CN101768310A - Beta-crystal polypropylene composition for inner container of water heater and preparation method thereof - Google Patents
Beta-crystal polypropylene composition for inner container of water heater and preparation method thereof Download PDFInfo
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- CN101768310A CN101768310A CN200910247217A CN200910247217A CN101768310A CN 101768310 A CN101768310 A CN 101768310A CN 200910247217 A CN200910247217 A CN 200910247217A CN 200910247217 A CN200910247217 A CN 200910247217A CN 101768310 A CN101768310 A CN 101768310A
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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
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- 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 random copolymerized polypropylene composition for an inner container of a water heater. The composition comprises the following components in part by weight: (a) 100 parts of random copolymerized polypropylene, (b) 0.01 to 10 parts of heat stabilizer, (c) 0.01 to 10 parts of processing aid and (d) 0.01 to 10 parts of beta-crystal nucleating agent, wherein the processing aid is one or more of low molecular weight ester compound, metallic soap compound, stearic acid complex ester compound and amide compound. The beta-crystal random copolymerized polypropylene material overcomes the defect of insufficient rigidity of common random copolymerized polypropylene, and has high thermal deformation temperature; and the tensile strength is more than or equal to 27MPa, the elongation at break is more than or equal to 500 percent, the bending modulus is more than or equal to 1,300MPa, and the notch impact strength is more than or equal to 70kJ/m<2>.
Description
Technical field
The present invention relates to a kind of water heater liner with beta crystal atactic copolymerized polypropene 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, beta crystal-type nucleater is to use the most sophisticated nucleator in the polypropylene.
Beta crystal-type nucleater has effectively solved the insufficient shortcoming of common atactic copolymerized polypropene rigidity, obviously improves the tensile strength and the modulus in flexure of polypropylene material, and improves the heat-drawn wire 10-15 degree of atactic copolymerized polypropene.This makes the atactic copolymerized polypropene 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 atactic copolymerized polypropene 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: the atactic copolymerized polypropene 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 atactic copolymerized polypropene 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 atactic copolymerized polypropene) 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 invention provides the atactic copolymerized polypropene composition that a kind of water heater liner is used, described composition comprises following component:
(a) atactic copolymerized polypropene of 100 weight parts;
(b) in the atactic copolymerized polypropene 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 atactic copolymerized polypropene 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 atactic copolymerized polypropene 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, 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 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, rare earth element and organic compound form.
In a preferred embodiment of the present invention, described 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; Described aromatic amines compound generally can be but be not limited to aniline, to monomethylaniline, to ethylaniline, p-tert-butyl-aniline and combination thereof; The rare earth organic complex that described rare earth element and organic compound form comprises the title complex of lanthanon (as 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 rare earth element and organic compound formation comprises the salt of IIIB family rare earth element and C4-C28 carboxylic acid and the title complex that the C4-C28 carboxylic acid forms; Better, the rare earth organic complex of affiliated rare earth element and organic compound formation is selected from lanthanum: the mixture and the combination thereof of the mixture of quinacridone title complex, stearic acid lanthanum, oleic acid lanthanum, lauric acid lanthanum, stearic acid lanthanum and stearin, stearic acid lanthanum and stearic mixture, stearic acid samarium and stearin; The salt of described imido acid and IIA family metal comprises imido acid calcium; The mixture of described machine carboxylic acid and IIA family metal-salt comprises the mixture of pimelic acid and calcium stearate; Described 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 atactic copolymerized polypropene material that a kind of water heater liner is used, described material is made by atactic copolymerized polypropene composition of the present invention, and described composition comprises following component:
(a) atactic copolymerized polypropene of 100 weight parts;
(b) in the atactic copolymerized polypropene 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 atactic copolymerized polypropene 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 atactic copolymerized polypropene 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 atactic copolymerized polypropene material that water heater liner uses, described method comprises: with forcing machine with atactic copolymerized polypropene composition extruding pelletization of the present invention.
