Polyesteramide material as well as preparation method and application thereof

Abstract

The present invention relates to the technical field of polyesteramide materials, and discloses a polyesteramide material preparation method, which comprises: in the presence of a catalyst, carrying out a polymerization reaction on polycaprolactone and hexanediamine adipate to obtain a polyesteramide material, wherein the catalyst is prepared from 6-amino-1-hexanoic acid and tetrabutyl titanate, and the solvent is a solvent; wherein the weight average molecular weight of the polycaprolactone is 500 g / mol to 10000 g / mol. The method is simple in preparation process, the reaction temperature is lower than 300 DEG C, energy consumption is low, the obtained polyesteramide material has good mechanical properties, the tensile strength reaches 18 MPa or above, the elongation at break can reach 19% or above, meanwhile, good biodegradability is obtained, and the mass can be reduced by 50% within one month.

Description

Technical Field

[0001] The invention relates to the technical field of polyester amide, and in particular to a polyester amide material and a preparation method and application thereof. Background Art

[0002] Polyamide (PA), commonly known as nylon, is called nylon when used as fiber in my country. It refers to a type of polymer containing amide bonds (-NH-C(O)-) in the main chain of the molecule. Polyamide is the first of the five major engineering plastics. It has good wear resistance, oil resistance, self-lubricating properties, insulation and mechanical properties, and is widely used. Since its industrialization, polyamide has been widely used in textiles, automobiles, electronic appliances, packaging, sports products and other fields.

[0003] Degradable plastics are gaining more and more attention due to their eco-friendly characteristics. In the current research on fully degradable polymer materials, the more mature degradable plastics include polylactic acid, polycaprolactone, polyglycolide, etc. However, these degradable materials have poor mechanical properties and flexibility, which limits the promotion and application of degradable materials. In addition, the problem of traditional plastics being difficult to degrade and causing environmental pollution is becoming increasingly serious, and the country's further restrictions on the use of plastics mean that degradable plastics will replace traditional plastics in the future and be further promoted and used. Therefore, it is of great significance to develop related degradable polymer products.

[0004] CN113637158A discloses a high heat-resistant liquid crystal polyester amide film and a preparation method thereof, wherein the liquid crystal copolymer is made of the following monomers: p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, terephthalic acid, and 2-amino-6-hydroxybenzothiazole. Three steps are required to prepare the high molecular liquid crystal polyarylate amide, which has the disadvantages of many preparation steps and complex raw material types.

[0005] CN115850638A discloses a biodegradable polyurethane elastomer and a preparation method thereof and an elastomer sponge with a porous structure. The required raw materials are complex and the intrinsic viscosity loss of the product in the degradability test is 34%.

[0006] It can be seen that the preparation process of polyester amide has the problems of complicated synthesis route, complex raw materials, harsh reaction conditions, and low degradability of the obtained product. Therefore, it is urgent to provide a method for preparing polyester amide material with simple preparation process, mild reaction conditions, low energy consumption, high mechanical properties and biodegradability of polyester amide material. Summary of the invention

[0007] The purpose of the present invention is to overcome the problems of the prior art in that the polyester amide preparation process is complicated, the raw materials are complex, the reaction conditions are harsh, the polyester amide material has low biodegradability and poor mechanical properties, and to provide a polyester amide material and a preparation method and application thereof. The method has a simple preparation process, mild reaction conditions, and the obtained polyester amide material has good mechanical properties and high biodegradability.

[0008] In order to achieve the above object, the first aspect of the present invention provides a method for preparing a polyester amide material, the method comprising: in the presence of a catalyst, polymerizing polycaprolactone and hexamethylenediamine adipate to obtain a polyester amide material;

[0009] Wherein, the catalyst comprises 6-amino-1-hexanoic acid and tetrabutyl titanate;

[0010] Wherein, the weight average molecular weight of the polycaprolactone is 500g / moL-10000g / moL.

