CN109233242B - Polyphenyl ether resin composite material and preparation method and application thereof - Google Patents
Polyphenyl ether resin composite material and preparation method and application thereof Download PDFInfo
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- CN109233242B CN109233242B CN201810832518.XA CN201810832518A CN109233242B CN 109233242 B CN109233242 B CN 109233242B CN 201810832518 A CN201810832518 A CN 201810832518A CN 109233242 B CN109233242 B CN 109233242B
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- ether resin
- composite material
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- 239000000463 material Substances 0.000 title claims abstract description 113
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 85
- 239000000805 composite resin Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 64
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 46
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003063 flame retardant Substances 0.000 claims abstract description 42
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 38
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 38
- 239000007822 coupling agent Substances 0.000 claims abstract description 30
- 229920000098 polyolefin Polymers 0.000 claims abstract description 27
- 229920001971 elastomer Polymers 0.000 claims abstract description 25
- 239000000806 elastomer Substances 0.000 claims abstract description 25
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 24
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 24
- 229920001955 polyphenylene ether Polymers 0.000 claims description 27
- 229910021485 fumed silica Inorganic materials 0.000 claims description 26
- 239000011159 matrix material Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910001853 inorganic hydroxide Inorganic materials 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 3
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 description 22
- 229920006380 polyphenylene oxide Polymers 0.000 description 22
- 239000000203 mixture Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 230000035882 stress Effects 0.000 description 14
- 238000005325 percolation Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 239000008187 granular material Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- 239000004519 grease Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound 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 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 1
- NHNMTZZAQRAIOO-UHFFFAOYSA-N OP(O)(=O)OP(=O)(O)O.C1(=CC=CC=C1)C1=C(C(=C(C(=C1O)C1=CC=CC=C1)C1=CC=CC=C1)C(C)(C)C1=CC=C(C=C1)O)C1=CC=CC=C1 Chemical compound OP(O)(=O)OP(=O)(O)O.C1(=CC=CC=C1)C1=C(C(=C(C(=C1O)C1=CC=CC=C1)C1=CC=CC=C1)C(C)(C)C1=CC=C(C=C1)O)C1=CC=CC=C1 NHNMTZZAQRAIOO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- 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
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
-
- 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
- C08J2415/00—Characterised by the use of rubber derivatives
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
-
- 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
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a polyphenyl ether resin composite material which comprises the following components in parts by weight: the flame retardant is characterized by comprising polyphenyl ether resin, an elastomer, a flame retardant, polyolefin, a functional master batch, a main antioxidant and an auxiliary antioxidant, wherein the functional master batch comprises the following components in percentage by weight, based on 100% of the total weight of the functional master batch: 60-79% of resin base material; 20-39% of gas-phase nano silicon dioxide with a branched structure; 1-3% of a coupling agent; and the coupling agent is coated on the surface of the gas-phase nano silicon dioxide with the branched structure. The polyphenyl ether resin composite material provided by the invention has excellent high-temperature and high-pressure resistance on the basis of effectively maintaining the excellent properties of polyphenyl ether resin, and has obviously improved toughness and stress cracking resistance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyphenyl ether resin composite material and a preparation method thereof.
Background
The polyphenyl ether resin alloy has many excellent properties, such as high modulus, high temperature resistance, creep resistance, self-flame resistance and the like, and is widely used in the fields of electronic appliances, automobile parts, communication photovoltaics and the like. Polyphenylene ether resins having the above properties are also suitable for use in the manufacture of hot and cold water supply line valves. However, because the impact strength of the polyphenyl ether material is low, the toughness is poor, and the stress cracking resistance is poor, stress cracking is easily generated when the polyphenyl ether material is used for a water pipe valve, so that the application of the polyphenyl ether material in the field of water pipe valves is limited.
Disclosure of Invention
The invention aims to provide a polyphenyl ether resin composite material and a preparation method and application thereof, and aims to solve the problems that the existing polyphenyl ether resin has poor toughness and is easy to generate stress cracking in the application of preparing cold and hot water supply pipe valves.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a polyphenyl ether resin composite material which comprises the following components in parts by weight:
the functional master batch comprises the following components in percentage by weight, based on the total weight of the functional master batch as 100 percent:
60-79% of resin base material;
20-39% of gas-phase nano silicon dioxide with a branched structure;
1-3% of a coupling agent;
and the coupling agent is coated on the surface of the gas-phase nano silicon dioxide with the branched structure.
