CN111286075A - A kind of recyclable supramolecular polymer foam material and preparation method - Google Patents

Abstract

The invention discloses a recyclable supramolecular polymer foam material and a preparation method thereof, and belongs to the field of light materials. The method comprises the following steps: step 1: synthesizing, mixing, dissolving and foaming matrix resin, wherein a supramolecular polymer matrix is based on a 2-ureido-4 [1H ] -pyrimidone quadruple hydrogen bond structure, different polymers are selected as middle chain segments, different preparation methods are selected, and organic and inorganic fillers are added in a matching manner to prepare a series of supramolecular polymer materials; step 2: dissolving the polymer in a chloroform solvent, adding deionized water, mechanically stirring and mixing to prepare emulsion, and freeze-drying by liquid nitrogen to obtain the porous supramolecular polymer foam material. The produced material has better mechanical strength and can be directly applied. After the material is damaged, the material can be directly cleaned and then recycled to be dissolved again to prepare the foam material, so that the waste of raw materials is effectively avoided, the use cost is saved, and the economic benefit is improved.

Description

A kind of recyclable supramolecular polymer foam material and preparation method

technical field

The invention belongs to the field of lightweight materials, in particular to a recyclable supramolecular polymer foam material and a preparation method.

Background technique

Foam materials are also called microcellular plastics. The whole is covered with numerous interconnected or disconnected micropores and the apparent density is significantly reduced. Compared with pure plastics, it has many excellent properties, such as light weight, high specific strength, shock load absorption, good thermal and sound insulation properties, etc. Therefore, it has been widely used in industry, agriculture, construction, transportation and other fields.

Since its inception, foamed plastics have become more and more widely used and varieties are constantly enriched, among which the more common traditional foamed plastics are mainly polyurethane (PUR), polystyrene (PS), polyvinyl chloride (PVC), polyethylene (PE), phenolic Resin (PF) and other varieties. However, most of the traditional foam materials are thermosetting resin bases, which are difficult to recycle and degrade. Discarded foam materials such as lunch boxes will cause serious white pollution and greatly waste limited resources. Residues of the foaming agent used in the foaming process of the polymer in the foam material will cause secondary pollution to the environment and threaten human health.

To this end, the development of recyclable, green and non-polluting foam materials will greatly improve the above problems. Supramolecular polymers use non-covalent bonds to link polymerized monomers to form linear or network polymers with larger molecular weights, and at the same time have certain mechanical strength to ensure their applicability. By changing the chemical structure of supramolecular polymers, polymer materials with controllable mechanical strength and melting temperature can be prepared, which can meet the needs of various applications to a large extent.

Supramolecular polymer foam can be prepared by processing the supramolecular polymer by foaming technology. Due to the characteristics of the supramolecular polymer, the prepared supramolecular polymer foam can be reused by dissolving after simple cleaning, which is economical and environmentally friendly.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a kind of recyclable supramolecular polymer foam material and preparation method which can save the use cost and improve the economic benefit.

The object of the present invention is achieved through the following technical solutions:

In the present invention, the formula of the foam material adopts synthetic resin, plasticizer, filler and other raw materials.

Recyclable supramolecular polymer materials are composed of supramolecular polymer matrix, organic and inorganic fillers, plasticizers and other raw materials. The preparation process includes the synthesis, kneading, dissolving, foaming and other processes of the matrix resin. The supramolecular polymer matrix is based on the 2-ureido-4[1H]-pyrimidinone quadruple hydrogen bond structure. Different polymers are used as intermediate segments, different preparation methods are selected, and organic and inorganic fillers are added to prepare a series of Supramolecular polymer materials. Then, the polymer is dissolved in chloroform solvent, deionized water is added, an emulsion is prepared by mechanical stirring and mixing, and a porous supramolecular polymer foam material can be obtained by freeze-drying with liquid nitrogen.

