CN118048034B - Nano silicon dioxide modified ABS alloy composite material and preparation method thereof - Google Patents
Nano silicon dioxide modified ABS alloy composite material and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000000956 alloy Substances 0.000 title claims abstract description 72
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 48
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 79
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 55
- 239000003607 modifier Substances 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 12
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- -1 styrene-acrylonitrile-maleimide-benzoic acid Chemical compound 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 15
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 238000010559 graft polymerization reaction Methods 0.000 claims description 7
- 238000006011 modification reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- LKUOJDGRNKVVFF-UHFFFAOYSA-N 4-(2,5-dioxopyrrol-1-yl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1N1C(=O)C=CC1=O LKUOJDGRNKVVFF-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- FAGGUIDTQQXDSJ-UHFFFAOYSA-N 3-benzoylazepan-2-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCNC1=O FAGGUIDTQQXDSJ-UHFFFAOYSA-N 0.000 claims description 3
- BZMPMWPIDSKPBE-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile pyrrole-2,5-dione Chemical compound O=C1NC(=O)C=C1.N#CC=CC=CC1=CC=CC=C1 BZMPMWPIDSKPBE-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 238000005452 bending Methods 0.000 abstract description 18
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229920002292 Nylon 6 Polymers 0.000 description 33
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 5
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000393 Nylon 6/6T Polymers 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of ABS alloy, and discloses a nano silicon dioxide modified ABS alloy composite material and a preparation method thereof, wherein the nano silicon dioxide modified ABS alloy composite material comprises, by weight, 20-60 parts of ABS resin, 40-80 parts of PA6 resin, 2-5 parts of heat-resistant compatibilizer modifier and 0.5-3 parts of polymer modified silicon dioxide. The heat-resistant compatibilizer modifier improves the compatibility between the ABS resin and the PA6 resin, and improves the stretching and bending properties of the alloy composite material. The polymer with the surface modified by the nano silicon dioxide contains a segmented copolymer molecular chain of styrene and acrylonitrile, so that the dispersibility of the nano silicon dioxide in an alloy material is improved, the agglomeration problem of the nano silicon dioxide is overcome, and the nano silicon dioxide has a good enhancement effect. And the ABS alloy composite material has excellent heat resistance.
Description
Technical Field
The invention relates to the technical field of ABS (Acrylonitrile butadiene styrene) alloy, in particular to a nano silicon dioxide modified ABS alloy composite material and a preparation method thereof.
Background
The ABS resin is a terpolymer prepared by taking three monomers of acrylonitrile, butadiene and styrene as raw materials, and has good elasticity, toughness and processability. Has wide application in the manufacturing industry and chemical industry of mechanical instruments, electronics, electric appliances and the like. The ABS resin, PA6 (nylon 6), PC (polycarbonate) and the like are processed and compounded, so that an alloy material with more excellent performance can be obtained; therefore, development of a novel compatibilizer is required to be applied to ABS alloy materials. Chinese patent CN101735604B discloses a montmorillonite modified PA6/ABS alloy material and a preparation method thereof, wherein styrene-acrylonitrile-maleic anhydride copolymer, polystyrene-nylon 6 copolymer, polypropylene-nylon 6 copolymer and the like are used as compatilizers, graft montmorillonite master batch, PA6, ABS resin and the like are used as raw materials, and the prepared PA6/ABS alloy material has the advantages of high strength, high modulus, good heat resistance and the like. However, compared with montmorillonite, the nano silicon dioxide has higher mechanical and heat-resistant properties, high structural stability and difficult thermal decomposition. The nano silicon dioxide is applied to the ABS alloy material, and is an effective method for improving the mechanical property, heat resistance and other properties of the alloy material. However, overcoming the agglomeration of nano silicon dioxide and improving the dispersibility in the alloy matrix is a research difficulty.
Disclosure of Invention
The invention solves the problem of poor compatibility of ABS and PA6, and simultaneously solves the problem of poor dispersibility of nano silicon dioxide in the alloy of ABS/PA 6.
