CN101914262B - Beta crystal form polypropylene composite for water heater tank and preparation method thereof - Google Patents

Beta crystal form polypropylene composite for water heater tank and preparation method thereof Download PDF

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Publication number
CN101914262B
CN101914262B CN200910247219A CN200910247219A CN101914262B CN 101914262 B CN101914262 B CN 101914262B CN 200910247219 A CN200910247219 A CN 200910247219A CN 200910247219 A CN200910247219 A CN 200910247219A CN 101914262 B CN101914262 B CN 101914262B
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compsn
compound
acid
block copolymerization
copolymerization polypropylene
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CN101914262A (en
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孙刚
李扬
周英辉
丁超
陈广强
罗忠富
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Shanghai Kingfa Science and Technology Co Ltd
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Shanghai Kingfa Science and Technology Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers

Abstract

The invention provides a block polypropylene copolymer composite used for a water heater tank. The composite comprises the following components in parts by weight: 100 parts of block polypropylene copolymer, 0.01-10 parts of thermal stabilizer, 0.01-10 parts of processing aid and 0.01-10 parts of beta crystal form nucleating agent, wherein the processing aid is selected from one or more of low molecular weight ester compound, metallic soap compound, stearic acid complex ester compound and amide compound. The beta crystal form block polypropylene copolymer material of the invention solves the defect that the common block polypropylene copolymer has insufficient rigidity and has high heat deflection temperature; and the tensile strength of the material is not less than 24MPa, the elongationat break is not less than 300%, the flexural modulus is not less than 1200MPa, and the notch impact strength is not less than 50KJ/m<2>.

Description

Beta-crystal polypropylene composition for inner container of water heater and preparation method thereof
Technical field
The present invention relates to a kind of water heater liner with beta crystal block copolymerization 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, ME are complicated: shear-punching-drum-weld seam-weld various workpiece-heat-insulating layer foamings, but it is corrosion-resistant; Resistance to acids and bases is poor, is prone to fouling, and the weld is met high temperature and is prone to oxidation corrosion; 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 processing 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 is weightless " 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.Can find out that above two kinds of liner material ME are complicated, with high costs, have 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 Vestolen PP 7052 comes out; With outstanding thermal property and mechanical property in a lot of fields; As being widely used in injection moulding, film, the fiber production, this versatility and economy make Vestolen PP 7052 surpass SE, PS, become to be only second to poly second largest synthetic resins.Especially along with various crystalline polyacrylics have been realized business-like applying, make Vestolen PP 7052 that boundless prospect arranged on engineering plastics and functional materials.Wherein, beta crystal-type nucleater is to use the most sophisticated nucleator in the Vestolen PP 7052.
Beta crystal-type nucleater has effectively solved the insufficient shortcoming of common block copolymerization 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 block copolymerization polypropylene.This makes the block copolymerization polypropylene of beta crystal-type nucleater modification substitute traditional metal and ceramic water-heater inner bag becomes possibility.Adopt the water heater liner of beta crystal block copolymerization polypropylene manufacturing to have the following advantages: 1. cost is low: relatively in the market stainless steel inner container and enamel inner container; 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 spinoff 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 of this made is uniform and smooth, and self does not produce static, is not easy to be etched.5. high temperature resistant: the block copolymerization polypropylene that adopts the beta crystal-type nucleater modification 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: the beta crystal block copolymerization 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 Beta-crystalline polyacrylic (comprising the beta crystal block copolymerization polypropylene) can not satisfy empty requirement of shining usually.
Chinese patent CN 101358012A discloses a kind of water heater liner and has used polypropylene composite, and its formula system is Vestolen PP 7052 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, HS, hygienic advantages.
The invention provides the block copolymerization polypropylene compsn that a kind of water heater liner is used, said compsn comprises following component:
(a) block copolymerization polypropylene of 100 weight parts;
(b) in the block copolymerization 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 block copolymerization 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, said processing aid is selected from one or more in lower molecular weight ester cpds, metallic soap compound, Triple Pressed Stearic Acid complex ester compound and the amide compound;
(d) in the block copolymerization polypropylene of 100 weight parts, 0.01-10 weight part, better 0.01-8 weight part, better 0.02-5 weight part, the preferably beta crystal-type nucleater of 0.03-4 weight part.
In a preferred embodiment of the present invention, said 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, said 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, said phenolic compound comprises hindered phenol 1010, hindered phenol 1076, hindered phenol 330, hindered phenol 168, dihydroxyphenyl propane, bisphenol-c, DBPC 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, said amine compound is selected from naphthylamines, pentanoic, Ursol D, quinoline and combination thereof; Preferably, said 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, said 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 said acryl functional group and monothioester is a Tyox B; Preferably, said 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, said lower molecular weight ester cpds comprises the lower molecular weight stearate, like list, two or three Triple Pressed Stearic Acid alkyl esters; Preferably, said lower molecular weight ester cpds comprises methyl stearate, Stearic ethyl stearate, Triple Pressed Stearic Acid propyl ester, butyl stearate, glyceryl monostearate, three Triple Pressed Stearic Acid triglyceride level and combinations thereof; Preferably, said metallic soap compound comprises carboxylate salt, like lead salt, barium salt, cadmium salt, zinc salt and/or the calcium salt of carboxylic acid; Preferably, said 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, said Triple Pressed Stearic Acid complex ester compound comprises polyvalent alcohol list or many stearates; Preferably, said Triple Pressed Stearic Acid complex ester compound is selected from three poly-glycerol Stearinsaeures, poly-glycerol monostearate, sorbitol monostearate, ethylene glycol monostearate, YMS 2,, two poly-glycerol Stearinsaeures, trimerization Stearic diglyceride, poly-glycerol 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, said amide compound comprises carboxylic acid amide, like 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, said beta-nucleated dose of mixture, quinacridone red and combination thereof that is selected from salt, organic carboxyl acid and the IIA family metal-salt of rare earth organic complex, imido acid and IIA family metal that fragrant amide type compound, aromatic amines compound, REE and organic cpds form.