The invention also aims to provide a preparation method of the polyphenyl ether resin composite material, wherein the polyphenyl ether resin composite material comprises the following components in parts by weight:
the functional master batch comprises the following components in percentage by weight, based on the total weight of the functional master batch as 100 percent:
60-79% of resin base material;
20-39% of gas-phase nano silicon dioxide with a branched structure;
1-3% of a coupling agent;
the coupling agent is coated on the surface of the gas-phase nano silicon dioxide with the branched structure;
the preparation method of the polyphenyl ether resin composite material comprises the following steps:
weighing the components according to the formula of the polyphenyl ether resin composite material;
mixing the polyphenyl ether resin and the elastomer to obtain a first mixed material;
mixing the polyolefin, the flame retardant, the functional master batch, the main antioxidant and the auxiliary antioxidant to obtain a second mixed material;
and adding the first mixed material and the second mixed material from a main feeding port and a side feeding port respectively, and mixing, melting and extruding.
Correspondingly, the invention also provides a cold and hot water supply pipe valve which is made of the polyphenyl ether resin composite material.
According to the polyphenyl ether resin composite material provided by the invention, the flame retardant, the polyolefin, the functional master batch and other components are added into the matrix resin such as polyphenyl ether resin and elastomer, so that the impact resistance and the stress cracking resistance of the polyphenyl ether resin composite material are obviously improved on the basis of effectively maintaining the excellent properties such as the mechanical property, the flame retardant property and the heat resistance of the polyphenyl ether resin material, and the polyphenyl ether resin composite material can be well used for manufacturing and using cold and hot water supply pipe valves.
In particular, the polyphenylene ether resin composite material provided by the invention contains the gas-phase nano-silica with a branched structure, and the coupling agent is coated on the gas-phase nano-silica with the branched structure. On one hand, the coupling agent is coated on the surface of the nano particle, so that partial hydroxyl on the surface of the gas-phase nano silicon dioxide particle can be eliminated, and the agglomeration behavior of the gas-phase nano silicon dioxide particle is inhibited to a reasonable degree; meanwhile, the compatibility between the gas-phase nano silicon dioxide particles and the resin matrix is enhanced. On the other hand, the gas phase nano silicon dioxide has a branched structure and can be uniformly distributed in a polyphenyl ether resin matrix to form a nano particle percolation network, namely a network percolation structure, so that the material modulus is higher, and the gas phase nano silicon dioxide can be formed when the addition amount is lower. The network-like percolation structure is used as a skeleton structure of the polyphenyl ether resin composite material on the premise of ensuring the basic mechanical property, provides extra modulus and relaxation resistance when small strain occurs, improves the dimensional stability and stress resistance, namely is less prone to deformation under small stress, and prevents the material from cracking; when large strain occurs (the material is impacted), the dynamic damage-recombination behavior of the particles in the network percolation structure absorbs extra energy, and the particle network is damaged to absorb part of impact energy, so that the toughness and the impact resistance of the polyphenyl ether composite material are improved.
According to the preparation method of the polyphenyl ether resin composite material, all the components are mixed and then melted and extruded, the components can be uniformly dispersed by the preparation method, and the polyphenyl ether resin composite material has stable performance while the excellent performance is realized. In addition, the preparation method has the advantages of simple process, easily-controlled conditions, low cost and low equipment requirement, and is suitable for industrial production.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The invention provides a polyphenyl ether resin composite material which comprises the following components in parts by weight:
the functional master batch comprises the following components in percentage by weight, based on the total weight of the functional master batch as 100 percent:
60-79% of resin base material;
20-39% of gas-phase nano silicon dioxide with a branched structure;
1-3% of a coupling agent;
and the coupling agent is coated on the surface of the gas-phase nano silicon dioxide with the branched structure.
According to the polyphenyl ether resin composite material provided by the embodiment of the invention, the flame retardant, the polyolefin, the functional master batch and other components are added into the matrix resin such as polyphenyl ether resin and elastomer, so that the impact resistance and the stress cracking resistance of the polyphenyl ether resin composite material are obviously improved on the basis of effectively maintaining the excellent properties such as the mechanical property, the flame retardant property, the heat resistance and the like of the polyphenyl ether resin material, and the polyphenyl ether resin composite material can be well used for manufacturing and using cold and hot water supply pipe valves.
