CN117165046A - Polyester composite material toughened by ester-functionalized polyolefin elastomer and preparation method thereof - Google Patents

Abstract

The invention provides an ester group functionalized polyolefin elastomer toughened polyester composite material and a preparation method thereof. The polyester composite material comprises, by weight, 60-86 parts of polyester, 14-40 parts of ester-based functionalized polyolefin elastomer and 0-1 part of antioxidant. According to the invention, the problem of poor toughness of a single polyester material is solved by introducing the ester-functionalized polyolefin elastomer into the polyester, the formula and the preparation process of the polyester composite material are simple, the problem of volatilization of polar monomers does not exist in the preparation process, and the whole process is nontoxic and odorless and is suitable for mass production. The prepared polyester composite material has excellent mechanical properties, higher tensile strength and excellent toughness, achieves good balance between the strength and the toughness of the polyester material, and widens the application field of the polyester.

Description

Polyester composite material toughened by ester-functionalized polyolefin elastomer and preparation method thereof

Technical Field

The invention belongs to the field of polymer composite materials, and particularly relates to an ester-functionalized polyolefin elastomer toughened polyester composite material and a preparation method thereof.

Background

The polyester material is usually obtained by polycondensation of polyalcohol and polybasic acid, has better elasticity, better mechanical strength and heat resistance, and is engineering plastic with excellent performance and wide application. However, the polyester has low room temperature impact strength, poor toughness and large notch sensitivity, so that the application of the polyester is greatly limited. Therefore, at present, the toughening effect of polyester is mostly realized through blending modification. Among them, polyolefin elastomers are commonly used toughening modifiers, which have excellent low-temperature impact properties and toughening effects, but their nonpolar chain structures have poor compatibility with polyesters, greatly limiting their application as polyester toughening agents. To improve the compatibility between the non-polar polyolefin elastomer and the polar polyester, polar functional groups, such as carboxyl or ester groups, are typically grafted into the polyolefin elastomer backbone to improve the non-polar properties of the polyolefin elastomer. In the prior art, the polyolefin elastomer and the polar monomer containing carboxyl or ester group are subjected to grafting reaction in the presence of a free radical initiator, and the process is the functionalization of the polyolefin elastomer, and the functionalized polyolefin elastomer toughened polyester prepared is used as a compatibilizer-toughening agent, so that the compatibility of a blend is improved, and the toughness of a polymer material is improved.

Depending on the morphology of the polyolefin elastomer during the functionalization process, the process for preparing the functionalized polyolefin elastomer can be summarized as: grafting is carried out in solution, in the solid state and in the molten state. Among them, grafting in solution has the disadvantage of using a large amount of solvent, grafting in solid state has the disadvantage of uneven distribution of polar functional groups in the polyolefin elastomer main chain, and grafting in molten state has the disadvantage of partial volatilization of polar monomers.

CN1097605C reports a process for the preparation of carboxyl-or ester-functionalized polyolefins: preparing a mixture master batch of polyolefin, polar monomer, free radical initiator and coating, mixing the master batch with the polyolefin to be functionalized, and carrying out reaction extrusion to obtain the functionalized polyolefin. Wherein, the coating introduced by the master batch is coated on polyolefin to prevent the polar monomer from volatilizing; the polar monomer introduced by the master batch and the free radical initiator are uniformly dispersed in the polyolefin matrix, and the polar functional groups are grafted along the polyolefin chain in the form of uniformly distributed single monomer units, so that the optimal compatibility for preparing the composite material with the polar polymer is endowed. However, the case of the above-mentioned ester-functionalized polyolefin elastomer toughening modified polyester has not been reported yet.

Disclosure of Invention

In view of the above, the present invention aims to provide an ester group functionalized polyolefin elastomer toughened polyester composite material and a preparation method thereof. The invention can effectively improve the breaking elongation and notch impact strength of the polyester material by adopting the blend of the ester-functionalized polyolefin elastomer and the polyester, and has obvious toughening effect.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides an ester-functionalized polyolefin elastomer toughened polyester composite material, which comprises, by weight, 60-86 parts of polyester, 14-40 parts of ester-functionalized polyolefin elastomer and 0-1 part of antioxidant;

the ester-functionalized polyolefin elastomer is prepared from a polyolefin elastomer and a master batch;

the master batch is a mixture of polyolefin elastomer, ester-based functional monomer, free radical initiator and coating;

the ester functional monomer is selected from any one or more of maleate, fumarate or dimethyl itaconate.