In a preferred embodiment of the present invention, said fragrant amide type compound generally can be but be not limited to benzamide, to the methylbenzene acid amides, to the ethylbenzene acid amides, to tert.-butylbenzene acid amides and combination thereof; Said aromatic amines compound generally can be but be not limited to aniline, to monomethylaniline, to MEA, p-tert-butyl-aniline and combination thereof; The rare earth organic complex that said REE and organic cpds form comprises the title complex of lanthanon (like light rare earthss such as lanthanum, cerium, praseodymium, neodymium, yttriums) and organic heterocyclic molecule, fused ring compound, aliphatic carboxylic acid or aromatic carboxylic acid; Preferably, the rare earth organic complex of affiliated REE and organic cpds formation comprises the salt of IIIB family REE and C4-C28 carboxylic acid and the title complex that the C4-C28 carboxylic acid forms; Better, the rare earth organic complex of affiliated REE and organic cpds formation is selected from lanthanum: the mixture and the combination thereof of the mixture of quinacridone title complex, Triple Pressed Stearic Acid lanthanum, oleic acid lanthanum, LAURIC ACID 99 MIN lanthanum, Triple Pressed Stearic Acid lanthanum and stearin, Triple Pressed Stearic Acid lanthanum and stearic mixture, Triple Pressed Stearic Acid samarium and stearin; The salt of said imido acid and IIA family metal comprises imido acid calcium; The mixture of said machine carboxylic acid and IIA family metal-salt comprises the mixture of pimelic acid and calcium stearate; Said quinacridone is red to be selected from that quinacridone is red, quinacridone is red 122, the red E5B of quinacridone and combination thereof.
The invention provides the beta crystal block copolymerization polypropylene material that a kind of water heater liner is used, said material is processed by block copolymerization polypropylene compsn of the present invention, and said compsn comprises following component:
(a) block copolymerization polypropylene of 100 weight parts;
(b) in the block copolymerization 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 block copolymerization 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, said processing aid is selected from one or more in lower molecular weight ester cpds, metallic soap compound, Triple Pressed Stearic Acid complex ester compound and the amide compound;
(d) in the block copolymerization polypropylene of 100 weight parts, 0.01-10 weight part, better 0.01-8 weight part, better 0.02-5 weight part, the preferably beta crystal-type nucleater of 0.03-4 weight part.
The invention provides a kind of method for preparing the beta crystal block copolymerization polypropylene material that water heater liner uses, said method comprises: with forcing machine with block copolymerization polypropylene compsn extruding pelletization of the present invention.
The invention provides the inner bag that a kind of water-heater is used, said inner bag is processed by Beta-crystalline polyacrylic material of the present invention.
The invention provides the purposes of a kind of compsn in the preparation water heater liner, said compsn comprises following component:
(a) block copolymerization polypropylene of 100 weight parts;
(b) in the block copolymerization 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 block copolymerization 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, said processing aid is selected from one or more in lower molecular weight ester cpds, metallic soap compound, Triple Pressed Stearic Acid complex ester compound and the amide compound;
(d) in the block copolymerization polypropylene of 100 weight parts, 0.01-10 weight part, better 0.01-8 weight part, better 0.02-5 weight part, the preferably beta crystal-type nucleater of 0.03-4 weight part.
The invention provides a kind of water-heater, said water-heater comprises the inner bag that water-heater of the present invention is used.
The gentle low temperature impact strength of beta crystal block copolymerization polypropylene usable material chamber of the present invention is better, under high-speed stretch, shows high toughness and ductility, is difficult for embrittlement; Tensile strength>=24MPa; Tension set>=300%, modulus in flexure>=1200MPa, notched Izod impact strength>=50KJ/m 2Adopt the water heater liner of this material prepn to have excellent internal surface glossiness, excellent electric insulating, high temperature resistant, water-fast dirt, HS, 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 through 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 to special parameter.In addition, if if the minimum extent value of listing 1 and 2 and listed maximum range value 3,4 and 5, the scope below then could all reckon with: 1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, only if having other the explanation, each components contents scope of compsn with and preferable range between can be combined to form new technical scheme each other.
In the present invention, only if other explanations are arranged, the technical characterictic of each technical scheme can be combined to form new technical scheme each other.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 through combination.
In the present invention, only if other explanations are arranged, the multicomponent mixture of said 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, only if other explanations are arranged, all " parts " and percentage ratio (%) all refer to weight percentage.
In the present invention, only if other explanations are arranged, the percentage ratio sum of each component is 100% in all compsns.
In the present invention, only if other explanations are arranged, numerical range " a-b " expression a representes that to the breviary of any real number combination between the b wherein a and b are real numbers.For example all listed the whole real numbers between " 0-5 " among numerical range " 0-5 " expression this paper, " 0-5 " just the breviary of these combinations of values representes.
