Elongation at break | ％ | ISO527/2-93 | 75 |
| Flexural strength | MPa | ISO178-93 | 59 |
| Modulus in flexure | MPa | ISO178-93 | 2100 |
| Notched Izod impact strength | KJ/m 2 | ISO180-93 | 6.5 |
Adopt the blow molding processes to become water heater liner embodiment 3 gained materials, be processed into solar water heater then.This solar water heater voltage-withstand test, the empty solarization are tested and the full water test, and test result is as follows:
Voltage withstand class: 2.3MPa (wall thickness 5mm).
Full water shines not have in 38 days and leaks and metamorphism, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.
Low-temperature test 8 days, daytime temperature 0-2 ℃, night-5 are to 2 ℃, and nothing is leaked.
Freezer test 7 days, outside temperature-20 ℃ does not have distortion, leaks.
The empty solarization do not have the distortion flawless in 6 days, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.During empty the solarization, survey the inner bag temperature, the part reaches 145 ℃ of high temperature.
Embodiment 4
With 100 kilograms of homo-polypropylene PP S900 (Lanzhou petrochemical industry), 0.45 kilogram of thermo-stabilizer Irganox1010 (CIBA company), 0.45 kilogram of Irganox 168 (CIBA company), 0.2 kilogram processing aid calcium stearate (chemical industry win in the Shandong), 3.6 kilograms of dehydroabietic acid potassium (Shanghai traditional Chinese medicines) are melting mixing dispersion in 40: 1 the twin screw extruder in length-to-diameter ratio, extrusion temperature is 200 ℃, extruding pelletization finally obtains the homo-polypropylene material.
Above-mentioned homo-polypropylene material has solved the insufficient shortcoming of common homo-polypropylene rigidity, tensile strength 〉=37MPa, modulus in flexure 〉=1800MPa, notched Izod impact strength 〉=5KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ℃ | ISO75/1-93 | 119 |
| Tensile strength | MPa | ISO527/2-93 | 38.5 |
| Elongation at break | ％ | ISO527/2-93 | 78 |
| Flexural strength | MPa | ISO178-93 | 60 |
| Modulus in flexure | MPa | ISO178-93 | 2050 |
| Notched Izod impact strength | KJ/m | ISO180-93 | 7.0 |
Adopt the blow molding processes to become water heater liner embodiment 4 gained materials, be processed into solar water heater then.This solar water heater voltage-withstand test, the empty solarization are tested and the full water test, and test result is as follows:
Voltage withstand class: 2.4MPa (wall thickness 5mm).
Full water shines not have in 38 days and leaks and metamorphism, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.
Low-temperature test 8 days, daytime temperature 0-2 ℃, night-5 are to 2 ℃, and nothing is leaked.
Freezer test 7 days, outside temperature-20 ℃ does not have distortion, leaks.
The empty solarization do not have the distortion flawless in 6 days, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.During empty the solarization, survey the inner bag temperature, the part reaches 142 ℃ of high temperature.
Embodiment 5
With 100 kilograms of homo-polypropylene PP YPJ3860 (raising sub-petrochemical industry), 0.45 kilogram of thermo-stabilizer Irganox1010 (CIBA company), 0.45 kilogram of Irganox 168 (CIBA company), 0.2 kilogram processing aid calcium stearate (chemical industry win in the Shandong), 1.5 kilograms of p-tert-butyl benzoic acid oxyaluminum (Shanghai traditional Chinese medicines) are melting mixing dispersion in 40: 1 the twin screw extruder in length-to-diameter ratio, extrusion temperature is 200 ℃, extruding pelletization finally obtains the homo-polypropylene material.
Above-mentioned homo-polypropylene material has solved the insufficient shortcoming of common homo-polypropylene rigidity, tensile strength 〉=37MPa, modulus in flexure 〉=1800MPa, notched Izod impact strength 〉=5KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ℃ | ISO75/1-93 | 121 |
| Tensile strength | MPa | ISO527/2-93 | 37.5 |
| Elongation at break | ％ | ISO527/2-93 | 81 |
| Flexural strength | MPa | ISO178-93 | 58 |
| Modulus in flexure | MPa | ISO178-93 | 1950 |
| Notched Izod impact strength | KJ/m 2 | ISO180-93 | 7.1 |
Adopt extruding-out process to be processed into water heater liner embodiment 5 gained materials, be processed into solar water heater then.This solar water heater voltage-withstand test, the empty solarization are tested and the full water test, and test result is as follows:
Voltage withstand class: 2.2MPa (wall thickness 5mm).
Full water shines not have in 38 days and leaks and metamorphism, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.