In particular, the polyphenylene ether resin composite material provided by the embodiment of the invention contains fumed nano-silica with a branched structure, and the fumed nano-silica with the branched structure is coated with the coupling agent. On one hand, the coupling agent is coated on the surface of the nano particle, so that partial hydroxyl on the surface of the gas-phase nano silicon dioxide particle can be eliminated, and the agglomeration behavior of the gas-phase nano silicon dioxide particle is inhibited to a reasonable degree; meanwhile, the compatibility between the gas-phase nano silicon dioxide particles and the resin matrix is enhanced. On the other hand, the gas phase nano silicon dioxide has a branched structure and can be uniformly distributed in a polyphenyl ether resin matrix to form a nano particle percolation network, namely a network percolation structure, so that the material modulus is higher, and the gas phase nano silicon dioxide can be formed when the addition amount is lower. The network-like percolation structure is used as a skeleton structure of the polyphenyl ether resin composite material on the premise of ensuring the basic mechanical property, provides extra modulus and relaxation resistance when small strain occurs, improves the dimensional stability and stress resistance, namely is less prone to deformation under small stress, and prevents the material from cracking; when large strain occurs (the material is impacted), the dynamic damage-recombination behavior of the particles in the network percolation structure absorbs extra energy, and the particle network is damaged to absorb part of impact energy, so that the toughness and the impact resistance of the polyphenyl ether composite material are improved.
In particular, in the embodiment of the invention, the polyphenyl ether resin is used as a matrix component, so that the composite material can be endowed with better mechanical property. The polyphenylene ether resin can be 60 parts, 62 parts, 65 parts and 68 parts by weight. 70 parts, 75 parts, 78 parts and 80 parts. Preferably, the polyphenylene ether resin is at least one of a polymer of 2, 6-dimethylphenol and a copolymer of 2, 6-dimethylphenol and 2,3, 6-trimethylphenol, and has an intrinsic viscosity of 0.2 to 0.6 dl/g.
The elastomer can improve the toughness of the polyphenyl ether composite material, but in the embodiment of the invention, the elastomer is not enough to greatly improve the flexibility of the polyphenyl ether composite material, and the requirement of the polyphenyl ether composite material for a cold and hot water supply pipe valve is met. Specifically, the elastomer may be 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts by weight.
Preferably, the elastomer is at least one of styrene-butadiene rubber, hydrogenated styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, and acid anhydride-modified styrene-ethylene-butadiene-styrene block copolymer. Preferred elastomers contain aromatic ring structures and have good compatibility with polyphenylene ether resins. Meanwhile, the material contains a flexible chain segment, so that impact energy can be absorbed during impact, and the toughness of the material is obviously improved.
The flame retardant is used for improving the flame retardant property of the composite material. Preferably, the parts by weight of the flame retardant can be 5 parts, 8 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts and 15 parts.
The flame retardant is a compound flame retardant system formed by compounding a phosphorus flame retardant, a nitrogen flame retardant and an inorganic hydroxide according to the weight ratio of (1-3) to (1-2). The preferable flame retardant with specific content and specific composition can not only remarkably improve the flame retardant property of the composite material taking the polyphenylene oxide resin as the matrix; and the addition amount of the phosphorus flame retardant can obviously improve the resin fluidity during the molding process because the melting point of the phosphorus flame retardant is relatively low. Specifically, the phosphorus flame retardant is one or a mixture of more of triphenyl phosphate (TPP), tetraphenyl (bisphenol-A) diphosphate (BDP), tetraphenyl Resorcinol Diphosphate (RDP), arylenecondensed phosphate (PX-200) and coated red phosphorus; the nitrogen flame retardant is at least one of melamine and melamine urate; the inorganic hydroxide is at least one of aluminum hydroxide and magnesium hydroxide.
In the embodiment of the invention, the polyolefin can obviously increase the toughness, the flowability and the surface gloss of the alloy system and properly reduce the cost. Specifically, the polyolefin may be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts by weight. Preferably, the polyolefin is at least one of polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, and ethylene-butene copolymer.
