CN113603842B - Preparation of core-shell structure organic silicon toughening agent, toughening agent and application - Google Patents
Preparation of core-shell structure organic silicon toughening agent, toughening agent and application Download PDFInfo
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- CN113603842B CN113603842B CN202111056535.7A CN202111056535A CN113603842B CN 113603842 B CN113603842 B CN 113603842B CN 202111056535 A CN202111056535 A CN 202111056535A CN 113603842 B CN113603842 B CN 113603842B
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- 239000012745 toughening agent Substances 0.000 title claims abstract description 50
- 239000011258 core-shell material Substances 0.000 title claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 18
- 239000010703 silicon Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 229920002545 silicone oil Polymers 0.000 claims abstract description 28
- 239000010410 layer Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012792 core layer Substances 0.000 claims abstract description 12
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 10
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 10
- -1 acrylic ester Chemical class 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 229920001225 polyester resin Polymers 0.000 claims abstract description 5
- 239000004645 polyester resin Substances 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000007246 mechanism Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 7
- 239000000806 elastomer Substances 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- 229920006124 polyolefin elastomer Polymers 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a preparation method of a core-shell structure organic silicon toughening agent and application of the toughening agent in polycarbonate resin and polyester resin. The raw materials for preparing the toughening agent comprise styrene monomer, butadiene monomer, hydrogen-containing silicone oil, methylol acrylamide and acrylate monomer. The copolymer is a core-shell structure consisting of a core layer, a silicon oil layer and a shell structure. The core layer structure is a nonpolar layer formed by styrene grafted copolybutadiene, and the hydrogen-containing silicone oil chain segment is an independent silicone oil phase structure layer for connecting the core layer and the shell layer. The shell layer is a polar shell layer of a polar chain segment formed by acrylate graft copolymerization. Because the structure contains the silicone oil chain segment, the material can be endowed with good processing performance, the core layer structure contains the long-chain branch, the material can be endowed with good elasticity, and the acrylic ester polar group in the shell layer structure can endow the toughening agent with good compatibility with resin. The invention has simple production process, high production efficiency and low production cost, and can be used for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of toughening agents, in particular to preparation of a core-shell structure organic silicon toughening agent, the toughening agent and application of the toughening agent in polycarbonate resin and polyester resin.
Background
The existing toughening agent in the market realizes grafting toughening through POE (polyolefin elastomer) and rubber elastomer grafting GMA (glycidyl methacrylate), but the GMA is easy to self-polymerize at high temperature, so that the grafting rate of the POE elastomer is very low, and meanwhile, the POE elastomer and the rubber elastomer are easy to cause chain crosslinking under the action of free radicals in a system in the reaction process, so that the melt index of matrix resin is reduced, and the toughening effect is reduced. Therefore, the preparation of GMA grafted POE with high grafting rate and low crosslinking degree and the GMA grafted elastomer are the subjects of continuous research in the field of toughening technology.
Disclosure of Invention
In view of the shortcomings of the prior art, one of the objects of the present invention is to solve the problems of the prior art. For example, the invention aims to provide a preparation method of a core-shell structure organosilicon toughening agent which can endow materials with good processability and elasticity and has good compatibility with resin.
In order to achieve the above object, embodiment 1 of the present invention is as follows:
the preparation method of the core-shell structure organosilicon toughening agent comprises the following steps:
1) Styrene monomer, liquefied compressed butadiene monomer, deionized water, water-soluble initiator and emulsifier are subjected to emulsion polymerization reaction for a period of time under the protection of N 2 at a certain reaction temperature to prepare a nonpolar core layer in a core-shell structure; the reaction is more stable when the reaction is performed under the protection of N2;
2) Adding a certain amount of hydrogen-containing silicone oil into the prepared nuclear layer, controlling the reaction to carry out addition on unsaturated double bonds in the nuclear layer structure according to a coordination addition mechanism at a certain temperature under the action of a transition metal catalyst, and controlling the addition reaction time within a certain time to prepare a silicone oil layer introduced with an organosilicon structure;
3) Adding acrylic ester and methylol acrylamide into a silicone oil layer containing an organosilicon structure, and carrying out elimination reaction on hydroxyl dehydrogenation in the methylol acrylamide of unreacted hydrogen in hydrogen-containing silicone oil under the action of a transition metal catalyst; the acrylic ester monomer is subjected to emulsion polymerization reaction to prepare a shell layer with polar groups;
4) And demulsifying, filtering, washing, drying and purifying the product to obtain the organosilicon toughening agent with the core-shell structure.