The invention provides the inner bag that a kind of water-heater is used, described inner bag is made by Beta-crystalline polyacrylic 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) atactic copolymerized polypropene of 100 weight parts;
(b) in the atactic copolymerized polypropene 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 atactic copolymerized polypropene 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 atactic copolymerized polypropene 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, described water-heater comprises the inner bag that water-heater of the present invention is used.
The gentle low temperature impact strength of beta crystal atactic copolymerized polypropene usable material chamber of the present invention is better, shows high toughness and ductility under high-speed stretch, is difficult for embrittlement, tensile strength 〉=27MPa, tension set 〉=500%, modulus in flexure 〉=1300MPa, notched Izod impact strength 〉=70KJ/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 atactic copolymerized polypropene composition that one aspect of the present invention provides a kind of water heater liner to use, described composition comprises following component:
(a) atactic copolymerized polypropene of 100 weight parts;
(b) in the atactic copolymerized polypropene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the atactic copolymerized polypropene 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 atactic copolymerized polypropene of 100 weight parts, the beta crystal-type nucleater of 0.01-10 weight part.
In the present invention, described atactic copolymerized polypropene is conventional, and it can be a polypropylene commonly used arbitrarily in this area.In a preferred embodiment of the present invention, described atactic copolymerized polypropene is the atactic copolymerized polypropene of melt flow rate (MFR) at 0.01-100g/10min.In another preferred embodiment of the present invention, described atactic copolymerized polypropene comprises PP R4220 (Yanshan Petrochemical), PP SM256 (the big rattan of Malaysia), PP RP346R (CSPC).
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, 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.In a preferred embodiment of the present invention, described 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, 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 (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, described 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 described 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.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 (lark prestige).
In atactic copolymerized polypropene 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 atactic copolymerized polypropene 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 (vapour crust).
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 (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 (sky, Zhengzhou leads to food ingredients company limited).
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 (chemical industry is won in the Shandong).
In atactic copolymerized polypropene 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 atactic copolymerized polypropene of 100 weight parts.
In the present invention, described beta-nucleated dose is conventional, and which beta-nucleated dose those of ordinary skill in the art can direct derivation go 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 mixture and the quinacridone red that beta-nucleated dose of polypropylene (as homo-polypropylene) 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, rare earth element and organic compound form.
In the present invention, described 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, described fragrant amide type compound is selected from TMB-5 (Shanxi chemical institute).
In the present invention, described aromatic amines compound generally can be but be not limited to aniline, to monomethylaniline, to ethylaniline, p-tert-butyl-aniline and combination thereof.In a preferred embodiment of the present invention, described aromatic amines compound is selected from monomethylaniline (Shanghai traditional Chinese medicines).
In the present invention, the rare earth organic complex that described rare earth element and organic compound form can be specifically referring to CN02134498.1, for example the title complex of lanthanon (as 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 (as stearic acid, oleic acid, lauric acid, Succinic Acid, hexanodioic acid, pimelic acid, sebacic acid, diethyl caproic acid, fumaric acid, maleic anhydride, octyl group toxilic acid, epoxyoleic acid, amino acid, Whitfield's ointment, stearin, pentaerythritol ester).In another example of the present invention, under the rare earth organic complex that forms of rare earth element and organic compound can be referring to CN00117339.1, the title complex (can arrive page 2 the 5th referring to specification sheets page 1 the 2nd row reciprocal goes) that forms of the salt of IIIB family rare earth element and C4-C28 carboxylic acid and C4-C28 carboxylic acid for example.In a preferred embodiment of the present invention, the rare earth organic complex that affiliated rare earth element and organic compound form is selected from lanthanum: the mixture and the combination thereof of mixture, stearic acid lanthanum and stearic mixture, stearic acid samarium and the stearin of quinacridone title complex (referring to the embodiment 1 of CN02134498.1), stearic acid lanthanum, oleic acid lanthanum, lauric acid lanthanum, stearic acid lanthanum and stearin.