In the present invention, the composite system of polyphenylene ether resin, elastomer and polyolefin has relatively poor toughness and is liable to stress cracking during use. In view of this, fumed nano silica is added to the polyphenylene ether resin composite material according to the embodiment of the present invention. The fumed silica nanoparticles have an ultra-small particle diameter (about 100nm) and an ultra-high specific surface area, and thus, an ultra-high surface energy. Meanwhile, the surfaces of the fumed silica nanoparticles have a large number of hydroxyl groups, and the fumed silica nanoparticles tend to agglomerate into large-size particles in a resin matrix without any modification treatment, and are extremely unevenly distributed. From the processing point of view, it is not practical to directly and accurately feed the fumed silica nanoparticles into the matrix in a quantitative manner without preparing the fumed silica nanoparticles into the functional master batch in advance. In view of this, in the embodiment of the present invention, the fumed silica is added in the form of the functional masterbatch. Specifically, the coupling agent is coated on the surface of the fumed silica, so that the compatibility between fumed silica particles and a resin matrix is enhanced while partial hydroxyl groups are eliminated. The coating inhibits the agglomeration of the fumed silica particles to a reasonable degree, so that a contact type network percolation structure is formed in the matrix. Furthermore, the fumed silica particles in the embodiment of the invention are fumed silica with a branched structure, and compared with precipitated silica with a spherical structure, the fumed silica with a branched structure enables percolation behavior of the filler to occur at a lower filling concentration, that is, a network-shaped percolation structure can be formed when the addition amount of the fumed silica with a branched structure is lower, so as to prevent excessive silica from causing an excessive specific surface area and aggregation, which causes dispersion unevenness to affect the original performance of the fumed silica, and even causes the toughness of the composite material to be reduced.
Preferably, the fumed silica with a branched structure is fumed silica nanoparticles prepared by sintering treatment. The optimized fumed silica with the branched structure has a stable internal structure, and can still keep good stability after being prepared into the functional master batch, so that the valve for processing the cold and hot water supply pipe, which is prepared from the polyphenyl ether resin composite material, has excellent performance stability in the use process.
Further preferably, on the premise that the content of the functional master batch is relatively determined, the fumed silica with the branched structure accounts for 20-39% of the total weight of the functional master batch. When the content of the fumed nano-silica with a branched structure is too high, too much silica causes an excessively large specific surface area, and further aggregation occurs, so that dispersion is uneven, the performance which is originally exerted is affected, and even the toughness of the composite material is reduced.
Preferably, the coupling agent is at least one selected from the group consisting of vinyltrichlorosilane, vinyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
Preferably, the resin matrix is at least one selected from the group consisting of polyphenylene ether resin and polyolefin. Preferably, the resin matrix has good compatibility with the matrix material of the composite material.
The main antioxidant and the auxiliary antioxidant endow the polyphenyl ether resin composite material with the performance of resisting thermo-oxidative aging. In a preferred embodiment, the main antioxidant is one or a mixture of two of 3, 5-di-tert-butyl-4-hydroxyphenyl propionic acid octadecyl ester and beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester. Preferably, the auxiliary antioxidant is one or a mixture of two of bis (2, 4-di-tert-butyl) pentaerythritol diphosphite and tris (2, 4-di-tert-butylphenyl) phosphite. In specific embodiments, the content of the main antioxidant can be 0.2 part, 0.3 part, 0.4 part, 0.5 part and the like by weight; the content of the auxiliary antioxidant can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part and the like by weight.
The polyphenyl ether resin composite material provided by the embodiment of the invention further improves the modulus and the high temperature resistance of the polyphenyl ether on the basis of keeping the high modulus, self-flame retardance, high temperature resistance, creep resistance and other characteristics of the polyphenyl ether, and simultaneously obviously improves the impact property and the stress cracking resistance. The high modulus, high temperature resistance and creep resistance meet the requirements of cold and hot water supply pipe valve materials, meanwhile, the improvement of the impact resistance enables the valve to be more convenient and not easy to damage in the installation and use processes, and the improvement of the stress cracking resistance can ensure the valve to break due to high temperature or oil stains in the use process. The polyphenyl ether resin composite material for the cold and hot water supply pipe valve has strong oxidation resistance and long service life of products. These characteristics all correspond to the characteristics of the pipe fitting which will be used for a long time once installed. The polyphenyl ether resin composite material can be used for preparing pipe fittings and valves such as cold and hot water supply pipe valves, and can also be used for preparing related devices such as household appliances.
The polyphenylene ether resin composite material provided by the embodiment of the invention can be prepared by the following method.
