阅读说明：本技术 一种亚克力材料的韧性改性方法和亚克力材料 (Toughness modification method of acrylic material and acrylic material ) 是由 沈小英 顾祖良 于 2021-07-27 设计创作，主要内容包括：本发明涉及高分子材料技术领域,特别是涉及一种亚克力材料的韧性改性方法和亚克力材料。亚克力材料的韧性改性方法,采用聚甲基丙烯酸甲酯、马来酰亚胺、α-甲基丙烯酸、对氯乙烯苯、双乙基乙酸乙醇化-2,4-戊烷二酮化铝、金属有机框架材料、引发剂、格氏试剂作为原料,韧性改性方法包括以下步骤,S1：制得聚甲基丙烯酸甲酯预聚体；S2：使得双乙基乙酸乙醇化-2,4-戊烷二酮化铝接枝至S1制得的聚甲基丙烯酸甲酯中；S3：将剩余的引发剂与金属有机框架材料加入到S2制得的聚甲基丙烯酸甲酯预聚体中,得到固含量是40％～50％的改性甲基丙烯酸甲酯预聚体；S4：模压成亚克力板材,该方法有效地提高亚克力材料的韧性和强度。(The invention relates to the technical field of high polymer materials, in particular to a toughness modification method of an acrylic material and the acrylic material. The toughness modification method of the acrylic material adopts polymethyl methacrylate, maleimide, alpha-methacrylic acid, p-chlorostyrene, bis-ethyl-acetic acid ethylated-2, 4-pentanediketone aluminum, a metal organic framework material, an initiator and a Grignard reagent as raw materials, and comprises the following steps of S1: preparing a polymethyl methacrylate prepolymer; s2: grafting the aluminum diethanoylacetate ethylated-2, 4-pentanediketone to the polymethyl methacrylate prepared by the S1; s3: adding the rest initiator and metal organic framework material into the polymethyl methacrylate prepolymer prepared in S2 to obtain a modified methyl methacrylate prepolymer with the solid content of 40-50%; s4: the acrylic sheet is molded, and the method effectively improves the toughness and strength of the acrylic material.)

1. A method for modifying the toughness of an acrylic material is characterized by comprising the following steps: the following raw materials are adopted,

50 to 60 percent of polymethyl methacrylate

10 to 15 percent of maleimide

5 to 6 percent of alpha-methacrylic acid

5 to 10 percent of p-chloroethylene benzene

4 to 8 percent of diethylacetic acid ethylated-2, 4-pentanediketone aluminum

3 to 6 percent of metal organic framework material

0.1 to 1 percent of initiator

2% -4% of a Grignard reagent;

the method for modifying the toughness of the steel comprises the following steps,

s1: putting polymethyl methacrylate, maleimide, alpha-methacrylic acid, p-chlorostyrene and part of initiator into a reactor, and introducing nitrogen to remove oxygen to obtain a polymethyl methacrylate prepolymer;

s2: adding the polymethyl methacrylate prepolymer prepared in the step S1 into an ether solvent, adding a Grignard reagent and diethylacetic acid ethylated-2, 4-pentanediketone aluminum, and carrying out Grignard reaction to graft the diethylacetic acid ethylated-2, 4-pentanediketone aluminum into the polymethyl methacrylate prepolymer prepared in the step S1;

s3: adding the rest initiator and metal organic framework material into the polymethyl methacrylate prepolymer prepared in S2, and introducing hot water at 70-80 ℃ to continue to react for 15-30 min to obtain a modified methyl methacrylate prepolymer with the solid content of 40-50%;

s4: and (3) molding the modified methyl methacrylate prepolymer prepared in the step (S3) into an acrylic plate.

2. The method for modifying the toughness of an acrylic material according to claim 1, wherein: the initiator is one or two mixture of azodiisonitrile and azodiisoheptonitrile.

3. The method for modifying the toughness of an acrylic material according to claim 1, wherein the method comprises the following steps: the grignard reagent is magnesium chloride.

4. The method for modifying the toughness of an acrylic material according to claim 1, wherein the method comprises the following steps: in the step S2, after the grignard reaction is completed, ammonium chloride is added dropwise under the ice-water bath condition to extract the remaining grignard reagent.

5. The method for modifying the toughness of an acrylic material according to claim 1, wherein the method comprises the following steps: the ratio of the amount of initiator in S1 to the amount of initiator in S3 is 1: 0.5 to 1.

6. The method for modifying the toughness of an acrylic material according to claim 1, wherein the method comprises the following steps: in the step S1, the nitrogen gas is introduced for 20-30 min.

7. The method for modifying the toughness of an acrylic material according to claim 1, wherein the method comprises the following steps: the metal-organic framework material is an aluminum-based-organic framework material.