In the present invention, the salt of described 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 described 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, described 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 composition thereof.In a preferred embodiment of the present invention, the red quinacridone red (dark trade is gushed in Ningbo) that is selected from of described quinacridone.
In homopolymerization polypropylene composition of the present invention, described 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 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 beta crystal atactic copolymerized polypropene material that the present invention provides a kind of water heater liner to use on the other hand, described material is made by atactic copolymerized polypropene composition of the present invention, and described composition comprises following component:
(a) atactic copolymerized polypropene of 100 weight parts;
(b) in the atactic copolymerized polypropene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the atactic copolymerized polypropene 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 atactic copolymerized polypropene 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 atactic copolymerized polypropene material that water heater liner uses on the other hand, and described method comprises: with forcing machine with atactic copolymerized polypropene 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 atactic copolymerized polypropene, 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 described atactic copolymerized polypropene, thermo-stabilizer, processing aid, beta crystal-type nucleater extruding pelletization in the atactic copolymerized polypropene 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 Beta-crystalline polyacrylic 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) atactic copolymerized polypropene of 100 weight parts;
(b) in the atactic copolymerized polypropene of 100 weight parts, the thermo-stabilizer of 0.01-10 weight part;
(c) in the atactic copolymerized polypropene 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 atactic copolymerized polypropene 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, shows high toughness and ductility under high-speed stretch, is difficult for embrittlement, tensile strength 〉=27MPa, tension set 〉=500%, modulus in flexure 〉=1300MPa, notched Izod impact strength 〉=70KJ/m
2, 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 atactic copolymerized polypropene PP R4220 (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 atactic copolymerized polypropene material.
The gentle low temperature impact strength of above-mentioned atactic copolymerized polypropene usable material chamber is better, shows high toughness and ductility under high-speed stretch, is difficult for embrittlement, tensile strength 〉=27MPa, tension set 〉=500%, modulus in flexure 〉=1300MPa, notched Izod impact strength 〉=70KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ??℃ | ??ISO75/1-93 | ??106 |
| Tensile strength | ??MPa | ??ISO527/2-93 | ??28 |
| Elongation at break | ??％ | ??ISO527/2-93 | ??560 |
| Flexural strength | ??MPa | ??ISO178-93 | ??34 |
| Modulus in flexure | ??MPa | ??ISO178-93 | ??1380 |
| Notched Izod impact strength | ??KJ/m 2 | ??ISO180-93 | ??75 |
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: 1.6MPa (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 140 ℃ of high temperature.
Embodiment 2
With 100 kilograms of atactic copolymerized polypropene PP SM256 (the big rattan of Malaysia), 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 (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 atactic copolymerized polypropene material.
The gentle low temperature impact strength of above-mentioned atactic copolymerized polypropene usable material chamber is better, shows high toughness and ductility under high-speed stretch, is difficult for embrittlement, tensile strength 〉=27MPa, tension set 〉=500%, modulus in flexure 〉=1300MPa, notched Izod impact strength 〉=70KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ??℃ | ??ISO75/1-93 | ??108 |
| Tensile strength | ??MPa | ??ISO527/2-93 | ??29 |
| Elongation at break | ??％ | ??ISO527/2-93 | ??580 |
| Flexural strength | ??MPa | ??ISO178-93 | ??35 |
| Modulus in flexure | ??MPa | ??ISO178-93 | ??1420 |
| Notched Izod impact strength | ??KJ/m 2 | ??ISO180-93 | ??78 |
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: 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 146 ℃ of high temperature.
Embodiment 3
With 100 kilograms of atactic copolymerized polypropene PP RP346R (CSPC), 0.3 kilogram of thermo-stabilizer Irganox 1010 (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 (by 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 atactic copolymerized polypropene material.