Preferably, the content of the ester-functional monomer in the ester-functional polyolefin elastomer is 3 to 15wt%.

Preferably, the polyester composite material comprises, by weight, 65-81 parts of polyester, 19-35 parts of ester-based functionalized polyolefin elastomer and 0.1-0.8 part of antioxidant.

Preferably, the ester-functionalized polyolefin elastomer is prepared from 50 to 90 parts by weight of polyolefin elastomer and 10 to 50 parts by weight of master batch.

Preferably, the masterbatch is a mixture of 5 to 89 parts by weight of polyolefin elastomer, 10 to 40 parts by weight of ester-functional monomer, 0.5 to 2 parts by weight of radical initiator and 1 to 3 parts by weight of coating.

Preferably, the polyolefin elastomer is an ethylene/α -olefin random copolymer.

Preferably, the ethylene/α -olefin random copolymer has a weight average molecular weight of 150000 ～ 250000 and a molecular weight distribution index of 1.5 to 2.5.

Preferably, the ethylene/α -olefin random copolymer has an α -olefin content of 20 to 35wt%.

Preferably, the alpha-olefin in the ethylene/alpha-olefin random copolymer is selected from any one or more of 1-butene, 1-hexene or 1-octene.

Preferably, the polyester is selected from any one or more of polyethylene terephthalate, polypropylene terephthalate or polybutylene terephthalate.

Preferably, the free radical initiator is selected from any one or more of benzoyl peroxide, cumene peroxide or tert-butyl perbenzoate.

Preferably, the coating is selected from paraffinic oil and/or microcrystalline wax.

Preferably, the antioxidant is selected from any one or more of antioxidant BHT, antioxidant 1098 or antioxidant 7070.

In a second aspect, the invention provides a method for preparing the polyester composite material, which comprises the following steps:

and uniformly mixing the polyester and the ester-functionalized polyolefin elastomer, uniformly mixing the obtained mixture with an optional antioxidant, extruding, and granulating to obtain the polyester composite material.

Preferably, the extrusion temperature is 130-260 ℃.

Compared with the prior art, the invention has the beneficial effects that:

the invention provides an ester-functionalized polyolefin elastomer toughened polyester composite material, which solves the problem of poor toughness of a single polyester material by introducing the ester-functionalized polyolefin elastomer into the polyester. The prepared polyester composite material has excellent mechanical properties, higher tensile strength and excellent toughness, achieves good balance between the strength and the toughness of the polyester material, and widens the application field of the polyester.

Detailed Description

The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Aiming at the problem of poor toughness of polyester materials in the prior art, the invention provides an ester-group functionalized polyolefin elastomer toughened polyester composite material which comprises, by weight, 60-86 parts of polyester, 14-40 parts of ester-group functionalized polyolefin elastomer and 0-1 part of antioxidant. 60-86 parts, which can be 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, 82 parts, 84 parts or 86 parts, etc.; 14-40 parts, which can be 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts or 40 parts, etc.; the 0 to 1 part may be 0 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part or the like. In the invention, the polyester composite material preferably comprises, by weight, 65-81 parts of polyester, 19-35 parts of ester-based functionalized polyolefin elastomer, 0.1-0.8 part of antioxidant, more preferably 70-76 parts of polyester, 24-30 parts of ester-based functionalized polyolefin elastomer and 0.1-0.5 part of antioxidant.

In the present invention, the polyester is selected from any one or more of polyethylene terephthalate, polypropylene terephthalate, or polybutylene terephthalate. The source of the polyester is not particularly limited, and the polyester may be a general commercial product.

In the present invention, the ester-functionalized polyolefin elastomer is prepared from a polyolefin elastomer and a masterbatch. Wherein the polyolefin elastomer is an ethylene/α -olefin random copolymer having a weight average molecular weight of 150000 ～ 250000, which may be 150000, 160000, 170000, 180000, 190000, 200000, 210000, 220000, 230000, 240000, 250000, or the like; the molecular weight distribution index is 1.5 to 2.5, and may be 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, or the like. The content of the alpha-olefin in the ethylene/alpha-olefin random copolymer is 20 to 35wt%, and the content can be 20wt%, 22wt%, 24wt%, 25wt%, 27wt%, 29wt%, 30wt%, 32wt%, 35wt%, etc. Wherein the alpha-olefin may be selected from any one or more of 1-butene, 1-hexene or 1-octene. In the present invention, the masterbatch is a mixture of a polyolefin elastomer, an ester-functional monomer, a free radical initiator, and a coating. The source of the ester-functional monomer, the radical initiator and the coating material is not particularly limited, and the present invention is applicable to general commercial products. Wherein the ester-based functional monomer is selected from any one or more of maleate, fumarate or dimethyl itaconate; the free radical initiator is selected from any one or more of benzoyl peroxide, cumene peroxide or tert-butyl perbenzoate; the coating is selected from paraffin oil and/or microcrystalline wax, and can be specifically selected from OILOB55 paraffin oil sold by ROL and/or W835 microcrystalline wax sold by WITCO chemical company.

