CN102827421B - Polypropylene material and preparation method thereof - Google Patents
Polypropylene material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polypropylene material and a preparation method for the polypropylene material. The polypropylene material is prepared in parts in weight: mixing 100 parts of polypropylene resin, 30-80 parts of flexibilizer, 2-4 parts of ethylene based multifunctional group monomer, 1.5-2.5 parts of hindered amine compound of a structure in a formula (I) and 0.15-0.25 parts of antioxygen, extruding, prilling and irradiating. Compared with a modified mode of mixing a light stabilizer and the polypropylene material in the prior art, the polypropylene material uses a modified mode that the hindered amine compound of the structure in the formula (I) serves as the light stabilizer to be mixed with the polypropylene material for irradiation. Firstly, the hindered amine compound contains end alkenyl groups with an unsaturated bond, and the hindered amine compound can be grafted on a macromolecule chain, so that the light stabilizer is not easy to move to a surface of the material; and secondly, modification is carried out by using irradiation, so that the material can form a three-dimensional space grid structure through crosslinking to limit movement of a molecular chain at the high temperature so as to improve heat-resistant property of the material.
Description
Technical field
The invention belongs to technical field of polymer materials, relate in particular to a kind of polypropylene material and preparation method thereof.
Background technology
Polypropylene is the macromolecular compound being obtained by polymerization by propylene, compares with other general-purpose thermoplastic plastics, has abundant raw material, an advantage such as cheap, relative density is little, proof stress, resistance to chemical attack, wear resistance are good.And, good, the easy processing of mechanics equalization performance, resistance to impact shock, resistance to flexing and the electrical insulating property of polypropylene material are good, be the best product of thermotolerance in resins for universal use, be widely used in the conventional fields such as daily necessities, textiles, automobile component and the manufacture of part medical apparatus.Though polypropylene from output and consumption, or from its existing performance, one of the most promising material in plastics beyond doubt.But polypropylene contains unsettled tertiary carbon group, be vulnerable to heat, oxygen and ultraviolet attack and the bad change of performance occurs, as xanthochromia, check surface and efflorescence, mechanical property significantly declines, and along with the prolongation in storage time, polyacrylic degraded meeting sustainable development, until lose use value.Therefore, many products all propose the requirement of long-term illumination aging resisting performance modification to polypropylene.
Polypropylene modification can be divided into chemical modification and two kinds of methods of physically modified.Chemical modification is mainly by copolymerization, grafting, the mode such as crosslinked, changes polyacrylic molecular structure to reach the object of modification; In whole process, there is not chemical reaction in physically modified, in polypropylene matrix, add inorganic materials, organic materials, other plastics, rubber, thermoplastic elastomer or have the interpolation auxiliary agent etc. of specific function, through means such as blend, enhancing or fillings, make the polypropylene composite material with excellent properties.
At present, the illumination aging resisting performance modification of polypropylene material, be mainly by adding various photostabilizers and heat-proof aging auxiliary agent and utilizing two kinds of synergies between auxiliary agent to realize, and photostabilizer and heat-proof aging auxiliary agent are to be directly scattered in material system by blend.But most of light stabilization aid comprises that various photomask agent, UV light absorber, radical scavenger etc. are all organic compound or the oligopolymer that molecular weight is lower, and its speed to material surface migration is very fast.When these auxiliary agents are added in polypropylene, the in the situation that of high temperature or UV-irradiation, there is the trend of separating out to product surface gradually.
Application number is that the Chinese patent of CN96197212.2 discloses a kind of radiation tolerant polypropylene and product thereof, polypropylene by 50% ~ 99% and 1% ~ 50% polyethylene blend, add the anti-irradiation transparent polypropylenes of preparation such as hindered amine stabilizer, auxiliary antioxidant and nucleator.The interpolation of stablizer is only by the method for physical blending, and it is easy to move to material surface; And hindered amine stabilizer is soluble in the organic solvents such as methylcarbonate, while usining its photostabilizer life-time service as sealing material, also can be dissolved in solvent and separate out, cause the illumination aging resisting performance of material to decline.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of polypropylene material and preparation method thereof, and the illumination aging resisting performance of this polypropylene material is better.
