CN110527085B

CN110527085B - Polyester amide material and preparation method thereof

Info

Publication number: CN110527085B
Application number: CN201810545530.2A
Authority: CN
Inventors: 徐日炜; 盛佳; 余鼎声
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2018-05-25
Filing date: 2018-05-25
Publication date: 2021-01-19
Anticipated expiration: 2038-05-25
Also published as: CN110527085A

Abstract

The invention discloses a polyester amide material and a preparation method thereof, the polyester amide material is obtained by reacting bisoxazoline and a biscarboxyl compound, wherein the biscarboxyl compound and the bisoxazoline generate ring-opening addition polymerization reaction, and when the biscarboxyl compound comprises biscarboxyl POSS, the polyester amide material with a side group containing POSS can be prepared.

Description

Polyester amide material and preparation method thereof

Technical Field

The invention relates to a POSS-based polymer, in particular to a polyesteramide material with POSS as a side group and a preparation method thereof.

Background

Cage silsesquioxane (POSS) is a nano-sized organic-inorganic hybrid Si-O-Si structured compound. POSS has great advantages in the aspect of material modification, such as uniform size of POSS, easy and uniform dispersion in a matrix, strong designability of the types of organic functional groups on the surface of POSS, and unique performance endowed by POSS. Due to the special structure of POSS, the POSS-based polymer prepared by using POSS as a raw material has good improvement on the aspects of thermal stability, mechanical property, hydrophobicity and the like, so that the POSS has huge application prospects in the fields of biomedicine, electronics, optics and magnetism, sensors, catalysis and the like.

POSS generally improves polymer properties in two forms, physical modification and chemical modification. The physical modification is generally blending modification of POSS in the form of rigid particles with polymer doping, wherein POSS exists in the form of filler and enhances the properties of the modified polymer. The chemical modification is to introduce POSS into the molecular chain of the polymer in a chemical reaction mode, and modify the polymer from the molecular structure. Chemical modification optimizes the polymer structure directly from the molecular layer side and is therefore the most efficient and most widely used method.

The polyesteramide is a resin with excellent comprehensive performance, and a plurality of methods for synthesizing the polyesteramide exist at present, but the method for preparing the polyesteramide with good thermal stability, excellent mechanical property and good hydrophobicity by introducing POSS (polyhedral oligomeric silsesquioxane) to a polyesteramide side chain is not reported in a public way.

Disclosure of Invention

In order to overcome the above problems, the present inventors have made intensive studies, and have obtained through a ring-opening addition polymerization reaction of bisoxazoline and a biscarboxyl compound, the biscarboxyl compound and the bisoxazoline undergo a ring-opening addition polymerization reaction, and when the biscarboxyl compound includes biscarboxyl POSS, a polyesteramide material having POSS as a side group can be prepared.

The invention aims to provide a polyester amide material obtained by reacting bisoxazoline and a biscarboxyl compound.

Wherein the bisoxazoline is selected from one or more of 1,3-PBO, 1,4-PBO and BOZ, preferably 1,3-PBO,

the biscarboxyl compound includes a carboxylic diacid compound,

the carboxylic diacid compound is selected from one or more of alkane diacid, aliphatic diacid and aromatic diacid, is preferably alkane diacid, and is more preferably one or more of succinic acid, adipic acid and sebacic acid.

Wherein the dicarboxyl compound further comprises a dicarboxyl POSS,

the mass ratio of the substance of the carboxylic diacid compound and the dicarboxy POSS is 1:0 to 0:1, preferably 0.95:0.05 to 0.6:0.4, more preferably 0.95:0.05 to 0.7:0.3,

wherein the structural formula of the dicarboxyl POSS is shown as the formula (I):

wherein, in the formula (I), m is more than or equal to 1; n is 0 to 4; r1, R2, R3, R4, R5, R6 and R7 are each independently selected from hydrogen, alkyl, phenyl, substituted phenyl or alicyclic.

Wherein the alkyl is selected from C1-C9 alkyl, preferably C2-C8 alkyl, more preferably n-propyl, isopropyl, n-butyl, isobutyl or isooctyl,

the substituted phenyl is alkyl substituted phenyl or nitro substituted phenyl, preferably p-tolyl, o-tolyl or m-tolyl,

the alicyclic group is C3-C8 alicyclic group, preferably C3-C6 alicyclic group, such as cyclopropyl group, cyclobutyl group, cyclopentyl group or cyclohexyl group.

