CN110615872A

CN110615872A - Epoxy group-containing core-shell structure compatilizer and preparation method thereof

Info

Publication number: CN110615872A
Application number: CN201910828272.3A
Authority: CN
Inventors: 王启瑶; 任雪峰; 孙佳男; 覃韦崴
Original assignee: Eversun Polycarbon Sci & Tech Corp
Current assignee: Eversun Polycarbon Sci & Tech Corp
Priority date: 2019-09-03
Filing date: 2019-09-03
Publication date: 2019-12-27
Anticipated expiration: 2039-09-03
Also published as: CN110615872B

Abstract

The invention relates to the technical field of polymer additives, in particular to a compatilizer containing an epoxy group core-shell structure and a preparation method thereof, and the compatilizer comprises the following steps: 1) respectively dissolving hydroxy phosphate and calcium acetate in deionized water to obtain a mixture A and a mixture B, then uniformly mixing and stirring the mixture A and the mixture B to obtain a mixture C, adding a dispersing agent into the mixture C, and heating and stirring to obtain a water phase mixture; 2) adding an azo initiator and tert-dodecyl mercaptan into a styrene monomer, and stirring until the azo initiator is completely dissolved to obtain an oil phase mixture; 3) and slowly adding the oil phase mixture into the water phase mixture, heating and stirring, dripping the glycidyl methacrylate pre-emulsion into the mixture, and heating to react to obtain the compatilizer with the surface containing epoxy groups. The compatilizer can be polymerized in a suspension polymerization mode to synthesize the compatilizer containing epoxy groups and having a core-shell structure, and the synthesized compatilizer has good compatibility with a polymer material matrix.

Description

Epoxy group-containing core-shell structure compatilizer and preparation method thereof

Technical Field

The invention relates to the technical field of polymer additives, in particular to a compatilizer containing an epoxy group core-shell structure and a preparation method thereof.

Background

GMA (glycidyl methacrylate) molecular structure has an acrylate double bond with high activity, so that the GMA can be grafted to a polymer, and an epoxy group carried by GMA can react with various other functional groups, so that a functionalized polymer is formed. GMA can be grafted and modified by adopting methods such as solution grafting, melt grafting, solid phase grafting, irradiation grafting and the like, and can also form a functional copolymer with ethylene, acrylic ester and the like. The functionalized polymers can be used as toughening agents to toughen engineering plastics or as compatibilizers to improve the compatibility of a blending system.

The terpolymer of GMA, styrene and acrylonitrile can be used as a chain extender of recycled materials such as PA, PC, PBT, PET and the like, a delustering agent of alloys such as PC/ABS, PA/ABS, PBT/ABS and the like, and a compatilizer of alloys such as ABS/PBT, ABS/PET, PC/ABS and the like.

In common epoxy group-containing compatilizers, GMA monomers and other monomers are subjected to free radical copolymerization in an emulsion polymerization or solution polymerization mode, the ring opening of epoxy groups is promoted due to the fact that an emulsifier is used in emulsion polymerization to enable the system to be alkaline, emulsion breaking and condensation processes are needed in post-treatment, in addition, the process is complex due to the fact that a solvent is used in solution polymerization, and the solvent needs to be distilled and recycled.

Disclosure of Invention

In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a compatilizer with an epoxy group-containing core-shell structure, the polymerization method adopts a suspension polymerization mode, the polymerization process is simple, and in the polymerization process, by adding a glycidyl methacrylate pre-emulsion polymerization component, the epoxy group-containing compatilizer with the core-shell structure can be synthesized, so that glycidyl methacrylate molecular chains are gathered on a shell layer, and the epoxy group-containing compatilizer has better compatibility with a polymer material matrix.

The invention also aims to provide the epoxy group-containing compatilizer prepared by the preparation method, the compatilizer has high epoxy group content and good compatibility is prepared by polymerizing glycidyl methacrylate and styrene monomer, and in addition, the epoxy group-containing compatilizer with a core-shell structure can be synthesized by glycidyl methacrylate pre-emulsion polymerization components added in the polymerization process, so that glycidyl methacrylate molecular chains are gathered on a shell layer, and the prepared compatilizer has better compatibility with a polymer material matrix.

