CN107903508B - Aramid fiber reinforced polypropylene micro-foaming composite material and preparation method thereof - Google Patents
Aramid fiber reinforced polypropylene micro-foaming composite material and preparation method thereof Download PDFInfo
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- CN107903508B CN107903508B CN201711346361.1A CN201711346361A CN107903508B CN 107903508 B CN107903508 B CN 107903508B CN 201711346361 A CN201711346361 A CN 201711346361A CN 107903508 B CN107903508 B CN 107903508B
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- aramid fiber
- polypropylene
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- composite material
- foaming
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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 125
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 86
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 86
- -1 polypropylene Polymers 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000005187 foaming Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000004088 foaming agent Substances 0.000 claims abstract description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 11
- 239000003607 modifier Substances 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002981 blocking agent Substances 0.000 claims abstract description 6
- 239000004760 aramid Substances 0.000 claims description 26
- 238000001125 extrusion Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000001746 injection moulding Methods 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000004611 light stabiliser Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000002216 antistatic agent Substances 0.000 claims description 3
- 238000005282 brightening Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical group CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims 1
- 229920003235 aromatic polyamide Polymers 0.000 claims 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims 1
- 229940124543 ultraviolet light absorber Drugs 0.000 claims 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000002787 reinforcement Effects 0.000 abstract description 4
- 230000004927 fusion Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
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- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- YHEPZZFDBQOSSN-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate;1-o-methyl 10-o-(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound COC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1.C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 YHEPZZFDBQOSSN-UHFFFAOYSA-N 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0085—Use of fibrous compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Molding Of Porous Articles (AREA)
Abstract
The invention relates to the technical field of high polymer materials, in particular to an aramid fiber reinforced polypropylene micro-foaming composite material and a preparation method thereof, wherein the aramid fiber reinforced polypropylene micro-foaming composite material is prepared from a raw material composition, and the raw material composition comprises the following components in parts by weight: 74-87 parts of co-polypropylene, 2-5 parts of foaming agent, 3-6 parts of compatilizer, 10-20 parts of aramid fiber, 15-25 parts of isocyanate modifier, 20-30 parts of amino blocking agent, 0.05-0.1 part of catalyst, 0.2-0.4 part of antioxidant, 0.5-1 part of lubricant and 0-2 parts of optional auxiliary agent. According to the invention, the aramid fiber modified by grafting is added into polypropylene, so that the fusion degree of the aramid fiber and the polypropylene is improved, the aramid fiber is distributed in a net shape in the polypropylene and is mutually entangled with a polypropylene chain segment to play a role of skeleton reinforcement, the growth of foam holes is effectively supported in the foaming process, the foam merging of the foam holes is inhibited, and the polypropylene micro-foaming material with fine and uniform foam holes is obtained.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an aramid fiber reinforced polypropylene micro-foaming composite material and a preparation method thereof.
Background
The polypropylene has the advantages of light weight, high mechanical strength, good thermal stability, chemical corrosion resistance and the like, is widely applied to parts such as automobile door panels, instrument panels, central passages and the like, is safe, comfortable, light in weight and energy-saving, and becomes the main trend of the industrial development of automobiles. However, polypropylene is a semi-crystalline material, has low melt strength, cannot support the growth of foam cells, easily causes the defects of foam merging, foam crossing and the like, often becomes a source of foam body breakage when stressed, reduces the mechanical property of the foam material, and restricts the application field of polypropylene. The introduction of fiber reinforcement is one of effective ways, so that the fiber reinforcement has more excellent mechanical properties after foaming to meet the use requirements of a finished piece, the glass fiber is mainly adopted to reinforce polypropylene, and the aramid fiber is a novel high-tech synthetic fiber with better performance than the glass fiber, has the characteristics of small relative density, ultrahigh strength, ultrahigh modulus, good thermal stability and the like, is widely applied to the fields of reinforced products, bulletproof fabrics, fiber cables and the like, but has smooth surface, large benzene ring steric effect, few chemical active groups, low reaction activity, poor compatibility with polypropylene matrix and direct influence on the mechanical properties of composite materials.
Disclosure of Invention
In view of the defects of the prior art, one of the purposes of the invention is to provide an aramid fiber reinforced polypropylene micro-foaming composite material which has excellent mechanical properties.
The invention also aims to provide a preparation method of the aramid fiber reinforced polypropylene micro-foaming composite material.
