GMA-acrylate auxiliary agent and application thereof in PLA / PBAT master batch

Abstract

The invention discloses a GMA-acrylate auxiliary agent and application thereof in a PLA / PBAT master batch. The auxiliary agent is prepared from the following components by high temperature and high pressure: 62-77% of soft water, 9-13% of a hard monomer, 7-11% of a soft monomer, 3-7% of a functional monomer, 1.3-3% of an emulsifier, 0.3-0.7% of an initiator, 2-7% of a modifier and 0.2-0.8% of an antifoaming agent. The GMA-acrylate auxiliary agent is mixed with the PLA and the PBAT, so that the compatibility of the prepared full-degradable blending master batch can be improved, and the melt index is greatly reduced.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, and particularly relates to a GMA-acrylate additive and application thereof in a PLA / PBAT masterbatch. Background Art

[0002] With the strengthening of the national plastic ban, the application and development of polylactic acid (PLA) / polybutylene adipate-terephthalate (PBAT) blends have received more and more attention. Bio-based material PLA is a polyester that is fully biodegradable and thermoplastic. PLA has the dual advantages of resources and environment. PLA has broad development prospects in the fields of biomedicine, building materials, and daily packaging due to its good biocompatibility and high transparency. However, PLA still has some defects, such as high brittleness, poor heat resistance, and long crystallization cycle, which greatly limits the application of PLA in daily life, automobiles, construction, electronic appliances and other fields. PBAT, as a new type of petroleum-based degradable copolyester, contains both flexible fatty chain segments and rigid benzene ring structures, has excellent mechanical properties and good thermal stability, and can be widely used in packaging, medical and agricultural mulch films and other fields. PLA / PBAT blends combine the advantages of both PLA and PBAT, achieve complementary performance, and have broad application prospects. However, PLA / PBAT blends have a two-phase structure and poor compatibility with each other, which affects the performance of the blend system. Conventional additives improve the compatibility of the blend system by physical means, forming hydrogen bonds and van der Waals forces at the phase interface, but the compatibilization effect is relatively poor, so it is necessary to improve it. Summary of the invention

[0003] In order to solve the above problems, the present invention aims to provide a processing aid for regulating the compatibility of PLA and PBAT. Its innovation lies in that the addition of a reactive compatibilizer is not only simple to operate, but also can improve the compatibility of the blending system, so it has high practical value and strong operability. The molecular structure of glycidyl methacrylate (GMA) contains active unsaturated double bonds that are easy to copolymerize, and epoxy groups that are easy to undergo ring-opening addition reactions with functional groups such as hydroxyl and carboxyl groups, thereby forming functionalized polymers. GMA monomers are relatively easy to prepare, and have the characteristics of high boiling point, low toxicity, weak volatility, and low corrosion to equipment. Therefore, GMA can be used as a functional monomer to graft and modify polyolefins, and can react with acrylates to prepare functionalized polymers, and as a compatibilizer to improve the compatibility of polymer blending systems. By grafting GMA with acrylates, the system produces more multifunctional polymers, and the compatibilization efficiency is regulated.

[0004] The invention provides a GMA-acrylate auxiliary agent, which is prepared from the following components through high temperature and high pressure: 62-77% of soft water, 9-13% of hard monomer, 7-11% of soft monomer, 3-7% of functional monomer, 1.3-3% of emulsifier, 0.3-0.7% of initiator, 2-7% of modifier and 0.2-0.8% of defoamer.

[0005] The hard monomer is one or any combination of ethyl methacrylate, methyl methacrylate and acrylonitrile;

[0006] The soft monomer is one or a combination of butyl acrylate and lauryl methacrylate;

[0007] The functional monomer is GMA;

[0008] The emulsifier is one or a combination of sodium acrylamide isopropyl sulfonate and sodium vinyl sulfonate;

[0009] The initiator is sodium persulfate;

[0010] The modifier is ammonia water;

[0011] The defoamer is an organosilicon defoamer.

[0012] The present invention also provides a method for preparing a GMA-acrylate auxiliary agent, the steps of which are as follows:

[0013] (1) Preparation of mixed monomers: 9-13% hard monomer, 7-11% soft monomer, and 3-7% GMA are stirred evenly at room temperature and set aside.

[0014] (2) Preparation of emulsifier solution: 15% of soft water and 1.3-3% of emulsifier are stirred evenly at room temperature and set aside.

[0015] (3) Preparation of initiator solution: 20% of the total soft water and 0.3-0.7% of the initiator are stirred evenly at room temperature and set aside.

[0016] (4) Add the remaining soft water, 20% of the mixed monomer, 5% of the emulsifier solution, and 2% of the initiator solution into the reactor, seal it, evacuate it to -(0.01-0.06)MPa, stir it at a speed of 100-130r / min, and keep it at 90°C for 1 hour; then continuously add the remaining mixed monomer, emulsifier solution, and initiator solution through a metering pump, and control the addition time to 2 hours; after the addition is completed, keep it at 80°C for 2 hours.