Correspondingly, the embodiment of the invention provides a preparation method of a polyphenyl ether resin composite material, wherein the polyphenyl ether resin composite material comprises the following components in parts by weight:
the functional master batch comprises the following components in percentage by weight, based on the total weight of the functional master batch as 100 percent:
60-79% of resin base material;
20-39% of gas-phase nano silicon dioxide with a branched structure;
1-3% of a coupling agent;
the coupling agent is coated on the surface of the gas-phase nano silicon dioxide with the branched structure;
the preparation method of the polyphenyl ether resin composite material comprises the following steps:
s01, weighing the components according to the formula of the polyphenyl ether resin composite material;
s02, mixing the polyphenyl ether resin and the elastomer to obtain a first mixed material;
s03, mixing the polyolefin, the flame retardant, the functional master batch, the main antioxidant and the auxiliary antioxidant to obtain a second mixed material;
and S04, adding the first mixed material and the second mixed material from the main feeding port and the side feeding port respectively, and mixing, melting and extruding.
According to the preparation method of the polyphenyl ether resin composite material provided by the embodiment of the invention, all the components are mixed and then melted and extruded, and the preparation method can uniformly disperse all the components, so that the polyphenyl ether resin composite material has stable performance while the excellent performance is realized. In addition, the preparation method has the advantages of simple process, easily-controlled conditions, low cost and low equipment requirement, and is suitable for industrial production.
In the embodiment of the present invention, the polyphenylene ether resin is preferably at least one of a polymer of 2, 6-dimethylphenol and a copolymer of 2, 6-dimethylphenol and 2,3, 6-trimethylphenol, and has an intrinsic viscosity of 0.2 to 0.6 dl/g.
Preferably, the elastomer is at least one of styrene-butadiene rubber, hydrogenated styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, and acid anhydride-modified styrene-ethylene-butadiene-styrene block copolymer.
Preferably, the flame retardant is a compound flame retardant system formed by compounding a phosphorus flame retardant, a nitrogen flame retardant and an inorganic hydroxide according to the weight ratio of (1-3) to (1-2).
Preferably, the polyolefin is at least one of polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, and ethylene-butene copolymer.
Preferably, the fumed silica with a branched structure is fumed silica nanoparticles prepared by sintering treatment.
Preferably, the coupling agent is at least one selected from the group consisting of vinyltrichlorosilane, vinyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
Preferably, the resin matrix is at least one selected from the group consisting of polyphenylene ether resin and polyolefin.
Preferably, the main antioxidant is one or a mixture of two of 3, 5-di-tert-butyl-4-hydroxyphenyl propionic acid octadecyl ester and beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester.
Preferably, the auxiliary antioxidant is one or a mixture of two of bis (2, 4-di-tert-butyl) pentaerythritol diphosphite and tris (2, 4-di-tert-butylphenyl) phosphite.
Specifically, in step S01, the formula of the polyphenylene ether resin composite material is as described above, and is not repeated here.
Preferably, the functional master batch is prepared by the following method:
drying the gas-phase nano-silica with the branched structure, then spraying the coupling agent on the gas-phase nano-silica with the branched structure for fully mixing, and carrying out heat treatment at 110-130 ℃ for 50-70 min;
feeding the resin matrix from a main feeding port, feeding the gas-phase nano-silica powder with a branched structure, which is treated by the coupling agent under a heating condition, from a side feeding port, and performing melt co-extrusion at the temperature of 200-300 ℃, wherein the rotating speed of a screw rod in the melt extrusion process is 260-300 rpm, and the vacuum degree is 0.5-0.8 MPa.
In the above steps S02 and S03, the mixing process may be performed in a conventional mixing manner, such as stirring, as long as the components are uniformly mixed.
In step S04, the first mixed material and the second mixed material may be fed through the main feeding port and the side feeding port, respectively, which are weight loss. Melt extrusion may be carried out using a screw machine, such as a twin screw machine. After the materials are fed into the screw machine, the materials are plasticized and melted under the action of high pressure and high temperature, during which time the components react with each other. In a preferred embodiment, the process conditions for melt extrusion are: the conditions of the melt extrusion treatment were: the temperature is 260-300 ℃, the vacuum degree is 0.5-0.8 MPa, and the rotating speed of the screw is 260-300 rpm. The melt extrusion process may be carried out using a twin screw extruder.
After melt extrusion, the method also comprises the processing steps of drawing strips, cooling, cutting into granules, drying the granules and the like.
The preparation method of the polyphenyl ether resin composite material can ensure that all components are uniformly dispersed, and the polyphenyl ether resin composite material has stable performance while realizing the excellent performance. In addition, the preparation method has the characteristics of simple process, easily controlled conditions, low cost and low equipment requirement, and is suitable for industrial production.
