A polymer material with good water retention and preparation method thereof

Abstract

The invention discloses a polymer material with good water retention, and the raw materials for preparation include, by weight, 10-30 parts of a first component, 15-25 parts of a second component, 1.25-8.25 parts of a third component, 1-5 parts of a catalyst, 0.05-3 parts of a heat stabilizer, and 1-3 parts of a tackifier. The polymer material with good water retention of the invention has good biodegradability, and can be applied to agricultural film to achieve the degradation of the film under specific environmental humidity and illumination after a certain service life, without causing white pollution to the environment, and can greatly improve the degradable tensile strength through the type and usage of the preferred raw material alkoxy branched alcohol, so that it has good mechanical strength.

Description

Technical Field

[0001] The invention relates to a polymer material with good water retention and a preparation method thereof, and mainly relates to the field of polymer compound compositions. Background Art

[0002] The production of polyester products has brought great convenience to human life, but it is accompanied by the environmental problem of white pollution. How to prepare polyester products with good degradation effect is the goal that scientists are constantly pursuing. PBAT material is a type of material with good degradation effect. In the process of producing PBAT materials, the selection of raw materials will affect the tensile strength and thermal stability of PBAT. Patent CN201910763669.9 selects glycerol, ethylene glycol, and sorbitol as plasticizers. In the process of preparing PBAT, due to their low boiling points, they are easily extracted during the decompression process and cannot achieve the full effect. Patent CN202110054292.7 enhances the branching degree of polyester materials by adding polyethers, but a large amount of polyethers is required to achieve a better branching effect, and it will also cause the thermal stability of polyester to decrease. Summary of the invention

[0003] In order to improve the thermal stability of polyester film and obtain a product with good mechanical properties, the first aspect of the present invention provides a polymer material with good water retention. The raw materials for preparation include, by weight, 10-30 parts of a first component, 15-25 parts of a second component, 1.25-8.25 parts of a third component, 1-5 parts of a catalyst, 0.05-3 parts of a heat stabilizer, and 1-3 parts of a tackifier.

[0004] As a preferred embodiment, the first component is selected from one or a combination of C2-C13 alkyl dicarboxylic acid and cycloalkyl dicarboxylic acid.

[0005] As a preferred embodiment, the cycloalkyl dibasic acid includes an aliphatic dibasic acid and an aromatic dibasic acid.

[0006] As a preferred embodiment, the molar ratio of the aliphatic dibasic acid to the aromatic dibasic acid is 1:(1.01-1.5).

[0007] As a preferred embodiment, the aromatic dibasic acid is selected from one or a combination of terephthalic acid, isophthalic acid, and phthalic acid.

[0008] As a preferred embodiment, the aliphatic dibasic acid is selected from one or a combination of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and malic acid.

[0009] As a preferred embodiment, the second component is selected from one or a combination of C2-C13 alkyl diols and cycloalkyl diols.

[0010] As a preferred embodiment, the second component is selected from neopentyl glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, dimer diol, hydroxy neopentyl glycol ester, dipropylene glycol, 1,4-butanediol, or a combination of several thereof.

[0011] As a preferred embodiment, the third component is selected from one or a combination of C1-C9 alkoxy branched alcohols.

[0012] As a preferred embodiment, the C1-C18 alkoxy branched alcohol is selected from one or a combination of ethoxylated glycerol, propoxylated glycerol, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, and stearic acid glycerol.

[0013] As a preferred embodiment, the number of alkoxylated units in the alkoxy branched alcohol is ≤9.

[0014] As a preferred embodiment, the mass fraction of the alkoxylated branched alcohol in the total preparation raw materials is 0.05-0.15%.

[0015] The applicant found in the experiment that the use of alkoxylated branched alcohols can improve the tensile strength of biodegradable copolyesters and have good thermal stability. The possible reasons are speculated to be: the introduction of alkoxylated branched alcohols can increase the degree of branching on the main chain of degradable polyester, increase the branching degree of degradable polyester, and form a stable cross-linked network inside the degradable polyester, thereby improving the tensile strength of the degradable polyester, and the introduction of alkoxylated branched alcohols with an alkoxylated unit number of ≤9 can increase the boiling point of the alkoxylated branched alcohols, avoid the alkoxylated branched alcohols from being extracted during the later vacuuming process, and allow the alkoxylated branched alcohols to be introduced into the branches of the degradable polyester as much as possible. The addition of alkoxylated branched alcohols with a mass fraction of 0.05-0.15% can improve the tensile strength of the degradable polyester without causing a decrease in the thermal stability of the degradable polyester.