The purpose of the invention is realized by the following technical scheme: a preparation method of a compatilizer containing an epoxy group core-shell structure comprises the following steps:

1) preparation of a water phase: respectively dissolving hydroxy phosphate and calcium acetate in deionized water according to parts by weight to obtain a mixture A and a mixture B, then uniformly mixing and stirring the mixture A and the mixture B to obtain a mixture C, adding a dispersing agent into the mixture C, heating to 70-90 ℃, and stirring at the speed of 200-400r/min for 30-60min to obtain an aqueous phase mixture for later use;

2) preparing an oil phase: adding an azo initiator and tert-dodecyl mercaptan into a styrene monomer according to the parts by weight, and stirring until the azo initiator is completely dissolved to obtain an oil phase mixture for later use;

3) preparation of the compatilizer: slowly adding the oil phase mixture obtained in the step 2) into the water phase mixture obtained in the step 1), heating to 70-90 ℃, stirring at the speed of 300-350r/min for 2-4h, then adding the prepared glycidyl methacrylate pre-emulsion in a dropwise manner, wherein the dropwise adding time is 50-70min, finally heating to 60-80 ℃ for reaction for 4-6h, and obtaining the compatilizer with epoxy groups on the surface after the reaction is finished.

In the step 1), the mixing weight ratio of the hydroxyl phosphate to the deionized water is 6-10: 30-50; the mixing weight ratio of the calcium acetate to the deionized water is 4-8:30-50, and the mixing weight ratio of the dispersing agent to the mixture C is 1-5: 74-108.

In the step 2), the mixing weight ratio of the azo initiator, the tertiary dodecyl mercaptan and the styrene monomer is 0.5-1.0:1-5: 30-60.

The polymerization method for preparing the compatilizer in the embodiment is simple to operate, the oil phase prepared in the step 2) is added into the water phase of the floating calcium hydroxy phosphate produced in the step 1) in the polymerization process to form a stable oil-in-water system, a core layer structure is generated, the finally added glycidyl methacrylate pre-emulsion polymerization component is matched with the floating water layer, the calcium hydroxy phosphate of the floating water layer is attached to the outer side of the core layer structure to form a shell layer, and the compatilizer containing epoxy groups and having a core-shell structure can be synthesized, so that glycidyl methacrylate molecular chains are aggregated in the shell layer, and the compatilizer has better compatibility with a polymer material matrix. In the preparation process, the heating temperature in the step 1) needs to be strictly controlled to be 70-90 ℃, if the temperature is too high, part of deionized water can volatilize, hydroxyl phosphate is dissolved in the deionized water to form a jelly to influence the subsequent fusion with other components, and if the temperature is too low, the solubility of the hydroxyl phosphate in the deionized water can be reduced to influence the softening effect on the deionized water; the stirring speed of 300-350r/min during the mixing of the oil phase and the water phase in the step 3) needs to be controlled, if the stirring speed is too high, the oil phase is not favorably added into the water phase to form an oil-in-water system, if the stirring speed is too low, particles of the formed oil-in-water microemulsion are too large, the particles are not favorably polymerized with the glycidyl methacrylate pre-emulsion, and dispersant molecules existing between the water phase and the oil phase play a role in preventing the oil phase droplets and the droplets from being mutually combined; in addition, in the step 3), the glycidyl methacrylate pre-emulsion is added in a dropwise manner, and meanwhile, the dropwise addition time needs to be strictly controlled to be 50-70min, the dropwise addition manner is adopted because the dropwise addition manner belongs to semi-continuous operation, the semi-continuous operation can ensure that a system is always in a starvation state in the polymerization reaction process, so that a compatilizer with more reactive functional groups on the surface can be formed, in addition, if the dropwise addition time is too short, the polymerization reaction of the glycidyl methacrylate pre-emulsion is not facilitated, the capability of forming a core-shell structure is further reduced, and if the dropwise addition time is too long, the continuity of the polymerization process can be influenced, so that the quality of the finally prepared compatilizer is further influenced. The compatibilizer of the embodiment is prepared by polymerizing glycidyl methacrylate and a styrene monomer to obtain the compatibilizer with high epoxy group content and good compatibility, in the polymerization process, carbon-carbon double bonds of the added glycidyl methacrylate pre-emulsion react with carbon-carbon double bonds of the styrene monomer, and epoxy groups, which are another functional groups of the glycidyl methacrylate pre-emulsion, do not participate in the reaction, so that the compatibilizer is reserved, and further the compatibilizer containing epoxy groups with a core-shell structure can be synthesized, so that glycidyl methacrylate molecular chains are gathered on a shell layer, and further the prepared compatibilizer has better compatibility with a polymer material matrix. The adopted calcium acetate is easy to dissolve in water and can further react with the hydroxyl phosphate to generate water-insoluble hydroxyl calcium phosphate, and the generated hydroxyl calcium phosphate is the main dispersant of the polymerization reaction, so that the suspension polymerization reaction can be stably carried out; tert-dodecyl mercaptan is a molecular regulator or a chain transfer agent, and is favorable for promoting azo group grafting of an azo initiator to be introduced onto a styrene monomer to prepare phenyl containing an azo group for polymerization, and is favorable for polymerization with glycidyl methacrylate pre-emulsion to form a compatilizer containing an epoxy group core-shell structure during subsequent emulsification of a water phase and oil phase mixture.