In the supramolecular polymer foam material, the supramolecular polymer matrix is based on the quadruple hydrogen bond structure as the end group and different polymers are selected as the intermediate segment, and further, the quadruple hydrogen bond system is based on the electron donor. The positional arrangement of the body (D) and the electron acceptor (A) are different, and there are two association modes of DADA and AADD in the double hydrogen bond, which is one or more of the following structures:

代表氢键，R¹和R²由以下所述的一种或两种结构组成in

Representing hydrogen bonds, R1 and R2 consist of ^one or ^both of the structures described below

1) C ₁ -C ₂₀ straight or branched alkyl;

2) C ₆ -C ₁₂ aryl groups;

3) C ₇ -C ₁₂ alkaryl;

4) C ₇ -C ₁₂ aralkyl groups;

5) C ₁ -C ₁₀ alkyl group containing 1-4 ureido substituents, and the ureido group is shown in the following formula:

wherein R ³ is any one of the following groups:

a)H

b) C ₁ -C ₆ straight or branched chain alkyl;

6) Polyolefin structure:

The polyolefin structure is one of the following:

wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and Y are any of the following groups:

c)H

d) C1-C6 straight or branched chain alkyl

e) C1-C6 straight or branched chain alkenyl

p is 10-100.

At the same time, the quadruple hydrogen bond group is connected to the polymer middle segment through R ¹ and (or) R ² to form the supramolecular polymer main chain, and the one that is not connected to the polymer middle segment becomes the supramolecular polymer side chain .

In the supramolecular polymer foam material, 10-100 quadruple hydrogen bond groups in the supramolecular polymer matrix are connected with the polymer intermediate segment.

Described supramolecular polymer foam material, its supramolecular polymer matrix is based on quadruple hydrogen bond structure as end group, and selects different polymers as intermediate segment, further, described supramolecular polymer foam material, its The polymer middle segment is one or more of the following structures,

1) Polyester structure:

The polyester structure is as follows

where ^R and Y are any of the following groups

a)H

b) C1-C6 straight or branched chain alkyl

n is 1-12 and m is 10-100.

2) Polyolefin structure:

The polyolefin structure is one of the following

wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and Y are any one of the following groups

c)H

d) C1-C6 straight or branched chain alkyl

e) C1-C6 straight or branched chain alkenyl

p and q are 10-100.

The supramolecular polymer foam material is characterized in that the supramolecular polymer matrix resin can be composed of one or more of the above-mentioned quadruple hydrogen bond supramolecular polymers.

The supramolecular polymer foam material can be compounded by the supramolecular polymer matrix resin and filler, and the filler content is 0-50% of the content of the whole material.

The supramolecular polymer foam material can be compounded by the supramolecular polymer matrix resin and the pigment, and the pigment content is 0-5% of the content of the whole material.

The supramolecular polymer foam material can be compounded by the above-mentioned supramolecular polymer matrix resin, one or more pigments and fillers.

The 2-ureido-4[1H]-pyrimidinone quadruple hydrogen bond structure is a synthetic structure, and the resin in the middle segment of the polymer can be a natural resin or a synthetic resin. The solvent for the preparation of supramolecular polymer matrix can be alkanes, halogenated alkanes, alcohols, esters, ethers, ketones, aromatic organic solvents, or mixtures thereof, such as cyclohexane, chloroform, ethanol , ethyl acetate, tetrahydrofuran, butanone, toluene, etc.

The beneficial effects of the present invention are:

A recyclable supramolecular polymer foam material is developed, which broadens the field of recyclable foam materials, and the production process of the material is simple and the cost is low. The produced material has good mechanical strength and can be directly applied. After the material is damaged, the foam material can be prepared by recycling and re-dissolving after direct cleaning, which can effectively avoid the waste of raw materials, save the use cost and improve the economic benefit.

Description of drawings

Fig. 1 is the result diagram of embodiment 1;

Fig. 2 is the result figure of embodiment 2;

Fig. 3 is the result diagram of embodiment 3;

Fig. 4 is the result graph of embodiment 4;

FIG. 5 is a graph of the results of Example 5. FIG.

Detailed ways

The specific embodiments of the present invention will be further described below in conjunction with the accompanying drawings:

A recyclable supramolecular polymer foam material and preparation method, comprising the following steps:

Step 1: Synthesis, kneading, dissolving and foaming of the matrix resin, the supramolecular polymer matrix is based on the 2-ureido-4[1H]-pyrimidinone quadruple hydrogen bond structure, and different polymers are selected as the intermediate segment, and the A series of supramolecular polymer materials were prepared by different preparation methods, and by adding organic and inorganic fillers;

Step 2: Dissolving the polymer in a chloroform solvent, adding deionized water, mechanically stirring and mixing to prepare an emulsion, and freeze-drying with liquid nitrogen to obtain a porous supramolecular polymer foam material.