In order to achieve the above object, the present invention provides an aramid fiber reinforced polypropylene micro-foamed composite material, which is prepared from a raw material composition, wherein the raw material composition comprises: 74-87 parts of co-polypropylene, 2-5 parts of foaming agent, 3-6 parts of compatilizer, 10-20 parts of aramid fiber, 15-25 parts of isocyanate modifier, 20-30 parts of amino blocking agent, 0.05-0.1 part of catalyst, 0.2-0.4 part of antioxidant, 0.5-1 part of lubricant and 0-2 parts of optional auxiliary agent.
The invention also provides a preparation method of the aramid fiber reinforced polypropylene micro-foaming composite material, which comprises the following steps:
(1) hydrolyzing aramid fibers to obtain hydrolyzed aramid fibers, and heating and refluxing the hydrolyzed aramid fibers, isocyanate modifiers and catalysts in an organic solvent in an inert gas protection atmosphere to obtain modified aramid fibers 1;
(2) reacting the modified aramid fiber 1 with an amino end-capping reagent in an organic solvent at 60-80 ℃ for 6-8 h to obtain a modified aramid fiber 2;
(3) uniformly mixing the modified aramid fiber 2, the co-polypropylene, the compatilizer, the antioxidant, the lubricant and the auxiliary agent, then putting the mixture into a main feed of a double-screw extruder, and performing melt extrusion and granulation to prepare a polypropylene composite material;
(4) and uniformly mixing the polypropylene composite material with a foaming agent, and performing injection molding to obtain the aramid fiber reinforced polypropylene chemical micro-foaming composite material.
Through the technical scheme, the invention has the following technical effects:
according to the invention, the aramid fiber modified by grafting is added into polypropylene, so that the fusion degree of the aramid fiber and the polypropylene is improved, the aramid fiber is distributed in a net shape in the polypropylene and is mutually entangled with a polypropylene chain segment to play a role of skeleton reinforcement, the growth of foam holes is effectively supported in the foaming process, the foam merging of the foam holes is inhibited, and the polypropylene micro-foaming material with fine and uniform foam holes is obtained.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides an aramid fiber reinforced polypropylene micro-foaming composite material which is prepared from a raw material composition, wherein the raw material composition comprises the following components in parts by weight: 74-87 parts of co-polypropylene, 2-5 parts of foaming agent, 3-6 parts of compatilizer, 10-20 parts of aramid fiber, 15-25 parts of isocyanate modifier, 20-30 parts of amino blocking agent, 0.05-0.1 part of catalyst, 0.2-0.4 part of antioxidant, 0.5-1 part of lubricant and 0-2 parts of optional auxiliary agent.
In order to improve the compatibility of the aramid fiber and the copolymerized polypropylene, the compatilizer is maleic anhydride grafted polypropylene under the preferable condition, and the grafting rate of the maleic anhydride is 1.5-2%.
In order to improve the degree of entanglement of aramid fibers in the co-polypropylene and the mechanical strength and melt strength of the co-polypropylene, the diameter of the aramid fibers is 10-15 mu m under the optimal conditions, and the length of the aramid fibers is 5-15 mm.
According to the invention, aramid fiber is modified by an isocyanate modifier, and an active group is grafted and introduced on the surface of the aramid fiber, so that the compatibility of the aramid fiber and the co-polymerized polypropylene is improved.
Preferably, the amino blocking agent is selected from dodecylamine and/or octadecylamine.
In order to further optimize the oxidation resistance of the polypropylene copolymer, under the preferable conditions, the antioxidant is at least one selected from hindered phenol antioxidant, thiosulfate antioxidant and phosphite antioxidant, and further preferably, the hindered phenol antioxidant is antioxidant 1010, the thiosulfate antioxidant is antioxidant DLTP, and the phosphite antioxidant is antioxidant 168.
In order to simplify the extrusion process of the co-polypropylene, the invention also adds a lubricant into the co-polypropylene, and the lubricant is at least one of polyethylene wax, calcium stearate, zinc stearate, montan wax and pentaerythritol stearate under the preferable conditions.