Preferably, in the step 3), the mixing weight ratio of the glycidyl methacrylate pre-emulsion to the premix is 20-40: 78-177. More preferably, in the step 3), the glycidyl methacrylate pre-emulsion is a mixture of a curing agent, glycidyl methacrylate and ethyl methacrylate according to a weight ratio of 0.05-0.5:8-10:0.5-1.0, and is prepared by stirring at a speed of 6000-10000r/min for 30-60 min; the curing agent is any one of BA, DAAM, ADH and MMA; wherein the density of the glycidyl methacrylate pre-emulsion is 1.031-1.053g/mL, and the glass transition temperature is 35-45 ℃.

The glycidyl methacrylate pre-emulsion prepared by the method has good intersolubility with water, and an epoxy group carried by the glycidyl methacrylate can react with various other functional groups to form a functionalized polymer, so that a compatilizer with high epoxy group content and good compatibility can be prepared; if the pre-emulsification operation is not carried out on the glycidyl methacrylate monomer in advance, the glycidyl methacrylate monomer cannot be dissolved with water, so that the glycidyl methacrylate monomer can only exist in the form of large liquid drops when being added into a reaction system and cannot be subjected to grafting reaction with a styrene monomer; in addition, the stirring speed needs to be strictly controlled to be 6000-10000r/min, and if the stirring speed is too low, the formation of emulsion by glycidyl methacrylate is not facilitated, and further the grafting reaction of the glycidyl methacrylate and other polymers is not facilitated.

Preferably, the hydroxy phosphate is at least one of calcium hydroxy phosphate, sodium hydroxy phosphate and N, N-dimethyl-N- (2-hydroxyethyl) hexadecyl quaternary ammonium phosphate; more preferably, the hydroxy phosphate is a mixture of calcium hydroxy phosphate, sodium hydroxy phosphate and N, N-dimethyl-N- (2-hydroxyethyl) hexadecyl quaternary ammonium phosphate in a weight ratio of 0.8-1.2:0.4-0.8: 0.1-0.5.

The hydroxy phosphate adopted in the embodiment is closer to the hydroxy in an organic matter in property and is not alkaline, so that hydrogen ions are more easily dissociated to display acidity, and the polymerization reaction of functional groups carried by glycidyl methacrylate is more facilitated.

Preferably, the azo initiator is at least two of azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyronitrile, azobiscyclohexylcarbonitrile, and dimethyl azobisisobutyrate; more preferably, the azo initiator is a mixture of azobisisobutyronitrile, azobisisoheptonitrile and azobisisoheptonitrile in a weight ratio of 0.8-1.2:0.4-0.8: 0.1-0.5.

In the embodiment, the type and the mixture ratio of the azo initiator are controlled, so that the initiation effect of the azo initiator mixture is enhanced, the free radical polymerization and the copolymerization reaction are initiated more favorably, the polymerization efficiency of the preparation method can be obviously improved, and the polymerization is facilitated to form the compatilizer containing an epoxy group core-shell structure; wherein the azodiisobutyronitrile is decomposed by heating to generate free radicals, which is more favorable for initiating a chain growth reaction.

Preferably, the dispersant is at least two of polyethylene glycol, polypropylene, polystyrene and microcrystalline paraffin; more preferably, the dispersant is a mixture of polyethylene glycol, polypropylene and polystyrene in a weight ratio of 0.8-1.2:0.1-0.5: 0.4-0.8.

The dispersing agent adopted in the embodiment has good dispersing effect of each component, is beneficial to dispersing the azo initiator in styrene monomer, accelerates the reaction, and is more beneficial to polymerizing with glycidyl methacrylate pre-emulsion to form the compatilizer containing an epoxy group core-shell structure when the subsequent water phase and oil phase mixture is emulsified.

The compatilizer containing epoxy group core-shell structure is prepared by adopting the preparation method.