Basic experimental method:

Dry chloroform was obtained by refluxing calcium hydride overnight and then distillation under reduced pressure. Dry tetrahydrofuran and toluene are refluxed with sodium silk and benzophenone overnight, and then pressure-distilled to obtain dry butanone, which is obtained by refluxing anhydrous sodium carbonate overnight and then vacuum distillation. Dried ethanol and dimethylformamide were soaked through 4A molecular sieve overnight and then distilled under reduced pressure.

2-ureido-4[1H]-pyrimidinone can be prepared by reacting the corresponding isocytosine with the corresponding isocyanate. Isocytosine can be prepared by the condensation reaction of the corresponding β-ketoester with guanidine.

Preparation of β-ketoesters:

Potassium monoethyl malonate and anhydrous magnesium chloride in ethyl acetate as a solvent generate an intermediate product containing magnesium, and then add the acid chloride of the corresponding acid, and carry out an addition reaction at room temperature. Hydrogen ions are then added for protonation and deacylation to give the product.

Preparation of synthons:

Synthon 1:

Methylisocytosine (65 g) and hexamethylene diisocyanate (HDI, 650 g) were stirred and reacted at 100° C. for 16 h under argon protection, and a white precipitate was obtained after the reaction was completed. After cooling to room temperature, 1 L of n-hexane was added and stirred vigorously for 1 h, filtered, washed with n-hexane, and dried in vacuo to obtain a white powder.

¹ H NMR (500 MHz, CDCl ₃ ): δ 13.1(1H), 11.8(1H), 10.1(1H), 5.8(1H), 3.3(4H), 2.1(3H), 1.6(4H), 1.4(4H) ).

FT-IR:ν(cm ^-1 )2935, 2281, 1698, 1668, 1582, 1524, 1256.

Synthon 2:

Propyl isocytosine (5 g) and hexamethylene diisocyanate (HDI, 50 g) were stirred and reacted at 90° C. for 24 h under argon protection, and a pale yellow transparent solution was obtained after the reaction was completed. The temperature was lowered to -20°C, white crystals were precipitated, 200 mL of n-hexane at -20°C was added, filtered and washed at low temperature, and dried in vacuo to obtain a white powder.

¹ H NMR (500 MHz, CDCl ₃ ): δ 13.28 (1H), 11.94 (1H), 10.20 (1H), 5.85 (1H), 3.29 (4H), 2.72 (1H), 1.62, 1.56, 1.27.

FT-IR:ν(cm ^-1 )3025,2941,2876,2301,1704,1649,1571,1462,1263,1242,752,790,726.

Preparation of supramolecular polymers:

Polymer 1:

22.4g hydrogenated polybutadiene diol HLBH-P3000 (Cray Valley Company, USA, linear hydroxyl terminated hydrogenated polybutadiene, 3.2kD) was vacuum dried at 100°C for 1h (the temperature should not be too high, and the time should not be too long to prevent prolonged Time heating and decomposition), cooling in a dry environment, adding 4.3 g of Syntheon 1, 500 mL of chloroform and a trace amount of dibutyltin dilaurate catalyst, and stirring the reaction at a constant temperature of 60 °C for 72 h under an argon atmosphere. After the reaction was completed, dry silica gel and a trace amount of dibutyltin dilaurate were added, and the reaction was continued for 24 h. After cooling to room temperature, the filtrate was collected by filtration, concentrated to 100 mL, and methanol was added to obtain a white precipitate. Washed with methanol and dried in vacuo to obtain a colorless and transparent elastomeric material.

¹ H NMR (500 MHz, CDCl ₃ ): δ 5.8, 4.1, 3.3-3.0, 2.9-2.8, 2.2, 1.6-1.0, 0.8.

FT-IR(neat):ν(cm ^-1 )3457,3336,3216,2959,2925,2855,1700,1664,1590,1525,1461,1379,1252,761.