In the present invention, only if other explanations are arranged, integer numerical range " a-b " expression a representes 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 open text of patent 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 is no longer 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, only if other explanations are arranged, said " 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, only if other explanations are arranged, said " aryl " expression C6-C20 aryl, for example C6-C12 aryl, C6-C10 aryl better are phenyl etc.
In the present invention, only if other explanations are arranged, said " 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, only if other explanations are arranged, said " 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, only if other explanations are arranged, said " lower molecular weight " generally represented molecular weight less than 1000, better less than 800, better less than 500, preferably less than 300.Preferably, said " lower molecular weight " expression 10-1000, better 20-800, better 30-500, the preferably molecular weight of 50-300.
The block copolymerization polypropylene compsn that one aspect of the present invention provides a kind of water heater liner to use, said compsn comprises following component:
(a) block copolymerization polypropylene of 100 weight parts;
(b) in the block copolymerization polypropylene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the block copolymerization polypropylene of 100 weight parts, the processing aid of 0.01-10 weight part, said processing aid are selected from one or more in lower molecular weight ester cpds, metallic soap compound, Triple Pressed Stearic Acid complex ester compound and the amide compound;
(d) in the block copolymerization polypropylene of 100 weight parts, the beta crystal-type nucleater of 0.01-10 weight part.
In the present invention, said block copolymerization polypropylene is conventional, and it can be a Vestolen PP 7052 commonly used arbitrarily in this area.In a preferred embodiment of the present invention, said block copolymerization polypropylene is the block copolymerization polypropylene of melt flow rate(MFR) at 0.01-100g/10min.In another preferred embodiment of the present invention, said block copolymerization polypropylene comprises PP B8101 (Yanshan Petrochemical), PP AW191 (the Taiwan good fortune is gathered); PP K9017 (platformization); PPCB5230 (Kpic), PP CB5290 (Kpic), PP EP540V (Korea S Da Lin).
In the present invention, said thermo-stabilizer is conventional, and it can be a thermo-stabilizer commonly used in this area.In a preferred embodiment of the present invention, said 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, phenolic compound commonly used comprises hindered phenol 1010, hindered phenol 1076, hindered phenol 330, hindered phenol 168, dihydroxyphenyl propane, bisphenol-c, DBPC 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, said phenolic compound is selected from Irganox 1010 (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, said 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, said amine compound is selected from NC-GX45 (the Guangzhou promise is speeded).
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, 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, said bi-ester of phosphite is selected from 627A (Compton).
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 said acryl functional group and monothioester is selected from DLTDP (refined treasured).
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.Said calixarene also can be the verivate 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, said calixarene is selected from tertiary butyl cup (8) aromatic hydrocarbons (lark prestige).
In block copolymerization polypropylene compsn of the present invention, the consumption of said thermo-stabilizer is generally the 0.01-10 weight part, better 0.05-2 weight part, and better 0.1-1 weight part is in the block copolymerization polypropylene of 100 weight parts.
In the present invention, the lower molecular weight ester cpds that is used as said processing aid is conventional, and it can be such as but not limited to the lower molecular weight stearate, like list, two or three Triple Pressed Stearic Acid alkyl esters.In a preferred embodiment of the present invention, said lower molecular weight ester cpds comprises methyl stearate, Stearic ethyl stearate, Triple Pressed Stearic Acid propyl ester, butyl stearate, glyceryl monostearate, three Triple Pressed Stearic Acid triglyceride level and combinations thereof.In another instance of the present invention, said lower molecular weight ester cpds is selected from glyceryl monostearate (vapour crust).
In the present invention, the metallic soap compound that is used as said processing aid is conventional, and it can be such as but not limited to carboxylate salt, like lead salt, barium salt, cadmium salt, zinc salt and/or the calcium salt of carboxylic acid.In a preferred embodiment of the present invention, said 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, said metallic soap compound is selected from Zinic stearas (Shandong friend and auxiliary agent ltd).
In the present invention, the Triple Pressed Stearic Acid complex ester compound that is used as said 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, said Triple Pressed Stearic Acid complex ester compound is selected from three poly-glycerol Stearinsaeures, poly-glycerol monostearate, sorbitol monostearate, ethylene glycol monostearate, YMS 2,, two poly-glycerol Stearinsaeures, trimerization Stearic diglyceride, poly-glycerol 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, said Triple Pressed Stearic Acid complex ester compound is selected from three poly-glycerol Stearinsaeures (sky, Zhengzhou leads to food ingredients ltd).
In the present invention; Amide compound as said processing aid is conventional; It can be such as but not limited to carboxylic acid amide, like 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, said amide compound is selected from amine hydroxybenzene (chemical industry is won in the Shandong).
In block copolymerization polypropylene compsn of the present invention, the consumption of said processing aid 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 block copolymerization polypropylene of 100 weight parts.
In the present invention, said beta-nucleated dose is conventional, and those of ordinary skill in the art combines its expertise can direct derivation to go out which beta-nucleated dose again according to description of the invention and can be used for the present invention.Usually, be used for mixture and the quinacridone red that beta-nucleated dose of Vestolen PP 7052 (like HOPP) is generally salt, organic carboxyl acid and the IIA family metal-salt of rare earth organic complex, imido acid and IIA family metal that fragrant amide type compound, aromatic amines compound, REE and organic cpds form.