Another aspect of the present invention provides a method for preparing the above-mentioned polyester amide material, comprising the steps of:

step 1, mixing raw materials, and reacting to obtain a reaction product;

step 2, carrying out post-treatment on the reaction product obtained in the step 1 to obtain a final product;

wherein in the step 1, dicarboxyl POSS is optionally added into the raw materials,

the dicarboxy POSS is prepared by the following steps:

step 1-1, dispersing POSS containing double bonds and alkyl dicarboxylic acid containing sulfydryl in a solvent, and then adding an initiator to perform reaction;

and (3) after the reaction in the step (1-2) is finished, carrying out post-treatment to obtain the polyhedral oligomeric silsesquioxane containing dicarboxyl.

In the step 1-1, the POSS containing the double bond is shown as a formula (III):

wherein, in the formula (III), m is more than or equal to 1; r1, R2, R3, R4, R5, R6, R7 are each independently selected from hydrogen, alkyl, phenyl, substituted phenyl or alicyclic;

and/or

The mercapto group-containing alkyl dicarboxylic acid is represented by the following formula:

wherein n is 0-4;

the molar ratio of the double-bond-containing POSS to the mercapto-containing alkyl dicarboxylic acid is 1: (1-2) of a first step,

in step 1-1, the solvent is tetrahydrofuran, and the initiator is a thermal initiator, preferably benzoyl peroxide, azobisisobutyronitrile or azobisisoheptonitrile.

In the step 1, the reaction is carried out in an air-isolated environment, the bisoxazoline, the dicarboxyl POSS, the carboxylic diacid compound and the solvent are sequentially added into a reactor, the reactants are heated to 140-160 ℃, stirred, heated to 180-220 ℃ after being dissolved, and reacted for 10-15 hours.

In the step 1, the air isolation environment is an oxygen-free and water-free environment, preferably a nitrogen or argon atmosphere, and more preferably a nitrogen atmosphere; the solvent is a high boiling point solvent, preferably one of dimethyl sulfoxide and N, N-dimethylformamide, more preferably N, N-dimethylformamide, wherein the addition amount of the solvent is such that the substance concentration of the dicarboxy POSS is 0mol/L to 3.3 mol/L.

According to the invention, the following beneficial effects are provided:

1. the side chain of the polyester amide material prepared by the invention contains a crystallized POSS group, so that the polyester amide material with the side chain containing POSS does not have crystallinity, but the side chain is crystallized.

2. The side chain of the polyester amide material prepared by the invention contains POSS, so that the polyester amide material has good thermal stability and hydrophobicity.

3. The polyesteramide prepared by the method provided by the invention has definite nano-base polymer and good application prospect in polymer synthesis and modification.

4. The method for preparing the polyesteramide provided by the invention has the advantages of simple operation of the preparation process, mild post-treatment and easy obtainment of the product.

Drawings

FIG. 1 is a graph comparing FT-IR measurements of the final products from examples 1-4 and comparative example 1, heptaisobutylbiscarboxyl POSS, succinic acid and 1, 3-PBO;

FIG. 2 is a comparative plot of TGA testing of the final products obtained in examples 1-4 and comparative example 1;

FIG. 3 is a comparison of polarizing microscopy tests of the final products from examples 1-4 and comparative example 1 with a heptaisobutylbiscarboxy POSS;

FIG. 4 is a graph comparing XRD testing of the final products obtained in examples 1-4 and comparative example 1 with heptaisobutyldicarboxyl POSS;

FIG. 5 is a DSC temperature rise contrast curve of the final products obtained in examples 1-4 and comparative example 1;

FIG. 6 is a graph comparing DSC decrease in temperature of final products obtained in examples 1-4 and comparative example 1;

FIG. 7 is a graph comparing water contact angle tests of final products obtained in examples 1-6 and comparative example 1.

FIG. 8 is a comparative graph of water contact angle tests of the final products obtained in examples 6, 7, 8 and comparative example 1.

FIG. 9 is a comparative graph of water contact angle tests of the final products obtained in examples 6 and 9 and comparative example 1.

FIG. 10 is a comparative graph of water contact angle tests of the final products obtained in examples 9, 10 and 11.

Detailed Description

The features and advantages of the present invention will become more apparent from the following detailed description of the invention.