Low-temperature test 8 days, daytime temperature 0-2 ℃, night-5 are to 2 ℃, and nothing is leaked.
Freezer test 7 days, outside temperature-20 ℃ does not have distortion, leaks.
The empty solarization do not have the distortion flawless in 6 days, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.During empty the solarization, survey the inner bag temperature, the part reaches 143 ℃ of high temperature.
Comparative Examples 1
Be used for the composition of water heater liner according to embodiment 1 preparation of CN101358012A, and the method identical with the embodiment of the invention 1 made inner bag and solar water heater.This solar water heater voltage-withstand test, the empty solarization are tested and the full water test, and test result is as follows:
Voltage withstand class: 1.2MPa (wall thickness 5mm).
Full water shines after 18 days and occurs leaking and metamorphism, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.
Behind the low-temperature test 3 days, daytime temperature 0-2 ℃, night-5 occur leaking to 2 ℃.
After the freezer test 2 days, outside temperature-20 ℃ distortion occurs, leaks.
Distortion appears in empty the solarization after 2 days, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.During empty the solarization, survey the inner bag temperature, the part reaches 143 ℃ of high temperature.
Embodiment 6
With 100 kilograms of homo-polypropylene PP B1101 (platformization), 2 kilograms of amine thermo-stabilizer NC-GX45 (the Guangzhou promise is speeded), 0.05 kilogram processing aid glyceryl monostearate (vapour crust), 0.03 kilogram of inorganic nucleator 5000 order talcum powder (Liaoning Heshan chemical industry) are melting mixing dispersion in 40: 1 the twin screw extruder in length-to-diameter ratio, extrusion temperature is 200 ℃, extruding pelletization finally obtains the homo-polypropylene material.
Above-mentioned homo-polypropylene material has solved the insufficient shortcoming of common homo-polypropylene rigidity, tensile strength 〉=37MPa, modulus in flexure 〉=1800MPa, notched Izod impact strength 〉=5KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ℃ | ISO75/1-93 | 120 |
| Tensile strength | MPa | ISO527/2-93 | 37.5 |
| Elongation at break | ％ | ISO527/2-93 | 92 |
| Flexural strength | MPa | ISO178-93 | 59 |
| Modulus in flexure | MPa | ISO178-93 | 1890 |
| Notched Izod impact strength | KJ/m 2 | ISO180-93 | 7.8 |
Adopt the blow molding processes to become water heater liner embodiment 6 gained materials, be processed into solar water heater then.This solar water heater voltage-withstand test, the empty solarization are tested and the full water test, and test result is as follows:
Voltage withstand class: 2.25MPa (wall thickness 5mm).
Full water shines not have in 38 days and leaks and metamorphism, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.
Low-temperature test 8 days, daytime temperature 0-2 ℃, night-5 are to 2 ℃, and nothing is leaked.
Freezer test 7 days, outside temperature-20 ℃ does not have distortion, leaks.
The empty solarization do not have the distortion flawless in 6 days, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.During empty the solarization, survey the inner bag temperature, the part reaches 143 ℃ of high temperature.
Embodiment 7
With 100 kilograms of homo-polypropylene PP B1101 (Korea S SK), 0.35 kilogram of thermo-stabilizer 627A (Compton), 0.2 kilogram processing aid calcium stearate (chemical industry win in the Shandong), 1.1 kilograms of triphenyl phosphite TPP (vapour crust) are melting mixing dispersion in 40: 1 the twin screw extruder in length-to-diameter ratio, extrusion temperature is 200 ℃, extruding pelletization finally obtains the homo-polypropylene material.
Above-mentioned homo-polypropylene material has solved the insufficient shortcoming of common homo-polypropylene rigidity, tensile strength 〉=37MPa, modulus in flexure 〉=1800MPa, notched Izod impact strength 〉=5KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ℃ | ISO75/1-93 | 123 |
| Tensile strength | MPa | ISO527/2-93 | 39.5 |
| Elongation at break | ％ | ISO527/2-93 | 78 |
| Flexural strength | MPa | ISO178-93 | 59 |
| Modulus in flexure | MPa | ISO178-93 | 1950 |
| Notched Izod impact strength | KJ/m 2 | ISO180-93 | 6.9 |
Adopt the blow molding processes to become water heater liner embodiment 7 gained materials, be processed into solar water heater then.This solar water heater voltage-withstand test, the empty solarization are tested and the full water test, and test result is as follows:
Voltage withstand class: 2.35MPa (wall thickness 5mm).
Full water shines not have in 38 days and leaks and metamorphism, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.
Low-temperature test 8 days, daytime temperature 0-2 ℃, night-5 are to 2 ℃, and nothing is leaked.