The master batch may be prepared according to the method disclosed in chinese patent CN 1097605C. In some embodiments of the present invention, the master batch is preferably prepared by mixing 5 to 89 parts by weight (which may be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 89 parts, etc.) of the polyolefin elastomer, 10 to 40 parts by weight (which may be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, etc.), 0.5 to 2 parts by weight (which may be 0.5 parts, 0.7 parts, 1.0 parts, 1.2 parts, 1.5 parts, 1.7 parts, 2.0 parts, etc.), and 1 to 3 parts by weight (which may be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2.0 parts, 2.2 parts, 2.4 parts, 2.6, 2.8 parts, or 3.0 parts, etc.) of the radical initiator in a high speed machine. The rotational speed of the mixing is 800-1200 rpm, preferably 900-1000 rpm; the mixing time is 3 to 10 minutes, preferably 3 to 5 minutes.

The ester-functionalized polyolefin elastomer may be prepared according to the method disclosed in chinese patent CN 1097605C. In some embodiments of the invention, the ester-functionalized polyolefin elastomer is the product of a reaction extrusion of 50 to 90 parts by weight of a polyolefin elastomer and 10 to 50 parts by weight of a masterbatch, the reaction extrusion temperature being 120 to 160 ℃, preferably 130 ℃, and the material residence time being 3 to 7 minutes, preferably 5 minutes. Wherein, 50 to 90 weight parts can be 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts or 90 parts, etc.; the 10 to 50 parts by weight may be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts or the like.

The ester group functionalized polyolefin elastomer prepared from the polyolefin elastomer and the master batch is grafted in the form of uniformly distributed single monomer units along the main chain of the polyolefin elastomer, wherein the content of the ester group functionalized monomer is 3-15 wt%, can be 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, etc., and is preferably 3-12 wt%.

In the invention, the antioxidant is selected from any one or more of antioxidant BHT, antioxidant 1098 or antioxidant 7070. The source of the antioxidant is not particularly limited, and the antioxidant is a general commercial product.

The polyester composite material toughened by the ester-functionalized polyolefin elastomer solves the problem of poor toughness of a single polyester material by introducing the ester-functionalized polyolefin elastomer into the polyester. The prepared polyester composite material has excellent mechanical property, higher tensile strength and excellent toughness, achieves good balance between the strength and the toughness of the polyester material, and can effectively widen the application field of the polyester.

The invention also provides a preparation method of the polyester composite material, which comprises the following steps:

and uniformly mixing the polyester and the ester-functionalized polyolefin elastomer, uniformly mixing the obtained mixture with an optional antioxidant, extruding, and granulating to obtain the polyester composite material.

According to the invention, the polyester is homogeneously mixed with the ester-functional polyolefin elastomer to give a mixture. In some embodiments of the present invention, it is preferred to mix the dry dehydrated polyester with the ester-functionalized polyolefin elastomer in a high speed mixer to obtain a mixture. The rotational speed of the mixing is 1600-2400 rpm, and the mixing time is 3-7 min, preferably 5min. The step of "drying and water removal" in the present invention is not particularly limited, and may be carried out by technical means well known to those skilled in the art.

And then, uniformly mixing the obtained mixture with an optional antioxidant, extruding, and granulating to obtain the polyester composite material. In some embodiments of the present invention, it is preferred that the resulting mixture and optional antioxidant are mixed uniformly and then fed into a co-rotating twin screw extruder for extrusion and pelletization to obtain the polyester composite. The feeding frequency of the double-screw extruder is 4-7 Hz, preferably 5Hz; the rotating speed of the screw is 60-110 r/min, preferably 80r/min; the temperature of each section of the extruder is 130-260 ℃, preferably 140-150 ℃; the temperature of the head is 240-260 ℃, preferably 255 ℃. In some embodiments of the invention, the extrudate is preferably cooled in water and then pelletized after the extrusion is completed, and preferably further comprising a drying step after the pelletization is completed. The operations of extrusion, cooling, pelletization and drying are not particularly limited in the present invention, and may be carried out according to technical means well known to those skilled in the art.