In the present invention, said fragrant amide type compound generally can be but be not limited to benzamide, to the methylbenzene acid amides, to the ethylbenzene acid amides, to tert.-butylbenzene acid amides and combination thereof.In a preferred embodiment of the present invention, said fragrant amide type compound is selected from TMB-5 (Shanxi chemical institute).
In the present invention, said aromatic amines compound generally can be but be not limited to aniline, to monomethylaniline, to MEA, p-tert-butyl-aniline and combination thereof.In a preferred embodiment of the present invention, said aromatic amines compound is selected from monomethylaniline (Shanghai traditional Chinese medicines).
In the present invention; The rare earth organic complex that said REE and organic cpds form can be specifically referring to CN02134498.1, for example the title complex of lanthanon (like light rare earthss such as lanthanum, cerium, praseodymium, neodymium, yttriums) and organic heterocyclic molecule, fused ring compound, aliphatic carboxylic acid, aromatic carboxylic acid etc.Affiliated aliphatic carboxylic acid comprises monobasic or polynary, saturated or undersaturated C4-C30 carboxylic acid (like Triple Pressed Stearic Acid, oleic acid, LAURIC ACID 99 MIN, Succinic Acid, hexanodioic acid, pimelic acid, sebacic acid, diethylammonium caproic acid, fumaric acid, maleic anhydride, octyl group toxilic acid, epoxyoleic acid, amino acid, Whitfield's ointment, stearin, pentaerythritol ester).In another instance of the present invention; Under the rare earth organic complex that forms of REE and organic cpds can be referring to CN00117339.1, the title complex that forms of the salt of IIIB family REE and C4-C28 carboxylic acid and C4-C28 carboxylic acid (can go referring to specification sheets page 1 the reciprocal the 2nd and arrive page 2 the 5th and go) for example.In a preferred embodiment of the present invention, the rare earth organic complex that affiliated REE and organic cpds form is selected from lanthanum: the mixture and the combination thereof of mixture, Triple Pressed Stearic Acid lanthanum and stearic mixture, Triple Pressed Stearic Acid samarium and the stearin of quinacridone title complex (referring to the embodiment 1 of CN02134498.1), Triple Pressed Stearic Acid lanthanum, oleic acid lanthanum, LAURIC ACID 99 MIN lanthanum, Triple Pressed Stearic Acid lanthanum and stearin.
In the present invention, the salt of said imido acid and IIA family metal specifically can be referring to CN1210103, for example imido acid calcium etc. (specifically referring to Instructions Page 2 the 20th row of CN1210103A to page 3 the 27th row).
In the present invention, the mixture of said machine carboxylic acid and IIA family metal-salt can be referring to CN1004076B, for example the mixture of pimelic acid and calcium stearate.
In the present invention, said quinacridone is red generally can be but be not limited to that quinacridone is red, quinacridone is red 122, the red E5B of quinacridone and compsn thereof.In a preferred embodiment of the present invention, the red quinacridone red (dark trade is gushed in Ningbo) that is selected from of said quinacridone.
In block copolymerization polypropylene compsn of the present invention, said beta-nucleated dose consumption 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 block copolymerization polypropylene of 100 weight parts.
In the present invention, polymer compsn of the present invention can also comprise other additives that usually use this area, for example inhibitor, static inhibitor, whipping agent, lubricant, impact modifier, softening agent, tinting material and weighting agent.
In the present invention, inhibitor can be any inhibitor that usually use this area.In according to a preferred embodiment of the invention, inhibitor 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, amide gp, 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 isobutylates 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, SULPHOSUCCINIC 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 spun glass with circle and non-circular cross sections, sheet glass, granulated glass sphere, thomel, talcum powder, mica, wollastonite, calcined clay, kaolin, zeyssatite, sal epsom, Magnesium Silicate q-agent, permanent white, titanium oxide, aluminium carbonate sodium, barium ferrite, potassium titanate and their mixture.
Spun glass with non-circular cross sections is meant the spun glass with following xsect, and said xsect has the major axis of long slant range in the vertical vertical and cross section taken in correspondence with spun glass.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 xsect 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 spun glass has disclosed in EP 0190001 and EP 0196194.
The beta crystal block copolymerization polypropylene material that the present invention provides a kind of water heater liner to use on the other hand, said material is processed by block copolymerization polypropylene compsn of the present invention, and said compsn comprises following component:
(a) block copolymerization polypropylene of 100 weight parts;
(b) in the block copolymerization polypropylene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the block copolymerization polypropylene of 100 weight parts, the processing aid of 0.01-10 weight part, said processing aid are selected from one or more in lower molecular weight ester cpds, metallic soap compound, Triple Pressed Stearic Acid complex ester compound and the amide compound;
(d) in the block copolymerization polypropylene of 100 weight parts, the beta crystal-type nucleater of 0.01-10 weight part.
The present invention provides a kind of method for preparing the beta crystal block copolymerization polypropylene material that water heater liner uses on the other hand, and said method comprises: with forcing machine with block copolymerization polypropylene compsn extruding pelletization of the present invention.
In a preferred embodiment of the present invention, said water heater liner is following with the preparation method of polypropylene material:
Is that melting mixing is disperseed in 40: 1 the twin screw extruder with block copolymerization polypropylene, thermo-stabilizer, processing aid, beta crystal-type nucleater in length-to-diameter ratio, and extruding pelletization finally obtains product.