Further, the ratio of the amount of the styrene monomer to the amount of the liquefied compressed butadiene monomer in the step 1) is 4:6 to 6:4; a proper amount of styrene monomer is helpful for maintaining the heat resistance of the toughening agent;
the ratio of the amount of the substances of the hydrogen-containing silicone oil to the butadiene monomer is 1: 0.5-1:1;
The ratio of the amount of the methylol acrylamide to the amount of the acrylic acid ester substance is 1:1.5-1:1.8; the increase of the content of the acrylic ester substance is beneficial to improving the compatibility of the toughening agent and the ester polymer.
Further, the ratio of the amount of the styrene monomer to the amount of the liquefied compressed butadiene monomer in the step 1) is 4:6 to 6:4;
The ratio of the amount of unreacted unsaturated double bond substances of the core layer polymer to the amount of substances of silicon-hydrogen bonds of the hydrogen-containing silicone oil in the step 2) is 1: 0.5-1:1;
The amount of the substance containing the silicon hydrogen bond of the silicon oil layer with the organic silicon structure in the step 3): amount of methylol acrylamide substance: the mass amount of the acrylate is 1:1:5-1:1:8.
Further, the weight ratio of the core layer to the silicone oil layer to the shell layer is 1:3:2;2:5:3; 1:2:1.
Further, the mass fraction of the hydrogen-containing silicone oil is selected from one of low hydrogen-containing silicone oil of 0.18%, 0.35% and 0.75%, the high hydrogen-containing silicone oil is 1.0% -1.6% of the mass fraction of hydrogen, the high hydrogen-containing silicone oil is favorable for improving the reaction rate, but the crosslinking degree is improved at the same time, and the crosslinking degree of the toughening agent is easily controlled when the toughening agent is selected from low hydrogen-containing silicone oil.
Further, the water-soluble initiator in the step 1) is one of potassium persulfate and Azobisisobutyronitrile (AIBN), and the water-soluble initiator has the following purposes: can be dissolved in water and initiates the reaction of the monomer in the small liquid drops under the action of the emulsifier.
The emulsifier in the step 1) is one of Tween 20, benzzeol 35 and zeol 51, and the purpose of the emulsifier is as follows: emulsifying the oil-soluble monomer into small oil drops to make the emulsion uniform and stable, which is favorable for the rapid and uniform reaction of the polymerization reaction
Further, the reaction temperature in the step 1) is controlled to be 65-75 ℃; the reaction temperature in the step 2) is controlled between 55 ℃ and 65 ℃; the reaction temperature in the step 3) is controlled to be 80-85 ℃.
Further, the reaction time in the step 1) is controlled to be 4-5 hours; the reaction time in the step 2) is controlled to be 3-4 hours; and in the step 3), the reaction time is controlled to be 6-8 hours.
Further, the transition metal catalyst in the step 2) and the step 3) is one of platinum, palladium, rhodium and nickel, and the transition metal catalyst has higher catalytic activity;
the acrylic ester in the step 3) is one of butyl acrylate and ethyl acrylate.
The invention also discloses a core-shell structure organic silicon toughening agent, which comprises the following components: the toughening agent prepared by the preparation method.
The invention also discloses an application of the core-shell structure organic silicon toughening agent, which comprises the following steps: the toughener prepared by the preparation method of the embodiment 1 is melted and blended with polycarbonate resin particles and polyester resin particles through double screws to granulate, so as to obtain a granulated product, and the granulated product is injection molded into a sample, and the mechanical property is tested.
The invention has the following beneficial technical effects: the acrylate structure for the core layer has good compatibility with the carbon and polyester, the organosilicon belongs to the middle layer, the material processing performance is good, and the styrene-butadiene copolymer elasticity for the core layer structure is good; because the organic silicon molecular chain is different from the common polymer chain of the carbon element, the organic silicon molecular chain belongs to a nonpolar molecular chain segment, the intermolecular force of the organic silicon is only dispersive, the intermolecular force is weak, and the organic silicon molecular chain is mostly used as an intermolecular lubricant, so that the dispersibility of the organic silicon among carbon-containing polymers is improved, silicon atoms externally display positive electricity, and carbon atoms display electropositivity, which is a factor of good high-temperature heat stability of the silicon element, the hydrogen-containing silicone oil selected by the invention has high reactivity and high reaction conversion rate, and the prepared toughening agent product has stable performance;
The invention has better processing performance than common MBS, and is especially suitable for toughening polycarbonate rigid groups and compatible toughening polyester polar groups.
Detailed Description
The present invention will be described in detail for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, but the specific embodiments described herein are only for explaining the present invention and are not limited to the present invention.