[0016] As a preferred embodiment, the catalyst is selected from one or a combination of tetraisopropyl titanate, tetrabutyl titanate, zirconium alkoxide, tin alkoxide, and acetate compounds.

[0017] As a preferred embodiment, the heat stabilizer is selected from one or a combination of phosphate ester, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate.

[0018] As a preferred embodiment, the tackifier is selected from one or a combination of petroleum resin, rosin resin, terpene resin, and isocyanate.

[0019] As a preferred embodiment, the tackifier is a combination of terpene resin and isocyanate.

[0020] As a preferred embodiment, the weight ratio of the terpene resin to the isocyanate is 1:(1-2).

[0021] During the experiment, the applicant found that when the tackifier is a combination of terpene resin and isocyanate with a weight ratio of 1:(1-2), the tensile properties can be further improved. The terpene resin and isocyanate can increase the branching degree of the degradable ester chain, promote the formation of a more stable cross-linked network, and further improve the mechanical strength.

[0022] The second aspect of the present invention provides a method for preparing a polymer material with good water retention, characterized in that it comprises the following steps:

[0023] (1) Add the first component, the second component, the third component and the catalyst into a reaction kettle in sequence, introduce argon, raise the temperature to 190-240°C, and react for 2-4 hours;

[0024] (2) Continue to raise the temperature to 250-260°C, reduce the pressure to 3-5 kPa, and react for 1-2 hours;

[0025] (3) Add catalyst and heat stabilizer, continue to reduce pressure to 0.05-0.2 kPa, and react for 1.5-3 hours;

[0026] (4) adding a tackifier, mixing and stirring, transferring the obtained mixed product to an extruder, and extruding a film to obtain a film.

[0027] As a preferred embodiment, the weight ratio of the catalyst added in step 1 to step 3 is 1:(0.1-1).

[0028] More preferably, the weight ratio of the catalyst added in step 1 to step 3 is 1:(0.3-0.5).

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] (1) The polymer material with good water retention properties of the present invention has good biodegradability. After a certain service life is completed, the film can be degraded under specific environmental humidity and light without causing white pollution to the environment. The polymer material is particularly suitable for use in agricultural film production. It has strong hydrophobicity and good water retention effect on plants, which is beneficial to the growth of young plants.

[0031] (2) The polymer material with good water retention of the present invention can significantly improve the degradable tensile strength by optimizing the type and amount of the raw material alkoxy branched alcohol used in the preparation, so that it has good mechanical strength.

[0032] (3) The polymer material with good water retention properties of the present invention has good transparency and maintains sufficient thermal stability by optimizing the types and amounts of catalysts, thermal stabilizers and tackifiers used. DETAILED DESCRIPTION

[0033] The present invention is described in detail below by way of examples. It is necessary to point out here that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by professionals and technicians in this field based on the content of the present invention above still belong to the scope of protection of the present invention.

[0034] In addition, unless otherwise stated, all raw materials used were commercially available.

[0035] Example 1

[0036] A polymer material with good water retention performance. The raw materials for preparing the material include, by weight, 20 parts of a first component, 20 parts of a second component, 3.55 parts of a third component, 3 parts of a catalyst, 1.55 parts of a heat stabilizer, and 2 parts of a tackifier.

[0037] The first component is a combination of adipic acid and terephthalic acid in a weight ratio of 1:1.2.

[0038] The second component is 1,4-butanediol.

[0039] The third component is glyceryl stearate, purchased from Hubei Xinkang Pharmaceutical Chemical Co., Ltd.

[0040] The catalyst is tetraisopropyl titanate.

[0041] The heat stabilizer is butyl phosphate.

[0042] The tackifier is terpene resin and isocyanate, with a weight ratio of 1:1. The terpene resin is purchased from Shenzhen Yoshida Chemical Co., Ltd., model BT28D, and the isocyanate is purchased from Yantai Wanhua, model PM-200.

[0043] A method for preparing a polymer material with good water retention:

[0044] (1) The first component, the second component, the third component and the catalyst were added to the reaction kettle in sequence, argon was introduced, the temperature was raised to 210°C, and the reaction was carried out for 3 hours;

[0045] (2) Continue to raise the temperature to 255°C, reduce the pressure to 4 kPa, and react for 1.5 hours;

[0046] (3) Add catalyst and heat stabilizer, continue to reduce pressure to 0.15 kPa, and react for 2 h;

[0047] (4) adding a tackifier, mixing and stirring, transferring the obtained mixed product to an extruder, and extruding a film to obtain a film.