[0011] The second aspect of the present invention provides a polyester amide material prepared by the method described in the first aspect.

[0012] The third aspect of the present invention provides application of the polyester amide material described in the second aspect in degradable plastics.

[0013] Through the above technical solution, the present invention achieves the following beneficial effects:

[0014] The present invention selects specific types of polycaprolactone and 66 salt as raw materials, uses a mixture of 6-amino-1-hexanoic acid and tetrabutyl titanate as a catalyst, adopts a one-pot method, reacts under normal pressure, and prepares a polyester amide material. The method uses simple raw materials, a simple preparation process, a reaction temperature below 300°C, and low energy consumption. The obtained polyester amide material has good mechanical properties, a tensile strength of more than 18MPa, an elongation at break of more than 19%, and also obtains better biodegradability, and the mass can be reduced by 50% within 1 month. DETAILED DESCRIPTION

[0015] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0016] In the present invention, under the action of a catalyst, 66 salt is first polymerized to form polyhexamethylene adipamide (PA66), and polycaprolactone and PA66 undergo copolymerization to form polyester amide. The above reaction steps are as follows:

[0017]

[0018] The first aspect of the present invention provides a method for preparing a polyester amide material, wherein the method comprises: in the presence of a catalyst, polymerizing polycaprolactone and hexamethylenediamine adipate to obtain a polyester amide material;

[0019] Wherein, the catalyst comprises 6-amino-1-hexanoic acid and tetrabutyl titanate;

[0020] The weight average molecular weight of the polycaprolactone is 500 g / mol-10000 g / mol, for example, 500 g / mol, 2000 g / mol, or 10000 g / mol.

[0021] In the present invention, when the weight average molecular weight of the polycaprolactone is too high, the end groups of the polycaprolactone will be reduced under the same feed mass, thereby reducing the reactivity of the polycaprolactone and making it difficult to obtain the target product polyesteramide; when the weight average molecular weight of the polycaprolactone meets the above range, the reactivity of the polycaprolactone is higher, and it is easier to obtain a polyesteramide material with good thermal stability.

[0022] Preferably, the weight average molecular weight of the polycaprolactone is 1000 g / mol-5000 g / mol.

[0023] In the present invention, there is no particular limitation on the source of polycaprolactone, which can be purchased from the market or prepared by itself, for example, it can be purchased from Maclean Company, model P917306.

[0024] According to some embodiments of the present invention, the polycaprolactone is a homopolymer of caprolactone.

[0025] According to some embodiments of the present invention, the mass ratio of hexamethylenediamine adipate to polycaprolactone is 0.25-2.3:1.

[0026] In the present invention, when polycaprolactone and hexamethylenediamine adipate meet the above conditions, effective copolymerization of the two raw materials can be achieved.

[0027] According to some embodiments of the present invention, the amount of the catalyst is 0.5 wt%-1.5 wt% based on the mass of the polycaprolactone.

[0028] According to some embodiments of the present invention, the mass ratio of 6-amino-1-hexanoic acid to tetrabutyl titanate is 0.5-2:1.

[0029] In the present invention, when the catalyst meets the above conditions, it can catalyze the copolymerization of 66 salt and polycaprolactone under normal pressure.

[0030] According to some embodiments of the present invention, the polymerization reaction temperature is 190-250° C., and the reaction time is 3-8 h.

[0031] In the present invention, the effect of catalyzing the copolymerization of 66 salt and polycaprolactone under normal pressure can be achieved by introducing a suitable catalyst.

[0032] According to some embodiments of the present invention, the preparation method further comprises a drying process. Preferably, the drying process comprises: a temperature of 45-55° C. and a time of 5-12 hours.

[0033] The second aspect of the present invention provides a polyester amide material prepared by the method described in the first aspect.

[0034] The third aspect of the present invention provides application of the polyester amide material described in the second aspect in degradable plastics.