The gentle low temperature impact strength of above-mentioned atactic copolymerized polypropene usable material chamber is better, shows high toughness and ductility under high-speed stretch, is difficult for embrittlement, tensile strength 〉=27MPa, tension set 〉=500%, modulus in flexure 〉=1300MPa, notched Izod impact strength 〉=70KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ??℃ | ??ISO75/1-93 | ??105 |
| Tensile strength | ??MPa | ??ISO527/2-93 | ??28 |
| Elongation at break | ??％ | ??ISO527/2-93 | ??590 |
| Flexural strength | ??MPa | ??ISO178-93 | ??35 |
| Modulus in flexure | ??MPa | ??ISO178-93 | ??1380 |
| Notched Izod impact strength | ??KJ/m 2 | ??ISO180-93 | ??80 |
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: 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 148 ℃ of high temperature.
Embodiment 4
With 100 kilograms of atactic copolymerized polypropene PP R4220 (Yanshan Petrochemical), 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 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 atactic copolymerized polypropene material.
The gentle low temperature impact strength of above-mentioned atactic copolymerized polypropene usable material chamber is better, shows high toughness and ductility under high-speed stretch, is difficult for embrittlement, tensile strength 〉=27MPa, tension set 〉=500%, modulus in flexure 〉=1300MPa, notched Izod impact strength 〉=70KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ??℃ | ??ISO75/1-93 | ??107 |
| Tensile strength | ??MPa | ??ISO527/2-93 | ??27 |
| Elongation at break | ??％ | ??ISO527/2-93 | ??600 |
| Flexural strength | ??MPa | ??ISO178-93 | ??33 |
| Modulus in flexure | ??MPa | ??ISO178-93 | ??1350 |
| Notched Izod impact strength | ??KJ/m | ??ISO180-93 | ??81 |
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: 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 141 ℃ of high temperature.
Embodiment 5
With 100 kilograms of atactic copolymerized polypropene PP SM256 (the big rattan of Malaysia), 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 atactic copolymerized polypropene material.
The gentle low temperature impact strength of above-mentioned atactic copolymerized polypropene usable material chamber is better, shows high toughness and ductility under high-speed stretch, is difficult for embrittlement, tensile strength 〉=27MPa, tension set 〉=500%, modulus in flexure 〉=1300MPa, notched Izod impact strength 〉=70KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ??℃ | ??ISO75/1-93 | ??102 |
| Tensile strength | ??MPa | ??ISO527/2-93 | ??28.5 |
| Elongation at break | ??％ | ??ISO527/2-93 | ??500 |
| Performance | Unit | Testing standard | Test result |
| Flexural strength | ??MPa | ??ISO178-93 | ??31 |
| Modulus in flexure | ??MPa | ??ISO178-93 | ??1320 |
| Notched Izod impact strength | ??KJ/m 2 | ??ISO180-93 | ??75 |
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 146 ℃ 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 atactic copolymerized polypropene PP SM256 (the big rattan of Malaysia), 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 atactic copolymerized polypropene material.
The gentle low temperature impact strength of above-mentioned atactic copolymerized polypropene usable material chamber is better, shows high toughness and ductility under high-speed stretch, is difficult for embrittlement, tensile strength 〉=27MPa, tension set 〉=500%, modulus in flexure 〉=1300MPa, notched Izod impact strength 〉=70KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ??℃ | ??ISO75/1-93 | ??108 |
| Tensile strength | ??MPa | ??ISO527/2-93 | ??29 |
| Elongation at break | ??％ | ??ISO527/2-93 | ??560 |
| Flexural strength | ??MPa | ??ISO178-93 | ??34 |
| Modulus in flexure | ??MPa | ??ISO178-93 | ??1350 |
| Notched Izod impact strength | ??KJ/m 2 | ??ISO180-93 | ??77 |
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: 2.37MPa (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 147 ℃ of high temperature.
Embodiment 7
With 100 kilograms of atactic copolymerized polypropene PP SM256 (the big rattan of Malaysia), 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 atactic copolymerized polypropene material.