The invention provides a kind of polypropylene material, mainly by following raw material, after blend, irradiation, prepared:
Acrylic resin 100 weight parts;
Toughner 30 ~ 80 weight parts;
Vinyl polyfunctional monomer 2 ~ 4 weight parts;
Hindered amine compound 1.5 ~ 2.5 weight parts of formula (I) structure;
Oxidation inhibitor 0.15 ~ 0.25 weight part;
Wherein, m=1 ~ 9, n=3 ~ 10.
Preferably, described antioxidant is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid or β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid.
Preferably, described vinyl polyfunctional monomer is trivinyl polyfunctional monomer or divinyl polyfunctional monomer.
Preferably, described trivinyl polyfunctional monomer is Viscoat 295, pentaerythritol triacrylate or cyanacrylate.
Preferably, described divinyl polyfunctional monomer is polyethyleneglycol diacrylate or PDDA.
Preferably, described toughner is thermoplastic elastomer.
Preferably, described thermoplastic elastomer is POE, styrene-butadiene-styrene, hydrogenated styrene-butadiene-styrene multipolymer, terpolymer EP rubber, natural rubber, styrene-butadiene rubber(SBR), paracril or isoprene-isobutylene rubber.
The preparation method who the invention provides a kind of polypropylene material, comprises the following steps:
The hindered amine compound of formula (I) structure of the vinyl polyfunctional monomer of the toughner of the acrylic resin of 100 weight parts, 30 ~ 80 weight parts, 2 ~ 4 weight parts, 1.5 ~ 2.5 weight parts is mixed with the antioxidant of 0.15 ~ 0.25 weight part, extruding pelletization, obtains polypropylene material after irradiation;
Wherein, m=1 ~ 9, n=3 ~ 10.
Preferably, the temperature of described extruding pelletization is 180 ℃ ~ 200 ℃.
Preferably, the radiation dose rate of described irradiation is 1000 ~ 5000rad/min, and irradiation dose is 5 ~ 30kGy.
The invention provides a kind of polypropylene material and preparation method thereof, this polypropylene material raw material comprises the acrylic resin of 100 weight parts, the hindered amine compound of formula (I) structure of the vinyl polyfunctional monomer of the toughner of 30 ~ 80 weight parts, 2 ~ 4 weight parts, 1.5 ~ 2.5 weight parts and the oxidation inhibitor of 0.15 ~ 0.25 weight part, raw material mixes through extruding pelletization, obtains polypropylene material after radiation.Directly carry out modification with polypropylene material blend with prior art photostabilizer and compare, it is that photostabilizer and polypropylene material blend are by radiation modification that the present invention utilizes the hindered amine compound of formula (I) structure.First, the end alkenyl group that the hindered amine compound of formula (I) structure contains unsaturated link(age), can be grafted on macromolecular chain through irradiation technique, form carbon-carbon bond, therefore photostabilizer is difficult for to material surface migration, also soluble separating out not, and the light stability of material strengthens; Secondly, the method for employing irradiation is carried out modification also can make material by being cross-linked to form three-dimensional space grid structure, has limited molecular chain motion at high temperature, thereby improves the resistance toheat of polypropylene material.
Experimental result shows, polypropylene material of the present invention tensile strength of material, modulus in flexure and normal temperature IZOD notched Izod impact strength retention after accelerated light ageing are all greater than 80%.
Embodiment
The invention provides a kind of polypropylene material, mainly by following raw material, prepared: the acrylic resin of 100 weight parts, the toughner of 30 ~ 80 weight parts, the vinyl polyfunctional monomer of 2 ~ 4 weight parts, the hindered amine compound of the formula of 1.5 ~ 2.5 weight parts (I) structure and the oxidation inhibitor of 0.15 ~ 0.25 weight part.
In formula (I), m=1 ~ 9, n=3 ~ 10.M is preferably 1 ~ 6, and more preferably 2 ~ 4.
Wherein, described toughner is preferably 40 ~ 80 weight parts, more preferably 50 ~ 70 weight parts.Described toughner is preferably thermoplastic elastomer, more preferably POE (POE), styrene-butadiene-styrene (SBS), hydrogenated styrene-butadiene-styrene multipolymer (SEBS), terpolymer EP rubber (EPDM), natural rubber (NR), styrene-butadiene rubber(SBR) (SBR), paracril (NBR) or isoprene-isobutylene rubber (IR), then be preferably POE, styrene-butadiene-styrene, terpolymer EP rubber or isoprene-isobutylene rubber.Toughner and the polypropene blended low-temperature impact toughness that can improve polypropylene material.