[0048] The weight ratio of the catalyst added in step 1 to step 3 is 1:0.4.

[0049] Example 2

[0050] A polymer material with good water retention performance. The raw materials for preparing the material include, by weight, 15 parts of a first component, 15 parts of a second component, 2.25 parts of a third component, 2 parts of a catalyst, 1 part of a heat stabilizer, and 1.25 parts of a tackifier.

[0051] The first component is a combination of adipic acid and terephthalic acid in a weight ratio of 1:1.12.

[0052] The second component is 1,4-butanediol and neopentyl glycol, with a weight ratio of 9:1.

[0053] The third component is propoxylated glycerol, which is purchased from Nantong Chenrun Chemical Co., Ltd.

[0054] The catalyst is tetraisopropyl titanate.

[0055] The heat stabilizer is butyl phosphate.

[0056] The tackifier is terpene resin and isocyanate, with a weight ratio of 1:1.5. The terpene resin is purchased from Shenzhen Yoshida Chemical Co., Ltd., model BT28D, and the isocyanate is purchased from Yantai Wanhua, model PM-200.

[0057] A method for preparing a polymer material with good water retention:

[0058] (1) The first component, the second component, the third component and the catalyst were added to the reaction kettle in sequence, argon was introduced, the temperature was raised to 200°C, and the reaction was carried out for 3.5 hours;

[0059] (2) Continue to raise the temperature to 250°C, reduce the pressure to 5 kPa, and react for 2 h;

[0060] (3) Add catalyst and heat stabilizer, continue to reduce pressure to 0.1 kPa, and react for 3 hours;

[0061] (4) adding a tackifier, mixing and stirring, transferring the obtained mixed product to an extruder, and extruding a film to obtain a film.

[0062] Example 3

[0063] A polymer material with good water retention and a preparation method thereof, wherein the specific steps are the same as those of Example 1, except that the third component is decoxylated trimethylolpropane.

[0064] Example 4

[0065] A polymer material with good water retention and a preparation method thereof, wherein the specific steps are the same as those of Example 1, except that the third component is glycerol.

[0066] Example 5

[0067] A polymer material with good water retention and a preparation method thereof, wherein the specific steps are the same as those of Example 1, except that the mass fraction of the alkoxylated branched alcohol in the total preparation raw materials is 0.03%.

[0068] Performance Testing

[0069] 1. Tensile strength: The tensile strength of the prepared film was tested according to GB 13022-1991 standard.

[0070] 2. Elongation at break: The elongation at break of the prepared film was tested according to GB 13022-1991 standard.

[0071] 3. Hydrophobicity test: The hydrophobicity of the prepared film was tested according to GB / T 20000.2-2009 standard, and the contact angle between the film surface and water was tested.

[0072] Examples 1-5 were tested according to the above standards, and the results are shown in Table 1.

[0073] Table 1

[0074]

[0075]

Claims

1. A polymer material with good water retention, characterized in that: The raw materials for preparation include, by weight, 10-30 parts of the first component, 15-25 parts of the second component, 1.25-8.25 parts of the third component, 1-5 parts of the catalyst, 0.05-3 parts of the heat stabilizer, and 1-3 parts of the tackifier; The first component is a combination of adipic acid and terephthalic acid in a weight ratio of 1:(1.01-1.5); The second component is 1,4-butanediol, The third component is glycerol stearate, and the catalyst is tetraisopropyl titanate. The heat stabilizer is butyl phosphate, The tackifier is terpene resin and isocyanate, and the weight ratio is 1:(1-2).

2. A method for preparing a polymer material with good water retention according to claim 1, characterized in that: The following steps are involved: (1) Add the first component, the second component, the third component and the catalyst into a reaction kettle in sequence, introduce argon, raise the temperature to 190-240°C, and react for 2-4 hours; (2) Continue to raise the temperature to 250-260°C, reduce the pressure to 3-5 kPa, and react for 1-2 hours; (3) Add catalyst and heat stabilizer, continue to reduce pressure to 0.05-0.2 kPa, and react for 1.5-3 hours; (4) adding a tackifier, mixing and stirring, transferring the obtained mixed product to an extruder, and extruding a film to obtain a film.

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