Example 1:
(1) 104g of styrene, 500g of deionized water, 81g of liquefied butadiene and 5g of emulsifier Tween 20 are weighed and added into a 3L reaction kettle, 6g of potassium persulfate containing an initiator is dripped into the reaction kettle at the speed of 10 drops/min, the temperature in the reaction kettle is controlled to be 65 ℃, nitrogen is introduced to enable the deionized water and the reaction kettle to be free of oxygen, the pressure of the reaction kettle is controlled to be 4MPa, and the pressure is relieved after the reaction is finished for 5 hours.
(2) 475G of low-hydrogen silicone oil with the mass fraction of hydrogen of 0.35% is added, 5g of platinum catalyst is added, the reaction temperature is controlled to be 60 ℃, and the reaction is carried out for 4 hours under the protection of nitrogen.
(3) 150G of methylolacrylamide are added and 190g of butyl acrylate are added. 5g of a platinum catalyst was added under nitrogen protection, and 6g of potassium persulfate was added dropwise at a rate of 10 drops/min. The reaction temperature is controlled to 80 ℃ and the reaction time is controlled to 6 hours.
(4) And after the reaction is finished, demulsification, filtration, washing, drying and purification are carried out to obtain the organosilicon toughening agent with the core-shell structure.
Example 2:
(1) 208g of styrene, 1000g of deionized water, 162g of liquefied butadiene and 35 g of emulsifier benzyl are weighed and added into a 5L reaction kettle, 6g of potassium persulfate containing an initiator is dripped into the reaction kettle at the speed of 10 drops/min, the temperature in the reaction kettle is controlled to be 65 ℃, nitrogen is introduced to enable the deionized water and the reaction kettle to be free of oxygen, the pressure of the reaction kettle is controlled to be 4MPa, the reaction is carried out for 5 hours, and the pressure is relieved after the reaction is finished.
(2) 950G of low-hydrogen silicone oil with the mass fraction of hydrogen of 0.18% is added, 5g of platinum catalyst is added, the reaction temperature is controlled to be 60 ℃, and the reaction is carried out for 4 hours under the protection of nitrogen.
(3) 300G of methylolacrylamide are added and 375g of butyl acrylate are added. Under the protection of nitrogen, 5g of platinum catalyst and 6g of potassium persulfate are added dropwise at a speed of 10 drops/min, the reaction temperature is controlled to 80 ℃, and the reaction time is controlled to 6h.
(4) And after the reaction is finished, demulsification, filtration, washing, drying and purification are carried out to obtain the organosilicon toughening agent with the core-shell structure.
Example 3:
(1) Weighing 416g of styrene, 2000g of deionized water, 324g of liquefied butadiene and 51 g of emulsifier by weight, adding into a 10L reaction kettle together, dripping 6g of potassium persulfate containing an initiator into the reaction kettle at a speed of 10 drops/min, controlling the temperature in the reaction kettle to be 65 ℃, introducing nitrogen to ensure that the deionized water and the reaction kettle are free of oxygen, controlling the pressure in the reaction kettle to be 4MPa, reacting for 5 hours, releasing pressure after the reaction is finished,
(2) 1900G of low-hydrogen silicone oil with the mass fraction of hydrogen of 0.75% is added, 5g of platinum catalyst is added, the reaction temperature is controlled to be 60 ℃, and the reaction is carried out for 4 hours under the protection of nitrogen.
(3) 600G of methylolacrylamide are added and 750g of butyl acrylate are added. 5g of a platinum catalyst was added under nitrogen protection, and 6g of potassium persulfate was added dropwise at a rate of 10 drops/min. The reaction temperature is controlled to 80 ℃ and the reaction time is controlled to 6 hours.
(4) And after the reaction is finished, demulsification, filtration, washing, drying and purification are carried out to obtain the organosilicon toughening agent with the core-shell structure.
By the method of the above example 1.2.3, a core-shell structure organic silicon toughening agent can be prepared, and the toughening agent is widely applied to polycarbonate resin and polyester resin.
The application of the core-shell structure organosilicon toughening agent is as follows:
and (3) melting and granulating the core-shell structure organosilicon toughening agent and polycarbonate resin (PC) in a double-screw extruder according to the proportion of 3%.
In order to further illustrate the excellent performance of the toughening agent, the pelleting product mixed with the toughening agent is subjected to injection molding on an injection molding machine at the temperature of 240-260 ℃ to prepare a sample strip to be tested, and the strength test of the injection molded sample strip and a PC without the toughening agent is carried out, wherein the sample of the same amount of common toughening agent is injected.
The results of the strength test of PC (100%), 3% MBS addition and the inventive samples are shown in Table 1:
(test sample size) table 1 strength test results of injection molded bars:
Through the strength test, the PC sample using the core-shell structure organosilicon toughening agent has the advantages of maximum tensile strength, best impact strength and best flexibility.