Described vinyl polyfunctional monomer is preferably 2.5 ~ 4 weight parts, more preferably 2.5 ~ 3.5 weight parts.Described vinyl polyfunctional monomer is preferably trivinyl polyfunctional monomer or divinyl polyfunctional monomer.Described trivinyl polyfunctional monomer is preferably Viscoat 295 (TMPTA), pentaerythritol triacrylate (PETA) or cyanacrylate (TAIC), more preferably Viscoat 295 or cyanacrylate; Described divinyl polyfunctional monomer is preferably polyethyleneglycol diacrylate (PEGDA) or PDDA (PDDA), more preferably PDDA.Due to polypropylene material easily degraded under radiation parameter, and vinyl polyfunctional monomer can impel polypropylene material crosslinked, therefore the use of vinyl polyfunctional monomer can reduce irradiation dosage used, suppresses to a certain extent degraded and the performance degradation of polypropylene material.
The hindered amine compound of described formula (I) structure is preferably 1.5 ~ 2.2 weight parts, 1.5 ~ 2 weight parts more preferably, the end alkenyl group that it contains unsaturated link(age), can be grafted on macromolecular chain through irradiation technique, form carbon-carbon bond, photostabilizer is difficult for to material surface migration, is also difficult for separating out because being dissolved in organic solvent, improved the resistance to light of polypropylene material.
Described oxidation inhibitor is preferably 0.15 ~ 0.22 weight part, more preferably 0.17 ~ 0.2 weight part.Described oxidation inhibitor is preferably 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid or β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid.
The present invention also provides the preparation method of above-mentioned polypropylene material, comprise the following steps: the hindered amine compound of formula (I) structure of the vinyl polyfunctional monomer of the toughner of the acrylic resin of 100 weight parts, 30 ~ 80 weight parts, 2 ~ 4 weight parts, 1.5 ~ 2.5 weight parts is mixed with the antioxidant of 0.15 ~ 0.25 weight part, add blend granulation in twin screw extruder, extrusion temperature is 180 ℃ ~ 200 ℃, be preferably 190 ℃ ~ 200 ℃, after irradiation, obtain polypropylene material.
According to the present invention, the masterbatch that described extruding pelletization obtains is preferably dried to moisture content and is less than 1.5 ‰, afterwards, carries out irradiation.The irradiation source of described irradiation is irradiation source well known to those skilled in the art, preferably adopts Co-60 source.The radiation dose rate of described irradiation is 1000 ~ 5000rad/min, is preferably 2000 ~ 4500rad/min, 2500 ~ 4000rad/min more preferably, and radiation dose rate is 5 ~ 30kGy, is preferably 10 ~ 30kGy, more preferably 10 ~ 20kGy.
Traditional blend method, when improving some performance of polypropylene material, can cause the significantly sacrificing of other aspect performances conventionally, and wherein relatively more outstanding is exactly the balance between polypropylene material low-temperature flexibility and resistance toheat.In the present invention, adopt the method for blend softening agent to carry out modification to the low-temperature flexibility of polypropylene material, then utilize irradiation to carry out modification, after irradiation, polypropylene material can be cross-linked to form three-dimensional space grid structure, thereby the motion at high temperature of restriction molecule chain, the resistance toheat of raising polypropylene material.Simultaneously, between the hindered amine compound that also makes photostabilizer formula (I) structure by irradiation and macromolecular chain, forming chemical bond is connected, photostabilizer is difficult for to material surface migration, is also difficult for separating out because being dissolved in organic solvent, improved the resistance to light of polypropylene material.
Wherein, the hindered amine compound of described formula (I) structure is preferably prepared according to following steps: A) compound of formula (II) structure is reacted in protective atmosphere with protection reagent, obtain the intermediate product of amido protecting; B) intermediate product of described amido protecting is reacted with the end ene compound of formula (III) structure, after deprotection, obtain the hindered amine compound of formula (I) structure.Described protective atmosphere is protective atmosphere well known to those skilled in the art, is preferably nitrogen.
Wherein, m=1 ~ 9, n=310, X is Cl, Br or I.M is preferably 1 ~ 6, and more preferably 2 ~ 4.