Correspondingly, the embodiment of the invention also provides a cold and hot water supply pipe valve, and the cold and hot water supply pipe valve is made of the polyphenyl ether resin composite material.
As the polyphenyl ether resin composite material is prepared by adding the flame retardant, the polyolefin, the functional master batch and other components into matrix resins such as polyphenyl ether resin, elastomer and the like, the impact resistance and the stress cracking resistance of the polyphenyl ether resin composite material are obviously improved on the basis of effectively maintaining the excellent properties such as the mechanical property, the flame retardant property, the heat resistance and the like of the polyphenyl ether resin material, so that the polyphenyl ether resin composite material can be well used for manufacturing and using cold and hot water supply pipe valves.
The following description will be given with reference to specific examples. In the following embodiments, the polyphenylene oxide resin is a product of Mitsubishi engineering plastics, the elastomer is a product of the Bailingpetrochemical division, China petrochemical group asset management and management company, Inc., the polyolefin is a product of the Shanghai petrochemical company, China petrochemical company, Shanghai petrochemical company, Inc., the functional master batch is prepared according to the above method, and the antioxidant and the auxiliary antioxidant are products of the Shanghai Jinhai Yabao Fine chemical company, Inc.
Example 1
The formula composition of the polyphenyl ether resin composite material is shown in table 1, and specifically comprises the following components: 70 parts of polyphenylene oxide resin (PPO), 5 parts of elastomer, 8 parts of flame retardant, 1 part of polyolefin, 15.7 parts of functional master batch, 0.2 part of main antioxidant and 0.1 part of auxiliary antioxidant; the functional master batch comprises the following components in percentage by weight, based on the total weight of the functional master batch as 100 percent: 70% of polyphenyl ether resin base material, 28% of fumed silica with a branched structure and 2% of coupling agent.
The preparation method of the polyphenyl ether resin composite material comprises the following steps: 70 parts of polyphenylene oxide resin (PPO) and 5 parts of elastomer are added from a first weightless feeder port, 8 parts of flame retardant, 1 part of polyolefin, 15.7 parts of functional master batch, 0.2 part of main antioxidant and 0.1 part of auxiliary antioxidant are added from a second weightless feeder port after high mixing, and then the mixture is plasticized, melted, extruded, pulled into strips, cooled and cut into granules by a double-screw extruder. The pellets were dried in a blower drying oven at 110 ℃ for 2h and then injection molded to produce test bars or articles.
Example 2
The formula composition of the polyphenyl ether resin composite material is shown in table 1, and specifically comprises the following components: 70 parts of polyphenylene oxide resin (PPO), 10 parts of elastomer, 8 parts of flame retardant, 1 part of polyolefin, 10.7 parts of functional master batch, 0.2 part of main antioxidant and 0.1 part of auxiliary antioxidant; the functional master batch comprises the following components in percentage by weight, based on the total weight of the functional master batch as 100 percent: 68% of polyphenyl ether resin base material, 30% of fumed silica with a branched structure and 2% of coupling agent.
The preparation method of the polyphenyl ether resin composite material comprises the following steps: 70 parts of polyphenylene oxide resin (PPO) and 10 parts of elastomer are added from a first weightless feeder port, 8 parts of flame retardant, 1 part of polyolefin, 10.7 parts of functional master batch, 0.2 part of main antioxidant and 0.1 part of auxiliary antioxidant are added from a second weightless feeder port after high mixing, and then the mixture is plasticized, melted, extruded, pulled into strips, cooled and cut into granules by a double-screw extruder. The pellets were dried in a blower drying oven at 110 ℃ for 2h and then injection molded to produce test bars or articles.
Example 3
The formula composition of the polyphenyl ether resin composite material is shown in table 1, and specifically comprises the following components: 70 parts of polyphenylene oxide resin (PPO), 15 parts of elastomer, 8 parts of flame retardant, 1 part of polyolefin, 5.7 parts of functional master batch, 0.2 part of main antioxidant and 0.1 part of auxiliary antioxidant; the functional master batch comprises the following components in percentage by weight, based on the total weight of the functional master batch as 100 percent: 73% of polyphenyl ether resin base material, 25% of fumed silica with a branched structure and 2% of coupling agent.