The compatilizer of the invention is prepared by polymerizing glycidyl methacrylate and styrene monomer to prepare the compatilizer with high epoxy group content and good compatibility, and in addition, the epoxy group-containing compatilizer with a core-shell structure can be synthesized by the polymerization component of glycidyl methacrylate pre-emulsion added in the polymerization process, so that the molecular chain of glycidyl methacrylate is gathered on the shell layer, and the prepared compatilizer has better compatibility with the polymer material matrix.

The invention has the beneficial effects that: the preparation method of the epoxy group-containing core-shell structure compatilizer has simple polymerization process, and the epoxy group-containing compatilizer with a core-shell structure can be synthesized by adding glycidyl methacrylate pre-emulsion polymerization components in the polymerization process, so that glycidyl methacrylate molecular chains are gathered on a shell layer and have better compatibility with a polymer material matrix.

The epoxy group-containing compatilizer prepared by the preparation method has a core-shell structure, and is prepared by polymerizing glycidyl methacrylate and styrene monomers to prepare the compatilizer with high epoxy group content and good compatibility.

Drawings

FIG. 1 is an infrared spectrum of a compatibilizer prepared in example 3;

FIG. 2 is a schematic diagram showing the effect of the addition of the compatibilizer prepared in example 3 on the notched impact strength of a PA6/ABS alloy;

FIG. 3 is a schematic representation of the effect of the addition of the compatibilizer prepared in example 3 on the tensile strength of a PA6/ABS alloy;

FIG. 4 is a graph showing the effect of varying amounts of compatibilizer (the compatibilizer prepared in example 3) on the notched impact strength of PA6/ABS alloy;

FIG. 5 is a graph showing the effect of varying amounts of compatibilizer (the compatibilizer prepared in example 3) on the tensile strength of a PA6/ABS alloy.

Detailed Description

For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and accompanying fig. 1-5, which are not intended to limit the present invention.

Example 1

A preparation method of a compatilizer containing an epoxy group core-shell structure comprises the following steps:

1) preparation of a water phase: respectively dissolving hydroxy phosphate and calcium acetate in deionized water according to parts by weight to obtain a mixture A and a mixture B, then uniformly mixing and stirring the mixture A and the mixture B to obtain a mixture C, then adding a dispersing agent into the mixture C, heating to 70 ℃, and stirring at the speed of 200r/min for 30min to obtain a water phase mixture for later use;

3) preparation of the compatilizer: slowly adding the oil phase mixture obtained in the step 2) into the water phase mixture obtained in the step 1), heating to 70 ℃, stirring at the speed of 300r/min for 2h, then adding the prepared glycidyl methacrylate pre-emulsion in a dropwise manner for 50min, finally heating to 60 ℃ for reaction for 4h, and obtaining the compatilizer with epoxy groups on the surface after the reaction is finished.

In the step 1), the mixing weight ratio of the hydroxyl phosphate to the deionized water is 6: 30; the mixing weight ratio of calcium acetate to deionized water was 4:30, and the mixing weight ratio of dispersant to mixture C was 1: 74.

In the step 2), the mixing weight ratio of the azo initiator, the tertiary dodecyl mercaptan and the styrene monomer is 0.5:1: 30.

The mixing weight ratio of the glycidyl methacrylate pre-emulsion and the premix added in the step 3) is 20: 78; the glycidyl methacrylate pre-emulsion is prepared by mixing BA, glycidyl methacrylate and ethyl methacrylate according to the weight ratio of 0.0:8:0.5 and stirring at the speed of 6000r/min for 30 min; wherein the glycidyl methacrylate pre-emulsion has a density of 1.031g/mL and a glass transition temperature of 35 ℃.

The hydroxy phosphate is a mixture of calcium hydroxy phosphate, sodium hydroxy phosphate and N, N-dimethyl-N- (2-hydroxyethyl) hexadecyl quaternary ammonium phosphate in a weight ratio of 0.8:0.4: 0.1.

The dispersing agent is a mixture of polyethylene glycol, polypropylene and polystyrene according to a weight ratio of 0.8:0.1: 0.4.

Example 2

1) preparation of a water phase: respectively dissolving hydroxy phosphate and calcium acetate in deionized water according to parts by weight to obtain a mixture A and a mixture B, then uniformly mixing and stirring the mixture A and the mixture B to obtain a mixture C, then adding a dispersing agent into the mixture C, heating to 75 ℃, and stirring at the speed of 250r/min for 37min to obtain an aqueous phase mixture for later use;

3) preparation of the compatilizer: slowly adding the oil phase mixture obtained in the step 2) into the water phase mixture obtained in the step 1), heating to 75 ℃, stirring at a speed of 317r/min for 2.5h, then adding the pre-emulsion of glycidyl methacrylate prepared in advance in a dropwise manner, wherein the dropwise addition time is 55min, finally heating to 65 ℃ for reaction for 4.5h, and obtaining the compatilizer with an epoxy group on the surface after the reaction is finished.