The invention provides a polyester amide material which is obtained by reacting bisoxazoline and a dicarboxyl compound.

According to the invention, the bisoxazoline is one or more of 2,2'- (1, 3-phenylene) -bisoxazoline (1,3-PBO), 2' - (1, 4-phenylene) -bisoxazoline (1,4-PBO) and 2, 2-bisoxazoline BOZ, and is preferably 1, 3-PBO.

According to the invention, the dicarboxyl compound comprises a carboxylic diacid compound, wherein the carboxylic diacid compound is selected from one or more of alkane diacid, aliphatic diacid and aromatic diacid, preferably alkane diacid, more preferably one or more of succinic acid, adipic acid and sebacic acid, such as succinic acid.

According to a preferred embodiment of the invention, the ratio of the amounts of substance of bisoxazoline and biscarboxyl compound is 1: 1.

according to the invention, the dicarboxyl compound further comprises dicarboxyl POSS, wherein the mass ratio of diacid to dicarboxyl POSS is 1: 0-0: 1, preferably 0.095: 0.05-0.6: 0.4, more preferably 0.95:0.05 to 0.7: 0.3.

According to the invention, the structural formula of the dicarboxy POSS is shown as the formula (I):

wherein, in formula (I), m ≧ 1, preferably m ═ 1 or 2, more preferably m ═ 2; n is 0 to 4, preferably 0 to 2, and more preferably 0; r₁、R₂、R₃、R₄、R₅、R₆、R₇Each independently selected from hydrogen, alkyl, phenyl, substituted phenyl or alicyclic group, preferably, R₁、R₂、R₃、R₄、R₅、R₆、R₇Are selected from the same alkyl or phenyl group, more preferably from the same alkyl or phenyl group, most preferably the same alkyl group.

According to the invention, the alkyl group is selected from C₁～C₉Is preferably C₂～C₈More preferably n-propyl, isopropyl, n-butyl, isobutyl or isooctyl, for example isobutyl.

According to the invention, the substituted phenyl group is an alkyl-substituted phenyl group or a nitro-substituted phenyl group, preferably a p-tolyl, o-tolyl or m-tolyl group.

According to the invention, the alicyclic group is a C3-C8 alicyclic group, preferably a C3-C6 alicyclic group, such as a cyclopropane group, a cyclobutane group, a cyclopentane group, a cyclohexane group, and more preferably a cyclopentane group or a cyclohexane group.

According to the invention, the dicarboxy POSS are selected from the group consisting of those represented by formulas (II-1) to (II-4):

most preferably, according to the present invention, the biscarboxyl POSS has the structure shown in formula (II-1).

In the invention, bis-oxazoline and bis-carboxyl compounds are used as raw materials, the bis-carboxyl compounds preferably comprise diacid and bis-carboxyl POSS, and the polyester amide material with the side group containing POSS is prepared through ring-opening addition polymerization reaction, wherein the bis-carboxyl POSS replaces part of diacid to carry out addition polymerization with the bis-oxazoline, the main chain of the prepared polyester amide material contains an amide group and an ester group, and the side chain contains POSS.

In the invention, the POSS is contained in the side chain, so that the polyester amide material has excellent thermal stability, crystallinity and hydrophobicity. For example, the T of the polyesteramide having POSS as a pendant group was determined by TGA testing of the final products of inventive examples 1 to 4 and comparative example 1_d5％、T_d10％And the carbon residue rate at 800 ℃ is obviously higher than that of the polyester amide without the dicarboxyl POSS, and the water contact angle test can obtain that when the mass ratio of succinic acid to the dicarboxyl POSS is 0.7:0.3, the hydrophobic angle of the polyester amide with the POSS contained in the side group reaches 147 degrees.

Another aspect of the present invention is to provide a method for preparing a polyesteramide, preferably a polyesteramide material as described above, comprising the steps of:

step 1, mixing raw materials, and reacting to obtain a reaction product;

according to the present invention, in step 1, the starting material comprises bisoxazoline and a biscarboxyl compound, preferably bisoxazoline, diacid and biscarboxyl POSS, more preferably 1,3-PBO, succinic acid and biscarboxyl POSS.

According to the invention, the 1,3-PBO is preferably a commercially available product, for example from Chiese chemical industry, Inc., and the succinic acid is preferably a commercially available product, for example from Michelin reagent, Inc. The dicarboxy POSS is preferably self-made.

