CN113603842A - 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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- 239000012745 toughening agent Substances 0.000 title claims abstract description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000011258 core-shell material Substances 0.000 title claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 27
- 239000010703 silicon Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 229920002545 silicone oil Polymers 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010410 layer Substances 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
- 239000012792 core layer Substances 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 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
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000003921 oil Substances 0.000 claims abstract description 6
- 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
- 238000004519 manufacturing process Methods 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 239000000126 substance Substances 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
- 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 6
- 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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 238000007259 addition reaction Methods 0.000 claims description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- 238000000034 method 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
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 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
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229940065472 octyl acrylate Drugs 0.000 claims description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 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
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 239000005062 Polybutadiene Substances 0.000 abstract 1
- -1 acrylic ester Chemical class 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229920002857 polybutadiene Polymers 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
- 238000012360 testing method Methods 0.000 description 6
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 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
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity 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
- 230000006872 improvement Effects 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 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 an organosilicon toughening agent with a core-shell structure and application of the toughening agent in polycarbonate resin and polyester resin. The raw materials for preparing the toughening agent comprise a styrene monomer, a butadiene monomer, hydrogen-containing silicone oil, hydroxymethyl acrylamide and an acrylate monomer. The copolymer is a core-shell structure consisting of a core layer, a silicon oil layer and a shell layer structure. The core layer structure is a nonpolar layer formed by styrene grafted polybutadiene, and the hydrogen-containing silicone oil chain segment is an independent silicone oil phase structure layer connecting the core layer and the shell layer. The shell layer is a polar shell layer of a polar chain segment formed by grafting and copolymerizing acrylic ester. The structure contains a silicone oil chain segment, so that the material can be endowed with good processing performance, the core layer structure contains a long-chain branch, so that the material can be endowed with good elasticity, and the shell layer structure contains an acrylate polar group, so that the toughening agent can be endowed 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 an organic silicon toughening agent with a core-shell structure, the toughening agent and application of the organic silicon 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 grafted GMA (glycidyl methacrylate), but GMA easily self-polymerizes at high temperature, so that the grafting rate of the POE elastomer is low, and chain crosslinking is easily caused under the action of free radicals in a system by the POE elastomer and the rubber elastomer 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 ratio and low crosslinking degree and GMA grafted elastomer are the subject of continuous research in the field of toughening technology.
Disclosure of Invention
In view of the shortcomings of the prior art, an object of the present invention is to solve the above problems of the prior art. For example, the invention aims to provide a preparation method of a core-shell structure organic silicon toughening agent which can endow materials with good processability and elasticity and has good compatibility with resin.
In order to achieve the above object, a 1 st embodiment of the present invention is:
a preparation method of an organosilicon toughening agent with a core-shell structure comprises the following steps:
1) styrene monomer, liquefied compressed butadiene monomer, deionized water, water-soluble initiator and emulsifier are reacted at certain temperature and N2Preparing a nonpolar nuclear layer in a nuclear shell structure through emulsion polymerization for a period of time under protection; the reaction is more stable when the reaction is carried out under the protection of N2;
2) adding a certain amount of hydrogen-containing silicone oil into the prepared core layer, controlling the reaction at a certain temperature under the action of a transition metal catalyst, and performing addition reaction on unsaturated double bonds in the core layer structure according to a coordination addition mechanism, wherein the addition reaction time is controlled within a certain time, so as to prepare a silicone oil layer introduced with an organic silicon structure;
3) adding acrylate and hydroxymethyl acrylamide into a silicone oil layer containing an organic silicon structure, and dehydrogenating unreacted hydrogen in hydrogen-containing silicone oil to hydroxyl in the hydroxymethyl acrylamide to perform elimination reaction under the action of transition metal; preparing a shell layer with polar groups by an acrylate monomer through emulsion polymerization;
4) the product is demulsified, filtered, washed, dried and purified to obtain the organic silicon toughening agent with the core-shell structure.