The technical scheme provided by the invention is as follows:
The nano silicon dioxide modified ABS alloy composite material is characterized by comprising the following raw materials, by weight, 20-60 parts of ABS resin, 40-80 parts of PA6 resin, 2-5 parts of a heat-resistant compatibilizer modifier and 0.5-3 parts of polymer modified silicon dioxide;
The preparation method of the nano silicon dioxide modified ABS alloy composite material comprises the following steps: 20-60 parts of ABS resin, 40-80 parts of PA6 resin, 2-5 parts of heat-resistant compatibilizer modifier and 0.5-3 parts of polymer modified silicon dioxide are added into a double-screw extruder, the temperature of the extruder 1-4 sections is 220-240 ℃, the screw rotating speed is 30-50r/min, and extrusion granulation is carried out, so that the nano silicon dioxide modified ABS alloy composite material is obtained.
The preparation method of the heat-resistant compatibilizer modifier comprises the following steps:
Adding sodium dodecyl sulfate (30-45 mol) and 15mol (40-55 mol) of styrene, acrylonitrile and 4-maleimidobenzoic acid into distilled water in a nitrogen atmosphere, uniformly mixing, adding potassium persulfate, heating to 70-85 ℃, reacting for 3-4h, cooling, demulsifying by using an aluminum sulfate aqueous solution, washing the product by distilled water and ethanol in sequence, and drying to obtain the styrene-acrylonitrile-maleimidobenzoic acid polymer. The preparation reaction mechanism is as follows:
Adding a styrene-acrylonitrile-maleimidobenzoic acid polymer into N, N-dimethylformamide, uniformly mixing, adding thionyl chloride, reacting for 4-8 hours in a nitrogen atmosphere, heating to 65-75 ℃, concentrating the solution, washing with acetone, drying, adding the product into the N, N-dimethylformamide, uniformly mixing, and adding caprolactam, wherein the proportion of the styrene-acrylonitrile-maleimidobenzoic acid polymer, the thionyl chloride and the caprolactam is 100g (400-600 g) (50-120 g); reacting for 10-18h at room temperature, concentrating the solution, washing with acetone, and drying to obtain the styrene-acrylonitrile-maleimide benzoyl caprolactam polymer. The preparation reaction mechanism is as follows:
Uniformly mixing a styrene-acrylonitrile-maleimidobenzoyl caprolactam polymer and caprolactam in a nitrogen atmosphere, and adding elemental sodium, wherein the proportion of the caprolactam to the elemental sodium is 100g (80-200 g) (0.4-1 g); heating to 130-145 ℃, performing graft polymerization for 18-36h, washing with ethanol after the reaction, and drying to obtain the heat-resistant compatibilizer modifier. The preparation reaction mechanism is as follows:
The preparation method of the polymer modified silicon dioxide comprises the following steps: adding nano silicon dioxide into N, N-dimethylformamide, dispersing by ultrasonic, adding a styrene-acrylonitrile-maleimide benzoic acid polymer, carrying out surface modification reaction, concentrating the solution, washing with ethanol, and drying to obtain polymer modified silicon dioxide.
Wherein the proportion of the nano silicon dioxide and the styrene-acrylonitrile-maleimide benzoic acid polymer is 100g (60-120 g).
Wherein the temperature of the surface modification reaction is 120-140 ℃ and the reaction time is 10-20h.
The invention has the technical effects that: the invention uses styrene, acrylonitrile and 4-maleimide benzoic acid as comonomers to carry out polymerization reaction to obtain a styrene-acrylonitrile-maleimide benzoic acid polymer, then carboxyl of a side chain of the polymer is subjected to thionyl chloride and then reacts with caprolactam to obtain a styrene-acrylonitrile-maleimide benzoyl caprolactam polymer, finally, an active caprolactam structure introduced by the side chain is subjected to graft polymerization reaction in an initiation system of caprolactam and simple substance sodium, so that a nylon 6 molecular chain is introduced into the side chain of the polymer to obtain the novel heat-resistant compatibilizer modifier.
The side chain of the styrene-acrylonitrile-maleimide benzoic acid polymer contains active carboxyl, and can perform interaction such as esterification reaction with hydroxyl on the surface of nano silicon dioxide at high temperature, so that the polymer can be modified on the surface of nano silicon dioxide, and the surface organic modification of the nano silicon dioxide is realized.