According to the present invention, a dicarboxy POSS is prepared by the steps of:

step 1-1 reaction of a double bond-containing POSS (denoted as POSS-CH ═ CH)₂) Dispersing the mixture and alkyl dicarboxylic acid containing sulfydryl in a solvent, and then adding an initiator to perform reaction;

and (3) after the reaction in the step (1-2) and the step (1-1) is finished, post-processing is carried out to obtain POSS containing dicarboxyl.

According to the present invention, in step 1-1, a POSS containing a double bond is represented by formula (III):

wherein, in formula (III): m.gtoreq.1, preferably m ═ 1 or 2, for example m ═ 1; r₁、R₂、R₃、R₄、R₅、R₆、R₇Each independently selected from hydrogen, alkyl, phenyl, substituted phenyl or alicyclic group, preferably R₁、R₂、R₃、R₄、R₅、R₆、R₇Selected from the same alkyl, phenyl or alicyclic groups, more preferably from the same alkyl or phenyl groups, such as alkyl groups.

According to the invention, in formula (III), the alkyl group is chosen from n-propyl, isopropyl, n-butyl, isobutyl or isooctyl, for example isobutyl.

According to the invention, the structure of the POSS containing the double bond is shown as the formula (III-1):

according to the invention, the mercapto group-containing alkyl dicarboxylic acid is of the formula (IV):

wherein n is 0 to 4, preferably 0 to 2, and more preferably 0.

According to a preferred embodiment of the present invention, the mercapto group-containing alkyl dicarboxylic acid is mercaptosuccinic acid.

In the present invention, to ensure that the POSS containing the double bond can be reacted completely, a slight excess of the mercapto-containing alkyl dicarboxylic acid is added.

According to the invention, the molar ratio of POSS containing double bonds to mercapto-containing alkyl dicarboxylic acids is 1: (1-2), preferably 1: (1 to 1.5), more preferably 1: (1-1.2), for example 1: 1.

According to the present invention, in step 1-1, the solvent is tetrahydrofuran; the initiator is a thermal initiator, preferably, the initiator is selected from one or more of benzoyl peroxide, azobisisobutyronitrile or azobisisoheptonitrile, and more preferably, the initiator is Azobisisobutyronitrile (AIBN).

According to the present invention, in step 1-1, the reaction is carried out at 50 to 90 ℃, preferably at 60 to 85 ℃, and more preferably at 80 ℃.

According to the invention, in step 1-1, the reaction is carried out under a protective atmosphere, which is a nitrogen or argon atmosphere, preferably a nitrogen atmosphere.

According to the invention, in step 1-2, the post-treatment comprises rotary evaporation, precipitation, suction filtration and drying in sequence. Wherein the precipitation is carried out in water or acetonitrile, preferably in deionized water.

In the invention, the adding of dicarboxyl POSS replaces partial carboxylic diacid compound to react with bisoxazoline, so that a small amount of POSS is added to play a role in modifying the generated polyester amide, and the ratio of oxazoline ring to carboxylic acid ring is 1:1, namely the mass ratio of the bisoxazoline to the biscarboxyl compound is 1:1, and the biscarboxyl POSS and the carboxylic diacid compound both contain two carboxyl groups, so that the biscarboxyl POSS replaces part of the carboxylic diacid compound to perform ring-opening addition polymerization reaction with the bisoxazoline.

According to the present invention, the mass ratio of the substance of the carboxylic diacid compound to the biscarboxy POSS is 1:0 to 0:1, preferably 0.95:0.05 to 0.6:0.4, more preferably 0.95:0.05 to 0.7 to 0.3, most preferably 0.95:0.05, 0.9:0.1, 0.85:0.15, 0.8:0.2,0.7:0.3.

According to the invention, in step 1, a reaction device is firstly prepared, and as the reaction system needs to be isolated from the environment of air, the reaction device needs to be connected with a pumping device for removing oxygen and water vapor in the reaction device, and inert gas is introduced into the reaction device. This is because it is necessary to remove oxygen from the apparatus in order to prevent oxygen or moisture from inhibiting the addition polymerization reaction, thereby ensuring a water-free and oxygen-free environment.

According to the invention, the reaction system of step 1 is ensured in an air-isolated environment, specifically, a reactor connected with a pumping device is pumped and exhausted three times, and nitrogen or argon, preferably nitrogen, is introduced.