In the step 1), the mixing weight ratio of the hydroxyl phosphate to the deionized water is 7: 35; the mixing weight ratio of calcium acetate to deionized water was 5:35, and the mixing weight ratio of dispersant to mixture C was 2: 82.

In the step 2), the mixing weight ratio of the azo initiator, the tertiary dodecyl mercaptan and the styrene monomer is 0.7:2: 35.

The mixing weight ratio of the glycidyl methacrylate pre-emulsion and the premix added in the step 3) is 25: 103; the glycidyl methacrylate pre-emulsion is prepared by mixing DAAM, glycidyl methacrylate and ethyl methacrylate according to the weight ratio of 0.125:8.5:0.675 and stirring at the speed of 7000r/min for 35 min; wherein the glycidyl methacrylate pre-emulsion has a density of 1.037g/mL and a glass transition temperature of 38 ℃.

The hydroxy phosphate is a mixture of calcium hydroxy phosphate, sodium hydroxy phosphate and N, N-dimethyl-N- (2-hydroxyethyl) hexadecyl quaternary ammonium phosphate in a weight ratio of 0.9:0.5: 0.2.

The dispersing agent is a mixture of polyethylene glycol, polypropylene and polystyrene according to a weight ratio of 0.9:0.2: 0.5.

Example 3

1) preparation of a water phase: respectively dissolving hydroxy phosphate and calcium acetate in deionized water according to parts by weight to obtain a mixture A and a mixture B, then uniformly mixing and stirring the mixture A and the mixture B to obtain a mixture C, then adding a dispersing agent into the mixture C, heating to 80 ℃, and stirring at the speed of 300r/min for 45min to obtain a water phase mixture for later use;

3) preparation of the compatilizer: slowly adding the oil phase mixture obtained in the step 2) into the water phase mixture obtained in the step 1), heating to 80 ℃, stirring at the speed of 325r/min for 3h, then adding the prepared glycidyl methacrylate pre-emulsion in a dropwise manner for 60min, finally heating to 70 ℃ for reaction for 5h, and obtaining the compatilizer with epoxy groups on the surface after the reaction is finished.

In the step 1), the mixing weight ratio of the hydroxyl phosphate to the deionized water is 8: 40; the mixing weight ratio of calcium acetate to deionized water was 6:40, and the mixing weight ratio of dispersant to mixture C was 3: 90.

In the step 2), the mixing weight ratio of the azo initiator, the tertiary dodecyl mercaptan and the styrene monomer is 0.8:3: 40.

The mixing weight ratio of the glycidyl methacrylate pre-emulsion and the premix added in the step 3) is 30: 128; the glycidyl methacrylate pre-emulsion is a mixture of ADH, glycidyl methacrylate and ethyl methacrylate according to the weight ratio of 0.25:9:0.75, and is prepared by stirring at the speed of 8000r/min for 30 min; wherein the glycidyl methacrylate pre-emulsion has a density of 1.043g/mL and a glass transition temperature of 40 ℃.

The hydroxy phosphate is a mixture of calcium hydroxy phosphate, sodium hydroxy phosphate and N, N-dimethyl-N- (2-hydroxyethyl) hexadecyl quaternary ammonium phosphate in the weight ratio of 1.0:0.6: 0.3.

The dispersing agent is a mixture of polyethylene glycol, polypropylene and polystyrene according to a weight ratio of 1.0:0.3: 0.6.

Example 4

1) preparation of a water phase: respectively dissolving hydroxy phosphate and calcium acetate in deionized water according to parts by weight to obtain a mixture A and a mixture B, then uniformly mixing and stirring the mixture A and the mixture B to obtain a mixture C, adding a dispersing agent into the mixture C, heating to 85 ℃, and stirring at the speed of 350r/min for 52min to obtain a water phase mixture for later use;

3) preparation of the compatilizer: slowly adding the oil phase mixture obtained in the step 2) into the water phase mixture obtained in the step 1), heating to 85 ℃, stirring at the speed of 340r/min for 3.5h, then adding the pre-emulsion of glycidyl methacrylate prepared in advance in a dropwise manner, wherein the dropwise addition time is 65min, finally heating to 75 ℃ for reaction for 5.5h, and obtaining the compatilizer with epoxy groups on the surface after the reaction is finished.