In order to further improve the comprehensive performance of the composite material, the invention also adds an auxiliary agent into the composite material, wherein the auxiliary agent is selected from at least one of an ultraviolet absorbent, a light stabilizer, a surface brightening agent, an antistatic agent and a coloring agent, and further preferably, the ultraviolet absorbent is selected from at least one of UV-9, UV-531 and UVP-327; the light stabilizer is selected from at least one of light stabilizer 292, light stabilizer 622, light stabilizer 770 and light stabilizer 944; the surface brightening agent is selected from one of erucamide, glyceryl monostearate and oleamide; the antistatic agent is selected from at least one of polyether ester amide, propylene oxide copolymer and ethylene oxide; the colorant is at least one selected from carbon black, lemon yellow, indigo and phthalocyanine green.
The invention also provides a preparation method of the aramid fiber reinforced polypropylene micro-foaming composite material, which comprises the following steps:
(1) hydrolyzing aramid fibers to obtain hydrolyzed aramid fibers, and heating and refluxing the hydrolyzed aramid fibers, isocyanate modifiers and catalysts in an organic solvent in an inert gas protection atmosphere to obtain modified aramid fibers 1;
(2) reacting the modified aramid fiber 1 with an amino end-capping reagent in an organic solvent at 60-80 ℃ for 6-8 h to obtain a modified aramid fiber 2;
(3) uniformly mixing the modified aramid fiber 2, the co-polypropylene, the compatilizer, the antioxidant, the lubricant and the auxiliary agent, then putting the mixture into a main feed of a double-screw extruder, and performing melt extrusion and granulation to prepare a polypropylene composite material;
(4) and uniformly mixing the polypropylene composite material with a foaming agent, and performing injection molding to obtain the aramid fiber reinforced polypropylene chemical micro-foaming composite material.
According to the invention, firstly, the aramid fiber is hydrolyzed, active groups such as amino and carboxyl are introduced on the surface of the aramid fiber, and meanwhile, the ultrasonic effect is adopted, so that the function of the aramid fiber can be realized, the surface roughness and the specific surface area of the aramid fiber are increased, and a sufficient contact place is provided for the subsequent grafting reaction; then, modifying aramid fibers by using an isocyanate modifier, and then grafting a nonpolar molecular chain on the surface of the aramid fibers by using amino end capping treatment.
Under the preferable conditions, the hydrolysis process of the aramid fiber comprises the following steps: and (3) carrying out ultrasonic treatment on the aramid fiber in water at the temperature of 60-80 ℃ for 6-12 hours.
Under the preferable condition, in the step (1), the heating reflux temperature is 80-90 ℃, and the heating reflux time is 4-8 h.
In the present invention, preferably, in step (3), the melt extrusion process is: the extrusion temperature is 180-200 ℃, the screw rotating speed is 350-400 r/min, and the vacuum degree is-0.06-0.08 MPa.
Preferably, in the step (2), the injection molding temperature is 190-210 ℃.
The present invention will be described in detail below by way of examples. In the following examples, the copolymerized polypropylene (BX3920) was purchased from SK of korea; blowing agent (EE204) was purchased from Nippon Yonghe chemical industry Co., Ltd; maleic anhydride grafted polypropylene (CMG5701) is available from Ready to Ready.
Example 1
An aramid fiber reinforced polypropylene micro-foaming composite material is prepared from the following substances in parts by weight:
the preparation method of the aramid fiber reinforced polypropylene micro-foaming composite material comprises the following steps:
(1) immersing 10 parts by weight of aramid fiber in 500mL of water, then carrying out sealed ultrasonic hydrolysis for 6h at 60 ℃, filtering, and carrying out vacuum drying on a filtered product for 24h at 40 ℃ to obtain hydrolyzed aramid fiber;
(2) adding the hydrolyzed aramid fiber prepared in the step (1), 15 parts by weight of toluene diisocyanate and 0.075 part by weight of dibutyltin dilaurate into 200mL of toluene solution, heating and refluxing for 4h at 90 ℃ in a nitrogen atmosphere, naturally cooling to room temperature, performing centrifugal washing by using a high-speed centrifuge, and performing vacuum drying on a centrifugal product for 24h at 60 ℃ to obtain a modified aramid fiber 1;
(3) adding 1 part by weight of modified aramid fiber and 20 parts by weight of dodecylamine into 200mL of toluene solution, and stirring and reacting at the constant temperature of 60 ℃ for 6 hours; naturally cooling to room temperature, then centrifugally washing by using a high-speed centrifuge, and carrying out vacuum drying on the centrifugal product at 60 ℃ for 24 hours to obtain modified aramid fibers 2;
(4) 2 parts of modified aramid fiber, 87 parts of copolymerized polypropylene BX3920, 3 parts of CMG5701 (the grafting ratio is 1.8%), 0.1 part of antioxidant 1010, 0.1 part of antioxidant 168 and 0.5 part of calcium stearate by weight are mixed in a high-speed mixer for 10min, and the mixture is put into a main feed of a co-rotating double-screw extruder and subjected to melt extrusion and granulation to prepare a polypropylene composite material; wherein the extrusion temperature of the extruder is 200 ℃, the rotating speed of the screw is 400r/min, and the vacuum degree is-0.08 MPa.