Further, the mass ratio of the styrene monomer to the liquefied compressed butadiene monomer in the step 1) is 4:6 to 6: 4; the proper amount of styrene monomer is beneficial to maintaining the heat resistance of the toughening agent;
the mass ratio of the hydrogen-containing silicone oil to the butadiene monomer is 1: 0.5-1: 1;
the amount ratio of the methylol acrylamide to the acrylate substance is 1: 1.5-1: 1.8; the improvement of the content of the acrylate substance is beneficial to improving the compatibility of the toughening agent and the ester polymer.
Further, the mass ratio of the styrene monomer to the liquefied compressed butadiene monomer in the step 1) is 4:6 to 6: 4;
the ratio of the amount of the unreacted unsaturated double bond substances of the core layer polymer in the step 2) to the amount of the hydrogen-containing silicone oil silicon hydrogen bond substances is 1: 0.5-1: 1;
the amount of the silicon-hydrogen bond substances of the silicon oil layer containing the organic silicon structure in the step 3) is as follows: amount of methylolacrylamide material: the amount of acrylate is 1:1:5 to 1:1: 8.
Further, the weight ratio of the core layer to the silicon oil layer to the shell layer is 1:3: 2; 2:5: 3; 1:2: 1.
Furthermore, the mass fraction of the hydrogen-containing silicone oil is selected from one of 0.18%, 0.35% and 0.75% of medium and low hydrogen-containing silicone oil, and the high hydrogen-containing silicone oil means that the mass fraction of hydrogen is 1.0-1.6%, the high hydrogen-containing mass fraction is favorable for improving the reaction rate, but the crosslinking degree can be improved, and the crosslinking degree of the toughening agent selected from the low hydrogen-containing silicone oil is easy to control.
Further, in the step 1), the water-soluble initiator is one of potassium persulfate and AIBN (azobisisobutyronitrile), and the water-soluble initiator is used as follows: can be dissolved in water and can initiate the monomer to react in small droplets under the action of an emulsifier.
The emulsifier in the step 1) is one of Tween 20, Brij 35 and Miezao 51, and the purpose of the emulsifier is as follows: emulsify the oil-soluble monomer into oil drops to ensure that the emulsion is uniform and stable, and is favorable for the rapid and uniform reaction of 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 to be 55-65 ℃; 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 h; the reaction time in the step 2) is controlled to be 3-4 h; the reaction time in the step 3) is controlled to be 6-8 h.
Further, the catalyst in the step 2) and the step 3) is one of transition metals of platinum, palladium, rhodium and nickel, and the transition metal catalyst has high catalytic activity;
the acrylate in the step 3) is one of butyl acrylate, methyl acrylate, poly octyl acrylate and ethyl acrylate.
The invention also discloses an organosilicon toughening agent with a core-shell structure, which comprises: 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 toughening agent prepared by the preparation method of the embodiment 1 is subjected to melt blending granulation with polycarbonate resin particles and polyester resin particles through a double screw to obtain a granulated product, the granulated product is subjected to injection molding to obtain 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 polycarbonate and the polyester, the organic silicon 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 a common polymer chain of a carbon element, the organic silicon molecular chain belongs to a nonpolar molecular chain segment, the intermolecular force of the organic silicon is only dispersion force, 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 that the high-temperature resistance and the heat stability of the silicon element are good;
the processing performance of the invention is more excellent than that of common MBS, and the invention is particularly suitable for toughening polycarbonate rigid groups and compatiblizing and 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 intended to limit the present invention.
Example 1:
(1) weighing 104g of styrene, 500g of deionized water, 81g of liquefied butadiene and 5g of emulsifier Tween 20, adding the weighed materials into a 3L reaction kettle, dropwise adding 6g of potassium persulfate containing an initiator into the reaction kettle at the speed of 10 drops/min, controlling the temperature in the reaction kettle to be 65 ℃, introducing nitrogen to ensure that oxygen is not contained in the deionized water and the reaction kettle, controlling the pressure of the reaction kettle to be 4MPa, and releasing the pressure after the reaction is finished for 5 hours.