The compound of described formula (II) structure is that model well known to those skilled in the art is the photostabilizer of GW-944.
In steps A, the compound of described formula (II) structure is 1:2 ~ 2.5 with the mol ratio of protection reagent, is preferably 1:2 ~ 2.2.The reaction times of described reaction is 3.5 ~ 4.5h.Amount of substance and the reaction times of controlling protection reagent, make to only have two amino on piperidine ring protected in GW-944.Described steps A reaction is preferably carried out in organic solvent, and described organic solvent is organic solvent well known to those skilled in the art, is preferably methylene dichloride.
Described blocking group is carbalkoxy class amido protecting group, acyl group class amido protecting group or alkyls amido protecting group.Follow easily principle protected and easy deprotection and select blocking group, described blocking group is preferably carbalkoxy class amido protecting group.
Described carbalkoxy class amido protecting group is preferably carbobenzoxy-(Cbz), tertbutyloxycarbonyl, tablet held before the breast by officials methoxycarbonyl, allyloxycarbonyl, trimethylsilyl ethoxycarbonyl, methoxycarbonyl or ethoxycarbonyl, more preferably tertbutyloxycarbonyl (Boc) or tablet held before the breast by officials methoxycarbonyl (Fmoc).
Described acyl group class amido protecting group is preferably phthaloyl, p-toluenesulfonyl, trifluoroacetyl group, ortho-nitrophenyl alkylsulfonyl, p-nitrophenyl alkylsulfonyl, pivaloyl group or benzoyl, more preferably p-toluenesulfonyl or trifluoroacetyl group.
Described alkyls amido protecting group is preferably trityl, 2,4-dimethoxy-benzyl, to methoxy-benzyl or benzyl, more preferably trityl or benzyl.
The selection of blocking group affects the selection of deprotection reaction condition in protective reaction and step B in steps A, adopts the condition contrary with protective reaction pH value to carry out deprotection.According to blocking group, can select to protect accordingly reagent, described protection reagent is preferably the amido protecting agents such as tert-Butyl dicarbonate, chloroformic acid benzyl ester, chloroformic acid-9-fluorenyl methyl esters, fluorenes methoxy carbonyl acyl succinimide or allyl chlorocarbonate.
The intermediate product of the amido protecting obtaining in steps A, without carrying out separating-purifying, can directly add the end ene compound of formula (III) structure to carry out next step reaction.
According to the present invention, in described step B, the mol ratio of the end ene compound of the intermediate product of amido protecting and formula (III) structure is 1:1 ~ 4, be preferably 1: 1 ~ and 3, more preferably 1: 1.5 ~ 2.2.
In described step B, the intermediate product of amido protecting is 9 ~ 15h with the reaction times that the end ene compound of formula (III) structure reacts.The product obtaining after deprotection, through purification step, obtains the hindered amine compound of pure formula (I) structure, and described purification step is preferably column chromatography for separation and purifies, and more preferably the mixed solution of normal hexane and ethyl acetate carries out column chromatography for separation purification.
In the present invention; after utilizing blocking group that the amino on piperidine ring is protected; end ene compound is by the halogen and the not protected amino nucleophilic reaction that occurs of end; and then be connected with GW-944; the unsaturated link(age) wherein containing can be grafted on macromolecular chain through irradiation technique, forms carbon-carbon bond.
While using as photostabilizer, after the piperidine ring oxidation of hindered amine compound, generate nitroxyl free radical, nitroxyl free radical can be by the approach of transferring energy, make to get back to ground state in the singlet oxygen of excited state, thereby stop singlet oxygen to cause the generation of polymer degradation reaction, nitroxyl free radical also can further be caught free radical simultaneously, improves the light stabilising effect of hindered amine compound.And hindered amine compound of the present invention is owing to being connected with macromolecular material by chemical bond, be not therefore soluble in organic solvent and separate out, light stability is strong.
According to the present invention, described GW-944 is preferably prepared according to following steps: S1) cyanuric chloride and tertiary hexylamine are reacted in solvent, obtain the intermediate product of formula (IV) structure; S2) intermediate product of described formula (IV) structure is reacted in protective atmosphere with hexanediamine piperidines, obtain the GW-944 of formula (II) structure.Wherein, described solvent is organic solvent well known to those skilled in the art, is preferably toluene.Described protective atmosphere is protective atmosphere well known to those skilled in the art, is preferably nitrogen.