(5) After the polypropylene composite material is uniformly mixed with 2.7 parts by weight of foaming agent (EE204), the chopped aramid fiber reinforced polypropylene chemical micro-foaming composite material is prepared by injection molding at 200 ℃.
Example 2
An aramid fiber reinforced polypropylene micro-foaming composite material is prepared from the following substances in parts by weight:
the preparation method of the aramid fiber reinforced polypropylene micro-foaming composite material comprises the following steps:
(1) soaking 15 parts by weight of aramid fiber in 500mL of water, then carrying out sealed ultrasonic hydrolysis for 8h at 80 ℃, filtering, and carrying out vacuum drying on a filtered product for 36h at 50 ℃ to obtain hydrolyzed aramid fiber;
(2) adding the hydrolyzed aramid fiber prepared in the step (1), 20 parts by weight of toluene diisocyanate and 0.1 part by weight of dibutyltin dilaurate into 200mL of toluene solution, heating and refluxing for 6h at 80 ℃ in a nitrogen atmosphere, naturally cooling to room temperature, performing centrifugal washing by using a high-speed centrifuge, and performing vacuum drying on a centrifugal product for 36h at 50 ℃ to obtain modified aramid fiber 1;
(3) adding 1 part by weight of modified aramid fiber and 25 parts by weight of octadecylamine into 200mL of toluene solution, and then stirring and reacting at the constant temperature of 70 ℃ for 7 hours; naturally cooling to room temperature, then carrying out centrifugal washing by using a high-speed centrifuge, and carrying out vacuum drying on the centrifugal product at 60 ℃ for 36 hours to obtain modified aramid fibers 2;
(4) mixing 2 parts of modified aramid fiber, 80 parts of copolymerized polypropylene BX3920, 5 parts of CMG5701 (the grafting ratio is 1.8%), 0.2 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.5 part of polyethylene wax in a high-speed mixer for 10min, putting the mixture into main feed of a co-rotating double-screw extruder, and performing melt extrusion and granulation to prepare a polypropylene composite material; wherein the extrusion temperature of the extruder is 180 ℃, the rotating speed of the screw is 350r/min, and the vacuum degree is-0.06 MPa.
(5) The chopped aramid fiber reinforced polypropylene chemical micro-foaming composite material is prepared by uniformly mixing the polypropylene composite material with 4.5 parts by weight of foaming agent (EE204) and injection molding at 190 ℃.
Example 3
An aramid fiber reinforced polypropylene micro-foaming composite material is prepared from the following substances in parts by weight:
the preparation method of the aramid fiber reinforced polypropylene micro-foaming composite material comprises the following steps:
(1) soaking 20 parts by weight of aramid fiber in 500mL of water, then carrying out sealed ultrasonic hydrolysis for 8h at 70 ℃, filtering, and carrying out vacuum drying on a filtered product for 48h at 50 ℃ to obtain hydrolyzed aramid fiber;
(2) adding the hydrolyzed aramid fiber prepared in the step (1), 25 parts by weight of diphenylmethane diisocyanate and 0.1 part by weight of dibutyltin dilaurate into 200mL of toluene solution, heating and refluxing for 6h at 85 ℃ in a nitrogen atmosphere, naturally cooling to room temperature, performing centrifugal washing by using a high-speed centrifuge, and performing vacuum drying on the centrifugal product for 48h at 50 ℃ to obtain modified aramid fiber 1;
(3) adding 1 part by weight of modified aramid fiber and 30 parts by weight of octadecylamine into 200mL of toluene solution, and then stirring and reacting at the constant temperature of 70 ℃ for 7 hours; naturally cooling to room temperature, then centrifugally washing by using a high-speed centrifuge, and carrying out vacuum drying on the centrifugal product at 50 ℃ for 48 hours to obtain modified aramid fibers 2;
(4) 2 parts of modified aramid fiber, 74 parts of copolymerized polypropylene BX3920, 6 parts of CMG5701 (the grafting ratio is 2%), 0.2 part of antioxidant 1010, 0.2 part of antioxidant 168, 0.75 part of calcium stearate, 0.5 part of light stabilizer 292, 0.5 part of oleamide and 1 part of carbon black are mixed in a high-speed mixer for 10min, and the mixture is put into a main feed of a co-rotating double-screw extruder to be subjected to melt extrusion and granulation to prepare the polypropylene composite material; wherein the extrusion temperature of the extruder is 200 ℃, the rotating speed of the screw is 400r/min, and the vacuum degree is-0.06 MPa.