[0017] (5) Add 2-7% of a modifier and 0.2-0.8% of a defoamer, stir thoroughly for 1 hour, let stand and cool, and then dry at 110° C. to obtain the GMA-acrylate additive of the present invention.

[0018] The present invention also provides a fully degradable blended masterbatch, including a PLA / PBAT masterbatch and a GMA-acrylate additive; in the PLA / PBAT masterbatch, PLA accounts for 65-80%, and PBAT accounts for 20-35%; in the fully degradable blended masterbatch, the GMA-acrylate additive is added in an amount of 3%, 5%, 7%, and 9% of the total mass ratio of the blended masterbatch. The fully degradable blended masterbatch is prepared by mixing PLA, PBAT, and GMA-acrylate additives at 185°C and kneading for 15 minutes.

[0019] The beneficial effects of the present invention are:

[0020] The present invention prepares a GMA-acrylate auxiliary agent, and adds the auxiliary agent to PLA and PBAT as a reactive compatibilizer. During the blending process, a multifunctional polymer is formed in situ, and the functional groups on the molecular chain react with the terminal functional groups of PLA or PBAT, so that the physical adhesion between the two phases of PLA and PBAT is converted into chemical adhesion, thereby improving the compatibility of the PLA / PBAT blending system and greatly reducing the melt index. As a small molecule compatibilizer, GMA-acrylate is not only easy to disperse in PLA and PBAT, but also easier to regulate material properties and realize industrial production, which is of great significance to the application of biodegradable materials in medical materials, packaging materials, etc. In addition, the raw material formula of the GMA-acrylate auxiliary agent of the present invention is relatively simple, and it is easy to operate and process. DETAILED DESCRIPTION

[0021] In order to better understand the technical content of the present invention, specific embodiments are provided below to further illustrate the present invention.

[0022] Example 1

[0023] A GMA-acrylate additive is prepared by high temperature and high pressure from the following components: 62-77% soft water, 9-13% hard monomer, 7-11% soft monomer, 3-7% functional monomer, 1.3-3% emulsifier, 0.3-0.7% initiator, 2-7% modifier, 0.2-0.8% defoamer. The hard monomer is one or any combination of ethyl methacrylate, methyl methacrylate, and acrylonitrile; the soft monomer is one or a combination of butyl acrylate and lauryl methacrylate; the functional monomer is GMA; the emulsifier is one or a combination of sodium acrylamide isopropyl sulfonate and sodium vinyl acid sulfonate; the initiator is sodium persulfate; the modifier is ammonia water; and the defoamer is an organosilicon defoamer.

[0024] In this embodiment, the formula ratio shown in Table 1 is used when preparing the GMA-acrylate auxiliary agent; in Formula 1, the hard monomer is ethyl methacrylate, the soft monomer is lauryl methacrylate, and the emulsifier is a mixture of sodium acrylamide isopropyl sulfonate and sodium vinyl acid sulfonate; in Formula 2, the hard monomer is a mixture of methyl methacrylate and acrylonitrile, the soft monomer is butyl acrylate, and the emulsifier is sodium acrylamide isopropyl sulfonate.

[0025] The preparation steps of GMA-acrylate additive are as follows:

[0026] (1) Preparation of mixed monomers: Stir hard monomer, soft monomer and GMA evenly at room temperature and set aside.

[0027] (2) Preparation of emulsifier solution: Soft water accounting for 15% of the total amount and emulsifier are stirred evenly at room temperature and set aside.

[0028] (3) Preparation of initiator solution: Soft water accounting for 20% of the total amount and the initiator are stirred evenly at room temperature and set aside.

[0029] (4) Add the remaining soft water, 20% of the mixed monomer, 5% of the emulsifier solution, and 2% of the initiator solution into the reactor, seal it, evacuate it to -(0.01-0.06)MPa, stir it at a speed of 100-130r / min, and keep it at 90°C for 1 hour; then continuously add the remaining mixed monomer, emulsifier solution, and initiator solution through a metering pump, and control the addition time to 2 hours; after the addition is completed, keep it at 80°C for 2 hours.

[0030] (5) Adding a modifier and a defoamer, stirring thoroughly for 1 hour, standing to cool, and then drying at 110° C. to obtain the GMA-acrylate auxiliary agent of the present invention.

[0031] Table 1 Preparation formula of GMA-acrylate additive

[0032]

[0033] Example 2

[0034] A fully degradable blended masterbatch, including a PLA / PBAT masterbatch and a GMA-acrylate additive. In the PLA / PBAT masterbatch, PLA accounts for 65-80% and PBAT accounts for 20-35%. In this embodiment, 70% PLA and 30% PBAT are mixed, and GMA-acrylate additives prepared according to Formula 1 and Formula 2 of Example 1 are added respectively, and a fully degradable blended masterbatch is prepared at 185°C and kneaded for 15 minutes. The addition ratio of the GMA-acrylate additive accounts for 3%, 5%, 7%, and 9% of the total mass ratio of the blended masterbatch.

[0035] The melt index tests were carried out on PLA, PBAT, PLA / PBAT masterbatch and fully degradable blended masterbatch respectively. The test conditions were 190°C and 2.16 kg. The results are shown in Table 2.

