CN1328311C - Compatible blend, its preparation and use - Google Patents

Abstract

The invention discloses a compatible blend, a preparation method and application thereof. Thermoplastic polyurethane (TPU) is obtained from the reaction of macromolecular diols, diisocyanates and short-chain diols. It contains both soft and hard segments, exhibits elasticity and thermoplasticity, and has two phases corresponding to hard and soft phases, respectively. Glass transition temperature, elasticity and wear resistance are excellent, but the price is high. Ethylene-octene copolymer (POE) has poor elasticity and abrasion resistance, and its price is low. The invention creatively blends these two kinds of elastomer materials to make a novel thermoplastic elastomer, and obtains a novel material having both the advantages of the two materials. The compatible blend of the present invention has the advantages of firmness, wear resistance, corrosion resistance, aging resistance, less pollution, good processability and good use performance, so it not only meets the performance requirements of specific applications, but also greatly reduces the cost of TPU , Broaden the use of TPU and POE.

Description

A kind of compatible blend and its preparation method and application

technology

The invention relates to the field of polymer materials, in particular to a compatible blend and its preparation method and application.

Background technique

Thermoplastic elastomers are a class of materials that combine the properties of vulcanized rubber with the processability of common thermoplastics, usually they consist of block copolymers with a heterogeneous microstructure, such as styrene-butadiene-styrene block copolymers (SBS), polyurethane elastomer multi-block copolymer, etc. In addition, thermoplastic elastomers can also be made by melt blending harder thermoplastic materials with rubber-like materials.

Thermoplastic polyurethane (TPU) is obtained from the reaction of macromolecular diols, diisocyanates and short-chain diols. It contains both soft and hard segments, exhibits elasticity and thermoplasticity, and has two phases corresponding to hard and soft phases, respectively. The glass transition temperature, elasticity and wear resistance are excellent, but the price is high, and its application is greatly limited.

Shorten the content of the invention

The purpose of the present invention is to solve the above-mentioned problem of high price of thermoplastic polyurethane, and provide a compatible blend with the same performance as thermoplastic polyurethane and low cost.

Another object of the present invention is to provide a method for preparing the above-mentioned compatible blend.

Another object of the present invention is to provide the application of the above-mentioned compatible blend in the preparation of thermoplastic elastomers.

The compatible blend of the present invention contains the following components: 5-80% by weight of thermoplastic polyurethane (TPU), 20-95% by weight of ethylene-octene copolymer (POE), and 5-10% by weight of compatibilizer. Due to the different polarity and high interfacial tension of TPU and POE, these two polymer materials are incompatible, and the mechanical properties of the partially proportioned blends are even lower than those of the individual components. To obtain high-performance TPU/POE blends, compatibilizers must be used during blending. In order to improve the compatibility between components, a compatible blend is obtained.

The aforementioned thermoplastic polyurethane is polyester polyurethane or polyether polyurethane or a blend thereof; the ethylene-octene copolymer is an ethylene-octene copolymer thermoplastic copolymer.

The above-mentioned compatibilizers are ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), POE-MAH (POE grafted maleic anhydride), POE-MA (POE grafted methacrylic acid), SEBS- One or a mixture of MAH (SEBS grafted maleic anhydride), aminated POE-MAH, aminated POE-MA, aminated SEBS-MAH.

Wherein the compatibilizer is all known compatibilizers that can be used in blends, including: unsaturated carboxylic acid or its derivatives (ester, acid halide, anhydride or amide), with unsaturated carboxylic acid or its derivatives or with Elastomers or polyolefins grafted with vinyl hydrocarbons, styrene-ethylene/butylene-styrene (SEBS) triblock copolymers grafted with maleic anhydride, ethylene-vinyl acetate (EVA), ethylene-acrylic acid Copolymer (EAA). Graft-modified elastomers are preferably used as compatibilizers, especially graft-modified POEs such as maleic anhydride (MAA), glycidyl methacrylate (GMA) or methacrylic acid (MA) are used as grafts. Branch monomer modified POE. The grafting reaction can be carried out according to the free radical graft copolymerization method, and the grafting of POE with ethylenically unsaturated grafting monomers can be carried out in a solution (preferably aromatic hydrocarbon) at 50-200°C (preferably 80-150°C) , or in the molten state (preferably in an extruder) at 170-300°C (preferably 200-250°C). The free radical initiator required for the grafting reaction is preferably a peroxide or an azo compound, and free radicals can also be generated by means of γ-rays or electron radiation.

The preparation method of the above-mentioned compatible blend is characterized in that the following components are mixed and homogenized by a mixer, kneader or extruder at a temperature of 180-300°C.