In the step 1), the mixing weight ratio of the hydroxyl phosphate to the deionized water is 9: 45; the mixing weight ratio of calcium acetate to deionized water was 7:45, and the mixing weight ratio of dispersant to mixture C was 4: 98.

In the step 2), the mixing weight ratio of the azo initiator, the tertiary dodecyl mercaptan and the styrene monomer is 0.9:4: 45.

The mixing weight ratio of the glycidyl methacrylate pre-emulsion and the premix added in the step 3) is 35: 153; the glycidyl methacrylate pre-emulsion is prepared by mixing MMA, glycidyl methacrylate and ethyl methacrylate according to the weight ratio of 0.345:9.5:0.915 and stirring at the speed of 9000r/min for 55 min; wherein the glycidyl methacrylate pre-emulsion has a density of 1.048g/mL and a glass transition temperature of 42 ℃.

The hydroxy phosphate is a mixture of calcium hydroxy phosphate, sodium hydroxy phosphate and N, N-dimethyl-N- (2-hydroxyethyl) hexadecyl quaternary ammonium phosphate according to the weight ratio of 1.1:0.7: 0.4.

The dispersing agent is a mixture of polyethylene glycol, polypropylene and polystyrene according to a weight ratio of 1.1:0.4: 0.7.

Example 5

1) preparation of a water phase: respectively dissolving hydroxy phosphate and calcium acetate in deionized water according to parts by weight to obtain a mixture A and a mixture B, then uniformly mixing and stirring the mixture A and the mixture B to obtain a mixture C, then adding a dispersing agent into the mixture C, heating to 90 ℃, and stirring at the speed of 400r/min for 60min to obtain a water phase mixture for later use;

3) preparation of the compatilizer: slowly adding the oil phase mixture obtained in the step 2) into the water phase mixture obtained in the step 1), heating to 90 ℃, stirring at the speed of 350r/min for 4h, then adding the prepared glycidyl methacrylate pre-emulsion in a dropwise manner for 70min, finally heating to 80 ℃ for reaction for 6h, and obtaining the compatilizer with epoxy groups on the surface after the reaction is finished.

In the step 1), the mixing weight ratio of the hydroxyl phosphate to the deionized water is 10: 50; the mixing weight ratio of calcium acetate to deionized water was 8:50, and the mixing weight ratio of dispersant to mixture C was 5: 108.

In the step 2), the mixing weight ratio of the azo initiator, the tertiary dodecyl mercaptan and the styrene monomer is 1.0:5: 60.

The mixing weight ratio of the glycidyl methacrylate pre-emulsion and the premix added in the step 3) is 40: 177; the glycidyl methacrylate pre-emulsion is prepared by mixing a curing agent, glycidyl methacrylate and ethyl methacrylate according to the weight ratio of 0.5:10:1.0 and stirring at the speed of 10000r/min for 60 min; the curing agent is a mixture of BA and DAAM according to the weight ratio of 0.8: 0.4; wherein the glycidyl methacrylate pre-emulsion has a density of 1.053g/mL and a glass transition temperature of 45 ℃.

The hydroxy phosphate is a mixture of calcium hydroxy phosphate, sodium hydroxy phosphate and N, N-dimethyl-N- (2-hydroxyethyl) hexadecyl quaternary ammonium phosphate in a weight ratio of 1.2:0.8: 0.5.

The dispersing agent is a mixture of polyethylene glycol, polypropylene and polystyrene according to a weight ratio of 1.2:0.5: 0.8.

Comparative example 1

1) preparation of a water phase: according to the weight parts, hydroxyl phosphate is dissolved in deionized water to obtain a mixture A, then a dispersing agent is added into the mixture A, the mixture A is heated to 70 ℃, and the mixture A is stirred for 30min at the speed of 200r/min to obtain a water phase mixture for later use;

In the step 1), the mixing weight ratio of the hydroxy phosphate to the deionized water is 6:30, and the mixing weight ratio of the dispersing agent to the mixture C is 1: 74.

Comparative example 2

2) preparing an oil phase: adding an azo initiator and n-dodecyl mercaptan into a styrene monomer according to the parts by weight, and stirring until the azo initiator is completely dissolved to obtain an oil phase mixture for later use;

In the step 1), the mixing weight ratio of the hydroxyl phosphate to the deionized water is 8: 40; the mixing weight ratio of calcium acetate to deionized water was 6:40, and the mixing weight ratio of dispersant to mixture C was 3: 98.