(5) The chopped aramid fiber reinforced polypropylene chemical micro-foaming composite material is prepared by uniformly mixing the polypropylene composite material with 4.75 parts by weight of foaming agent (EE204) and injection molding at 210 ℃.
Example 4
An aramid fiber reinforced polypropylene micro-foaming composite material is prepared from the following substances in parts by weight:
the preparation method of the aramid fiber reinforced polypropylene micro-foaming composite material comprises the following steps:
(1) soaking 15 parts by weight of aramid fiber in 500mL of water, then carrying out sealed ultrasonic treatment at 75 ℃ for 12h, filtering, and carrying out vacuum drying on a filtered product at 50 ℃ for 24h to obtain hydrolyzed aramid fiber;
(2) adding the hydrolyzed aramid fiber prepared in the step (1), 22 parts by weight of isophorone diisocyanate and 0.05 part by weight of stannous octoate into 200mL of toluene solution, heating and refluxing for 8h at 85 ℃ in a nitrogen atmosphere, naturally cooling to room temperature, performing centrifugal washing by using a high-speed centrifuge, and performing vacuum drying on a centrifugal product for 24h at 50 ℃ to obtain a modified aramid fiber 1;
(3) adding 1 part by weight of modified aramid fiber and 28 parts by weight of octadecylamine into 200mL of toluene solution, and then stirring and reacting at the constant temperature of 80 ℃ for 8 hours; naturally cooling to room temperature, then centrifugally washing by using a high-speed centrifuge, and carrying out vacuum drying on the centrifugal product at 50 ℃ for 24 hours to obtain modified aramid fibers 2;
(4) 2 parts of modified aramid fiber, 80 parts of copolymerized polypropylene BX3920, 5 parts of CMG5701 (the grafting ratio is 1.8%), 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168, 1 part of polyethylene wax, 0.2 part of UV-531, 0.5 part of light stabilizer 292, 0.3 part of oleamide, 0.1 part of ethylene oxide and 0.2 part of carbon black are mixed in a high-speed mixer for 10min, and are put into a main feed of a co-rotating double-screw extruder to be subjected to melt extrusion and granulation to prepare the polypropylene composite material; wherein the extrusion temperature of the extruder is 200 ℃, the rotating speed of the screw is 400r/min, and the vacuum degree is-0.08 MPa;
(5) the chopped aramid fiber reinforced polypropylene chemical micro-foaming composite material is prepared by uniformly mixing the polypropylene composite material with 2 parts by weight of foaming agent (EE204) and injection molding at the temperature of 190-210 ℃.
Example 5
An aramid fiber reinforced polypropylene micro-foaming composite material is prepared from the following substances in parts by weight:
the preparation method of the aramid fiber reinforced polypropylene micro-foamed composite material is the same as that in example 1.
Comparative example 1
The process of example 1 was followed except that the aramid fiber was not subjected to hydrolysis treatment (i.e., step (1) was not included in the preparation process).
Comparative example 2
The process of example 1 was followed except that the aramid fiber was not subjected to the graft modification treatment (i.e., step (2) was not included in the preparation process).
Comparative example 3
The process of example 1 was followed except that the aramid fiber after the graft modification was not subjected to the end-capping treatment (i.e., step (3) was not included in the preparation process).
And (3) testing: the main physical property indexes of the aramid fiber reinforced polypropylene micro-foamed composite materials prepared in the embodiments 1 to 5 and the comparative examples 1 to 3 are tested according to related detection standards, and the detection standards and detection results of the tensile strength, the notched impact strength of the cantilever beam, the bending strength, the bending modulus and the average diameter of the foam pores are shown in the following table 1.