According to the invention, under inert atmosphere, bis-oxazoline, carboxylic diacid compound, bis-carboxyl POSS and solvent are sequentially added into a reactor to obtain a reactant.

According to the present invention, in step 2, the solvent is a high boiling point solvent, preferably dimethyl sulfoxide or N, N-dimethylformamide, more preferably N, N-dimethylformamide.

In the invention, the molecular weight of the product is greatly related to the amount of the raw material substances, and in order to ensure that the raw materials can be uniformly mixed and obtain a product with a larger molecular weight, the solvent is added in an amount, after the solvent is added, the amount concentration of the substance of the dicarboxy POSS is 0 mol/L-3.3 mol/L, preferably 0 mol/L-1.0 mol/L, and more preferably 0.1 mol/L-1.0 mol/L.

According to the invention, under the protection of inert gas, the reactants are stirred and heated to 140-160 ℃, preferably to 150 ℃ until the solid reactants are completely dissolved.

In the present invention, the synthesis of polyesteramide is a ring-opening addition polymerization reaction, and the reaction temperature of the reactants is determined according to the melting temperature and the decomposition temperature of the raw materials. For example, the succinic acid has a melting temperature of 185 ℃ and a decomposition temperature of 235 ℃; the melting temperature of the dicarboxy POSS is about 157 ℃; the melting temperature of the 1,3-PBO is 147-151 ℃, and the ring-opening temperature of the oxazoline ring is 180 ℃.

According to the invention, in order to ensure that the reactants can be completely dissolved and the ring-opening addition polymerization reaction can be carried out, after the solid reactants are dissolved, the temperature is raised to 180-200 ℃, the stirring reaction is continued for 10-15 h, preferably, the reaction temperature is 190-200 ℃, the reaction time is 10-12 h, more preferably, the reaction temperature is 200, and the reaction time is 12h, so as to obtain the reaction product.

And 2, carrying out post-treatment on the reaction product obtained in the step 1 to obtain a final product.

According to the invention, in step 2, the reaction product obtained in step 1 is subjected to post-treatment, wherein the post-treatment comprises precipitation, filtration and drying, and preferably, the reaction product is subjected to precipitation, suction filtration and vacuum drying under air to obtain a final product.

In the invention, the vacuum drying temperature has important influence on the product, the vacuum drying temperature is low, the solvent volatilization time is long, the cost is increased, and the temperature is high, so that the degradation of the reaction product can be caused.

According to the invention, the vacuum drying temperature is 40-50 ℃, preferably 45-50 ℃.

According to a preferred embodiment of the invention, the reaction equations for the polyesteramides are shown in formulae (IV) to (V):

examples

The invention is further described below by means of specific examples. However, these examples are only illustrative and do not limit the scope of the present invention. In the examples, the means used are conventional in the art unless otherwise specified.

The raw materials and instruments used in the examples were as follows:

nitrogen, high purity, available from beijing as a source such as spring limited;

succinic acid, analytical grade, mclin reagents inc;

1,3-PBO, analytically pure, Chishiai (Shanghai) chemical industry development Co., Ltd;

n, N-dimethylformamide, analytically pure, beijing chemical plant;

deionized water, analytically pure, self-made.

Example 1

Sequentially adding 0.005mol of heptaisobutyl vinyl POSS, 0.02mol of mercaptosuccinic acid and 100ml of tetrahydrofuran into a reactor connected with a nitrogen device, stirring until reactants are completely dissolved, adding 0.1g of AIBN into the reactor, pressing the nitrogen device, removing air in the reactor until the reactor is filled with nitrogen components, carrying out oil bath reaction for 1h, then transferring to a room temperature environment for reaction for 12h, and then carrying out post-treatment such as suction filtration, recrystallization, drying and the like on the reaction product to obtain heptaisobutyl B type dicarboxyl POSS;

sequentially adding 0.01mol of 1,3-PBO, 0.0095mol of succinic acid and 0.0005mol of heptaisobutyl ethyl dicarboxyl POSS into a reactor connected with a pumping device, adding 3ml of N, N-dimethylformamide, placing the reactor in an environment of 150 ℃ and stirring for 5min to ensure that reactants are completely dissolved, heating to 200 ℃, and reacting for 12h under the condition of stirring;

after the reaction is finished, precipitating and filtering the obtained reaction product by using deionized water, and drying in vacuum at the temperature of 45 ℃ to obtain the final product.