In the step 2), the mixing weight ratio of the azo initiator, the n-dodecyl mercaptan and the styrene monomer is 0.8:3: 40.

Comparative example 3

3) preparation of the compatilizer: slowly adding the oil phase mixture obtained in the step 2) into the water phase mixture obtained in the step 1), heating to 90 ℃, stirring at the speed of 350r/min for 4h, then directly adding the prepared glycidyl methacrylate pre-emulsion at one time, dropwise adding for 70min, finally heating to 80 ℃, reacting for 6h, and obtaining the compatilizer with epoxy groups on the surface after the reaction is finished.

Comparative example 4

A PA6/ABS alloy containing the epoxy group-containing core-shell structure compatibilizer prepared in example 3 above comprises the following raw materials in parts by weight:

the compatibilizer has the epoxy group-containing core-shell structure prepared in example 3.

The lubricant comprises a mixture of butyl stearate and oleamide according to a weight ratio of 0.8: 0.4.

The PA6/ABS alloy is prepared by the following method:

A. sequentially adding barium sulfate, an antioxidant 1010, a compatilizer, a light stabilizer and a lubricant into a reaction device according to the parts by weight, and stirring uniformly to obtain a premix for later use;

B. and D, adding the premix obtained in the step A into an extrusion device, heating to 230 ℃ for 30min, and then extruding and granulating the premix to obtain the PA6/ABS alloy.

1. The results of infrared light detection of the compatibilizer prepared in example 3 are shown in FIG. 1, and it can be seen from the spectrum at 906cm^-1An epoxy group antisymmetric vibration peak appears, and the existence of the epoxy group is proved.

2. The impact of the notch strength and tensile strength of the PA6/ABS alloy (exemplified by the PA6/ABS alloy prepared in comparative example 4) prepared by compounding the compatibilizer prepared in the specific example 3 and the impact of the amount of the compatibilizer on the notch strength and tensile strength of the PA6/ABS alloy (exemplified by the PA6/ABS alloy prepared in comparative example 4) are shown in FIGS. 2-5, and it can be seen that after a certain amount of the compatibilizer is added, the alloy reaches the super-toughness level and has little impact on the tensile strength and flexural strength.

3. The alloys obtained by compounding the compatibilizers obtained in the specific examples 1-5 and the comparative examples 1-3 with PA6/ABS alloy were tested for tensile strength (GB/T228-.

TABLE 1

Item	Tensile Strength (MPa)	Flexural Strength (MPa)	Notched impact strength (KJ. m.)²)
				Example 1	68.57	81.25	99.10
Example 2	69.24	84.41	99.50
				Example 3	71.94	86.38	99.84
Example 4	67.38	84.01	99.40
				Example 5	68.05	85.78	98.98
Comparative example 1	48.95	62.23	76.10
				Comparative example 2	54.27	40.12	75.12
Comparative example 3	50.28	42.35	76.89

From the above results, it can be seen that the compatibilizers prepared in examples 1 to 5 of the present invention have excellent mechanical properties, and the compatibilizers can significantly improve the tensile strength, bending strength and impact strength of the PA6/ABS alloy, and meanwhile, the synthesized compatibilizers have a core-shell structure and contain epoxy groups.

Compared with example 1, in comparative example 1, calcium acetate is not added when the aqueous phase of the compatilizer is prepared, various physical property tests are carried out on the prepared compatilizer, and analysis shows that the tensile strength, the bending strength and the impact strength of the compatilizer are relatively reduced; the calcium acetate is added when the aqueous phase of the compatilizer is prepared, so that various mechanical properties of the prepared compatilizer can be optimized, and the prepared compatilizer has excellent heat resistance, mechanical strength, chemical resistance and impact resistance and is suitable for large-scale production.

Compared with the example 3, in the comparative example 2, n-dodecyl mercaptan is used for replacing tertiary dodecyl mercaptan when the oil phase of the compatilizer is prepared, various physical property tests are carried out on the prepared compatilizer, and analysis shows that the bending strength and the impact strength of the compatilizer are relatively reduced, and the tensile strength is remarkably reduced; the invention is proved that the addition of the tert-dodecyl mercaptan can improve the polymerization degree of the compatilizer during the preparation of the oil phase of the compatilizer, further optimize various mechanical properties of the prepared compatilizer, and ensure that the prepared compatilizer has excellent heat resistance, mechanical properties and toughness, chemical resistance and impact resistance, and is suitable for large-scale production.