The blends described above are useful in the preparation of thermoplastic elastomers.

Beneficial effects of the present invention: thermoplastic polyurethane (TPU) is obtained by reacting macromolecular diol, diisocyanate and short chain diol, contains soft segment and hard segment at the same time, exhibits elasticity and thermoplasticity, and has corresponding hard segment respectively The two glass transition temperatures of the soft phase and the soft phase are excellent in elasticity and wear resistance, but the price is high. Ethylene-octene copolymer (POE) has poor elasticity and wear resistance, and its price is low. The invention creatively blends these two kinds of elastomer materials to make a novel thermoplastic elastomer, and obtains a novel material having both the advantages of the two materials. The compatible blend of the present invention has the advantages of firmness, wear resistance, corrosion resistance, aging resistance, less pollution, good processability and good use performance, so it not only meets the performance requirements of specific applications, but also greatly reduces the cost of TPU , Broaden the use of TPU and POE. The blend of the present invention has good processability and use performance, and can be applied to products that require good flexibility, wear resistance, tear resistance, wet skid resistance and low temperature resistance, such as shoe soles and car windshields Wind and rain rubber strips on glass can also be used in occasions that require good rigidity and elasticity, such as the manufacture of rollers and elastic dams, as well as replacing polyvinyl chloride materials and rubber materials.

Detailed ways

Example 1

1.1 Preparation of compatibilizer by grafting reaction

1.1.1 Maleic anhydride grafted POE

In a 2-liter stirred vessel equipped with a reflux condenser, a nitrogen inlet tube, an airtight stirrer and a dropping funnel heated by an oil bath, 50 g of ethylene-octyl Polyethylene copolymer (POE) (MFI=13) was dissolved in 12500 ml of xylene, and then 60 g of maleic anhydride (MAA) was added. To the above solution was added dropwise 40 g of benzoyl peroxide dissolved in 100 ml of xylene at 130° C. over 60 minutes. The solution was stirred for a further 60 minutes and, after cooling to 80° C., 2.5 liters of acetone were added. The graft copolymer which precipitated out was filtered off with suction, washed in 2.5 liters of acetone, filtered off again with suction and dried in vacuo at 80° C. for 8 hours. The grafting ratio of MAA was determined by infrared spectroscopy.

1.1.2 Glycidyl methacrylate grafted POE

Using 60 g of glycidyl methacrylate (GMA) instead of maleic anhydride, grafting was carried out according to Example 1.1.1.

1.1.3 Acrylamide grafting POE

Using 60 grams of acrylamide instead of maleic anhydride, grafting was carried out according to Example 1.1.1.

1.1.4 Methacrylic acid grafted POE

Using 60 g of methacrylic acid (MA) instead of maleic anhydride, the grafting was carried out according to Example 1.1.1.

1.2 Amination of graft polymer compatibilizer

1.2.1 Amination of POE-maleic anhydride grafts

In a small twin-screw experimental extruder, 100 grams of POE-maleic anhydride grafts and 5 grams of amino-terminated polyether (single amino functional group, molecular weight 2000) were mixed and extruded at 150 ° C. The amino-terminated polyether and POE- The maleic anhydride graft reacted completely.

1.2.2 Amination of POE-methacrylic acid grafts

In a small twin-screw experimental extruder, 100 grams of POE-methacrylic acid grafts and 5 grams of amino-terminated polyether (single amino functional group, molecular weight 2000) were mixed and extruded at 150 ° C. The amino-terminated polyether and POE- The maleic anhydride graft reacted completely.

1.2.3 Amination of SEBS-maleic anhydride grafts

In a small twin-screw experimental extruder, 100 grams of SEBS-maleic anhydride grafts and 5 grams of amino-terminated polyether (single amino functional group, molecular weight 2000) were mixed and extruded at 150 ° C. The amino-terminated polyether and POE- The maleic anhydride graft reacted completely.

1.3 Composition of thermoplastic polyurethane (TPU) and ethylene-octene copolymer (POE) blends

Blends were prepared using the following materials:

Thermoplastic Polyurethane Elastomers:

Polyester thermoplastic polyurethane (TPU1): S85A, BASF.

Polyether thermoplastic polyurethane (TPU2): lrogran A65 P4324, Huntsman.

Thermoplastic Polyolefin Copolymers:

Ethylene-octene copolymer (POE): 8130, Dow Chemical.

Compatibilizer:

XR1 ethylene-vinyl acetate resin (EVA): UE508, Taiwan Polymer Chemicals Co., Ltd.

XR2 ethylene-acrylic acid resin (EAA): 1410, Dow Chemical.