Example 2

The procedure of example 1 was repeated except that 0.01mol of 1,3-PBO, 0.009mol of succinic acid and 0.001mol of heptaisobutylethylene biscarboxy POSS were added.

Example 3

The procedure of example 1 was repeated except that 0.01mol of 1,3-PBO, 0.0085mol of succinic acid and 0.0015mol of heptaisobutylacetic biscarboxy POSS were added.

Example 4

The procedure of example 1 was repeated except that 0.01mol of 1,3-PBO, 0.008mol of succinic acid and 0.002mol of heptaisobutylethane-type dicarboxy POSS were added.

Example 5

The procedure of example 1 was repeated except that 0.01mol of 1,3-PBO, 0.007mol of succinic acid and 0.003mol of heptaisobutylethyl dicarboxy POSS were added.

Example 6

The procedure of example 1 was repeated except that 0.01mol of 1,3-PBO and 0.01mol of heptaisobutylethane-type dicarboxy POSS were added.

Example 7

The procedure of example 1 was repeated except that 0.01mol of 1,3-PBO and 0.01mol of heptaisobutylpropyl dicarboxy POSS were added.

Example 8

The procedure of example 1 was repeated except that 0.01mol of 1,3-PBO and 0.01mol of heptaisobutyloctyl-type dicarboxy POSS were added.

Example 9

The procedure of example 1 was repeated except that 0.01mol of 1,3-PBO and 0.01mol of heptaphenylethy dicarboxy POSS were added.

Example 10

The procedure of example 1 was repeated except that 0.01mol of 1,4-PBO and 0.01mol of heptaisobutylethane-type dicarboxy POSS were added.

Example 11

The procedure of example 1 was repeated except that 0.01mol of BOZ and 0.01mol of heptaisobutylethane-type dicarboxy POSS were added.

Comparative example 1

The procedure of example 1 was repeated using the same batches of succinic acid and 1,3-PBO as in example 1 except that 0.01mol of 1,3-PBO and 0.01mol of succinic acid were added and no heptaisobutylethyl dicarboxyl POSS was added.

Examples of the experiments

Experimental example 1

FT-IR testing was performed on the final products obtained in comparative example 1 and examples 1-4, as well as heptaisobutylbiscarboxydiPOSS, succinic acid and 1,3-PBO, and the FT-IR curves obtained are shown in FIG. 1, and curves 1, 2, 3, 4 and 5 in FIG. 1 are the FT-IR curves of the final products obtained in comparative example 1, example 2, example 3 and example 4, respectively;

as can be seen from figure 1,the polyesteramide generated by ring-opening addition polymerization reaction of 3-PBO, succinic acid and heptaisobutyl ethyl dicarboxyl POSS is 3341cm^-1At position 1534cm^-1Has a very obvious-NH characteristic peak at 1740cm^-1A characteristic peak of carbonyl group at 1659cm and-O-C ═ O^-1Has a characteristic peak of-NH-CO carbonyl of 3090cm^-1The characteristic peak of benzene ring appears at 2058cm^-1A characteristic peak of an alkyl group (similar to that of heptaisobutyl) appeared at 1101cm^-1POSS cage Si-O-Si structure characteristic peak is formed, and raw material succinic acid is 1698cm^-1At 1709cm of carboxy and dicarboxy POSS^-1The characteristic peak of carboxyl at the position disappears, and the oxazoline is at 919cm^-1The characteristic peak of the five-membered ring disappears, 1661cm^-1The characteristic peak of the-C ═ N bond at position disappeared, thus demonstrating that the oxazoline ring opening reacted with the dicarboxy POSS to form polyesteramide and that the POSS cage was successfully incorporated into the polyesteramide side chain.

Experimental example 2

The final products obtained in comparative example 1 and examples 1 to 4 were subjected to TGA test, and the TGA curves are shown in FIG. 2, and data of the temperature at 5% of thermal weight loss (Td 5%), the temperature at 10% of thermal weight loss (Td 10%) and the char yield at 800 ℃ of the final products are shown in Table 1.