8. The method for modifying the toughness of an acrylic material according to claim 1, wherein the method comprises the following steps: in the S1, polymethyl methacrylate, maleimide, alpha-methacrylic acid, p-chlorostyrene and part of the initiator are put into a reactor to react at 80 to 90 ℃.

9. The method for modifying the toughness of an acrylic material according to claim 1, wherein the method comprises the following steps: in S2, the grignard reaction was performed at room temperature under reflux.

10. An acrylic material is characterized in that: the acrylic material is prepared by adopting the toughness modification method of the acrylic material as defined in any one of claims 1-9.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a toughness modification method of an acrylic material and the acrylic material.

Background

Acrylic, commonly known as organic glass, can be divided into transparent plates, translucent plates and colored plates, and is called plastic crystal, and has the advantages of strong corrosion resistance, high strength and the like, so that the acrylic is an excellent material for manufacturing furniture.

However, the current application of acrylic in furniture still has the following defects: the acrylic material has good and remarkable performance in the aspect of hardness, but has poor function in the aspect of toughness, when the acrylic material is used as furniture, the acrylic material can only be used as a hard material, however, in practical application, people often expect that the furniture has good toughness so as to improve experience, and therefore, the application of the acrylic material in the furniture is still limited.

Disclosure of Invention

One of the purposes of the invention is to provide a method for modifying the toughness of an acrylic material, which can effectively improve the toughness and strength of the acrylic material, and avoid the defects in the prior art.

In order to achieve one of the above-mentioned objects of the invention,

provides a toughness modification method of an acrylic material, which adopts the following raw materials,

50 to 60 percent of polymethyl methacrylate

10 to 15 percent of maleimide

5 to 6 percent of alpha-methacrylic acid

5 to 10 percent of p-chloroethylene benzene

4 to 8 percent of diethylacetic acid ethylated-2, 4-pentanediketone aluminum

3 to 6 percent of metal organic framework material

0.1 to 1 percent of initiator

2% -4% of a Grignard reagent;

the method for modifying the toughness of the steel comprises the following steps,

s1: putting polymethyl methacrylate, maleimide, alpha-methacrylic acid, p-chlorostyrene and part of initiator into a reactor, and introducing nitrogen to remove oxygen to obtain a polymethyl methacrylate prepolymer;

s2: adding the polymethyl methacrylate prepolymer prepared in the step S1 into an ether solvent, adding a Grignard reagent and diethylacetic acid ethylated-2, 4-pentanediketone aluminum, and carrying out Grignard reaction to graft the diethylacetic acid ethylated-2, 4-pentanediketone aluminum into the polymethyl methacrylate prepolymer prepared in the step S1;

s3: adding the rest initiator and metal organic framework material into the polymethyl methacrylate prepolymer prepared in S2, and introducing hot water at 70-80 ℃ to continue to react for 15-30 min to obtain a modified methyl methacrylate prepolymer with the solid content of 40-50%;

s4: and (3) molding the modified methyl methacrylate prepolymer prepared in the step (S3) into an acrylic plate.

Wherein the initiator is one or a mixture of two of azodiisobutanedinitrile and azodiisoheptanecarbonitrile.

Wherein the grignard reagent is magnesium chloride.

In the step S2, after the grignard reaction is completed, ammonium chloride is added dropwise under the ice-water bath condition to extract the remaining grignard reagent.

So as to prevent the Grignard reagent from influencing the subsequent reaction.

Wherein the ratio of the amount of initiator in S1 to the amount of initiator in S3 is 1: 0.5 to 1.

Wherein in the step S1, the nitrogen gas is introduced for 20min to 30 min.

Wherein the metal-organic framework material is an aluminum-based-organic framework material. The aluminum in the aluminum-based organic framework material can be well oxidized under the condition of exposing the air, and the problem that the acrylic material is easy to corrode is prevented.

In the step S1, polymethyl methacrylate, maleimide, alpha-methacrylic acid, p-chlorostyrene and a part of an initiator are fed into a reactor and reacted at 80 to 90 ℃.

In S2, the grignard reaction was performed at room temperature under reflux.

The method for modifying the toughness of the acrylic material has the beneficial effects that:

(1) according to the invention, the p-chlorobenzene ring is grafted on the polymethyl methacrylate, and the p-chloroethylene provides the benzene ring with steric hindrance, so that the repulsion force between molecular chains of the polymethyl methacrylate is increased, the entanglement degree between the molecular chains is reduced, the ductility of the polymethyl methacrylate is increased, the surface toughness of the acrylic material is favorably improved, the chlorine atoms in the p-chloroethylene provide sites for the Grignard reaction, the further modification reaction of the polymethyl methacrylate is facilitated, and the toughness and the strength of the polymethyl methacrylate are improved.