The preparation method of the polyphenyl ether resin composite material comprises the following steps: 70 parts of polyphenylene oxide resin (PPO) and 15 parts of elastomer are added from a first weightless feeder port, 8 parts of flame retardant, 1 part of polyolefin, 5.7 parts of functional master batch, 0.2 part of main antioxidant and 0.1 part of auxiliary antioxidant are added from a second weightless feeder port after high mixing, and then the mixture is plasticized, melted, extruded, pulled into strips, cooled and cut into granules by a double-screw extruder. The pellets were dried in a blower drying oven at 110 ℃ for 2h and then injection molded to produce test bars or articles.
Example 4
The formula composition of the polyphenyl ether resin composite material is shown in table 1, and specifically comprises the following components: 70 parts of polyphenylene oxide resin (PPO), 20 parts of elastomer, 8 parts of flame retardant, 1 part of polyolefin, 0.7 part of functional master batch, 0.2 part of main antioxidant and 0.1 part of auxiliary antioxidant; the functional master batch comprises the following components in percentage by weight, based on the total weight of the functional master batch as 100 percent: 68% of polyphenyl ether resin base material, 31% of fumed silica with a branched structure and 1% of coupling agent.
The preparation method of the polyphenyl ether resin composite material comprises the following steps: 70 parts of polyphenylene oxide resin (PPO) and 20 parts of elastomer are added from a first weightless feeder port, 8 parts of flame retardant, 1 part of polyolefin, 0.7 part of functional master batch, 0.2 part of main antioxidant and 0.1 part of auxiliary antioxidant are added from a second weightless feeder port after high mixing, and then the mixture is plasticized, melted, extruded, pulled into strips, cooled and cut into granules by a double-screw extruder. The pellets were dried in a blower drying oven at 110 ℃ for 2h and then injection molded to produce test bars or articles.
Comparative example 1
The formula composition of the polyphenyl ether resin composite material is shown in table 1, and specifically comprises the following components: 90.7 parts of polyphenylene oxide resin (PPO), 8 parts of flame retardant, 1 part of polyolefin, 0.2 part of main antioxidant and 0.1 part of auxiliary antioxidant.
The preparation method of the polyphenyl ether resin composite material comprises the following steps: 90.7 parts of polyphenylene oxide resin (PPO) is added from a first weightless feeder port, 8 parts of flame retardant, 1 part of polyolefin, 0.2 part of main antioxidant and 0.1 part of auxiliary antioxidant are added from a second weightless feeder port after being subjected to high mixing, and then the mixture is subjected to plasticizing, melting, extruding, bracing, cooling and granulating by a double-screw extruder. The pellets were dried in a blower drying oven at 110 ℃ for 2h and then injection molded to produce test bars or articles.
And (3) performance testing:
the polyphenylene ether resin composites prepared in the above examples 1 to 4 and the polyphenylene ether resin composite prepared in comparative example 1 were subjected to the performance tests as in table 2, respectively. The related performance test method is as follows:
(1) tensile strength: the tensile strength was tested according to ASTM D638.
(2) Bending strength: the flexural strength was tested according to ASTM D790.
(3) Flexural modulus: the flexural strength was tested according to ASTM D790.
(4) Notched Izod impact: the notched Izod impact is measured according to ASTM D256.
(5) Heat distortion temperature: the heat distortion temperature impact is measured according to ASTM D648.
(6) Flame retardancy: the flame retardancy is tested according to UL94 standard.
(7) And (3) punching experiment: in the punching experiment, an injection molded part is fixed on a fixture, and a small hole with the diameter of 5mm and the thickness of 32mm is punched, so that the part is qualified if no crack occurs in the whole punching process, and is unqualified if the part cracks.
(8) Grease resistance test: the grease resistance test is that after the punching test, a grease (natural grease or synthetic grease) is coated around the punched part, the sample is static for 24-72 hours, if no cracking phenomenon occurs, the sample is qualified, otherwise, the sample is unqualified.
The relevant properties of the materials of examples 1 to 4 and comparative example 1 are shown in Table 2.
TABLE 1
TABLE 2
As can be seen from table 2, compared with comparative example 1 which does not contain an elastomer and a functional master batch, the polyphenylene ether resin composite materials prepared in examples 1 to 4 have significantly improved flexural modulus and impact resistance and significantly improved stress cracking resistance on the basis of effectively maintaining excellent properties of the polyphenylene ether resin material, such as mechanical properties, flame retardancy, and heat resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The polyphenyl ether resin composite material is characterized by comprising the following components in parts by weight:
the functional master batch comprises the following components in percentage by weight, based on the total weight of the functional master batch as 100 percent:
60-79% of resin base material;
20-39% of gas-phase nano silicon dioxide with a branched structure;
1-3% of a coupling agent;
and the coupling agent is coated on the surface of the gas-phase nano silicon dioxide with the branched structure.