Compared with example 5, in comparative example 3, the glycidyl methacrylate pre-emulsion is directly added at one time when the compatilizer is prepared, and various physical property tests are carried out on the prepared compatilizer, and analysis shows that the tensile strength, the bending strength and the impact strength of the compatilizer are relatively reduced; the invention shows that the glycidyl methacrylate pre-emulsion is added with the compatilizer which is favorable for forming a functional group with more reactivity on the surface by adopting a dropwise adding mode when the compatilizer is prepared, and further, various mechanical properties of the prepared compatilizer are optimized, so that the prepared compatilizer has excellent heat resistance, strong mechanical properties, chemical resistance and impact resistance, and is suitable for large-scale production.

The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.

Claims

1. A preparation method of a compatilizer containing an epoxy group core-shell structure is characterized by comprising the following steps: the method comprises the following steps:

1) preparation of a water phase: respectively dissolving hydroxy phosphate and calcium acetate in deionized water according to parts by weight to obtain a mixture A and a mixture B, then uniformly mixing and stirring the mixture A and the mixture B to obtain a mixture C, adding a dispersing agent into the mixture C, heating and stirring to obtain a water phase mixture for later use;

3) preparation of the compatilizer: slowly adding the oil phase mixture obtained in the step 2) into the water phase mixture obtained in the step 1), heating and stirring to obtain a premix, adding the prepared glycidyl methacrylate pre-emulsion into the premix in a dropwise manner, heating for reaction, and obtaining the compatilizer with an epoxy group on the surface after the reaction is finished.

2. The process according to claim 1, wherein the epoxy group-containing core-shell structure-containing compatibilizer comprises: in the step 1), the heating temperature is 70-90 ℃, and the heating and stirring speed is 200-400 r/min.

3. The process according to claim 1, wherein the epoxy group-containing core-shell structure-containing compatibilizer comprises: in the step 1), the mixing weight ratio of the hydroxyl phosphate to the deionized water is 6-10: 30-50; the mixing weight ratio of the calcium acetate to the deionized water is 4-8: 30-50.

4. The epoxy group-containing core-shell structure compatibilizing agent according to claim 1, wherein: in the step 1), the mixing weight ratio of the dispersing agent to the mixture C is 1-5:74-108, and the dispersing agent is at least two of polyethylene glycol, polypropylene, polystyrene and microcrystalline wax.

5. The process according to claim 1, wherein the epoxy group-containing core-shell structure-containing compatibilizer comprises: in the step 2), the mixing weight ratio of the azo initiator, the tertiary dodecyl mercaptan and the styrene monomer is 0.5-1.0:1-5: 30-60.

6. The process according to claim 1, wherein the epoxy group-containing core-shell structure-containing compatibilizer comprises: in the step 3), the temperature rise is 70-90 ℃, the stirring speed is 300-350r/min, and the stirring time is 2-4 h; the dripping time of the glycidyl methacrylate pre-emulsion is 50-70min, the heating temperature for reaction is 60-80 ℃, and the reaction time is 4-6 h.

7. The process according to claim 1, wherein the epoxy group-containing core-shell structure-containing compatibilizer comprises: in the step 3), the mixing weight ratio of the glycidyl methacrylate pre-emulsion to the premix is 20-40: 78-177.

8. The process according to claim 1, wherein the epoxy group-containing core-shell structure-containing compatibilizer comprises: in the step 3), the glycidyl methacrylate pre-emulsion is prepared by mixing a curing agent, glycidyl methacrylate and ethyl methacrylate according to the weight ratio of 0.05-0.5:8-10:0.5-1.0 and stirring for 30-60min at the speed of 6000 plus 10000 r/min; the curing agent is any one of BA, DAAM, ADH and MMA; wherein the density of the glycidyl methacrylate pre-emulsion is 1.031-1.053g/mL, and the glass transition temperature is 35-45 ℃.

9. The epoxy group-containing core-shell structure compatibilizing agent according to claim 1, wherein: the hydroxyl phosphate is at least one of calcium hydroxyl phosphate, sodium hydroxyl phosphate and N, N-dimethyl-N- (2-hydroxyethyl) hexadecyl quaternary ammonium phosphate; the azo initiator is at least two of azodiisobutyronitrile, azodiisoheptonitrile, azoisobutyronitrile, azodicyclohexyl formonitrile and azodiisobutyrate dimethyl ester.

10. A compatilizer with an epoxy group-containing core-shell structure, which is characterized in that: the compatibilizer is prepared by the preparation method of any one of claims 1 to 9.