(2) The invention adopts the Grignard reaction to graft the bis-ethyl-ethanolate ethylated-2, 4-pentanediketone aluminum as a metal organic on the polymethyl methacrylate, the bis-ethyl-ethanolate ethylated-2, 4-pentanediketone aluminum can effectively supplement the metal flexibility of the polymethyl methacrylate, and the bis-ethyl-ethanolate ethylated-2, 4-pentanediketone aluminum has active hydroxyl and can be better grafted with the polymethyl methacrylate.

(3) The invention introduces the metal organic framework material which can prevent the problem that the polymethyl methacrylate is easy to deform and crack after being deformed.

In order to achieve the second object of the present invention,

also provides an acrylic material, which is prepared by adopting the toughness modification method of the acrylic material.

Detailed Description

The invention is further described with reference to the following examples.

Example 1

The embodiment discloses a toughness modification method of an acrylic material, which adopts the following raw materials,

50% of polymethyl methacrylate, 10% of maleimide, 5% of alpha-methacrylic acid, 5% of p-chlorostyrene, 4% of bis-ethyl-acetic acid ethylated-2, 4-pentane-aluminum diketone, 3% of metal organic framework material, 0.1% of initiator and 2% of Grignard reagent;

the method for modifying the toughness of the steel comprises the following steps,

s1: putting polymethyl methacrylate, maleimide, alpha-methacrylic acid, p-chlorostyrene and part of initiator into a reactor, and introducing nitrogen to remove oxygen to obtain a polymethyl methacrylate prepolymer;

s2: adding the polymethyl methacrylate prepolymer prepared in the step S1 into an ether solvent, adding a Grignard reagent and diethylacetic acid ethylated-2, 4-pentanediketone aluminum, and carrying out Grignard reaction to graft the diethylacetic acid ethylated-2, 4-pentanediketone aluminum into the polymethyl methacrylate prepolymer prepared in the step S1;

s3: adding the rest initiator and metal organic framework material into the polymethyl methacrylate prepolymer prepared in S2, and introducing 70 ℃ hot water to continue to react for 15min to obtain a modified methyl methacrylate prepolymer with the solid content of 40%;

s4: and (3) molding the modified methyl methacrylate prepolymer prepared in the step (S3) into an acrylic plate.

In the embodiment, the initiator is one or two of azodiisobutanedinitrile and azodiisoheptanecarbonitrile.

In this example, the grignard reagent is magnesium chloride.

In this example, in S2, after the grignard reaction is completed, ammonium chloride is added dropwise under the ice-water bath condition to extract the remaining grignard reagent.

In this embodiment, the ratio of the amount of the initiator in S1 to the amount of the initiator in S3 is 1: 0.5.

in this embodiment, in S1, the nitrogen gas is introduced for 20min to 30 min.

In this embodiment, the metal-organic framework material is an aluminum-based-organic framework material.

In this example, in S1, polymethyl methacrylate, maleimide, α -methacrylic acid, p-chlorostyrene, and a part of an initiator were charged into a reactor and reacted at 80 ℃.

In this example, in S2, the grignard reaction was performed at room temperature under reflux.

Example 2

The embodiment discloses a toughness modification method of an acrylic material, which adopts the following raw materials,

60% of polymethyl methacrylate, 15% of maleimide, 6% of alpha-methacrylic acid, 10% of p-chlorostyrene, 8% of bis-ethyl-acetic acid ethylated-2, 4-pentane-aluminum diketide, 6% of metal organic framework material, 1% of initiator and 4% of Grignard reagent;

the method for modifying the toughness of the steel comprises the following steps,

s1: putting polymethyl methacrylate, maleimide, alpha-methacrylic acid, p-chlorostyrene and part of initiator into a reactor, and introducing nitrogen to remove oxygen to obtain a polymethyl methacrylate prepolymer;

s2: adding the polymethyl methacrylate prepolymer prepared in the step S1 into an ether solvent, adding a Grignard reagent and diethylacetic acid ethylated-2, 4-pentanediketone aluminum, and carrying out Grignard reaction to graft the diethylacetic acid ethylated-2, 4-pentanediketone aluminum into the polymethyl methacrylate prepolymer prepared in the step S1;

s3: adding the rest initiator and metal organic framework material into the polymethyl methacrylate prepolymer prepared in S2, and introducing hot water at 80 ℃ to continue to react for 30min to obtain a modified methyl methacrylate prepolymer with the solid content of 50%;

s4: and (3) molding the modified methyl methacrylate prepolymer prepared in the step (S3) into an acrylic plate.

In the embodiment, the initiator is one or two of azodiisobutanedinitrile and azodiisoheptanecarbonitrile.

In this example, the grignard reagent is magnesium chloride.