According to the invention, the heat-resistant compatibilizer modifier and the polymer modified silicon dioxide are added into the PA6/ABS alloy, the heat-resistant compatibilizer modifier contains a segmented copolymer molecular chain of styrene and acrylonitrile, and simultaneously nylon 6 molecular chains are grafted, so that the heat-resistant compatibilizer modifier has strong interfacial bonding with the ABS resin and the PA6 resin, and the polymer can be used as a compatibilizer of the ABS resin and the PA6 resin, so that the compatibility between the ABS resin and the PA6 resin is obviously improved, and the stretching and bending properties of the alloy composite material are improved.
The polymer modified silica has good compatibility with ABS, so that the dispersibility of the nano silica in PA6/ABS alloy can be improved, the agglomeration problem of the nano silica is overcome, the nano silica has good enhancement effect, and the tensile property and bending property of the alloy composite material are further improved. The tensile strength of the alloy composite material is up to 92.4MPa, and the elongation at break is up to 520.1%. The bending strength and the bending modulus reach 118.4MPa and 2.415GPa at most.
The molecular chain of the heat-resistant compatibilizing modifier contains poly-N-phenyl maleimide block molecular chain, has strong high-temperature decomposition resistance and nano silicon dioxide has strong heat resistance, and the heat resistance of the alloy composite material is improved by adding the poly-N-phenyl maleimide block molecular chain and nano silicon dioxide into the PA6/ABS alloy, so that the tensile property and the bending property of the alloy composite material are reduced slightly after high-temperature ageing.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is intended to be illustrative of the invention and not restrictive.
The model of the nano silicon dioxide is XH-SiO 2 -30; average particle diameter 30nm; the purity is more than 99.9 percent.
Example 1
In a nitrogen atmosphere, adding 0.45mmol of sodium dodecyl sulfate, 30mmol of styrene, 15mmol of acrylonitrile and 55mmol of 4-maleimidobenzoic acid into 40mL of distilled water, uniformly mixing, adding 0.08mmol of potassium persulfate, heating to 75 ℃, reacting for 4 hours, cooling, demulsifiing by using an aluminum sulfate aqueous solution, washing the product by distilled water and ethanol in sequence, and drying to obtain the styrene-acrylonitrile-maleimidobenzoic acid polymer.
Adding 20g of styrene-acrylonitrile-maleimide-benzoic acid polymer into 100mL of N, N-dimethylformamide, uniformly mixing, adding 80g of thionyl chloride, heating to 75 ℃ in nitrogen atmosphere, reacting for 4 hours, concentrating the solution, washing with acetone, drying, adding the product into 120mL of N, N-dimethylformamide, uniformly mixing, adding 10g of caprolactam, reacting for 10 hours at room temperature, concentrating the solution, washing with acetone, and drying to obtain the styrene-acrylonitrile-maleimide-benzoyl caprolactam polymer.
In nitrogen atmosphere, 20g of styrene-acrylonitrile-maleimidobenzoyl caprolactam polymer and 16g of caprolactam are uniformly mixed, 0.08g of simple substance sodium is added, the temperature is raised to 135 ℃ for graft polymerization reaction for 18 hours, and after the reaction, ethanol is used for washing and drying, thus obtaining the heat-resistant compatibilizer modifier.
Adding 1g of nano silicon dioxide into 20mLN, N-dimethylformamide, dispersing by ultrasonic, adding 0.6g of styrene-acrylonitrile-maleimide benzoic acid polymer, heating to 120 ℃, carrying out surface modification reaction for 12h, concentrating the solution, washing with ethanol, and drying to obtain the polymer modified silicon dioxide.
200G of ABS resin, 800gPA g of resin, 20g of heat-resistant compatibilizer modifier and 5g of polymer modified silicon dioxide are added into a double-screw extruder, the temperature of the extruder 1-4 sections is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and the screw rotating speed is 30r/min, and extrusion granulation is carried out, so that the nano silicon dioxide modified ABS alloy composite material is obtained.