Polymer 2:

22.4g hydrogenated polybutadiene diol HLBH-P3000 (Cray Valley Company, USA, linear hydroxyl terminated hydrogenated polybutadiene, 3.2kD) was vacuum dried at 100°C for 1h (the temperature should not be too high, and the time should not be too long to prevent prolonged Time heating and decomposition), cooled in a dry environment, added 5.0 g of Syntheon 1, 500 mL of chloroform and a trace amount of dibutyltin dilaurate catalyst, and stirred the reaction at a constant temperature of 60 °C for 72 h under an argon atmosphere. After the reaction was completed, dry silica gel and a trace amount of dibutyltin dilaurate were added, and the reaction was continued for 24 h. After cooling to room temperature, the filtrate was collected by filtration, concentrated to 100 mL, and methanol was added to obtain a white precipitate. Washed with methanol and dried in vacuo to obtain a colorless and transparent elastomeric material.

¹ H NMR (500 MHz, CDCl ₃ ): δ 5.8, 4.1, 3.3-3.0, 2.9-2.8, 2.2, 1.6-1.0, 0.8.

FT-IR(neat):ν(cm ^-1 )3457,3336,3216,2959,2925,2855,1700,1664,1590,1525,1461,1379,1252,761.

Polymer 3:

22.4g hydrogenated polybutadiene diol HLBH-P3000 (Cray Valley Company, USA, linear hydroxyl terminated hydrogenated polybutadiene, 3.2kD) was vacuum dried at 100°C for 1h (the temperature should not be too high, and the time should not be too long to prevent prolonged Time heating and decomposition), cooling in a dry environment, adding 4.3 g of Syntheon 1, 500 mL of chloroform and a trace amount of dibutyltin dilaurate catalyst, and stirring the reaction at a constant temperature of 60 °C for 72 h under an argon atmosphere. After the reaction was completed, dry silica gel and a trace amount of dibutyltin dilaurate were added, and the reaction was continued for 24 h. After cooling to room temperature, the filtrate was collected by filtration, concentrated to 100 mL, and methanol was added to obtain a white precipitate. Washed with methanol and dried in vacuo to obtain a colorless and transparent elastomeric material.

¹ H NMR (500 MHz, CDCl ₃ ): δ 5.8, 5.4, 4.9, 4.5, 3.3, 3.2, 2.2, 2.0, 1.6, 1.3, 0.9.

FT-IR(neat):ν(cm ^-1 )=2918, 2846, 1699, 1667, 1587, 1526, 1440, 1257, 966, 911.

Example 1:

1 according to the following group distribution ratio

Supramolecular polymer 1 10g

Chloroform 200mL

Deionized water 200mL

2 Preparation methods

The supramolecular polymer was dissolved in 200 mL of chloroform, added with 200 mL of deionized water, vigorously shaken to form an emulsion, and freeze-dried in liquid nitrogen to obtain a porous supramolecular polymer foam material.

The material is recycled and reused by repeating the above steps after simple cleaning.

Example 2:

1 according to the following group distribution ratio

2 Preparation methods

The supramolecular polymer and carbon nanotubes were dissolved in 200 mL of chloroform, added with 200 mL of deionized water, vigorously shaken to form an emulsion, and freeze-dried in liquid nitrogen to obtain a porous supramolecular polymer foam material.

The material is recycled and reused by repeating the above steps after simple cleaning.

Example 3

1 according to the following group distribution ratio

2 Preparation methods

The supramolecular polymer and graphene were dissolved in 200 mL of chloroform, added with 200 mL of deionized water, vigorously shaken to form an emulsion, and freeze-dried in liquid nitrogen to obtain a porous supramolecular polymer foam material.

The material is recycled and reused by repeating the above steps after simple cleaning.

Example 4

1 according to the following group distribution ratio

2 Preparation methods

The supramolecular polymer and nano-hydroxyapatite were dissolved in 200 mL of chloroform, added with 200 mL of deionized water, vigorously shaken to form an emulsion, and freeze-dried in liquid nitrogen to obtain a porous supramolecular polymer foam material.

The material is recycled and reused by repeating the above steps after simple cleaning.

Example 5

1 according to the following group distribution ratio

2 Preparation methods

Supramolecular polymers 1 and 2 were dissolved in 200 mL of chloroform, added with 200 mL of deionized water, vigorously shaken to form an emulsion, and freeze-dried in liquid nitrogen to obtain a porous supramolecular polymer foam material.