Table 1: performance Table of each of the composites in examples 1 to 5 and comparative examples 1 to 3
From table 1 it can be derived: the chopped aramid fiber improves the mechanical property of polypropylene and the foaming property of polypropylene, and the unmodified aramid fiber has poor reinforcing effect on polypropylene.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. The aramid fiber reinforced polypropylene micro-foaming composite material is characterized by being prepared from the following substances in parts by weight: 74-87 parts of co-polypropylene, 2-5 parts of foaming agent, 3-6 parts of compatilizer, 10-20 parts of aramid fiber, 15-25 parts of isocyanate modifier, 20-30 parts of amino blocking agent, 0.05-0.1 part of catalyst, 0.2-0.4 part of antioxidant, 0.5-1 part of lubricant and 0-2 parts of optional auxiliary agent;
the compatilizer is maleic anhydride grafted polypropylene, and the grafting rate of maleic anhydride is 1.5-2%;
the isocyanate modifier is selected from at least one of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate;
the amino blocking agent is selected from dodecylamine and/or octadecylamine;
the preparation method of the aramid fiber reinforced polypropylene micro-foaming composite material comprises the following steps:
(1) hydrolyzing aramid fibers to obtain hydrolyzed aramid fibers, and heating and refluxing the hydrolyzed aramid fibers, isocyanate modifiers and catalysts in an organic solvent in an inert gas protection atmosphere to obtain modified aramid fibers 1;
(2) reacting the modified aramid fiber 1 with an amino end-capping reagent in an organic solvent at 60-80 ℃ for 6-8 h to obtain a modified aramid fiber 2;
(3) uniformly mixing the modified aramid fiber 2, the co-polypropylene, the compatilizer, the antioxidant, the lubricant and the auxiliary agent, then putting the mixture into a main feed of a double-screw extruder, and performing melt extrusion and granulation to prepare a polypropylene composite material;
(4) and uniformly mixing the polypropylene composite material with a foaming agent, and performing injection molding to obtain the aramid fiber reinforced polypropylene chemical micro-foaming composite material.
2. The aramid fiber reinforced polypropylene micro-foamed composite material according to claim 1, wherein the diameter of the aramid fiber is 10-15 μm; and/or
The length of the aramid fiber is 5-15 mm.
3. The aramid fiber-reinforced polypropylene microfoamed composite according to claim 1, wherein the auxiliary agent is selected from at least one of an ultraviolet light absorber, a light stabilizer, a surface brightening agent, an antistatic agent, and a coloring agent.
4. The preparation method of the aramid fiber reinforced polypropylene micro-foamed composite material according to any one of claims 1 to 3, characterized by comprising the following steps:
(1) hydrolyzing aramid fibers to obtain hydrolyzed aramid fibers, and heating and refluxing the hydrolyzed aramid fibers, isocyanate modifiers and catalysts in an organic solvent in an inert gas protection atmosphere to obtain modified aramid fibers 1;
(2) reacting the modified aramid fiber 1 with an amino end-capping reagent in an organic solvent at 60-80 ℃ for 6-8 h to obtain a modified aramid fiber 2;
(3) uniformly mixing the modified aramid fiber 2, the co-polypropylene, the compatilizer, the antioxidant, the lubricant and the auxiliary agent, then putting the mixture into a main feed of a double-screw extruder, and performing melt extrusion and granulation to prepare a polypropylene composite material;
(4) and uniformly mixing the polypropylene composite material with a foaming agent, and performing injection molding to obtain the aramid fiber reinforced polypropylene chemical micro-foaming composite material.
5. The preparation method of claim 4, wherein the process for hydrolyzing the aramid fiber is as follows: and (3) carrying out ultrasonic treatment on the aramid fiber in water at the temperature of 60-80 ℃ for 6-12 hours.
6. The preparation method according to claim 4, wherein, in the step (1), the temperature of the heating reflux is 80-90 ℃; and/or
The heating reflux time is 4-8 h.
7. The production method according to any one of claims 4 to 6, wherein in the step (3), the melt extrusion process is: the extrusion temperature is 180-200 ℃, the screw rotating speed is 350-400 r/min, and the vacuum degree is-0.06-0.08 MPa; and/or
In the step (4), the injection molding temperature is 190-210 ℃.
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| CN103059413A (en) * | 2013-01-16 | 2013-04-24 | 合肥杰事杰新材料股份有限公司 | Novel plastic-base enhanced foaming composite material as well as preparation method and application thereof |
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