Example 2
In a nitrogen atmosphere, adding 0.5mmol of sodium dodecyl sulfate, 35mmol of styrene, 15mmol of acrylonitrile and 50mmol of 4-maleimidobenzoic acid into 60mL of distilled water, uniformly mixing, adding 0.1mmol of potassium persulfate, heating to 85 ℃, reacting for 3 hours, cooling, demulsifiing by using an aluminum sulfate aqueous solution, washing the product by distilled water and ethanol in sequence, and drying to obtain the styrene-acrylonitrile-maleimidobenzoic acid polymer.
Adding 20g of styrene-acrylonitrile-maleimide-benzoic acid polymer into 150mL of N, N-dimethylformamide, uniformly mixing, adding 100g of thionyl chloride, heating to 65 ℃ in nitrogen atmosphere, reacting for 8h, concentrating the solution, washing with acetone, drying, adding the product into 150mL of N, N-dimethylformamide, uniformly mixing, adding 16g of caprolactam, reacting for 12h at room temperature, concentrating the solution, washing with acetone, and drying to obtain the styrene-acrylonitrile-maleimide-benzoyl caprolactam polymer.
In nitrogen atmosphere, 20g of styrene-acrylonitrile-maleimidobenzoyl caprolactam polymer and 26g of caprolactam are uniformly mixed, 0.13g of simple substance sodium is added, the temperature is raised to 145 ℃, graft polymerization reaction is carried out for 18h, and after the reaction, ethanol is used for washing and drying, thus obtaining the heat-resistant compatibilizer modifier.
Adding 1g of nano silicon dioxide into 30mLN, N-dimethylformamide, dispersing by ultrasonic, adding 0.8g of styrene-acrylonitrile-maleimide benzoic acid polymer, heating to 140 ℃, carrying out surface modification reaction for 10h, concentrating the solution, washing with ethanol, and drying to obtain the polymer modified silicon dioxide.
200G of ABS resin, 800gPA g of resin, 35g of heat-resistant compatibilizer modifier and 18g of polymer modified silicon dioxide are added into a double-screw extruder, the temperature of the extruder 1-4 sections is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and the screw rotating speed is 50r/min, and extrusion granulation is carried out, so that the nano silicon dioxide modified ABS alloy composite material is obtained.
Example 3
In a nitrogen atmosphere, adding 0.4mmol of sodium dodecyl sulfate, 30mmol of styrene, 15mmol of acrylonitrile and 55mmol of 4-maleimidobenzoic acid into 60mL of distilled water, uniformly mixing, adding 0.1mmol of potassium persulfate, heating to 70 ℃, reacting for 4 hours, cooling, demulsifiing by using an aluminum sulfate aqueous solution, washing the product by distilled water and ethanol in sequence, and drying to obtain the styrene-acrylonitrile-maleimidobenzoic acid polymer.
Adding 20g of styrene-acrylonitrile-maleimide-benzoic acid polymer into 150mL of N, N-dimethylformamide, uniformly mixing, adding 120g of thionyl chloride, heating to 75 ℃ in nitrogen atmosphere, reacting for 8 hours, concentrating the solution, washing with acetone, drying, adding the product into 200mL of N, N-dimethylformamide, uniformly mixing, adding 24g of caprolactam, reacting for 18 hours at room temperature, concentrating the solution, washing with acetone, and drying to obtain the styrene-acrylonitrile-maleimide-benzoyl caprolactam polymer.
In nitrogen atmosphere, 20g of styrene-acrylonitrile-maleimidobenzoyl caprolactam polymer and 40g of caprolactam are uniformly mixed, 0.2g of simple substance sodium is added, the temperature is raised to 130 ℃, graft polymerization reaction is carried out for 36h, and after the reaction, ethanol is used for washing and drying, thus obtaining the heat-resistant compatibilizer modifier.
Adding 1g of nano silicon dioxide into 40mLN, N-dimethylformamide, dispersing by ultrasonic, adding 1.2g of styrene-acrylonitrile-maleimide benzoic acid polymer, heating to 130 ℃, carrying out surface modification reaction for 20h, concentrating the solution, washing with ethanol, and drying to obtain polymer modified silicon dioxide.