(2) Adding 475g of low-hydrogen silicone oil with the hydrogen content of 0.35 percent by mass, adding 5g of platinum catalyst, controlling the reaction temperature to be 60 ℃, and reacting for 4 hours under the protection of nitrogen.
(3) 150g of methylolacrylamide are added and 190g of butyl acrylate are added. 5g of platinum catalyst is added under the protection of nitrogen, and 6g of potassium persulfate is added dropwise at the rate of 10 drops/min. The reaction temperature is controlled to be 80 ℃, and the reaction time is controlled to be 6 h.
(4) And demulsifying, filtering, washing, drying and purifying after the reaction is finished to obtain the organic silicon toughening agent with the core-shell structure.
Example 2:
(1) weighing 208g of styrene, 1000g of deionized water, 162g of liquefied butadiene and 10g of emulsifier Brinzer, adding the weighed materials into a 5L reaction kettle, dropwise adding 6g of potassium persulfate containing an initiator into the reaction kettle at the speed of 10 drops/min, controlling the temperature in the reaction kettle to be 65 ℃, introducing nitrogen to ensure that no oxygen exists in the deionized water and the reaction kettle, controlling the pressure of the reaction kettle to be 4MPa, and releasing the pressure after the reaction is finished for 5 hours.
(2) Adding 950g of low hydrogen-containing silicone oil with the hydrogen content of 0.18 percent by mass, adding 5g of platinum catalyst, controlling the reaction temperature to be 60 ℃, and reacting for 4 hours under the protection of nitrogen.
(3) 300g of methylolacrylamide are added and 375g of butyl acrylate are added. Adding 5g of platinum catalyst under the protection of nitrogen, dropwise adding 6g of potassium persulfate according to the speed of 10 drops/min, controlling the reaction temperature to be 80 ℃, and controlling the reaction time to be 6 h.
(4) And demulsifying, filtering, washing, drying and purifying after the reaction is finished to obtain the organic silicon 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, adding the weighed materials into a 10L reaction kettle, dropwise adding 6g of potassium persulfate containing initiator into the reaction kettle at the speed of 10 drops/min, controlling the temperature in the reaction kettle to be 65 ℃, introducing nitrogen to ensure that oxygen is not contained in the deionized water and the reaction kettle, controlling the pressure of the reaction kettle to be 4MPa, and releasing the pressure after the reaction is finished for 5h,
(2) 1900g of low-hydrogen silicone oil with the hydrogen content of 0.75 percent by mass is added, 5g of platinum catalyst is added, the reaction temperature is controlled at 60 ℃, and the reaction is carried out for 4 hours under the protection of nitrogen.
(3) 600g of methylolacrylamide and 750g of butyl acrylate were added. 5g of platinum catalyst is added under the protection of nitrogen, and 6g of potassium persulfate is added dropwise at the rate of 10 drops/min. The reaction temperature is controlled to be 80 ℃, and the reaction time is controlled to be 6 h.
(4) And demulsifying, filtering, washing, drying and purifying after the reaction is finished to obtain the organic silicon toughening agent with the core-shell structure.
By the method of the above embodiment 1.2.3, the core-shell structure organosilicon 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:
melting and granulating the core-shell structure organic silicon 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, a sample strip to be tested is prepared by injection molding a granulated product mixed with the toughening agent on an injection molding machine at the temperature of 240-260 ℃, and the strength test is carried out by testing the injection molded sample strip and PC without the toughening agent and injecting a common toughening agent sample with the same amount.
The results of the strength tests of the PC (100%), the MBS with 3% addition and the sample according to the invention 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 organic silicon toughening agent of the invention is obviously obtained, and has the maximum tensile strength, the best impact strength and the best flexibility.
While the present invention has been particularly shown and described with reference to embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein 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, as defined in the claims.