[0036] Table 2 Melt index results

[0037]

[0038] Comparative Example 1

[0039] The amount of the functional monomer in the second formulation of Example 1 was increased to 9%, and the other raw materials and preparation method remained unchanged. The prepared additive was stratified during the cooling stage and could not be used.

[0040] Comparative Example 2

[0041] The GMA-acrylate additive in Example 2 was replaced with commercially available ECO-100 (Kaneka High Performance Materials Co., Ltd.), and the addition ratio accounted for 3%, 5%, and 7% of the total mass ratio of the blended masterbatch. The other raw materials and preparation method of the blended masterbatch remained unchanged. The obtained blended masterbatch was subjected to a melt index test under the test conditions of 190°C and 2.16 kg, and the results are shown in Table 3.

[0042] Table 3 Melt index results of blended masterbatch containing ECO-100

[0043]

[0044] Comparative Example 3

[0045] The GMA-acrylate additive in Example 2 was replaced with commercially available MBS-M722 (Mitsubishi Corporation), and the addition ratio accounted for 3%, 5%, and 7% of the total mass ratio of the blended masterbatch, and the other raw materials and preparation method of the blended masterbatch remained unchanged. The obtained blended masterbatch was subjected to a melt index test under the test conditions of 190°C and 2.16 kg, and the results are shown in Table 4.

[0046] Table 4 Melt index results of blended masterbatch containing MBS-M722

[0047]

[0048] From the melt index test results of Example 2, it can be seen that the compatibility of the PLA / PBAT blending system can be significantly improved by matching PLA and PBAT in a certain ratio and adding the prepared GMA-acrylate additive to PLA and PBAT at a specific content, and the melt index of the fully degradable blending masterbatch can be greatly reduced, and the melt index can be reduced from 17.12g / 10min to 9.72g / 10min at the lowest. At the same time, it can be seen from the results of Comparative Examples 2 and 3 that the GMA-acrylate additive of the present invention has a better compatibilization effect on the PLA / PBAT blending system when the addition ratio accounts for 3%, 5%, and 7% of the total mass ratio of the blending masterbatch than the commercially available additives ECO-100 and MBS-M722.

Claims

1. A GMA-acrylate additive, characterized in that: The invention is prepared by the following components under high temperature and high pressure: 62-77% of soft water, 9-13% of hard monomer, 7-11% of soft monomer, 3-7% of functional monomer, 1.3-3% of emulsifier, 0.3-0.7% of initiator, 2-7% of modifier and 0.2-0.8% of defoamer; the hard monomer is one or any combination of ethyl methacrylate, methyl methacrylate and acrylonitrile; the functional monomer is GMA.

2. The GMA-acrylate auxiliary agent according to claim 1, characterized in that: The soft monomer is one or a combination of butyl acrylate and lauryl methacrylate.

3. The GMA-acrylate auxiliary agent according to claim 2, characterized in that: The emulsifier is one or a combination of sodium acrylamide isopropyl sulfonate and sodium vinyl sulfonate.

4. The GMA-acrylate auxiliary agent according to claim 3, characterized in that: The initiator is sodium persulfate; the modifier is ammonia water; and the defoamer is an organosilicon defoamer.

5. The method for preparing the GMA-acrylate auxiliary agent according to claim 1, characterized in that: Here are the steps: (1) Mixed monomer preparation: 9-13% hard monomer, 7-11% soft monomer, and 3-7% GMA are stirred evenly at room temperature and set aside; (2) Preparation of emulsifier solution: 15% of soft water and 1.3-3% of emulsifier are stirred evenly at room temperature and set aside; (3) Preparation of initiator solution: 20% of the total soft water and 0.3-0.7% of the initiator are stirred evenly at room temperature and set aside; (4) Add the remaining soft water, 20% of the mixed monomer, 5% of the emulsifier solution, and 2% of the initiator solution to the reaction kettle, seal it, evacuate it to -(0.01-0.06)MPa, stir it at a speed of 100-130r / min, and keep it at 90°C for 1 hour; then continuously add the remaining mixed monomer, emulsifier solution, and initiator solution through a metering pump, and the dropwise addition time is controlled to be 2 hours; after the addition is completed, keep it at 80°C for 2 hours; (5) Add 2-7% of a modifier and 0.2-0.8% of a defoamer, stir thoroughly for 1 hour, let stand to cool, and then dry at 110° C. to obtain a GMA-acrylate additive.

6. A fully degradable blending masterbatch, characterized in that: It includes PLA / PBAT masterbatch and GMA-acrylate additive; in the PLA / PBAT masterbatch, PLA accounts for 65-80%, and PBAT accounts for 20-35%; in the fully degradable blended masterbatch, the added proportion of GMA-acrylate additive accounts for 3%, 5%, 7%, and 9% of the total mass ratio of the blended masterbatch.

7. The method for preparing the fully degradable blended masterbatch according to claim 6, characterized in that: A fully biodegradable blending masterbatch was prepared by mixing PLA, PBAT and GMA-acrylate additive at 185°C for 15 minutes.

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