The temperature of reaction of described step S1 is 0 ℃ ~ 10 ℃.Three chlorine atomic reaction activity of cyanuric chloride are all higher, and therefore facile hydrolysis need to react at low temperatures.Cyanuric chloride reacts with tertiary hexylamine and produces HCl, need to add acid binding agent to improve speed of reaction, and acid binding agent described in the present invention is preferably the NaOH aqueous solution.
Described step S2 preferably reacts under the condition of acid binding agent, and described acid binding agent is preferably the NaOH aqueous solution.
In the present invention, described step S2 is specially: S21) under 50 ℃ ~ 70 ℃ conditions, be preferably 55 ℃ ~ 65 ℃, reaction 3 ~ 5h, the intermediate product generation nucleophilic substitution reaction of quadrol piperidines and formula (IV) structure; S22) above-mentioned reaction system is warming up to 160 ℃ ~ 200 ℃, is preferably 170 ℃ ~ 185 ℃, reaction 5 ~ 7h, the product generation polycondensation of nucleophilic substitution, obtains GW-944.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of hindered amine compound provided by the invention and preparation method thereof is described in detail.
In following examples, agents useful for same is commercially available.
The preparation of embodiment 1GW-944
1.1 by below 120ml toluene condition of ice bath borehole cooling to 10 ℃, add 40g cyanuric chloride, stir, slowly drip the toluene solution 50ml that is dissolved with 27.52g tert-Octylamine, after reaction 2h, the NaOH aqueous solution 50ml that dropping mass concentration is 20%, reaction 2h, standing, separate organic phase, the NaOH solution washing that is 10% by mass concentration, obtains the organic phase that contains intermediate product IV.
1.2 by the organic phase that contains 0.2mol intermediate product IV obtaining in 1.1, and the NaOH aqueous solution that 0.2mol hexanediamine piperidines and 50ml mass concentration are 20% adds in 500ml autoclave, in nitrogen replacement still after air three times, inflated with nitrogen to pressure is 2MPa, is heated to 60 ℃, after stirring reaction 4h, be warming up to 180 ℃, reaction 6h, cooling, filters, after the NaOH solution washing that organic phase is 10% by mass concentration, revolve and steam except desolventizing, obtain GW-944, average molecular mass is 2240.
According to GB2410-80, utilize transmittance/mist degree tester to test the GW-944 obtaining in 1.2, obtain its transmittance T
425nm>96%, T
450nm>96%.
Utilize nucleus magnetic resonance respectively the GW-944 obtaining in 1.2 to be analyzed, obtain its hydrogen spectrum and carbon and compose, result is as follows:
1HNMR（CDCl
3,ppm）：4.0(-NH),3.49(-CH
2),3.35(-CH
2),2.63(-CH),2.44(-CH),2.26(-CH),1.32(-NH),1.49-CH),1.31(-CH),0.94(-CH
3)。
13CNMR（CDCl
3,ppm）：180.7,176.5,160.4,61.1,54.5,51.5,45,42,39.7,29.5,29,22.7,14.1。
Embodiment 2
Under the condition of nitrogen protection, by the GW-944 obtaining in 0.2mol 1.2,0.4mol tert-Butyl dicarbonate, 0.18mol salt of wormwood and 120ml methylene dichloride mix and blend, after reaction 4h, add 0.3mol allyl bromide 98, continues reaction 10h.Add dilute hydrochloric acid the pH value of reaction solution to be adjusted to 5.0, removal of solvent under reduced pressure, extracted with diethyl ether, anhydrous Na
2sO
4be dried, obtain the hindered amine compound of formula (I) structure after n-hexane/ethyl acetate column chromatography is purified, its average molecular mass is 2960.