XR3 According to the POE of embodiment 1.1.1 MAA grafting

XR4 POE grafted with GMA according to Example 1.1.2

XR5 POE grafted with acrylamide according to Example 1.1.3

XR6 POE grafted with methacrylic acid according to Example 1.1.3

XR7 SEBS-maleic anhydride graft copolymer: Kraton FG1901X, Shell.

XR8 compatibilizer according to embodiment 1.2.1 POE-maleic anhydride graft amination

XR9 compatibilizer according to Example 1.2.2.POE-MA graft amination

XR10 Compatibilizer according to Example 1.2.3 SEBS-maleic anhydride graft amination

Examples 2-16

In a Brabender Plasticorder with a kneading chamber, a mixture of 20 g (50% by weight) of TPU1, 18 g (45% by weight) of POE and 2 g (5% by weight) of compatibilizer XR1 was kneaded at 190°C for 6 minute. In order to measure the mechanical properties, the kneaded blend was pressed into a 2mm thick sheet at 200°C on a flat vulcanizing agent, and the tensile strength was measured according to GB/T 525-1998 Thermoplastic Rubber Tensile Stress-Strain Performance Test Method and elongation at break (see Table 1 for results).

Using the raw materials shown in Table 1, the blends were prepared according to the above blending method, and the corresponding tensile strength and elongation at break tests were carried out. V1-V3 is a comparative example of the present invention, wherein 5% of the compatibilizer in V1 is replaced with POE, 5% of the compatibilizer in V2 is replaced with SEBS, and 5% of the compatibilizer in V3 is replaced with ethylene-propylene copolymer elastomer ( EPR) instead.

The tensile strength and elongation at break values of the blends are listed in Table 1. The data in table 1 shows that the tensile strength and elongation at break of the TPU/POE blend containing compatibilizer of the present invention are all higher than the TPU/POE blend without compatibilizer, while partially blending The elongation at break of the system is higher than that of pure TPU and pure POE, and the resulting blend combines the excellent properties of TPU and POE.

Composition (% by weight) and properties of Table 1 blends

Example or Comparative Example Blend composition (% by weight) Tensile strength (MPa) Elongation at break (%) Example 2 TPU1(50) POE(45) XR1(5) 37.2 850 Example 3 TPU1(50) POE(45) XR2(5) 38.3 1360 Example 4 TPU1(50) POE(45) XR3(5) 33.5 1120 Example 5 TPU1(50) POE(45) XR4(5) 35.6 1210 Example 6 TPU1(50) POE(45) XR5(5) 36.1 1280 Example 7 TPU1(50) POE(45) XR6(5) 32.1 1070 Example 8 TPU1(50) POE(45) XR7(5) 32.8 1200 Example 9 TPU1(50) POE(45) XR8(5) 37.8 1410 Example 10 TPU1(50) POE(45) XR9(5) 36.3 1570 Example 11 TPU1(50) POE(45) XR10(5) 35.7 1430 Example 12 TPU1(50) POE(15) XR3(5) 35.6 1610 Example 13 TPU1(50) POE(35) XR3(5) 34.7 1580 Example 14 TPU2(50) POE(45) XR3(5) 32.8 1260 Example 15 TPU2(80) POE(15) XR3(5) 34.9 1690 Example 16 TPU2(60) POE(35) XR3(5) 34.1 1620 Comparative Example V1 TPU1(50) POE(45) POE(5) 6.1 510 Comparative example V2 TPU1(50) POE(45) SEBS(5) 6.2 495 Comparative Example V3 TPU1(50) POE(45) EPR(5) 5.9 500 Pure TPU1 35.0 1250 Pure TPU2 32.2 1360 Pure POE 10.8 1080

Claims (5)

1. A compatible blend, characterized in that it consists of the following components: 5-80% by weight of thermoplastic polyurethane, 20-95% by weight of ethylene-octene copolymer, and 5-10% by weight of compatibilizer. 2. The blend according to claim 1, characterized in that said thermoplastic polyurethane is polyester polyurethane or polyether polyurethane or a blend thereof; said ethylene-octene copolymer is ethylene-octene copolymer thermoplastic copolymers. 3. The blend according to claim 1, characterized in that the compatibilizer is ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, POE-MAH, POE-MA, SEBS-MAH, aminated POE - One or a mixture of MAH, aminated POE-MA, and aminated SEBS-MAH. 4. A method for preparing the blend according to claim 1, characterized in that at 180-300°C, each component is mixed and homogenized in proportion through a mixer, kneader or extruder. 5. The use of the blend according to claim 1 in the preparation of thermoplastic elastomers.