Freezer test 7 days, outside temperature-20 ℃ does not have distortion, leaks.
The empty solarization do not have the distortion flawless in 6 days, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.During empty the solarization, survey the inner bag temperature, the part reaches 147 ℃ of high temperature.
Embodiment 8
With 100 kilograms of homo-polypropylene PP B1101 (platformization), 0.35 kilogram of thermo-stabilizer DLTDP (refined treasured), 0.2 kilogram processing aid glyceryl monostearate (vapour crust), 1.1 kilograms of sodium-acetates (Shanghai chemical reagent work) are melting mixing dispersion in 40: 1 the twin screw extruder in length-to-diameter ratio, extrusion temperature is 200 ℃, extruding pelletization finally obtains the homo-polypropylene material.
Above-mentioned homo-polypropylene material has solved the insufficient shortcoming of common homo-polypropylene rigidity, tensile strength 〉=37MPa, modulus in flexure 〉=1800MPa, notched Izod impact strength 〉=5KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ℃ | ISO75/1-93 | 125 |
| Tensile strength | MPa | ISO527/2-93 | 37.2 |
| Elongation at break | ％ | ISO527/2-93 | 69 |
| Flexural strength | MPa | ISO178-93 | 56 |
| Modulus in flexure | MPa | ISO178-93 | 1870 |
| Notched Izod impact strength | KJ/m 2 | ISO180-93 | 7.2 |
Adopt the blow molding processes to become water heater liner embodiment 8 gained materials, be processed into solar water heater then.This solar water heater voltage-withstand test, the empty solarization are tested and the full water test, and test result is as follows:
Voltage withstand class: 2.37MPa (wall thickness 5mm).
Full water shines not have in 38 days and leaks and metamorphism, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.
Low-temperature test 8 days, daytime temperature 0-2 ℃, night-5 are to 2 ℃, and nothing is leaked.
Freezer test 7 days, outside temperature-20 ℃ does not have distortion, leaks.
The empty solarization do not have the distortion flawless in 6 days, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.During empty the solarization, survey the inner bag temperature, the part reaches 146 ℃ of high temperature.
Embodiment 9
With 100 kilograms of homo-polypropylene PP H710 (Korea S SK), 0.35 kilogram of thermo-stabilizer to tertiary butyl cup (8) aromatic hydrocarbons (lark prestige), 0.2 kilogram processing aid amine hydroxybenzene (chemical industry win in the Shandong), 1.1 kilograms of sodium-acetates (Shanghai chemical reagent work) are melting mixing dispersion in 40: 1 the twin screw extruder in length-to-diameter ratio, extrusion temperature is 200 ℃, extruding pelletization finally obtains the homo-polypropylene material.
Above-mentioned homo-polypropylene material has solved the insufficient shortcoming of common homo-polypropylene rigidity, tensile strength 〉=37MPa, modulus in flexure 〉=1800MPa, notched Izod impact strength 〉=5KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ℃ | ISO75/1-93 | 121 |
| Tensile strength | MPa | ISO527/2-93 | 38.8 |
| Elongation at break | ％ | ISO527/2-93 | 87 |
| Flexural strength | MPa | ISO178-93 | 56 |
| Modulus in flexure | MPa | ISO178-93 | 1900 |
| Notched Izod impact strength | KJ/m 2 | ISO180-93 | 8.5 |
Adopt the blow molding processes to become water heater liner embodiment 9 gained materials, be processed into solar water heater then.This solar water heater voltage-withstand test, the empty solarization are tested and the full water test, and test result is as follows:
Voltage withstand class: 2.38MPa (wall thickness 5mm).
Full water shines not have in 38 days and leaks and metamorphism, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.
Low-temperature test 8 days, daytime temperature 0-2 ℃, night-5 are to 2 ℃, and nothing is leaked.
Freezer test 7 days, outside temperature-20 ℃ does not have distortion, leaks.
The empty solarization do not have the distortion flawless in 6 days, 35 ℃-40 ℃ of external temperatures in the daytime wherein, about 30 ℃ of nocturnal temperatures.During empty the solarization, survey the inner bag temperature, the part reaches 147 ℃ of high temperature.