In the present invention, available other materials also can be with said block copolymerization polypropylene, thermo-stabilizer, processing aid, beta crystal-type nucleater extruding pelletization in the block copolymerization polypropylene compsn of the present invention.
The inner bag that the present invention also provides a kind of water-heater to use, said inner bag is processed by Beta-crystalline polyacrylic material of the present invention.
Usually, the technology for preparing said 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 compsn in the preparation water heater liner, and said compsn comprises following component:
(a) block copolymerization polypropylene of 100 weight parts;
(b) in the block copolymerization polypropylene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the block copolymerization polypropylene of 100 weight parts, the processing aid of 0.01-10 weight part, said processing aid are selected from one or more in lower molecular weight ester cpds, metallic soap compound, Triple Pressed Stearic Acid complex ester compound and the amide compound;
(d) in the block copolymerization polypropylene of 100 weight parts, the beta crystal-type nucleater of 0.01-10 weight part.
The gentle low temperature impact strength of product chambers of the present invention is better, under high-speed stretch, shows high toughness and ductility, is difficult for embrittlement, tensile strength>=24MPa, tension set>=300%, modulus in flexure>=1200MPa, notched Izod impact strength>=50KJ/m 2, adopt the water heater liner of this material prepn 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 block copolymerization polypropylene PP B8101 (Yanshan Petrochemical), 0.5 kilogram of thermo-stabilizer Irganox 1010 (CIBA company), 0.5 kilogram of Irganox 168 (CIBA company); 0.5 kilogram processing aid EBS (chemical industry win in the Shandong), 0.05 kilogram of terephthalic acid (replacement) Cyclohexamide (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 block copolymerization polypropylene material.
The gentle low temperature impact strength of above-mentioned block copolymerization polypropylene usable material chamber is better, under high-speed stretch, shows high toughness and ductility, is difficult for embrittlement; Tensile strength>=24MPa; Tension set>=300%, modulus in flexure>=1200MPa, notched Izod impact strength>=50KJ/m 2, performance is following:
Performance Unit Testing standard Test result
Vicat softening point ℃ ISO75/1-93 110
Tensile strength MPa ISO527/2-93 25
Elongation at break ％ ISO527/2-93 360
Flexural strength MPa ISO178-93 32
Modulus in flexure MPa ISO178-93 1350
Notched Izod impact strength KJ/m 2 ISO180-93 55
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 following:
Voltage withstand class: 1.9MPa (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 141 ℃ of high temperature.
Embodiment 2
With 100 kilograms of block copolymerization polypropylene PP AW191 (the Taiwan good fortune is gathered), 0.5 kilogram of thermo-stabilizer Irganox 1010 (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 TMB-5 (substituted benzene acid amides) (Shanxi chemical institute) 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 block copolymerization polypropylene material.
The gentle low temperature impact strength of above-mentioned block copolymerization polypropylene usable material chamber is better, under high-speed stretch, shows high toughness and ductility, is difficult for embrittlement; Tensile strength>=24MPa; Tension set>=300%, modulus in flexure>=1200MPa, notched Izod impact strength>=50KJ/m 2, performance is following:
Performance Unit Testing standard Test result
Vicat softening point ℃ ISO75/1-93 111
Tensile strength MPa ISO527/2-93 26
Elongation at break ％ ISO527/2-93 380
Flexural strength MPa ISO178-93 33
Modulus in flexure MPa ISO178-93 1250
Notched Izod impact strength KJ/m 2 ISO180-93 57
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 following:
Voltage withstand class: 1.8MPa (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 block copolymerization polypropylene PP K9017 (platformization), 0.3 kilogram of thermo-stabilizer Irganox1010 (CIBA company), 0.5 kilogram of Irganox 168 (CIBA company); 1.2 kilogram processing aid EBS (chemical industry win in the Shandong), 1.4 kilograms of lanthanums: quinacridone title complex (through embodiment 1 preparation of CN02134498.1) is melting mixing dispersion in 40: 1 the twin screw extruder in length-to-diameter ratio; Extrusion temperature is 200 ℃; Extruding pelletization finally obtains the block copolymerization polypropylene material.
The gentle low temperature impact strength of above-mentioned block copolymerization polypropylene usable material chamber is better, under high-speed stretch, shows high toughness and ductility, is difficult for embrittlement; Tensile strength>=24MPa; Tension set>=300%, modulus in flexure>=1200MPa, notched Izod impact strength>=50KJ/m 2, performance is following:
Performance Unit Testing standard Test result
Vicat softening point ℃ ISO75/1-93 113
Tensile strength MPa ISO527/2-93 25
Elongation at break ％ ISO527/2-93 360
Flexural strength MPa ISO178-93 32
Modulus in flexure MPa ISO178-93 1220
Notched Izod impact strength KJ/m 2 ISO180-93 58
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 following:
Voltage withstand class: 1.7MPa (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 block copolymerization polypropylene PP CB5230 (Kpic), 0.3 kilogram of thermo-stabilizer Irganox 1010 (CIBA company), 0.5 kilogram of Irganox 168 (CIBA company); 1.2 the mixture (embodiment 1 of CN00117339.1) of kilogram processing aid EBS (chemical industry win in the Shandong), 1.4 kilograms of Triple Pressed Stearic Acid lanthanums and stearin is melting mixing dispersion in 40: 1 the twin screw extruder in length-to-diameter ratio; Extrusion temperature is 200 ℃; Extruding pelletization finally obtains the block copolymerization polypropylene material.