In this example, in S2, after the grignard reaction is completed, ammonium chloride is added dropwise under the ice-water bath condition to extract the remaining grignard reagent.

In this embodiment, the ratio of the amount of the initiator in S1 to the amount of the initiator in S3 is 1: 1.

in this embodiment, in S1, the nitrogen gas is introduced for 30 min.

In this embodiment, the metal-organic framework material is an aluminum-based-organic framework material.

In this example, in S1, polymethyl methacrylate, maleimide, α -methacrylic acid, p-chlorostyrene, and a part of an initiator were charged into a reactor and reacted at 90 ℃.

In this example, in S2, the grignard reaction was performed at room temperature under reflux.

Example 3

The embodiment discloses a toughness modification method of an acrylic material, which adopts the following raw materials,

55% of polymethyl methacrylate, 14% of maleimide, 5.5% of alpha-methacrylic acid, 7% of p-chlorostyrene, 6% of bis-ethyl-acetic acid ethylated-2, 4-pentane-aluminum diketone, 4% of metal organic framework material, 0.5% of initiator and 3% of Grignard reagent;

the method for modifying the toughness of the steel comprises the following steps,

s1: putting polymethyl methacrylate, maleimide, alpha-methacrylic acid, p-chlorostyrene and part of initiator into a reactor, and introducing nitrogen to remove oxygen to obtain a polymethyl methacrylate prepolymer;

s2: adding the polymethyl methacrylate prepolymer prepared in the step S1 into an ether solvent, adding a Grignard reagent and diethylacetic acid ethylated-2, 4-pentanediketone aluminum, and carrying out Grignard reaction to graft the diethylacetic acid ethylated-2, 4-pentanediketone aluminum into the polymethyl methacrylate prepolymer prepared in the step S1;

s3: adding the rest initiator and metal organic framework material into the polymethyl methacrylate prepolymer prepared in S2, and introducing hot water at 75 ℃ to continue to react for 20min to obtain a modified methyl methacrylate prepolymer with the solid content of 45%;

s4: and (3) molding the modified methyl methacrylate prepolymer prepared in the step (S3) into an acrylic plate.

In the embodiment, the initiator is one or two of azodiisobutanedinitrile and azodiisoheptanecarbonitrile.

In this example, the grignard reagent is magnesium chloride.

In this example, in S2, after the grignard reaction is completed, ammonium chloride is added dropwise under the ice-water bath condition to extract the remaining grignard reagent.

In this embodiment, the ratio of the amount of the initiator in S1 to the amount of the initiator in S3 is 1: 0.8.

in this embodiment, in S1, the nitrogen gas is introduced for 25 min.

In this embodiment, the metal-organic framework material is an aluminum-based-organic framework material.

In this example, in S1, polymethyl methacrylate, maleimide, α -methacrylic acid, p-chlorostyrene, and a part of an initiator were charged into a reactor and reacted at 85 ℃.

In this example, in S2, the grignard reaction was performed at room temperature under reflux.

Comparative example 1

This example differs from example 1 in that aluminum bis-ethylacetate ethylated-2, 4-pentanediketone and grignard reagent are omitted, and other raw materials, the preparation method and the using method thereof are the same as those in example 1 and are not described again.

Comparative example 2

The difference between this example and example 1 is that the metal organic frame material is omitted, and the other raw materials, the preparation method and the using method thereof are the same as those in example 1, and are not described again here.

Effect verification:

the following performance tests were performed on the aqueous two-component polyurethane coating obtained in example 1 and the method for modifying the toughness of the acryl material obtained in comparative examples 1 to 2,

(1) transparency: slicing the acrylic material, and observing the transparency of the acrylic material by naked eyes;

(2) strength: loading 100kg on the surface of the acrylic material, and observing the deformation degree of the acrylic material;

(3) toughness: the acrylic material was bent 45 °, and the change in the acrylic material was observed to obtain the results table shown in table 1.

Table 1 properties of the acrylic materials of example 1 and comparative examples 1 to 2

Test number	Transparency	Strength of	Toughness of
				Example 1	Is transparent	No crack	Without obvious crease
Comparative example 1	Is transparent	Has cracks	Deformed surface with white mist
				Comparative example 2	Is transparent	Has cracks	With obvious crease lines

As can be seen from table 1, the transparency of the acrylic material obtained by ethylating aluminum bis-ethylacetate with aluminum bis-2, 4-pentanediketone, the grignard reagent and the metal organic framework material is not changed, and the hardness and toughness of the acrylic material obtained by the present invention are improved, which are better than those of the acrylic material obtained by comparative example 1 (omitting aluminum bis-ethylacetate with the grignard reagent) and the acrylic material obtained by comparative example 2 (the metal organic framework material), and it can be seen that the acrylic material of the present invention can be better applied to furniture.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.