CN1117808C - Cross-linked polypropylene resin and its application - Google Patents
Cross-linked polypropylene resin and its application Download PDFInfo
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- CN1117808C CN1117808C CN 00123620 CN00123620A CN1117808C CN 1117808 C CN1117808 C CN 1117808C CN 00123620 CN00123620 CN 00123620 CN 00123620 A CN00123620 A CN 00123620A CN 1117808 C CN1117808 C CN 1117808C
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Abstract
The present invention discloses a crosslinked polypropylene resin material which comprises 60 to 93 portions of polypropylene by weight, 5 to 25 portions of functionalized thermoplastic elastomer by weight and 2 to 15 portions of functionalized filling material by weight. The crosslinked polypropylene resin material of the present invention has the advantages of high crosslinking extent, few broken molecular chains of a main chain of the polypropylene, and good combination performance of the polypropylene crosslinked resin material. The crosslinked polypropylene resin material of the present invention is used as a structural material, such as hot and cold water supplying and discharging pipe materials, steel-plastic profiled bar door windows, chemical material conveying pipelines, agricultural irrigating and draining pipelines, automobile instrument panels, etc., in the fields of building materials, chemical industry, agriculture, automobiles, household appliances, etc.
Description
The present invention relates to a kind of cross-linked thermoplastic resin material, be specifically related to a kind of cross-linked polypropylene resin material.
Polyacrylic resin material is the big kind in the general-purpose plastics, and its output is big, and is cheap, is extensive use of in a lot of fields such as daily, household electrical appliances, agricultural, automobile.But polyacrylic resin material is low because of toughness, poor rigidity, and shortcoming such as anti-creep has not limited its application as structured material in works scope.
By chemical process that the polyvinyl resin material is appropriately crosslinked improving the research of its rigidity, toughness, anti-creep, character such as heat-resisting, existing many reports, however acrylic resin is carried out crosslinked report as structured material but seldom.European patent EP 0619343 and Japanese Patent JP6025631 disclose respectively and have a kind ofly connect hydrolyzable functional group such as organoalkoxysilane on the skill in polyolefin backbone in advance, the intermolecular connection of functional group on the differing molecular main chain during by functional group's hydrolysis, thereby polymer macromolecule is chain attachment, realize polyolefinic partial cross-linked.European patent EP 0479611 discloses a kind of method for preparing the crosslinkable ethylene copolymer, and it is to prepare respectively earlier to have two kinds of ethylene copolymers of different functional groups, and then makes two kinds of ethylene copolymer blends reactions obtain the cross-linked ethylene multipolymers.Patent GB961795 discloses a kind of method of adding dioxime and derivative crosslinked polyethylene, polypropylene, polybutene or its multipolymer.The Modern PlasticsInternational that publish in April, 1986, P71, introduced a kind of technology of crosslinked polypropylene, this technology obtains the cross-linked polypropylene resin material by the silane polycondensation, and this crosslinked polypropylene material can be used for electric wire foreskin, shrink film, pipe and pipe fitting joint etc.
All exist in the above-mentioned prior art under the effect of tertiary carbon atom adds in cross-linking system in the polypropylene backbone initiator, small molecules linking agent initiated polymerization owner splitting of chain, cross-linking efficiency is low, the shortcoming of cross-linked polypropylene resin material property difference.
The object of the present invention is to provide a kind of crosslinked polyacrylic resin material.
Another object of the present invention is to provide the application of this material in fields such as building materials, chemical industry, agricultural, automobile, household electrical appliances.
Cross-linked polypropylene resin material of the present invention comprises the polypropylene of parts by weight 60-93 part, the functionalization thermoplastic elastomer of 5-25 part, the functionalization filler of 2-15 part.
This polypropylene is homo-polypropylene, atactic copolymerized polypropene or block copolymerization polypropylene, and its melt flow rate is 0.3-10 gram/10 minutes.
This functionalization thermoplastic elastomer is the alpha olefin copolymer of ethene-4-10 carbon atom and the grafts of polyolefin blends, and its melt flow rate is 0.5-15 gram/10 minutes, and the blend ratio is 1: 2-2: 1.The alpha olefin copolymer of the carbon atom of ethene-4-10 wherein comprises ethylene-butene copolymer, ethylene-octene copolymer, polyolefine wherein comprises polyethylene, polypropylene, grafts wherein is to have the organic monomer that can produce the functional group of chemical reaction with the functionalization filler, is specially in MALEIC ANHYDRIDE, vinylformic acid, methacrylic acid, methylene-succinic acid and the unsaturated isocyanate organic monomer one or more.