TABLE 1

Sample (I)	T_d5％/℃	T_d10％/℃	Residual carbon rate at 800%
				Comparative example 1	205.3	262.0	5.66
Example 1	240.6	286.4	6.93
				Example 2	251.8	276.7	11.68
Example 3	277.0	290.7	22.10
				Example 4	256.6	290.6	24.83

With reference to FIG. 2 and Table 1, the pendant group is the T of a polyesteramide of POSS_d5％、T_d10％And the carbon residue rate at 800 ℃ is obviously higher than that of the polyester amide without the dicarboxyl POSS, and when the mass ratio of the succinic acid to the dicarboxyl POSS is 0.8:0.2, the carbon residue rate at 800 ℃ of the polyester amide with the POSS as the side group is the highest. The thermal stability of the polyester amide is obviously improved after the dicarboxyl POSS is added.

Experimental example 3

The final products obtained in comparative example 1, examples 1-4 and heptaisobutylbiscarboxy POSS were subjected to polarization microscope tests, the results of which are shown in fig. 3.

All the figures in FIG. 3 show the test results of the final product at parallel offsets and at orthogonal offsets, where group F represents the test results of the dicarboxy POSS and groups A-E represent the test results of the final products of comparative example 1, example 2, example 3, and example 4, respectively. The test structure shows that the double-carboxyl POSS has the phenomenon of light and shade alternation at the orthogonal polarization detection position, which indicates that the double-carboxyl POSS has good crystallinity; on the other hand, when the ratio of the amount of the substance added to the biscarboxyl POSS is 0, 0.05, 0.1, 0.15, 0.2, respectively, the resulting polyesteramide is dark at the orthogonal detection position, which is probably because the POSS content in the polyesteramide is too small, the crystal size of POSS is nano-scale, and the POSS is not observable by the polarizing microscope.

Experimental example 4

XRD tests were carried out on the final products obtained in comparative example 1, examples 1-4 and heptaisobutylbiscarboxydi POSS, and the results are shown in FIG. 4.

As can be seen from the XRD patterns of the dicarboxy POSS with different proportions, the dicarboxy POSS has peaks at 8.17 degrees, 11 degrees and 19.15 degrees, and accords with the peak-out position of the POSS, but the peaks are not very sharp, and probably because the existence of the carboxyl causes the crystallinity of the dicarboxy POSS to be reduced;

the polyester amide generated without POSS has no obvious peak and only bulges, which indicates that the polyester amide has an amorphous structure; when the amount ratio of the biscarboxy POSS species is 0.15, the resulting final product has the best crystallinity and the highest crystallinity, but when the amount ratio of succinic acid to the biscarboxy POSS species is 0.8: at 0.2, the crystallization degree of the final product tends to the crystallization degree of POSS, and the phenomenon is probably that the crystallization interference of POSS cages after the carboxyl on the POSS and oxazoline ring-opening reaction is reduced, so that the characteristic peak of the POSS cages is not sharp, the peak is increased by increasing the POSS content in a certain range, but the peak is appeared beyond the range, and the POSS is probably associated with the carboxyl POSS.

Experimental example 5

The final products obtained in comparative example 1 and examples 1 to 4 were subjected to DSC measurement, and the DSC curves are shown in FIGS. 5 and 6, and the data of the melting temperature and the crystallization temperature of the obtained products are shown in Table 2.

TABLE 2

With reference to table 2, fig. 5, fig. 6 and experimental example 3, when the polyester amide produced without adding dicarboxy POSS has no melting peak and crystallization peak, the polyester amide system with adding dicarboxy POSS has obvious melting peak and crystallization peak, and as the content of dicarboxy POSS increases, the strength of the melting peak and crystallization peak of the produced polyester amide gradually increases, which indicates that the polyester amide produced without adding dicarboxy POSS is amorphous structure, and the side chain of the polyester amide produced when adding dicarboxy POSS in the system has crystallinity, and the crystallinity tends to increase as the dicarboxy POSS gradually increases.

Experimental example 6

The final products obtained in comparative example 1 and examples 1 to 4 were subjected to a water contact angle test, and the test results are shown in fig. 7, and the water contact angle data of the obtained products are shown in table 3.