[0035] According to a particularly preferred embodiment of the present invention, the method for preparing the polyester amide material is as follows:

[0036] A certain amount of polycaprolactone (weight average molecular weight is 2000g / mol), the mass ratio of hexamethylenediamine adipate to polycaprolactone is 0.25-2.3:1, the amount of catalyst is 0.5wt%-1.5wt% (the mass ratio of 6-amino-1-hexanoic acid to tetrabutyl titanate in the catalyst is 0.5-2:1), react at 190-250°C for 3-8h, and then dry at 45-55°C for 5-12h to prepare a polyester amide material.

[0037] The present invention will be described in detail below through examples.

[0038] In the following examples, the weight average molecular weight of polycaprolactone is determined according to GB / T 27843-2011 Determination of low molecular weight component content of chemical polymers by gel permeation chromatography (GPC).

[0039] The raw materials in this example are all commercially available products.

[0040] Example 1

[0041] This example is used to illustrate the preparation of polyester amide material using the method of the present invention.

[0042] Weigh 7 g of polycaprolactone (weight average molecular weight of 500 g / mol), the mass ratio of hexamethylenediamine adipate to polycaprolactone is 1:1, add 0.07 g of a mixture of 6-amino-1-hexanoic acid and tetrabutyl titanate (the mass ratio of 6-amino-1-hexanoic acid to tetrabutyl titanate is 1:1), react at 190°C for 8 h, and then dry at 55°C for 12 h to prepare polyester amide material A1.

[0043] Example 2

[0044] This example is used to illustrate the preparation of polyester amide material using the method of the present invention.

[0045] Weigh 7 g of polycaprolactone (weight average molecular weight is 2000 g / mol), the mass ratio of hexamethylenediamine adipate to polycaprolactone is 1:1, add 0.07 g of a mixture of 6-amino-1-hexanoic acid and tetrabutyl titanate (the mass ratio of 6-amino-1-hexanoic acid to tetrabutyl titanate is 0.5:1), react at 250°C for 3h, and then dry at 45°C for 12h to prepare polyesteramide material A2.

[0046] Example 3

[0047] This example is used to illustrate the preparation of polyester amide material using the method of the present invention.

[0048] Weigh 7 g of polycaprolactone (weight average molecular weight is 10000 g / mol), the mass ratio of hexamethylenediamine adipate to polycaprolactone is 2:1, add 0.07 g of a mixture of 6-amino-1-hexanoic acid and tetrabutyl titanate (the mass ratio of 6-amino-1-hexanoic acid to tetrabutyl titanate is 2:1), react at 230°C for 5h, and then dry at 50°C for 12h to prepare polyesteramide material A3.

[0049] Example 4

[0050] This example is used to illustrate the preparation of polyester amide material using the method of the present invention.

[0051] Polyester amide material A4 was prepared according to the method of Example 1, except that the reaction temperature was 200°C.

[0052] Example 5

[0053] This example is used to illustrate the preparation of polyester amide material using the method of the present invention.

[0054] Polyester amide material A5 was prepared according to the method of Example 1, except that the reaction temperature was 210°C.

[0055] Example 6

[0056] This example is used to illustrate the preparation of polyester amide material using the method of the present invention.

[0057] Polyester amide material A6 was prepared according to the method of Example 1, except that the reaction temperature was 220°C.

[0058] Example 7

[0059] This example is used to illustrate the preparation of polyester amide material using the method of the present invention.

[0060] Polyester amide material A7 was prepared according to the method of Example 1, except that the reaction temperature was 230°C.

[0061] Example 8

[0062] This example is used to illustrate the preparation of polyester amide material using the method of the present invention.

[0063] Polyester amide material A8 was prepared according to the method of Example 1, except that the reaction temperature was 240°C.

[0064] Example 9

[0065] This example is used to illustrate the preparation of polyester amide material using the method of the present invention.

[0066] Polyester amide material A9 was prepared according to the method of Example 1, except that the reaction temperature was 250°C.