The material is recycled and reused by repeating the above steps after simple cleaning.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (7)

1. a recyclable supramolecular polymer foam material and preparation method, is characterized in that, comprises the following steps: Step 1: Synthesis, kneading, dissolving and foaming of the matrix resin, the supramolecular polymer matrix is based on the 2-ureido-4[1H]-pyrimidinone quadruple hydrogen bond structure, and different polymers are selected as the intermediate segment, and the A series of supramolecular polymer materials were prepared by different preparation methods, and by adding organic and inorganic fillers; Step 2: Dissolving the polymer in a chloroform solvent, adding deionized water, mechanically stirring and mixing to prepare an emulsion, and freeze-drying with liquid nitrogen to obtain a porous supramolecular polymer foam material. 2. a kind of recyclable supramolecular polymer foam material and preparation method according to claim 1, is characterized in that, described supramolecular polymer foam material, the supramolecular polymer matrix described in it is based on tetrad hydrogen The bond structure is used as the end group and different polymers are selected as the intermediate segment. Further, the quadruple hydrogen bond system is arranged according to the different positions of the electron donor (D) and the electron acceptor (A), and the double hydrogen bond exists. The two association modes of DADA and AADD are one or more of the following structures:

in

Representing hydrogen bonds, R1 and R2 consist of ^one or ^both of the structures described below 1) C ₁ -C ₂₀ straight or branched alkyl; 2) C ₆ -C ₁₂ aryl groups; 3) C ₇ -C ₁₂ alkaryl; 4) C ₇ -C ₁₂ aralkyl groups; 5) C ₁ -C ₁₀ alkyl group containing 1-4 ureido substituents, and the ureido group is shown in the following formula:

wherein R ³ is any one of the following groups: a)H b) C ₁ -C ₆ straight or branched chain alkyl; 6) Polyolefin structure: The polyolefin structure is one of the following:

wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and Y are any of the following groups: c)H d) C1-C6 straight or branched chain alkyl e) C1-C6 straight or branched chain alkenyl p is 10-100. 3. a kind of recyclable supramolecular polymer foam material and preparation method according to claim 1, is characterized in that, described supramolecular polymer foam material, in its described supramolecular polymer matrix, there are 10 - 100 quadruple hydrogen bonding groups attached to the polymer mid-segment. 4. a kind of recyclable supramolecular polymer foam material and preparation method according to claim 1, is characterized in that, described supramolecular polymer foam material, its supramolecular polymer matrix is based on quadruple hydrogen bond structure As the end group, and select different polymers as the intermediate segment, further, in the supramolecular polymer foam material, the polymer intermediate segment is one or more of the following structures, 1) Polyester structure: The polyester structure is as follows

where ^R and Y are any of the following groups a)H b) C1-C6 straight or branched chain alkyl n is 1-12, m is 10-100; 2) Polyolefin structure: The polyolefin structure is one of the following

wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and Y are any one of the following groups c)H d) C1-C6 straight or branched chain alkyl e) C1-C6 straight or branched chain alkenyl p and q are 10-100. 5. a kind of recyclable supramolecular polymer foam material and preparation method according to claim 1, is characterized in that, described supramolecular polymer foam material, it is characterized in that described supramolecular polymer matrix resin can be above-mentioned One or more of the quadruple hydrogen-bonded supramolecular polymers are compounded. 6. a kind of recyclable supramolecular polymer foam material and preparation method according to claim 1, is characterized in that, described supramolecular polymer foam material, but above-mentioned supramolecular polymer matrix resin and filler compound The content of filler is 0-50% of the content of the whole material; the supramolecular polymer foam material can be compounded by the above-mentioned supramolecular polymer matrix resin and pigment, and the content of pigment is 0-5% of the content of the whole material. %; the supramolecular polymer foam material can be compounded by the above-mentioned supramolecular polymer matrix resin and one or more of pigments and fillers. 7. a kind of recyclable supramolecular polymer foam material and preparation method according to claim 1, is characterized in that, described 2-ureido-4[1H]-pyrimidinone quadruple hydrogen bond structure is artificial synthesis structure, the resin in the middle segment of the polymer can be a natural resin or a synthetic resin; the solvent in the preparation process of the supramolecular polymer matrix can be alkanes, halogenated alkanes, alcohols, esters, ethers, ketones, Aromatic organic solvents, or mixtures thereof.

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