The gentle low temperature impact strength of above-mentioned atactic copolymerized polypropene usable material chamber is better, shows high toughness and ductility under high-speed stretch, is difficult for embrittlement, tensile strength 〉=27MPa, tension set 〉=500%, modulus in flexure 〉=1300MPa, notched Izod impact strength 〉=70KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ??℃ | ??ISO75/1-93 | ??109 |
| Tensile strength | ??MPa | ??ISO527/2-93 | ??28.8 |
| Elongation at break | ??％ | ??ISO527/2-93 | ??590 |
| Performance | Unit | Testing standard | Test result |
| Flexural strength | ??MPa | ??ISO178-93 | ??36 |
| Modulus in flexure | ??MPa | ??ISO178-93 | ??1380 |
| Notched Izod impact strength | ??KJ/m 2 | ??ISO180-93 | ??79 |
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: 2.36MPa (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 149 ℃ of high temperature.
Embodiment 8
With 100 kilograms of atactic copolymerized polypropene PP SM256 (the big rattan of Malaysia), 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 atactic copolymerized polypropene material.
The gentle low temperature impact strength of above-mentioned atactic copolymerized polypropene usable material chamber is better, shows high toughness and ductility under high-speed stretch, is difficult for embrittlement, tensile strength 〉=27MPa, tension set 〉=500%, modulus in flexure 〉=1300MPa, notched Izod impact strength 〉=70KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ??℃ | ??ISO75/1-93 | ??107 |
| Tensile strength | ??MPa | ??ISO527/2-93 | ??29.2 |
| Elongation at break | ??％ | ??ISO527/2-93 | ??570 |
| Flexural strength | ??MPa | ??ISO178-93 | ??37 |
| Modulus in flexure | ??MPa | ??ISO178-93 | ??1400 |
| Notched Izod impact strength | ??KJ/m 2 | ??ISO180-93 | ??75 |
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: 2.32MPa (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 atactic copolymerized polypropene PP SM256 (Malaysia big rattan), 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 atactic copolymerized polypropene material.
The gentle low temperature impact strength of above-mentioned atactic copolymerized polypropene usable material chamber is better, shows high toughness and ductility under high-speed stretch, is difficult for embrittlement, tensile strength 〉=27MPa, tension set 〉=500%, modulus in flexure 〉=1300MPa, notched Izod impact strength 〉=70KJ/m
2, performance is as follows:
| Performance | Unit | Testing standard | Test result |
| Vicat softening point | ??℃ | ??ISO75/1-93 | ??111 |
| Tensile strength | ??MPa | ??ISO527/2-93 | ??28 |
| Elongation at break | ??％ | ??ISO527/2-93 | ??540 |
| Flexural strength | ??MPa | ??ISO178-93 | ??38 |
| Modulus in flexure | ??MPa | ??ISO178-93 | ??1410 |
| Notched Izod impact strength | ??KJ/m 2 | ??ISO180-93 | ??72 |
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: 2.29MPa (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.
Claims (10)
1. atactic copolymerized polypropene composition that water heater liner is used, described composition comprises following component:
(a) atactic copolymerized polypropene of 100 weight parts;
(b) in the atactic copolymerized polypropene 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 atactic copolymerized polypropene 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 atactic copolymerized polypropene 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.
2. 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; 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.
3. composition as claimed in claim 1 is characterized in that, 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.
4. composition as claimed in claim 1, it is characterized in that described 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, rare earth element and organic compound form.
5. composition as claimed in claim 1 is characterized in that, described 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; Described aromatic amines compound generally can be but be not limited to aniline, to monomethylaniline, to ethylaniline, p-tert-butyl-aniline and combination thereof; The rare earth organic complex that described rare earth element and organic compound form comprises the title complex of lanthanon (as 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 rare earth element and organic compound formation comprises the salt of IIIB family rare earth element and C4-C28 carboxylic acid and the title complex that the C4-C28 carboxylic acid forms; Better, the rare earth organic complex of affiliated rare earth element and organic compound formation is selected from lanthanum: the mixture and the combination thereof of the mixture of quinacridone title complex, stearic acid lanthanum, oleic acid lanthanum, lauric acid lanthanum, stearic acid lanthanum and stearin, stearic acid lanthanum and stearic mixture, stearic acid samarium and stearin; The salt of described imido acid and IIA family metal comprises imido acid calcium; The mixture of described machine carboxylic acid and IIA family metal-salt comprises the mixture of pimelic acid and calcium stearate; Described quinacridone is red to be selected from that quinacridone is red, quinacridone is red 122, the red E5B of quinacridone and combination thereof.
