阅读说明：本技术 一种核壳结构有机硅增韧剂的制备、增韧剂及应用 (Preparation of core-shell structure organic silicon toughening agent, toughening agent and application ) 是由 董成干 孟凡吉 于 2021-09-09 设计创作，主要内容包括：本发明提供一种核壳结构有机硅增韧剂的制备方法、包含所述增韧剂在聚碳酸酯树脂以及聚酯树脂的应用。该增韧剂制备原料包括苯乙烯单体、丁二烯单体、含氢硅油、羟甲基丙烯酰胺、丙烯酸酯单体。该共聚物是由核层、硅油层、壳层结构组成的核壳结构。核层结构由苯乙烯接枝共聚丁二烯组成非极性层,含氢硅油链段是连接核层和壳层的独立硅油相结构层。壳层是由丙烯酸酯接枝共聚组成的极性链段的极性壳层。由于结构中含有硅油链段,可赋予材料很好的加工性能,核层结构中含有长支链可赋予材料很好的弹性,壳层结构中的丙烯酸酯类极性基团可赋予该增韧剂与树脂很好的相容性。本发明生产工艺简单,生产效率高,生产成本低廉,可用于大规模工业生产。(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.)

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.

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.