The gentle low temperature impact strength of above-mentioned block copolymerization polypropylene usable material chamber is better, under high-speed stretch, shows high toughness and ductility, is difficult for embrittlement; Tensile strength>=24MPa; Tension set>=300%, modulus in flexure>=1200MPa, notched Izod impact strength>=50KJ/m 2, performance is following:
Performance Unit Testing standard Test result
Vicat softening point ℃ ISO75/1-93 110
Tensile strength MPa ISO527/2-93 25.5
Elongation at break ％ ISO527/2-93 390
Flexural strength MPa ISO178-93 35
Modulus in flexure MPa ISO178-93 1380
Notched Izod impact strength KJ/m ISO180-93 52
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 following:
Voltage withstand class: 1.75MPa (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 block copolymerization polypropylene PP CB5290 (Kpic), 0.1 kilogram of thermo-stabilizer Irganox 1010 (CIBA company), 0.5 kilogram of Irganox 168 (CIBA company); 0.2 kilogram processing aid calcium stearate (chemical industry win in the Shandong), 5.5 kilograms of TMB-5 (Shanxi chemical institute) 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 block copolymerization polypropylene material.
The gentle low temperature impact strength of above-mentioned block copolymerization polypropylene usable material chamber is better, under high-speed stretch, shows high toughness and ductility, is difficult for embrittlement; Tensile strength>=24MPa; Tension set>=300%, modulus in flexure>=1200MPa, notched Izod impact strength>=50KJ/m 2, performance is following:
Performance Unit Testing standard Test result
Vicat softening point ℃ ISO75/1-93 115
Tensile strength MPa ISO527/2-93 27.8
Elongation at break ％ ISO527/2-93 310
Flexural strength MPa ISO178-93 37
Modulus in flexure MPa ISO178-93 1580
Notched Izod impact strength KJ/m 2 ISO180-93 51
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 following:
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 148 ℃ of high temperature.
Comparative Examples 1
Embodiment 1 according to CN101358012A prepares the compsn that is used for water heater liner, and processes inner bag and solar water heater with the embodiment of the invention 1 identical method.This solar water heater voltage-withstand test, the empty solarization are tested and the full water test, and test result is following:
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 block copolymerization polypropylene PP EP540V (Korea S Da Lin), 2 kilograms of thermo-stabilizer NC-GX45 (the Guangzhou promise is speeded); 0.05 kilogram processing aid glyceryl monostearate (vapour crust), 0.03 kilogram of phthalyl glycine calcium (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 block copolymerization polypropylene material.
The gentle low temperature impact strength of above-mentioned block copolymerization polypropylene usable material chamber is better, under high-speed stretch, shows high toughness and ductility, is difficult for embrittlement; Tensile strength>=24MPa; Tension set>=300%, modulus in flexure>=1200MPa, notched Izod impact strength>=50KJ/m 2, performance is following:
Performance Unit Testing standard Test result
Vicat softening point ℃ ISO75/1-93 112
Tensile strength MPa ISO527/2-93 25
Elongation at break ％ ISO527/2-93 340
Flexural strength MPa ISO178-93 36
Modulus in flexure MPa ISO178-93 1300
Notched Izod impact strength KJ/m 2 ISO180-93 55
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 following:
Voltage withstand class: 2.26MPa (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 7
With 100 kilograms of block copolymerization polypropylene PP EPS30R (Qilu Petrochemical), 0.35 kilogram of thermo-stabilizer 627A (Compton); 0.2 the mixture (Shanghai traditional Chinese medicines) of kilogram processing aid calcium stearate (chemical industry win in the Shandong), 1.1 kilograms of pimelic acid and calcium stearate is melting mixing dispersion in 40: 1 the twin screw extruder in length-to-diameter ratio; Extrusion temperature is 200 ℃; Extruding pelletization finally obtains the block copolymerization polypropylene material.
The gentle low temperature impact strength of above-mentioned block copolymerization polypropylene usable material chamber is better, under high-speed stretch, shows high toughness and ductility, is difficult for embrittlement; Tensile strength>=24MPa; Tension set>=300%, modulus in flexure>=1200MPa, notched Izod impact strength>=50KJ/m 2, performance is following:
Performance Unit Testing standard Test result
Vicat softening point ℃ ISO75/1-93 113
Tensile strength MPa ISO527/2-93 26
Elongation at break ％ ISO527/2-93 320
Flexural strength MPa ISO178-93 37
Modulus in flexure MPa ISO178-93 1350
Notched Izod impact strength KJ/m 2 ISO180-93 58
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 following:
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 147 ℃ of high temperature.
Embodiment 8
With 100 kilograms of block copolymerization polypropylene PP B8101 (Yanshan Petrochemical), 0.35 kilogram of thermo-stabilizer DLTDP (refined treasured); 0.2 kilogram processing aid glyceryl monostearate (vapour crust), 1.1 kilograms are melting mixing dispersion in 40: 1 the twin screw extruder to monomethylaniline (Shanghai traditional Chinese medicines) in length-to-diameter ratio; Extrusion temperature is 200 ℃; Extruding pelletization finally obtains the block copolymerization polypropylene material.