200G of ABS resin, 800gPA g of resin, 50g of heat-resistant compatibilizer modifier and 30g of polymer modified silicon dioxide are added into a double-screw extruder, the temperature of the extruder 1-4 sections is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and the screw rotating speed is 50r/min, and extrusion granulation is carried out, so that the nano silicon dioxide modified ABS alloy composite material is obtained.
Comparative example 1
200G of ABS resin and 800gPA g of resin are added into a double-screw extruder, the temperature of the extruder 1-4 sections is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and the screw rotating speed is 30r/min, and extrusion granulation is carried out, so that the ABS alloy composite material is obtained.
Comparative example 2
A heat resistant compatibilizing modifier was prepared as in example 1.
200G of ABS resin and 800gPA g of resin and 20g of heat-resistant compatibilizer modifier are added into a double-screw extruder, the temperature of the extruder 1-4 sections is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and the screw speed is 30r/min in sequence, and extrusion granulation is carried out, so that the modified ABS alloy composite material is obtained.
Comparative example 3
A heat resistant compatibilizing modifier was prepared as in example 1.
200G of ABS resin, 800gPA g of resin, 20g of heat-resistant compatibilizer modifier and 5g of nano silicon dioxide are added into a double-screw extruder, the temperature of the extruder 1-4 sections is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and the screw rotating speed is 30r/min, and extrusion granulation is carried out, so that the modified ABS alloy composite material is obtained.
Comparative example 4
Polymer modified silica was prepared as in example 1.
200G of ABS resin, 800gPA g of resin and 5g of polymer modified silicon dioxide are added into a double screw extruder, the temperature of the extruder 1-4 sections is 220 ℃, 235 ℃, 240 ℃ and 235 ℃ in sequence, the screw speed is 30r/min, and the modified ABS alloy composite material is obtained through extrusion granulation.
Comparative example 5
Styrene-acrylonitrile-maleimidobenzoyl caprolactam polymer and polymer modified silica were prepared as in example 1.
200G of ABS resin, 800gPA g of resin, 20g of styrene-acrylonitrile-maleimidobenzoyl caprolactam polymer and 5g of polymer modified silicon dioxide are added into a double-screw extruder, the temperature of the extruder 1-4 sections is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and the screw rotating speed is 30r/min, and extrusion granulation is carried out, so that the modified ABS alloy composite material is obtained.
And (3) injecting the modified ABS alloy into a spline by an injection molding machine, and performing mechanical property test. Tensile properties were tested according to GB/T1040.1-2018 standards. Flexural properties were tested according to GB/T9341-2008.
Placing the ABS alloy sample strip in an aging test box for accelerated thermal aging at 120 ℃ for 360 hours; and then carrying out mechanical property test.
TABLE 1 ABS alloy tensile Property test
Table 2 ABS alloy bending Performance test
In examples 1,2 and 3 of the present invention, the heat-resistant compatibilizing modifier and the polymer modified silica are added to the PA6/ABS alloy, and the tensile strength of the alloy tends to gradually increase and then slowly increase with the gradual increase of the amounts of the heat-resistant compatibilizing modifier and the polymer modified silica. The tensile strength is up to 92.4MPa, and the elongation at break is up to 520.1%. The bending strength and the bending modulus increase and then decrease slowly, up to 118.4MPa and 2.415GPa. The heat-resistant compatibilizer modifier contains a segmented copolymer molecular chain of styrene and acrylonitrile, and simultaneously is grafted with a nylon 6 molecular chain, so that the heat-resistant compatibilizer modifier has strong interfacial bonding with ABS resin and PA6 resin, and can be used as a compatibilizer of the ABS resin and the PA6 resin, the compatibility between the ABS resin and the PA6 resin is obviously improved, and the stretching and bending properties of the alloy composite material are improved.
Meanwhile, the side chain of the styrene-acrylonitrile-maleimide benzoic acid polymer contains active carboxyl, and can interact with hydroxyl on the surface of nano silicon dioxide in an esterification reaction and the like at high temperature, so that the polymer can be modified on the surface of the nano silicon dioxide, and the surface organic modification of the nano silicon dioxide is realized. The polymer contains a segmented copolymer molecular chain of styrene and acrylonitrile, has good compatibility with ABS, can improve the dispersibility of nano silicon dioxide in PA6/ABS alloy, overcomes the agglomeration problem of nano silicon dioxide, ensures that the nano silicon dioxide has good reinforcing effect, and further improves the tensile property and bending property of the alloy composite material.