6. beta crystal atactic copolymerized polypropene material that water heater liner is used, described material is made by the described atactic copolymerized polypropene composition of claim 1, and described composition comprises following component:
(a) atactic copolymerized polypropene of 100 weight parts;
(b) in the atactic copolymerized polypropene 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 atactic copolymerized polypropene 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 atactic copolymerized polypropene 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.
7. method for preparing the beta crystal atactic copolymerized polypropene material that water heater liner uses, described method comprises: with forcing machine with the described atactic copolymerized polypropene composition of claim 1 extruding pelletization.
8. inner bag that water-heater is used, described inner bag is made by the described Beta-crystalline polyacrylic material of claim 6.
9. the composition purposes in the preparation water heater liner, described composition comprises following component:
(a) atactic copolymerized polypropene of 100 weight parts;
(b) in the atactic copolymerized polypropene 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 atactic copolymerized polypropene 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 atactic copolymerized polypropene 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.
10. water-heater, described water-heater comprises the inner bag that the described water-heater of claim 8 is used.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910247217A CN101768310A (en) | 2009-12-28 | 2009-12-28 | Beta-crystal polypropylene composition for inner container of water heater and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910247217A CN101768310A (en) | 2009-12-28 | 2009-12-28 | Beta-crystal polypropylene composition for inner container of water heater and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665587A (en) * | 2012-09-21 | 2014-03-26 | 中国石油化工股份有限公司 | Polypropylene composition, polypropylene aggregates and preparation method thereof and polypropylene pressure pipeline |
| CN106009308A (en) * | 2016-05-27 | 2016-10-12 | 威迪亚（长泰）科技有限公司 | High heat-resistant elastomer mixed material and preparation method thereof |
| CN106188877A (en) * | 2016-09-05 | 2016-12-07 | 聊城大学 | A kind of β crystalline substance PPR pipe and preparation method |
| CN106380698A (en) * | 2016-09-05 | 2017-02-08 | 聊城大学 | Beta-crystal PPR pipe fitting and production method thereof |
| CN108410064A (en) * | 2018-04-02 | 2018-08-17 | 肇庆益晟商贸有限公司 | A kind of High-impact Polypropylene and preparation method and application of amion acetic acid modification |
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2009
- 2009-12-28 CN CN200910247217A patent/CN101768310A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665587A (en) * | 2012-09-21 | 2014-03-26 | 中国石油化工股份有限公司 | Polypropylene composition, polypropylene aggregates and preparation method thereof and polypropylene pressure pipeline |
| CN103665587B (en) * | 2012-09-21 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of polypropene composition and polypropylene granules and preparation method thereof and polypropylene pressure pipeline |
| CN106009308A (en) * | 2016-05-27 | 2016-10-12 | 威迪亚（长泰）科技有限公司 | High heat-resistant elastomer mixed material and preparation method thereof |
| CN106009308B (en) * | 2016-05-27 | 2019-01-22 | 威迪亚（长泰）科技有限公司 | A kind of high heat resistance elastomer mixing material and preparation method thereof |
| CN106188877A (en) * | 2016-09-05 | 2016-12-07 | 聊城大学 | A kind of β crystalline substance PPR pipe and preparation method |
| CN106380698A (en) * | 2016-09-05 | 2017-02-08 | 聊城大学 | Beta-crystal PPR pipe fitting and production method thereof |
| CN108410064A (en) * | 2018-04-02 | 2018-08-17 | 肇庆益晟商贸有限公司 | A kind of High-impact Polypropylene and preparation method and application of amion acetic acid modification |
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