The gentle low temperature impact strength of above-mentioned block copolymerization polypropylene usable material chamber is better, under high-speed stretch, shows high toughness and ductility, is difficult for embrittlement; Tensile strength>=24MPa; Tension set>=300%, modulus in flexure>=1200MPa, notched Izod impact strength>=50KJ/m 2, performance is following:
Performance Unit Testing standard Test result
Vicat softening point ℃ ISO75/1-93 112
Tensile strength MPa ISO527/2-93 26
Elongation at break ％ ISO527/2-93 340
Flexural strength MPa ISO178-93 38
Modulus in flexure MPa ISO178-93 1410
Notched Izod impact strength KJ/m 2 ISO180-93 57
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 following:
Voltage withstand class: 2.21MPa (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 block copolymerization polypropylene PP EPS30R (Qilu Petrochemical), 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 quinacridones red (dark trade is gushed in Ningbo) 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 block copolymerization polypropylene material.
The gentle low temperature impact strength of above-mentioned block copolymerization polypropylene usable material chamber is better, under high-speed stretch, shows high toughness and ductility, is difficult for embrittlement; Tensile strength>=24MPa; Tension set>=300%, modulus in flexure>=1200MPa, notched Izod impact strength>=50KJ/m 2, performance is following:
Performance Unit Testing standard Test result
Vicat softening point ℃ ISO75/1-93 114
Tensile strength MPa ISO527/2-93 25.8
Elongation at break ％ ISO527/2-93 360
Flexural strength MPa ISO178-93 37
Modulus in flexure MPa ISO178-93 1380
Notched Izod impact strength KJ/m 2 ISO180-93 56
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 following:
Voltage withstand class: 2.22MPa (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 (39)

1. block copolymerization polypropylene compsn that water heater liner is used, said compsn comprises following component:
(a) block copolymerization polypropylene of 100 weight parts;
(b) in the block copolymerization polypropylene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the block copolymerization polypropylene of 100 weight parts, the processing aid of 0.01-10 weight part, said processing aid are selected from one or more in lower molecular weight ester cpds, metallic soap compound, Triple Pressed Stearic Acid complex ester compound and the amide compound;
(d) in the block copolymerization polypropylene of 100 weight parts, the beta crystal-type nucleater of 0.01-10 weight part,
Beta crystal-type nucleater is selected from rare earth organic complex or its combination that fragrant amide compound, aromatic amines compound, REE and organic cpds form.
2. compsn as claimed in claim 1 is characterized in that, said 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.
3. compsn as claimed in claim 2 is characterized in that, said 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.
4. compsn as claimed in claim 3 is characterized in that, said phenolic compound is selected from hindered phenol 1010, hindered phenol 1076, hindered phenol 330, hindered phenol 168, dihydroxyphenyl propane, bisphenol-c, DBPC 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) or its combination.
5. compsn as claimed in claim 2 is characterized in that said amine compound is selected from naphthylamines, pentanoic, Ursol D, quinoline and combination thereof.
6. compsn as claimed in claim 2 is characterized in that, said 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.
7. compsn as claimed in claim 2 is characterized in that, said 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.
8. compsn as claimed in claim 2 is characterized in that, the mixture of said acryl functional group and monothioester is a Tyox B.
9. compsn as claimed in claim 2; It is characterized in that said 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.
10. compsn as claimed in claim 1 is characterized in that, said lower molecular weight ester cpds is the lower molecular weight stearate.
11. compsn as claimed in claim 10 is characterized in that, said lower molecular weight stearate is single, two or three Triple Pressed Stearic Acid alkyl esters.
12. compsn as claimed in claim 10 is characterized in that, said lower molecular weight ester cpds is selected from methyl stearate, Stearic ethyl stearate, Triple Pressed Stearic Acid propyl ester, butyl stearate, glyceryl monostearate, three Triple Pressed Stearic Acid triglyceride level or its combination.
13. compsn as claimed in claim 1 is characterized in that, said metallic soap compound comprises carboxylate salt.
14. compsn as claimed in claim 13 is characterized in that, said carboxylate salt is lead salt, barium salt, cadmium salt, zinc salt and/or the calcium salt of carboxylic acid.
15. compsn as claimed in claim 1; It is characterized in that said 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.
16. compsn as claimed in claim 1 is characterized in that, said Triple Pressed Stearic Acid complex ester compound comprises polyvalent alcohol list or many stearates.
17. compsn as claimed in claim 1; It is characterized in that said Triple Pressed Stearic Acid complex ester compound is selected from Tripolyglycerol monostearates, poly-glycerol monostearate, sorbitol monostearate, ethylene glycol monostearate, YMS 2,, dimerization Zerol, trimerization Stearic diglyceride, poly-glycerol SUNSOFT Q-182S, sorbyl alcohol SUNSOFT Q-182S, Unister E 275, polyglycol distearate, sorbitol anhydride SUNSOFT Q-182S, dimerization Stearic diglyceride and combination thereof.
18. compsn as claimed in claim 1 is characterized in that, said amide compound comprises carboxylic acid amide.
19. compsn as claimed in claim 18; It is characterized in that said carboxylic acid amide 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.
20. compsn as claimed in claim 1 is characterized in that, said fragrant amide type compound is selected from benzamide, to the methylbenzene acid amides, to the ethylbenzene acid amides, to tert.-butylbenzene acid amides or its combination.
21. compsn as claimed in claim 1 is characterized in that, said aromatic amines compound is selected from aniline, to monomethylaniline, to MEA, p-tert-butyl-aniline or its combination.