Utilize nucleus magnetic resonance respectively the hindered amine compound of the formula obtaining in embodiment 2 (I) structure to be analyzed, obtain its hydrogen spectrum and carbon spectrum, result is as follows:
1HNMR（CDCl
3,ppm）：5.87(-C=CH),5.19(-C=CH),3.73(-CH
2),3.49(-CH
2),2.63(-CH),2.44(-CH),2.26(-CH),2.0(-NH),1.49-CH
2),1.32(-CH),0.94(-CH
3)。
13CNMR（CDCl
3,ppm）：180.7,177.1,134.2,117.1,61.1,54.5,51.5,45,42,39.7,29.5,29,22.7,14.1。
Embodiment 3
By hindered amine compound and the 1.5g 3 of formula (I) structure obtaining in the 1000g polypropylene of oven dry, 300g POE, 30g TMPTA, 15g embodiment 2,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid mixes, be added to blend granulation in twin screw extruder, extrusion temperature is 180 ℃ ~ 200 ℃, head temperature is 190 ℃, the material of extruding pelletizing after running water is cooling, obtains masterbatch; After masterbatch is dried to water content and is less than 1.5 ‰, use in a vacuum Co-60 source irradiation, dose rate is 1000rad/min, and total absorption dose is 5kGy, obtains polypropylene material.
According to tensile strength, modulus in flexure, shock strength, vicat softening temperature and the gel content of the polypropylene material obtaining in 2546 couples of embodiment 3 of GB/T, test, the test result obtaining is as shown in table 1.
After utilizing UV-light accelerated deterioration to the polypropylene material accelerated light ageing obtaining in embodiment 3, the mechanical property of material is tested, and ultraviolet lighting total dose is 7.7 * 10
6rad, obtains the mechanical property retention of material after its accelerated light ageing, as shown in table 2.
Embodiment 4
By hindered amine compound and 1.5g β-(4-hydroxyl-3 of formula (I) structure obtaining in the 1000g polypropylene of oven dry, 500g SBS, 20g TMPTA, 18g embodiment 2,5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid mixes, be added to blend granulation in twin screw extruder, extrusion temperature is 180 ℃ ~ 200 ℃, head temperature is 190 ℃, the material of extruding pelletizing after running water is cooling, obtains masterbatch; After masterbatch is dried to water content and is less than 1.5 ‰, use in a vacuum Co-60 source irradiation, dose rate is 5000rad/min, and total absorption dose is 10kGy, obtains polypropylene material.
According to tensile strength, modulus in flexure, shock strength, vicat softening temperature and the gel content of the polypropylene material obtaining in 2546 couples of embodiment 4 of GB/T, test, the test result obtaining is as shown in table 1.
After utilizing UV-light accelerated deterioration to the polypropylene material accelerated light ageing obtaining in embodiment 4, the mechanical property of material is tested, and ultraviolet lighting total dose is 7.7 * 10
6rad, obtains the mechanical property retention of material after its accelerated light ageing, as shown in table 2.
Embodiment 5
By hindered amine compound and the 2g 3 of formula (I) structure obtaining in the 1000g polypropylene of oven dry, 600g SBS, 25g TAIC, 20g embodiment 2,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid mixes, be added to blend granulation in twin screw extruder, extrusion temperature is 180 ℃ ~ 200 ℃, head temperature is 190 ℃, the material of extruding pelletizing after running water is cooling, obtains masterbatch; After masterbatch is dried to water content and is less than 1.5 ‰, use in a vacuum Co-60 source irradiation, dose rate is 3000rad/min, and total absorption dose is 15kGy, obtains polypropylene material.
According to tensile strength, modulus in flexure, shock strength, vicat softening temperature and the gel content of the polypropylene material obtaining in 2546 couples of embodiment 5 of GB/T, test, the test result obtaining is as shown in table 1.
After utilizing UV-light accelerated deterioration to the polypropylene material accelerated light ageing obtaining in embodiment 5, the mechanical property of material is tested, and ultraviolet lighting total dose is 7.7 * 10
6rad, obtains the mechanical property retention of material after its accelerated light ageing, as shown in table 2.
Embodiment 6
By hindered amine compound and 2.5g β-(4-hydroxyl-3 of formula (I) structure obtaining in the 1000g polypropylene of oven dry, 800g IR, 40g PDDA, 22g embodiment 2,5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid mixes, be added to blend granulation in twin screw extruder, extrusion temperature is 180 ℃ ~ 200 ℃, head temperature is 190 ℃, the material of extruding pelletizing after running water is cooling, obtains masterbatch; After masterbatch is dried to water content and is less than 1.5 ‰, use in a vacuum Co-60 source irradiation, dose rate is 4100rad/min, and total absorption dose is 30kGy, obtains polypropylene material.