Claims (32)
1. inner bag that water-heater is used, described inner bag is made by the alpha-crystal form polypropylene material, and described alpha-crystal form polypropylene material is made by following homopolymerization polypropylene composition, and described composition comprises following component:
(a) homo-polypropylene of 100 weight parts;
(b) in the homo-polypropylene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the homo-polypropylene of 100 weight parts, the processing aid of 0.01-10 weight part, described processing aid are selected from one or more in lower molecular weight ester cpds, metallic soap compound, stearic acid complex ester compound and the amide compound;
(d) in the homo-polypropylene of 100 weight parts, the alpha-crystal form nucleator of 0.01-10 weight part,
Described α-nucleator comprises inorganic α-nucleator, organic α-nucleator and polymer-type α-nucleator; Described inorganic α-nucleator comprises talcum powder, silicon-dioxide, mica and combination thereof; Described organic α-nucleator comprises sorbyl alcohol type compound, branching amide compound and combination thereof; Described polymer-type α-nucleator comprises polyvinyl naphthenic hydrocarbon.
2. composition as claimed in claim 1 is characterized in that, in the homo-polypropylene of 100 weight parts, the consumption of described thermo-stabilizer is the 0.1-5 weight part.
3. composition as claimed in claim 1 is characterized in that, in the homo-polypropylene of 100 weight parts, the consumption of described thermo-stabilizer is the 0.2-3 weight part.
4. composition as claimed in claim 1 is characterized in that, in the homo-polypropylene of 100 weight parts, the consumption of described thermo-stabilizer is the 0.3-2 weight part.
5. composition as claimed in claim 1 is characterized in that, in the homo-polypropylene of 100 weight parts, the consumption of described processing aid is the 0.05-5 weight part.
6. composition as claimed in claim 1 is characterized in that, in the homo-polypropylene of 100 weight parts, the consumption of described processing aid is the 0.1-2 weight part.
7. composition as claimed in claim 1 is characterized in that, in the homo-polypropylene of 100 weight parts, the consumption of described processing aid is the 0.5-1 weight part.
8. composition as claimed in claim 1 is characterized in that, in the homo-polypropylene of 100 weight parts, the consumption of described alpha-crystal form nucleator is the 0.01-8 weight part.
9. composition as claimed in claim 1 is characterized in that, in the homo-polypropylene of 100 weight parts, the consumption of described alpha-crystal form nucleator is the 0.02-5 weight part.
10. composition as claimed in claim 1 is characterized in that, in the homo-polypropylene of 100 weight parts, the consumption of described alpha-crystal form nucleator is the 0.03-4 weight part.
11. composition as claimed in claim 1 is characterized in that, described thermo-stabilizer is selected from the mixture of phenolic compound, amine compound, bi-ester of phosphite, acryl functional group and monothioester or a kind of or its mixture in the calixarene.
12. composition as claimed in claim 11 is characterized in that, described phenolic compound is selected from alkyl list phenol, alkyl bis-phenol, sulfuration bis-phenol, triaizine compounds, hindered phenol compound, half hindered phenol compound, benzoic ether hindered phenol and combination thereof.
13. composition as claimed in claim 11 is characterized in that, described phenolic compound comprises hindered phenol 1010, hindered phenol 1076, hindered phenol 330, hindered phenol 168, dihydroxyphenyl propane, bisphenol-c, 2,6-ditertbutylparacresol, 1,3,5-trimethylammonium-2,4,6-three (3,5-tertiary butyl-4-hydroxy benzyl) benzene, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) Three methyl Benzene and 2,2 '-methylene bis (4-ethyl-6-tert.-butyl phenol) and combination thereof.
14. composition as claimed in claim 11 is characterized in that, described amine compound is selected from naphthylamines, pentanoic, Ursol D, quinoline and combination thereof.
15. composition as claimed in claim 11 is characterized in that, described amine compound is selected from diphenyl-para-phenylene diamine, diphenyl-para-phenylene diamine, 4-hydroxy-dodecanoic acid anilide and 4-hydroxyl octadecanoic acid anilide and combination thereof.
16. composition as claimed in claim 11 is characterized in that, described bi-ester of phosphite is selected from triphenyl phosphite, phosphorous acid hexichol one monooctyl ester, phosphorous acid hexichol ester in one last of the ten Heavenly stems, tricresyl phosphite (nonyl phenyl ester), the hot diphenyl ester of phosphorous acid and combination thereof.
17. composition as claimed in claim 11 is characterized in that, the mixture of described acryl functional group and monothioester is a Tyox B.
18. composition as claimed in claim 11, it is characterized in that described calixarene is selected from cup (a 4) aromatic hydrocarbons, cup (6) aromatic hydrocarbons, cup (8) aromatic hydrocarbons, to tertiary butyl cup (4) aromatic hydrocarbons, to tertiary butyl cup (6) aromatic hydrocarbons with to tertiary butyl cup (8) aromatic hydrocarbons and combination thereof.
19. composition as claimed in claim 1 is characterized in that, described lower molecular weight ester cpds comprises the lower molecular weight stearate.