TABLE 3

Sample (I)	Water contact angle/° c
		Comparative example 1	0
Example 1	115
		Example 2	135
Example 3	138
		Example 4	145
Example 5	147
		Example 6	145
Example 7	146
		Example 8	143
Example 9	133
		Example 10	140
Example 11	140

As can be seen from fig. 7 and table 3, when the content of the dicarboxy POSS is 0, the resulting polyester amide is hydrophilic, when the dicarboxy POSS is added, the synthesized polyester amide has hydrophobicity, and as the ratio of the dicarboxy POSS increases, the hydrophobicity of the polyester amide material increases, when the mass ratio of the dicarboxy POSS to the succinic acid is 0.3: at 0.7, the hydrophobic angle reached 147 °, showing excellent hydrophobicity.

The invention has been described in detail with reference to specific embodiments and illustrative examples, but it should be understood that the description is illustrative of the invention and is not intended to limit the scope of the invention. It will be understood by those skilled in the art that various changes, substitutions of equivalents and modifications can be made in the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these are within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims

1. A polyester amide material, which is obtained by reacting bisoxazoline and a dicarboxyl compound as raw materials,

the bisoxazoline is 2,2' - (1, 3-phenylene) -bisoxazoline,

the biscarboxyl compound comprises a carboxylic diacid compound,

the carboxylic diacid compound is selected from one or more of aliphatic diacid and aromatic diacid,

the biscarboxyl compounds also include biscarboxyl POSS,

the mass ratio of the carboxylic diacid compound to the dicarboxy POSS is 0.95: 0.05-0.6: 0.4,

the structural formula of the dicarboxy POSS is shown as the formula (I):

wherein, in the formula (I), m is more than or equal to 1; n is 0-4; r₁、R₂、R₃、R₄、R₅、R₆、R₇Each independently selected from hydrogen, alkyl, phenyl, substituted phenyl or alicyclic group,

the alkyl is selected from n-propyl, isopropyl, n-butyl, isobutyl or isooctyl,

the substituted phenyl is alkyl substituted phenyl or nitro substituted phenyl,

the alicyclic group is C3-C6 alicyclic group.

2. The polyesteramide material of claim 1, wherein the carboxylic diacid compound is an alkane diacid.

3. The polyesteramide material of claim 2, wherein the carboxylic diacid compound is one or more of succinic acid, adipic acid, and sebacic acid.

4. The polyesteramide material of claim 1,

the mass ratio of the carboxylic diacid compound to the dicarboxy POSS is 0.95: 0.05-0.7: 0.3.

5. The polyesteramide material of claim 1,

the substituted phenyl is p-tolyl, o-tolyl or m-tolyl,

the alicyclic group is a cyclopropane group, a cyclobutane group, a cyclopentane group or a cyclohexane group.

6. A method of preparing the polyesteramide material of any of claims 1 to 5, comprising the steps of:

step 1, mixing raw materials, and reacting to obtain a reaction product;

7. The method of claim 6 wherein in step 1, bis-carboxyl POSS is added to the feedstock,

the dicarboxy POSS is prepared by the following steps:

8. The method according to claim 7, wherein, in step 1-1,

the double bond containing POSS is represented by formula (III):

wherein, in the formula (III), m is more than or equal to 1; r₁、R₂、R₃、R₄、R₅、R₆、R₇Each independently selected from hydrogen, alkyl, phenyl, substituted phenyl or alicyclic;

and/or

wherein n is 0-4;

in the step 1-1, the solvent is tetrahydrofuran, and the initiator is a thermal initiator, and is benzoyl peroxide, azobisisobutyronitrile or azobisisoheptonitrile.

9. The method according to claim 8, wherein in the step 1, the reaction is carried out in an air-isolated environment, the bisoxazoline, the dicarboxy POSS, the carboxylic diacid compound and the solvent are sequentially added into a reactor, the reactants are heated to 140-160 ℃, stirred, and heated to 180-220 ℃ after being dissolved, and the reaction is carried out for 10-15 hours.

10. The method according to claim 9, wherein, in step 1,

the air-isolated environment is an oxygen-free and water-free environment,

the solvent is a high-boiling point solvent, wherein the addition amount of the solvent is such that the mass concentration of the substance of the dicarboxyl POSS is 0-3.3 mol/L, and the amount of the solvent is not 0 mol/L.

11. The method according to claim 10, wherein, in step 1,

the air-isolated environment is a nitrogen or argon atmosphere,

the solvent is one of dimethyl sulfoxide and N, N-dimethylformamide.

12. The method according to claim 11, wherein, in step 1,

the air-insulated environment is a nitrogen atmosphere,

the solvent is N, N-dimethylformamide.