22. compsn as claimed in claim 1 is characterized in that, the rare earth organic complex that said REE and organic cpds form is the title complex of lanthanon and organic heterocyclic molecule, fused ring compound, aliphatic carboxylic acid or aromatic carboxylic acid.
23. compsn as claimed in claim 22 is characterized in that, said lanthanon is selected from lanthanum, cerium, praseodymium, neodymium or yttrium.
24. compsn as claimed in claim 1 is characterized in that, the rare earth organic complex that said REE and organic cpds form is the salt of IIIB family REE and C4-C28 carboxylic acid or the title complex that the C4-C28 carboxylic acid forms.
25. compsn as claimed in claim 1; It is characterized in that the rare earth organic complex that said REE and organic cpds form is selected from lanthanum: the mixture of the mixture of quinacridone title complex, Triple Pressed Stearic Acid lanthanum, oleic acid lanthanum, LAURIC ACID 99 MIN lanthanum, Triple Pressed Stearic Acid lanthanum and stearin, Triple Pressed Stearic Acid lanthanum and stearic mixture, Triple Pressed Stearic Acid samarium and stearin or its combination.
26. compsn as claimed in claim 1 is characterized in that, in the Vestolen PP 7052 of 100 weight parts, the content of thermo-stabilizer is the 0.1-5 weight part.
27. compsn as claimed in claim 1 is characterized in that, in the Vestolen PP 7052 of 100 weight parts, the content of thermo-stabilizer is the 0.2-3 weight part.
28. compsn as claimed in claim 1 is characterized in that, in the Vestolen PP 7052 of 100 weight parts, the content of thermo-stabilizer is the 0.3-2 weight part.
29. compsn as claimed in claim 1 is characterized in that, in the Vestolen PP 7052 of 100 weight parts, the consumption of processing aid is the 0.05-5 weight part.
30. compsn as claimed in claim 1 is characterized in that, in the Vestolen PP 7052 of 100 weight parts, the consumption of processing aid is the 0.1-2 weight part.
31. compsn as claimed in claim 1 is characterized in that, in the Vestolen PP 7052 of 100 weight parts, the consumption of processing aid is the 0.5-1 weight part.
32. compsn as claimed in claim 1 is characterized in that, in the Vestolen PP 7052 of 100 weight parts, the consumption of beta crystal-type nucleater is the 0.01-8 weight part.
33. compsn as claimed in claim 1 is characterized in that, in the Vestolen PP 7052 of 100 weight parts, the consumption of beta crystal-type nucleater is the 0.02-5 weight part.
34. compsn as claimed in claim 1 is characterized in that, in the Vestolen PP 7052 of 100 weight parts, the consumption of beta crystal-type nucleater is the 0.03-4 weight part.
35. the beta crystal block copolymerization polypropylene material that water heater liner is used, said material is processed by the described block copolymerization polypropylene compsn of claim 1, and said compsn comprises following component:
(a) block copolymerization polypropylene of 100 weight parts;
(b) in the block copolymerization polypropylene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the block copolymerization polypropylene of 100 weight parts, the processing aid of 0.01-10 weight part, said processing aid are selected from one or more in lower molecular weight ester cpds, metallic soap compound, Triple Pressed Stearic Acid complex ester compound and the amide compound;
(d) in the block copolymerization polypropylene of 100 weight parts, the beta crystal-type nucleater of 0.01-10 weight part,
Beta crystal-type nucleater is selected from rare earth organic complex or its combination that fragrant amide compound, aromatic amines compound, REE and organic cpds form.
36. a method for preparing the beta crystal block copolymerization polypropylene material that water heater liner uses, said method comprises: with forcing machine with the described block copolymerization polypropylene compsn of claim 1 extruding pelletization.
37. the inner bag that water-heater is used, said inner bag is processed by the described Beta-crystalline polyacrylic material of claim 35.
38. the purposes of a compsn in the preparation water heater liner, said compsn comprises following component:
(a) block copolymerization polypropylene of 100 weight parts;
(b) in the block copolymerization polypropylene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the block copolymerization polypropylene of 100 weight parts, the processing aid of 0.01-10 weight part, said processing aid are selected from one or more in lower molecular weight ester cpds, metallic soap compound, Triple Pressed Stearic Acid complex ester compound and the amide compound;
(d) in the block copolymerization polypropylene of 100 weight parts, the beta crystal-type nucleater of 0.01-10 weight part,
Beta crystal-type nucleater is selected from rare earth organic complex or its combination that fragrant amide compound, aromatic amines compound, REE and organic cpds form.
39. a water-heater, said water-heater comprise the inner bag that the described water-heater of claim 37 is used.
CN200910247219A 2009-12-28 2009-12-28 Beta crystal form polypropylene composite for water heater tank and preparation method thereof Active CN101914262B (en)

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CN1446829A (en) * 2002-03-26 2003-10-08 住友化学工业株式会社 Propenyl polymer and injection moulded products made therefrom
CN1506401A (en) * 2002-12-06 2004-06-23 三井化学株式会社 Propylene resin composition and use thereof
CN101358012A (en) * 2008-09-11 2009-02-04 武汉大学 Combination and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1446829A (en) * 2002-03-26 2003-10-08 住友化学工业株式会社 Propenyl polymer and injection moulded products made therefrom
CN1506401A (en) * 2002-12-06 2004-06-23 三井化学株式会社 Propylene resin composition and use thereof
CN101358012A (en) * 2008-09-11 2009-02-04 武汉大学 Combination and application thereof

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