While the invention has been particularly shown and described with reference to embodiments thereof, changes in form and detail thereof may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the present invention is not limited by the embodiments of the present invention, and differences within the scope will be construed as being included in the present invention under the appended claims.
Claims (10)
1. A preparation method of a core-shell structure organosilicon toughening agent is characterized by comprising the following steps: the method comprises the following steps:
1) Styrene monomer, liquefied compressed butadiene monomer, deionized water, water-soluble initiator and emulsifier are subjected to emulsion polymerization reaction for a period of time under the protection of N2 at a certain reaction temperature to prepare a nonpolar core layer in a core-shell structure;
2) Adding a certain amount of hydrogen-containing silicone oil into the prepared nuclear layer, controlling the reaction to carry out addition on unsaturated double bonds in the nuclear layer structure according to a coordination addition mechanism at a certain temperature under the action of a transition metal catalyst, and controlling the addition reaction time within a certain time to prepare a silicone oil layer introduced with an organosilicon structure;
3) Adding acrylic ester and methylol acrylamide outside the silicone oil layer, and carrying out elimination reaction on the hydroxyl in the methylol acrylamide by unreacted hydrogen in the hydrogen-containing silicone oil under the action of a transition metal catalyst; the acrylic ester monomer is subjected to emulsion polymerization reaction to prepare a shell layer with polar groups;
4) And demulsifying, filtering, washing, drying and purifying the product to obtain the organosilicon toughening agent with the core-shell structure.
2. The method for preparing the core-shell structure organosilicon toughening agent according to claim 1, which is characterized in that:
the ratio of the amount of the substances of the styrene monomer to the liquefied compressed butadiene monomer in the step 1) is 4:6-6:4;
The ratio of the amount of unreacted unsaturated double bond substances of the core layer polymer to the amount of substances of silicon-hydrogen bonds of the hydrogen-containing silicone oil in the step 2) is 1: 0.5-1:1;
the amount of the substance containing the silicon hydrogen bond of the silicon oil layer with the organic silicon structure in the step 3): amount of methylol acrylamide substance: the mass quantity of the acrylic ester is 1:1.5-1:1.8.
3. The method for preparing the core-shell structure organosilicon toughening agent according to claim 1, which is characterized in that: the weight ratio of the core layer to the silicone oil layer to the shell layer is 1:3:2;2:5:3; 1:2:1.
4. The method for preparing the core-shell structure organosilicon toughening agent according to claim 1, which is characterized in that: the mass fraction of the hydrogen-containing silicone oil is selected from one of low hydrogen-containing silicone oil of 0.18%, 0.35% and 0.75%.
5. The method for preparing the core-shell structure organosilicon toughening agent according to claim 1, which is characterized in that: the water-soluble initiator in the step 1) is one of potassium persulfate and Azobisisobutyronitrile (AIBN); the emulsifier in the step 1) is one of Tween 20, benzyl 35 and herba Euphorbiae Helioscopiae 51.
6. The method for preparing the core-shell structure organosilicon toughening agent according to claim 1, which is characterized in that: the reaction temperature in the step 1) is controlled between 65 ℃ and 75 ℃; the reaction temperature in the step 2) is controlled between 55 ℃ and 65 ℃; the reaction temperature in the step 3) is controlled to be 80-85 ℃.
7. The method for preparing the core-shell structure organosilicon toughening agent according to claim 1, which is characterized in that: the reaction time in the step 1) is controlled to be 4-5 hours; the reaction time in the step 2) is controlled to be 3-4 hours; and in the step 3), the reaction time is controlled to be 6-8 hours.
8. The method for preparing the core-shell structure organosilicon toughening agent according to claim 1, which is characterized in that: the transition metal catalyst in the step 2) and the step 3) is one of platinum, palladium, rhodium and nickel; the acrylic ester in the step 3) is one of butyl acrylate and ethyl acrylate.
9. The core-shell structure organosilicon toughening agent is characterized in that: comprising the following steps: a toughening agent made by the method of making of claim 1.
10. The application of the core-shell structure organosilicon toughening agent is characterized in that: comprising the following steps: the toughening agent prepared by the preparation method of claim 1 is prepared into a pelletization product by melt blending and pelletization of double screws and polycarbonate resin particles and polyester resin particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111056535.7A CN113603842B (en) | 2021-09-09 | 2021-09-09 | Preparation of core-shell structure organic silicon toughening agent, toughening agent and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111056535.7A CN113603842B (en) | 2021-09-09 | 2021-09-09 | Preparation of core-shell structure organic silicon toughening agent, toughening agent and application |
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