20. composition as claimed in claim 19 is characterized in that, described lower molecular weight stearate is selected from list, two or three stearic acid alkyl esters.
21. composition as claimed in claim 1 is characterized in that, described lower molecular weight ester cpds comprises methyl stearate, Stearic ethyl stearate, stearic acid propyl ester, butyl stearate, glyceryl monostearate, three stearic acid triglyceride level and combinations thereof.
22. composition as claimed in claim 1 is characterized in that, described metallic soap compound comprises carboxylate salt.
23. composition as claimed in claim 22 is characterized in that, described carboxylate salt is selected from lead salt, barium salt, cadmium salt, zinc salt and/or the calcium salt of carboxylic acid.
24. composition as claimed in claim 1, it is characterized in that described metallic soap compound is selected from lead stearate, 2-ethyl acetic acid lead, lead salicylate, tribasic lead stearate, Dythal, tribasic Malaysia lead plumbate, barium stearate, orange osmanthus acid barium, ricinoleate acid barium, cadmium stearate, cadmium recinoleate, calcium stearate, calcium ricinoleate, Zinic stearas, Magnesium Stearate and combination thereof.
25. composition as claimed in claim 1 is characterized in that, described stearic acid complex ester compound comprises polyvalent alcohol list or many stearates.
26. composition as claimed in claim 1, it is characterized in that described stearic acid complex ester compound is selected from three Polyglycerine Stearinsaeures, Polyglycerine monostearate, sorbitol monostearate, ethylene glycol monostearate, polyethylene glycol mono stearate,, two Polyglycerine Stearinsaeures, trimerization Stearic diglyceride, Polyglycerine SUNSOFT Q-182S, sorbyl alcohol SUNSOFT Q-182S, Unister E 275, polyglycol distearate, sorbitol anhydride SUNSOFT Q-182S, dimerization Stearic diglyceride and combination thereof.
27. composition as claimed in claim 1 is characterized in that, described amide compound comprises carboxylic acid amide.
28. composition as claimed in claim 1, it is characterized in that described amide compound is selected from amine hydroxybenzene, stearic amide, ethylene bis stearic acid amide, ricinoleate acid acid amides, orange osmanthus acid acid amides, salicylamide, ethanamide, propionic acid amide, Palmiticacid acid amides and combination thereof.
29. composition as claimed in claim 1 is characterized in that, described polyvinyl naphthenic hydrocarbon is selected from polyvinyl tetramethylene, polyvinyl eyclohexane, polyvinyl pentamethylene, polyvinyl-2-methylcyclohexane and combination thereof.
30. composition as claimed in claim 1 is characterized in that, described α-nucleator is selected from talcum powder, silicon-dioxide, the phenylformic acid soap, sorbyl alcohol, carboxylic metallic salt, dehydroabietic acid, dehydroabietic acid soap, one or more of branching acid amides and polyvinyl naphthenic hydrocarbon.
31. the purposes of a composition in the preparation water heater liner, described composition comprises following component:
(a) homo-polypropylene of 100 weight parts;
(b) in the homo-polypropylene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the homo-polypropylene of 100 weight parts, the processing aid of 0.01-10 weight part, described processing aid are selected from one or more in lower molecular weight ester cpds, metallic soap compound, stearic acid complex ester compound and the amide compound;
(d) in the homo-polypropylene of 100 weight parts, the alpha-crystal form nucleator of 0.01-10 weight part,
Described α-nucleator comprises inorganic α-nucleator, organic α-nucleator and polymer-type α-nucleator; Described inorganic α-nucleator comprises talcum powder, silicon-dioxide, mica and combination thereof; Described organic α-nucleator comprises sorbyl alcohol type compound, branching amide compound and combination thereof; Described polymer-type α-nucleator comprises polyvinyl naphthenic hydrocarbon.
32. a water-heater, described water-heater comprise the inner bag that the described water-heater of claim 1 is used.
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| EP3006472A1 (en) * | 2014-10-07 | 2016-04-13 | Borealis AG | Process for the preparation of an alpha nucleated polypropylene |
| CN104693702A (en) * | 2015-03-03 | 2015-06-10 | 界首市天鸿新材料股份有限公司 | Macromolecule nucleating agent modified polyethylene glycol terephthalate |
| CN105601994B (en) * | 2016-02-29 | 2019-04-12 | 呈和科技股份有限公司 | A kind of reinforcement nucleating agent composition containing vinyl bis-stearamides |
| CN111205550A (en) * | 2020-03-20 | 2020-05-29 | 无锡鑫宏业线缆科技股份有限公司 | 125 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin cable material for new energy vehicle |
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