This functionalization filler comprises one or more in lime carbonate, titanium dioxide, silicon-dioxide, talcum powder, kaolin, wollastonite, mica and the whisker of silane coupling agent, titanate coupling agent, plumbic acid ester coupling agent treatment.
Cross-linked polypropylene resin material of the present invention further comprises the processing aid of parts by weight 0.5-5 part, the photostabilizer of 0.1-0.5 part, or the thermo-stabilizer of 0.1-0.5 part.
This processing aid comprises white oil, naphthenic oil, polyethylene wax, stearate and salt, N, one or more in the N one ethene two Unimac 5680 acid amides etc.
This photostabilizer comprises N, N one second, n-butyl dithiocarbamate nickel, 2,4,6-three (2-hydroxyl-4-n-butoxy phenyl)-1,3,5-triazine, Succinic Acid and (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines ethanol) polymkeric substance, sebacic acid two (2,2,6,6-tetramethyl--4-piperidines) one or both in alcohol etc.
This thermo-stabilizer comprises four, and [β (3,5 one di-tert-butyls, one 4 monohydroxy phenyl) propionic acid] pentaerythritol ester, 1,1,3-three (2-methyl-4-hydroxyl-5-t-butyl-phenyl) butane, 4,4-thiobis (6-tertiary butyl-3-methylphenol), tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) compound of two or more in ester, tricresyl phosphite (2,4-di-tert-butyl phenyl) ester, two ten diester of thio-2 acid, thio-2 acid 12 octadecyl esters etc.
" functionalization filler " will dilute good functionalization agent with thinner and evenly be sprayed in proportion on the filler by untreated filler is placed homogenizer, high-speed stirring 10 minutes, and drying obtains the functionalization filler.
" functionalization thermoplastic elastomer " by with ethylene-alpha-olefin copolymer and polyolefine in 1: 2-2: 1 ratio is pre-mixed, mix with grafted monomer again, on the twin screw extruder with 200-220 ℃ processing temperature under grafting, granulation, obtain the functionalization thermoplastic elastomer.
With the photostabilizer of the processing aid of the polypropylene of the functionalization thermoplastic elastomer of the functionalization filler of weight ratio 2-15 part, 5-25 part, 60-93 part, 0.5-5 part, 0.1-0.5 part, 0.1-0.5 part thermo-stabilizer in homogenizer after the pre-mixing, on twin screw extruder by 170-210 ℃ processing temperature extrude, granulation, obtain the cross-linked polypropylene resin material.
The purposes of cross-linked polypropylene resin material of the present invention is to use as structured material in fields such as building materials, chemical industry, agricultural, automobile, household electrical appliances, it is big to be used for work in-process requirement polypropylene viscosity, the good building materials of the long-term creep-resistant property of material are as cold and hot plumbing tubing, plastic-steel profiled material door and window, chemical material transport pipe, agricultural drainage and irrigation pipeline, automobile instrument panel etc.
The present invention adopts the functionalization thermoplastic elastomer to pass through chemical reaction connection filler and polymeric matrix as interfacial compatibilizer, obtain polypropylene composite material, when being subjected to external force, material does the time spent, the functionalization filler hinders the polypropylene macromolecular chain has played cross-linking set with the external force motion effect, therefore the chain rupture of polypropylene backbone molecule is few, the crosslinking degree height, polypropylene cross-linked resin material property is good.
Reference examples 1:
With the block copolymerization polypropylene of 100 parts of weight ratios, 0.5 part of white oil, 0.5 part stearic acid, 0.2 part 2,4,6-three (2 hydroxyls-4-n-butoxy phenyl)-1,3,5-triazine, four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester of 0.2 part are after pre-mixing, extrude under with 170-190-200-210 ℃ barrel zone temperature on the twin screw extruder, granulation, make polypropylene composite material.The mechanical property of this matrix material sees Table 1.
Embodiment 1:
The talcum powder that will be untreated places homogenizer, again with the aminopropyltriethoxywerene werene of 0.5% (comparing) with the weight of filler with 95% aqueous ethanolic solution dilution after, evenly be sprayed on the filler, high-speed stirring 10 minutes, drying obtains the functionalization filler.