The molecular chain of the heat-resistant compatibilizer modifier contains a poly-N-phenyl maleimide block molecular chain, has strong pyrolysis resistance and nano silicon dioxide has strong heat resistance, and the heat resistance of the alloy composite material is improved by adding the poly-N-phenyl maleimide block molecular chain and nano silicon dioxide into the PA6/ABS alloy, so that the tensile property and the bending property of the alloy composite material are reduced slightly after high-temperature thermal aging.
The alloy composite material of comparative example 1 is not added with a heat-resistant compatibilizer modifier, and the compatibility of the ABS resin and the PA6 resin is poor. And polymer modified silicon dioxide is not added, so that the mechanical properties such as stretching and bending of the alloy composite material are the worst. And after high-temperature heat aging, the mechanical property of the alloy composite material is greatly reduced, and the heat resistance is poor.
The alloy composite material of the comparative example 2 is added with the heat-resistant compatibilizer modifier, so that the compatibility of the ABS resin and the PA6 resin is good, and the tensile and bending properties are obviously higher than those of the alloy composite material of the comparative example 1. And the mechanical property of the alloy composite material is reduced slightly and the heat resistance is good after high-temperature heat aging. However, the absence of the addition of polymer modified silica resulted in lower tensile and flexural properties than in example 1.
Compared with the example 1 and the comparative example 2, the comparative example 3 adds the heat-resistant compatibilizing modifier and the unmodified nano silicon dioxide, and the nano silicon dioxide is not subjected to the surface modification of the styrene-acrylonitrile-maleimidobenzoic acid polymer, so that the nano silicon dioxide has poor dispersibility in the alloy composite material and has lower mechanical property than the example 1. However, when the amount of nano silica is small, the nano silica can play a certain role in strengthening although the dispersibility is poor, so that the mechanical properties of the alloy material can be improved, and the tensile and bending properties are higher than those of comparative example 2.
Comparative example 4 added polymer modified silica, but not heat resistant compatibilizer modifier, the ABS resin and PA6 resin were not well compatible and the mechanical properties of the alloy composite were lower than those of example 1.
In comparative example 5, styrene-acrylonitrile-maleimidobenzoyl caprolactam polymer and polymer modified silica were added, the styrene-acrylonitrile-maleimidobenzoyl caprolactam polymer did not contain nylon 6 molecular chains, and had very strong interfacial bonding with PA6 resin, and the effect of compatibilizing ABS resin and PA6 resin could not be achieved, resulting in poor compatibility between ABS resin and PA6 resin, and the mechanical properties of the alloy composite material were lower than those of example 1.
Example 4
A heat resistant compatibilizing modifier and a polymer modified silica were prepared as in example 1.
430G of ABS resin, 570gPA g of heat-resistant compatibilizer modifier and 5g of polymer modified silicon dioxide are added into a double-screw extruder, the temperature of the extruder 1-4 sections is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and the screw speed is 30r/min, and extrusion granulation is carried out, so that the nano silicon dioxide modified ABS alloy composite material is obtained.
Example 5
A heat resistant compatibilizing modifier and a polymer modified silica were prepared as in example 1.
600G of ABS resin, 400gPA g of resin, 20g of heat-resistant compatibilizer modifier and 5g of polymer modified silicon dioxide are added into a double-screw extruder, the temperature of the extruder 1-4 sections is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and the screw rotating speed is 30r/min, and extrusion granulation is carried out, so that the nano silicon dioxide modified ABS alloy composite material is obtained.
TABLE 3 mechanical property test of nano silicon dioxide modified ABS alloy composite material
The main differences between the ABS resin and the PA6 resin in the examples 1, 4 and 5 are that the ABS resin and the PA6 resin in the example 4 have different proportions, wherein the ABS resin and the PA6 resin in the example 4 have better mechanical properties, the tensile strength reaches 96.7MPa, the bending strength reaches 113.2MPA, the bending modulus reaches 119.2MPa and the bending modulus reaches 2.476GPa.