Claims (10)
1. A preparation method of an organosilicon toughening agent with a core-shell structure is characterized by comprising the following steps: the method comprises the following steps:
1) carrying out emulsion polymerization on styrene monomer, liquefied compressed butadiene monomer, deionized water, water-soluble initiator and emulsifier at a certain reaction temperature under the protection of N2 for a period of time to prepare a nonpolar core layer in a core-shell structure;
2) adding a certain amount of hydrogen-containing silicone oil into the prepared core layer, controlling the reaction at a certain temperature under the action of a transition metal catalyst, and performing addition reaction on unsaturated double bonds in the core layer structure according to a coordination addition mechanism, wherein the addition reaction time is controlled within a certain time, so as to prepare a silicone oil layer introduced with an organic silicon structure;
3) adding acrylate and hydroxymethyl acrylamide outside the silicone oil layer, and enabling unreacted hydrogen in the hydrogen-containing silicone oil to perform elimination reaction on hydroxyl in the hydroxymethyl acrylamide under the action of transition metal; preparing a shell layer with polar groups by an acrylate monomer through emulsion polymerization;
4) the product is demulsified, filtered, washed, dried and purified to obtain the organic silicon toughening agent with the core-shell structure.
2. The preparation method of the core-shell structure organosilicon toughening agent according to claim 1, characterized in that:
the mass ratio of the styrene monomer to the liquefied compressed butadiene monomer in the step 1) is 4:6 to 6: 4;
the ratio of the amount of the unreacted unsaturated double bond substances of the core layer polymer in the step 2) to the amount of the hydrogen-containing silicone oil silicon hydrogen bond substances is 1: 0.5-1: 1;
the amount of the silicon-hydrogen bond substances of the silicon oil layer containing the organic silicon structure in the step 3) is as follows: amount of methylolacrylamide material: the amount of acrylate is 1:1.5 to 1: 1.8.
3. The preparation method of the core-shell structure organosilicon toughening agent according to claim 1, characterized in that: the weight ratio of the core layer to the silicon oil layer to the shell layer is 1:3: 2; 2:5: 3; 1:2: 1.
4. The preparation method of the core-shell structure organosilicon toughening agent according to claim 1, characterized in that: the mass fraction of the hydrogen-containing silicone oil is selected from one of low hydrogen-containing silicone oil in 0.18%, 0.35% and 0.75%.
5. The preparation method of the core-shell structure organosilicon toughening agent according to claim 1, characterized in that: the water-soluble initiator in the step 1) is one of potassium persulfate and AIBN (azodiisobutyronitrile); the emulsifier in the step 1) is one of Tween 20, Brij 35 and Miezao 51.
6. The preparation method of the core-shell structure organosilicon toughening agent according to claim 1, characterized in that: the reaction temperature in the step 1) is controlled to be 65-75 ℃; the reaction temperature in the step 2) is controlled to be 55-65 ℃; the reaction temperature in the step 3) is controlled to be 80-85 ℃.
7. The preparation method of the core-shell structure organosilicon toughening agent according to claim 1, characterized in that: the reaction time in the step 1) is controlled to be 4-5 h; the reaction time in the step 2) is controlled to be 3-4 h; the reaction time in the step 3) is controlled to be 6-8 h.
8. The preparation method of the core-shell structure organosilicon toughening agent according to claim 1, characterized in that: the catalyst in the step 2) and the step 3) is one of transition metals of platinum, palladium, rhodium and nickel; the acrylate in the step 3) is one of butyl acrylate, methyl acrylate, poly octyl acrylate and ethyl acrylate.
9. An organosilicon toughening agent with a core-shell structure is characterized in that: the method comprises the following steps: a toughening agent obtained by the production method according to claim 1.
10. The application of the core-shell structure organosilicon toughening agent is characterized in that: the method comprises the following steps: the toughening agent prepared by the preparation method of claim 1 is subjected to melt blending granulation with polycarbonate resin particles and polyester resin particles by a double screw to obtain a granulated product.
Priority Applications (1)
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