Ethylene-butene copolymer and the polypropylene ratio premix in 1: 2 is got togather, with weight ratio be again the MALEIC ANHYDRIDE of above-mentioned fluoropolymer resin 5% with acetone diluted after, with the polymkeric substance uniform mixing, extrude through twin screw extruder, granulation, extrusion temperature 210-220-200-210 ℃, 60 rev/mins of screw speeds obtain the functionalization thermoplastic elastomer.
With the block copolymerization polypropylene of 90.4 parts of weight ratios, 4.8 parts functionalization thermoplastic elastomer, 4.8 parts functionalization filler, 0.5 part of white oil, 0.5 part stearic acid, 0.2 part 2,4,6-three (2-hydroxyl-4-n-butoxy phenyl)-1,3,5-triazine, 0.2 part four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, after pre-mixing, extrude under with 170-190-200-210 ℃ barrel zone temperature on the twin screw extruder, granulation, make the cross-linked polypropylene resin material.The mechanical property of this resin material sees Table 1.
Table 1 performance reference examples 1 embodiment 1 melt flow rate (restraining/10 minutes) 2.2 1.8 gel contents (%)
*0 18.5Izod notched Izod impact strength (J/m), 212.9 290.0 tensile yield strengths (MPa), 25.9 24.0 tension fracture elongation rate (%)＞500＞500 modulus in flexure (GPa) 1.0 1.1 flexural strengths (MPa), 25.1 25.1* materials refluxed in toluene solution 8 hours, its insolubles is through suction filtration, be dried to constant weight, weigh, the shared weight of deduction filler, calculate the weight percent that insolubles accounts for the material gross weight, be considered as the gel content of this material.
Embodiment 2:
The carbonic acid calcium that will be untreated places homogenizer, again with N-β (amine the ethyl)-γ amine propyl group-Trimethoxy silane of 0.5% (comparing) with the weight of filler with 95% aqueous ethanolic solution dilution after, evenly be sprayed on the filler high-speed stirring 10 minutes, drying obtains the functionalization filler.
Ethylene-octene copolymer and the polypropylene ratio premix in 1: 2 is got togather, with weight ratio be again the vinylformic acid of above-mentioned fluoropolymer resin 5% with acetone diluted after, with the polymkeric substance uniform mixing, extrude through twin screw extruder, granulation, extrusion temperature 200-210-220-200 ℃, 100 rev/mins of screw speeds obtain the functionalization thermoplastic elastomer.
With the block copolymerization polypropylene of 85.7 parts of weight ratios, 9.5 parts functionalization thermoplastic elastomer, 4.8 parts functionalization filler, 0.5 part of white oil, 0.5 part stearic acid, 0.2 part 2,4,6-three (2-hydroxyl-4-n-butoxy phenyl)-1,3,5-triazine, 0.2 part four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, after pre-mixing, extrude under with 170-190-200-210 ℃ barrel zone temperature on the twin screw extruder, granulation, make the cross-linked polypropylene resin material.The mechanical property of this resin material sees Table 2.Reference examples 2:
With the block copolymerization polypropylene of 100 parts of weight ratios, 0.5 part of white oil, 0.5 part stearic acid, 0.2 part 2,4,6-three (2-hydroxyl-4-n-butoxy phenyl)-1,3,5-triazine, 0.5 part linking agent divinylbenzene, 0.05 part diphenyl peroxide formic acid, after pre-mixing, extrude under with 170-190-200-210 ℃ barrel zone temperature on the twin screw extruder, granulation, make polypropylene composite material.This performance of composites sees Table 2.
Table 2 performance embodiment 2 reference examples 2 melt flow rates (restraining/10 minutes) 1.6 2.6 gel contents (%)
*23.3 1.6Izod notched Izod impact strength, (J/m) 400.0 263.0 tensile yield strengths, (MPa) 24.0 22.2 tension fracture elongation rates, (%)＞500＞500 modulus in flexure, (GPa) 1.0-flexural strength, (MPa) 25.6-
Embodiment 3:
The preparation of functionalization filler and functionalization thermoplastic elastomer is identical with embodiment 2.