Claims (9)
1. The nano silicon dioxide modified ABS alloy composite material is characterized by comprising the following raw materials, by weight, 20-60 parts of ABS resin, 40-80 parts of PA6 resin, 2-5 parts of a heat-resistant compatibilizer modifier and 0.5-3 parts of polymer modified silicon dioxide;
the preparation method of the heat-resistant compatibilizing modifier comprises the following steps:
S1, adding a styrene-acrylonitrile-maleimide-benzoic acid polymer into N, N-dimethylformamide, uniformly mixing, adding thionyl chloride, heating to 65-75 ℃ in a nitrogen atmosphere, reacting for 4-8 hours, concentrating the solution, washing, drying, adding the product into the N, N-dimethylformamide, uniformly mixing, adding caprolactam, reacting for 10-18 hours at room temperature, concentrating the solution, washing, and drying to obtain the styrene-acrylonitrile-maleimide-benzoyl caprolactam polymer;
Step S2, uniformly mixing a styrene-acrylonitrile-maleimide benzoyl caprolactam polymer and caprolactam in a nitrogen atmosphere, adding simple substance sodium, performing graft polymerization reaction, washing after the reaction, and drying to obtain a heat-resistant compatibilizer modifier;
The preparation method of the polymer modified silicon dioxide comprises the following steps: adding nano silicon dioxide into N, N-dimethylformamide, dispersing by ultrasonic, adding a styrene-acrylonitrile-maleimide benzoic acid polymer, carrying out surface modification reaction, concentrating the solution, washing and drying to obtain polymer modified silicon dioxide.
2. The nano silica modified ABS alloy composite material according to claim 1, wherein in the step S1, the proportion of the styrene-acrylonitrile-maleimidobenzoic acid polymer, the sulfoxide chloride and the caprolactam is 100g (400-600 g) (50-120 g).
3. The nano silicon dioxide modified ABS alloy composite material according to claim 1, wherein in the step S2, the proportion of styrene-acrylonitrile-maleimidobenzoyl caprolactam polymer, caprolactam and simple substance sodium is 100g (80-200 g) (0.4-1 g).
4. The nano silica modified ABS alloy composite according to claim 1, wherein in step S2, the temperature of the graft polymerization reaction is 130 to 145 ℃ and the reaction time is 18 to 36 hours.
5. The nano silica modified ABS alloy composite material according to claim 1, wherein the ratio of nano silica to styrene-acrylonitrile-maleimidobenzoic acid polymer is 100g (60-120 g).
6. The nano silica modified ABS alloy composite according to claim 1 wherein the surface modification reaction temperature is 120 to 140 ℃ and the reaction time is 10 to 20 hours in the preparation method of the polymer modified silica.
7. The nano silica modified ABS alloy composite according to claim 1 wherein the preparation method of the styrene-acrylonitrile-maleimidobenzoic acid polymer is as follows: adding sodium dodecyl sulfate, styrene, acrylonitrile and 4-maleimidobenzoic acid into distilled water in nitrogen atmosphere, uniformly mixing, adding potassium persulfate, heating to 70-85 ℃, reacting for 3-4h, cooling, demulsifying, washing and drying to obtain the styrene-acrylonitrile-maleimidobenzoic acid polymer.
8. The nano-silica modified ABS alloy composite material according to claim 7, wherein the ratio of styrene, acrylonitrile, 4-maleimidobenzoic acid is (30-45) mol to 15mol (40-55) mol.
9. The method for preparing the nano silica modified ABS alloy composite material according to any one of claims 1 to 8, wherein 20 to 60 parts by weight of ABS resin, 40 to 80 parts by weight of PA6 resin, 2 to 5 parts by weight of heat-resistant compatibilizer modifier and 0.5 to 3 parts by weight of polymer modified silica are added into a double-screw extruder, the temperature of the extruder 1 to 4 sections is 220 to 240 ℃, the screw rotating speed is 30 to 50r/min, and extrusion granulation is carried out, so that the nano silica modified ABS alloy composite material is obtained.
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| JPH0258512A (en) * | 1988-08-25 | 1990-02-27 | Tosoh Corp | N-(carboxyphenyl)maleimide copolymer |
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