[0067] Example 10

[0068] This example is used to illustrate the preparation of polyester amide material using the method of the present invention.

[0069] Polyester amide material A10 was prepared according to the method of Example 1, except that the drying temperature was 50°C.

[0070] Embodiment 11

[0071] This example is used to illustrate the preparation of polyester amide material using the method of the present invention.

[0072] Polyester amide material A11 was prepared according to the method of Example 1 except that the drying temperature was 55°C.

[0073] Comparative Example 1

[0074] The polyester amide material B1 was prepared according to the method of Example 1, except that polycaprolactone was replaced by caprolactone, the reaction was carried out at 230° C. for 4 h, and then dried at 45° C. for 12 h.

[0075] Comparative Example 2

[0076] The polyester amide material B2 was prepared according to the method of Example 1, except that the weight average molecular weight of the polycaprolactone was 40000 g / mol.

[0077] Comparative Example 3

[0078] Polyester amide material B3 was prepared according to the method of Example 1, except that the mass ratio of hexamethylenediamine adipate to polycaprolactone was 9:1.

[0079] Comparative Example 4

[0080] Polyester amide material B4 was prepared according to the method of Example 1, except that the mass ratio of 6-amino-1-hexanoic acid to tetrabutyl titanate was 5:1.

[0081] Comparative Example 5

[0082] Polyester amide material B5 was prepared according to the method of Example 1, except that the amount of 6-amino-1-hexanoic acid and tetrabutyl titanate used was 0.01 g.

[0083] Comparative Example 6

[0084] Polyesteramide material B6 was prepared according to the method of Example 1, except that the catalyst was antimony trioxide.

[0085] Test Case

[0086] The polyester amide materials A1-A11 and B1-B6 prepared in the above Examples 1-11 and Comparative Examples 1-6 were tested for mechanical properties and biodegradability, respectively. The specific results are shown in Table 1.

[0087] The mechanical properties were characterized by cold pressing film forming, and the instrument model was Shimadzu AGS-X.

[0088] The specific method for testing biodegradability is as follows: weigh a certain weight of polyester amide material, the mass is recorded as M0. Place it in a 1 mol / L NaOH aqueous solution at 25°C for immersion, take it out and weigh it after 30 days, the mass is recorded as M 30 ; According to M0 and M 30 The degradation rate of polyester amide material is calculated based on the data, recorded as △M. The specific results are shown in Table 1.

[0089] Degradation rate of polyester amide material (△M) = 100%*(M 30 -M0) / M0.

[0090] Table 1

[0091] Polyester amide material <![CDATA[M0 / g]]> <![CDATA[M 30 / g]]> △M / ％ Tensile strength / MPa Elongation at break / % A1 3.2 1.2 -62.50 19 20 A2 3.6 1.3 -63.89 18 19 A3 3.3 1.2 -63.64 20 21 A4 4.5 1.8 -60.00 22 25 A5 3.3 1.4 -57.58 25 23 A6 3.5 1.5 -57.14 24 22 A7 4.1 1.8 -56.10 23 24 A8 5.6 2.5 -55.36 24 25 A9 4.6 2.1 -54.35 23 23 A10 3.6 1.7 -52.78 21 25 A11 3.9 1.9 -51.28 23 22 B1 3.2 2.9 -9.38 13 12 B2 4.5 4.2 -6.67 15 13 B3 4.2 3.2 -23.81 17 12 B4 3.7 2.8 -24.32 14 9 B5 4.4 3.6 -18.18 15 11 B6 2.9 2.3 -26.10 12 7

[0092] It can be seen from the data of Examples 1-11 and Comparative Examples 1-6 that a polyester amide material can be prepared under normal pressure by using the specific types of polycaprolactone and 66 salt of the present invention as raw materials and a mixture of 6-amino-1-hexanoic acid and tetrabutyl titanate as a catalyst. The obtained polyester amide material has high tensile strength and elongation at break, and is highly biodegradable, with the mass being reduced by more than 50% within one month. In Comparative Example 1, polycaprolactone is replaced with caprolactone, and the tensile strength and elongation at break of the prepared polyester amide material are significantly reduced, and the biodegradability is also poor, with the mass being reduced by only 9.38% within one month.