Block copolymerization polypropylene with 90 parts of weight ratios, 5 parts functionalization thermoplastic elastomer, 5 parts functionalization filler, 1 part hard ester acid, 0.5 2 of part, 4,6-three (2-hydroxyl-4-n-butoxy phenyl)-1,3, the 5-triazine, 0.1 part four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.1 two ten diester of part thio-2 acid, through pre-mixing, on twin screw extruder, extrude granulation, extrusion temperature 200-200-200-200 ℃, screw speed is 40 rev/mins, obtain crosslinked polypropylene water-feeding pipes PP Pipe Compound, again through the single screw extrusion machine extruding pipe material, 200 ℃ of extrusion temperatures.According to national standard, test every performance index, this pipe performance sees Table 3.
Table 3 performance embodiment 5 notched Izod impact strength (J/m) 130 bending moduluses (GPa) 1.4 hot strengths (MPa) 32.0 thermal distorsion temperatures (℃) 97 brittle temperatures (℃)-20 compressive resistances (MPa) 8.0
Claims (8)
1. cross-linked polypropylene resin material, the polypropylene that comprises parts by weight 60-93 part, the thermoplastic elastomer of 5-25 part, the filler of 2-15 part, wherein said thermoplastic elastomer is the alpha olefin copolymer of ethene-4-10 carbon atom and the grafts of polyolefin blends, its melt flow rate is 0.5-15 gram/10 minutes, and wherein said filler comprises one or more in lime carbonate, titanium dioxide, silicon-dioxide, talcum powder, kaolin, wollastonite, mica and the whisker of silane coupling agent, titanate coupling agent, plumbic acid ester coupling agent treatment.
2. according to the material of claim 1, wherein said polypropylene is homo-polypropylene, atactic copolymerized polypropene or block copolymerization polypropylene, and its melt flow rate is 0.3-10 gram/10 minutes.
3. according to the material of claim 1, the alpha olefin copolymer of wherein said ethene-4-10 carbon atom is an ethylene-butene copolymer, ethylene-octene copolymer.
4. according to the material of claim 1, wherein said polyolefine is a polyethylene, polypropylene.
5. according to the material of claim 1, the grafting group of wherein said ethylene-alpha-olefin copolymer and polyolefin blends comprises one or more in MALEIC ANHYDRIDE, vinylformic acid, methacrylic acid, methylene-succinic acid and the unsaturated isocyanate organic monomer.
6. according to the material of claim 1, wherein further comprise the processing aid of parts by weight 0.5-5 part, the photostabilizer of 0.1-0.5 part, or the thermo-stabilizer of 0.1-0.5 part.
7. according to the material of claim 6, wherein said processing aid comprises white oil, naphthenic oil, polyethylene wax, stearate and salt, N, one or more in the N one ethene two Unimac 5680 acid amides.
The material of claim 1 in building materials, chemical industry, agricultural, automobile, field of household appliances as the application of structured material.
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| CN 00123620 CN1117808C (en) | 2000-08-25 | 2000-08-25 | Cross-linked polypropylene resin and its application |
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| CN 00123620 CN1117808C (en) | 2000-08-25 | 2000-08-25 | Cross-linked polypropylene resin and its application |
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Families Citing this family (14)
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| KR100683230B1 (en) * | 2006-02-16 | 2007-03-12 | 현대모비스 주식회사 | Polypropylene composite composition |
| CN101092496B (en) * | 2006-06-20 | 2011-08-17 | 上海金发科技发展有限公司 | High glazed, shock proof filled and modified polypropylene, preparation and application |
| CN102020805B (en) * | 2009-09-10 | 2012-07-18 | 中国石油化工股份有限公司 | Polypropylene resin composition and preparation method thereof |
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| CN103883812A (en) * | 2014-03-12 | 2014-06-25 | 青岛恒瑞塑料科技有限责任公司 | Inside spin type high-temperature-resisting ultra-quiet drainage pipe and manufacturing method thereof |
| CN104086853A (en) * | 2014-05-29 | 2014-10-08 | 安徽海纳川塑业科技有限公司 | Noise-reducing muted drainpipe |
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| CN110964249B (en) * | 2019-12-06 | 2022-08-05 | 万华化学（宁波）有限公司 | Injection molding polypropylene modified material capable of eliminating tiger stripes and preparation method thereof |
| CN114292364B (en) * | 2021-12-21 | 2022-12-02 | 日丰企业集团有限公司 | Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof |
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