According to tensile strength, modulus in flexure, shock strength, vicat softening temperature and the gel content of the polypropylene material obtaining in 2546 couples of embodiment 6 of GB/T, test, the test result obtaining is as shown in table 1.
After utilizing UV-light accelerated deterioration to the polypropylene material accelerated light ageing obtaining in embodiment 6, the mechanical property of material is tested, and ultraviolet lighting total dose is 7.7 * 10
6rad, obtains the mechanical property retention of material after its accelerated light ageing, as shown in table 2.
The partial properties of table 1 polypropylene material
Material mechanical performance retention after table 2 accelerated light ageing
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a polypropylene material, is characterized in that, mainly by following raw material, after blend, irradiation, is prepared:
The hindered amine compound of described formula (I) structure is prepared according to following steps:
A) compound of formula (II) structure is reacted in protective atmosphere with protection reagent, obtain the intermediate product of amido protecting; B) intermediate product of described amido protecting is reacted with the end ene compound of formula (III) structure, after deprotection, obtain the hindered amine compound of formula (I) structure;
Wherein, m=1～9, n=3～10, X is Cl, Br or I.
2. polypropylene material according to claim 1, is characterized in that, described antioxidant is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid or β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid.
3. polypropylene material according to claim 1, is characterized in that, described vinyl polyfunctional monomer is trivinyl polyfunctional monomer or divinyl polyfunctional monomer.
4. polypropylene material according to claim 3, is characterized in that, described trivinyl polyfunctional monomer is Viscoat 295, pentaerythritol triacrylate or cyanacrylate.
5. polypropylene material according to claim 3, is characterized in that, described divinyl polyfunctional monomer is polyethyleneglycol diacrylate or PDDA.
6. polypropylene material according to claim 1, is characterized in that, described toughner is thermoplastic elastomer.
7. polypropylene material according to claim 6, it is characterized in that, described thermoplastic elastomer is POE, styrene-butadiene-styrene, hydrogenated styrene-butadiene-styrene multipolymer, terpolymer EP rubber, natural rubber, styrene-butadiene rubber(SBR), paracril or isoprene-isobutylene rubber.
8. a preparation method for polypropylene material, is characterized in that, comprises the following steps:
The hindered amine compound of formula (I) structure of the vinyl polyfunctional monomer of the toughner of the acrylic resin of 100 weight parts, 30～80 weight parts, 2～4 weight parts, 1.5～2.5 weight parts is mixed with the antioxidant of 0.15～0.25 weight part, extruding pelletization, obtains polypropylene material after irradiation;
The hindered amine compound of described formula (I) structure is prepared according to following steps:
A) compound of formula (II) structure is reacted in protective atmosphere with protection reagent, obtain the intermediate product of amido protecting; B) intermediate product of described amido protecting is reacted with the end ene compound of formula (III) structure, after deprotection, obtain the hindered amine compound of formula (I) structure;
Wherein, m=1～9, n=3～10, X is Cl, Br or I.
9. preparation method according to claim 8, is characterized in that, the temperature of described extruding pelletization is 180 ℃～200 ℃.
10. preparation method according to claim 8, is characterized in that, the radiation dose rate of described irradiation is 1000～5000rad/min, and irradiation dose is 5～30kGy.
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| CN104403202B (en) * | 2014-12-15 | 2016-11-23 | 俞文文 | A kind of fire-retardant car roof material and preparation method thereof |
| CN112899878B (en) * | 2021-01-08 | 2022-04-15 | 东华大学 | Radiation-resistant polypropylene non-woven fabric |
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| CN1566189A (en) * | 2003-06-24 | 2005-01-19 | 理研科技股份有限公司 | Heat-resistant weather-resistant excellent insulating resin composition and insulated wire |
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| CN1566189A (en) * | 2003-06-24 | 2005-01-19 | 理研科技股份有限公司 | Heat-resistant weather-resistant excellent insulating resin composition and insulated wire |
| CN101602872A (en) * | 2009-07-06 | 2009-12-16 | 中国科学院长春应用化学研究所 | A kind of preparation method of radiation aging resistant polypropylenes |
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Effective date of registration: 20170105 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Applied Chemistry Inst., Chinese Academy of Sciences |