[0093] In Comparative Example 2, polycaprolactone with a high weight-average molecular weight was selected as the raw material, and the tensile strength and elongation at break of the prepared polyester amide material decreased, and the biodegradability was low, with the mass decreasing by only 6.67% within 1 month.

[0094] In Comparative Example 3, the dosage of hexamethylenediamine adipate was too much, and the tensile strength and elongation at break of the prepared polyester amide material decreased, and the biodegradability was low, with the mass decreasing by 23.81% within 1 month.

[0095] In Comparative Example 4, the proportion of 6-amino-1-hexanoic acid in the catalyst mixture is relatively large, and the tensile strength and elongation at break of the prepared polyester amide material decrease, the biodegradability is low, and the mass decreases by 24.32% within 1 month.

[0096] In Comparative Example 5, the amount of catalyst used was relatively small, and the tensile strength and elongation at break of the prepared polyester amide material decreased, and the biodegradability was low, with the mass decreasing by 18.18% within 1 month.

[0097] In Comparative Example 6, the catalyst was replaced with antimony trioxide, and the tensile strength and elongation at break of the prepared polyester amide material decreased, and the biodegradability was low, with the mass reduced by 26.10% within 1 month.

[0098] In summary, it can be seen from the results in Table 1 that by using the specific types of polycaprolactone and 66 salt of the present invention as raw materials and selecting a specific type of catalyst, a polyesteramide material can be prepared under normal pressure, and the obtained polyesteramide material has higher tensile strength and elongation at break, and also has higher biodegradability.

[0099] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations, such as changing the type of 66 salt and the catalyst, temperature / time of the reaction, different reaction modes, such as intermittent and continuous, etc. Any modification, equivalent substitution, improvement, etc. (such as the use of polycaprolactone derivatives, etc.) made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a polyester amide material, characterized in that: The method comprises: in the presence of a catalyst, polymerizing polycaprolactone and hexamethylenediamine adipate to obtain a polyester amide material; Wherein, the catalyst comprises 6-amino-1-hexanoic acid and tetrabutyl titanate; Wherein, the weight average molecular weight of the polycaprolactone is 500 g / mol-10000 g / mol.

2. The method according to claim 1, wherein: The weight average molecular weight of the polycaprolactone is 1000 g / mol-5000 g / mol.

3. The method according to claim 1, wherein: The polycaprolactone is a homopolymer of caprolactone.

4. The method according to any one of claims 1 to 3, wherein: The mass ratio of hexamethylenediamine adipate to the polycaprolactone is 0.25-2.3:

1.

5. The method according to any one of claims 1 to 4, wherein: Based on the mass of the polycaprolactone, the amount of the catalyst is 0.5wt%-1.5wt%.

6. The method according to any one of claims 1 to 5, wherein: The mass ratio of 6-amino-1-hexanoic acid to tetrabutyl titanate is 0.5-2:

1.

7. The method according to any one of claims 1 to 6, wherein: The polymerization reaction temperature is 190-250° C., and the reaction time is 3-8 hours.

8. The method according to any one of claims 1 to 7, wherein: The preparation method further comprises a drying process; Preferably, the drying treatment conditions include: temperature of 45-55° C. and time of 5-12 h.

9. A polyester amide material prepared by the method according to any one of claims 1 to 8; Preferably, the polyester amide material has a tensile strength of 18 MPa-25 MPa, an elongation at break of 19%-25%, and a biodegradability of 51.28%-63.89%.

10. Use of the polyester amide material according to claim 9 in degradable plastics.

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