2. The polyphenylene ether resin composite material according to claim 1, wherein the fumed silica having a branched structure is fumed silica nanoparticles prepared by sintering treatment.
3. The polyphenylene ether resin composite material according to claim 1, wherein the flame retardant is a composite flame retardant system in which a phosphorus flame retardant, a nitrogen flame retardant and an inorganic hydroxide are compounded in a weight ratio of (1 to 3) to (1 to 2).
4. The polyphenylene ether resin composite material according to any one of claims 1 to 3, wherein the coupling agent is at least one selected from the group consisting of vinyltrichlorosilane, vinyltrimethoxysilane, and γ - (methacryloyloxy) propyltrimethoxysilane.
5. The polyphenylene ether resin composite material according to any one of claims 1 to 3, wherein the resin matrix is at least one selected from the group consisting of polyphenylene ether resins and polyolefins.
6. The polyphenylene ether resin composite material according to any one of claims 1 to 3, wherein the polyphenylene ether resin is at least one of a polymer of 2, 6-dimethylphenol, a copolymer of 2, 6-dimethylphenol and 2,3, 6-trimethylphenol, and has an intrinsic viscosity of 0.2 to 0.6 dl/g.
7. The polyphenylene ether resin composite material according to any one of claims 1 to 3, wherein the elastomer is at least one of styrene-butadiene rubber, hydrogenated styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, acid anhydride-modified styrene-ethylene-butadiene-styrene block copolymer; and/or
The polyolefin is at least one of polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymer and ethylene-butene copolymer.
8. The preparation method of the polyphenyl ether resin composite material is characterized in that the polyphenyl ether resin composite material is composed of the following components in parts by weight:
the functional master batch comprises the following components in percentage by weight, based on the total weight of the functional master batch as 100 percent:
60-79% of resin base material;
20-39% of gas-phase nano silicon dioxide with a branched structure;
1-3% of a coupling agent;
the coupling agent is coated on the surface of the gas-phase nano silicon dioxide with the branched structure;
the preparation method of the polyphenyl ether resin composite material comprises the following steps:
weighing the components according to the formula of the polyphenyl ether resin composite material;
mixing the polyphenyl ether resin and the elastomer to obtain a first mixed material;
mixing the polyolefin, the flame retardant, the functional master batch, the main antioxidant and the auxiliary antioxidant to obtain a second mixed material;
and adding the first mixed material and the second mixed material from a main feeding port and a side feeding port respectively, and mixing, melting and extruding.
9. The method for preparing a polyphenylene ether resin composite material according to claim 8, wherein the functional master batch is prepared by the following method:
drying the gas-phase nano-silica with the branched structure, then spraying the coupling agent on the gas-phase nano-silica with the branched structure for fully mixing, and carrying out heat treatment at 110-130 ℃ for 50-70 min;
feeding the resin matrix from a main feeding port, feeding the gas-phase nano-silica powder with a branched structure, which is treated by the coupling agent under a heating condition, from a side feeding port, and performing melt co-extrusion at the temperature of 200-300 ℃, wherein the rotating speed of a screw rod in the melt extrusion process is 260-300 rpm, and the vacuum degree is 0.5-0.8 MPa.
10. A valve for a hot and cold water supply pipe, wherein the valve for a hot and cold water supply pipe is made of the polyphenylene ether resin composite material according to any one of claims 1 to 7.
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| CN103497500A (en) * | 2013-10-12 | 2014-01-08 | 苏州市沃特新材料科技有限公司 | Polyphenylene oxide resin alloy material and preparation method and application thereof |
| CN105504767A (en) * | 2016-01-04 | 2016-04-20 | 江苏沃特新材料科技有限公司 | Polyphenyl ether resin alloy material, preparation method thereof and refrigeration compressor |
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| CN103497500A (en) * | 2013-10-12 | 2014-01-08 | 苏州市沃特新材料科技有限公司 | Polyphenylene oxide resin alloy material and preparation method and application thereof |
| CN105504767A (en) * | 2016-01-04 | 2016-04-20 | 江苏沃特新材料科技有限公司 | Polyphenyl ether resin alloy material, preparation method thereof and refrigeration compressor |
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