In some embodiments of the invention, the polyester composite is prepared according to the following method: drying the polyester at 100-160 ℃ for 12-24 hours, preferably at 130 ℃ for 15 hours, then mixing the dried polyester with the ester-functionalized polyolefin elastomer and the optional antioxidant uniformly in a high-speed mixer (for example, at 1600-2400 rpm), adding the mixed materials into a hopper of a double-screw extruder, feeding at 4-7 Hz, at 60-110 r/min, cooling the extruded materials in water at 130-260 ℃ at the temperature of the extruder head of 240-260 ℃, preferably 255 ℃, cutting and granulating the materials in a cutting machine after cooling, and finally drying the materials in a drying device at 100-130 ℃ for 4-8 hours, preferably at 115 ℃ for 5 hours to obtain the final product, namely the polyester composite material.

The polyester composite material has the advantages of simple formula and preparation process, no problem of volatilization of polar monomers in the preparation process, no toxicity and no smell in the whole process, and suitability for mass production.

In order to further illustrate the present invention, the following examples are provided. The experimental materials used in the following examples of the present invention are all generally commercially available.

Preparation example 1

The master batch preparation step comprises the following steps: 72 parts (in parts by weight, the same applies hereinafter) of polyolefin elastomer particles (brand No. three well chemical DF740, the same applies hereinafter), 25 parts of maleate, 1 part by weight of benzoyl peroxide, 2 parts by weight of OILOB55 paraffin oil were mixed with a high speed mixer at 1000rpm for 5 minutes to obtain a master batch.

Preparation of ester group functionalized polyolefin elastomer: 40 parts of the master batch prepared above and 60 parts of polyolefin elastomer are dry mixed at room temperature, the dry mixture is placed in a twin-screw extruder for reaction extrusion granulation, the temperature of each section of the extruder is 120-160 ℃, and the material residence time is 5min, so that the ester-functionalized polyolefin elastomer with the ester-functionalized monomer content of 8.1 weight percent, which is used in examples 1-5, is obtained.

Preparation example 2

The master batch preparation step comprises the following steps: 85 parts of polyolefin elastomer particles, 12 parts of fumaric acid ester, 1 part by weight of tert-butyl perbenzoate and 2 parts by weight of OILOB55 paraffin oil were mixed with a high-speed mixer at 1000rpm for 5 minutes to obtain a master batch.

Preparation of ester group functionalized polyolefin elastomer: 50 parts of the master batch prepared above and 50 parts of polyolefin elastomer were dry-mixed at room temperature, and the dry mixture was placed in a twin-screw extruder for reaction extrusion granulation at a temperature of 120 to 160℃in each stage of the extruder for a material residence time of 5 minutes, to obtain an ester-functionalized polyolefin elastomer having an ester-functionalized monomer content of 3.2% by weight, which was used in example 6.

Preparation example 3

The master batch preparation step comprises the following steps: 79 parts of polyolefin elastomer particles, 18 parts of fumaric acid ester, 1 part by weight of tert-butyl perbenzoate, 2 parts by weight of OILOB55 paraffin oil were mixed with a high speed mixer at 1000rpm for 5 minutes to obtain a master batch.

Preparation of ester group functionalized polyolefin elastomer: 50 parts of the master batch prepared above and 50 parts of polyolefin elastomer were dry-mixed at room temperature, and the dry mixture was placed in a twin-screw extruder for reaction extrusion granulation at a temperature of 120 to 160℃in each stage of the extruder for a material residence time of 5 minutes, to obtain an ester-functionalized polyolefin elastomer having an ester-functionalized monomer content of 5.3% by weight, which was used in example 7.

Preparation example 4

The master batch preparation step comprises the following steps: 73 parts of polyolefin elastomer particles, 24 parts of fumaric acid ester, 1 part by weight of tert-butyl perbenzoate, 2 parts by weight of OILOB55 paraffin oil were mixed with a high-speed mixer at 1000rpm for 5 minutes to obtain a master batch.

Preparation of ester group functionalized polyolefin elastomer: 50 parts of the master batch prepared above and 50 parts of polyolefin elastomer were dry-mixed at room temperature, and the dry mixture was placed in a twin-screw extruder for reaction extrusion granulation at a temperature of 120 to 160℃in each stage of the extruder for a material residence time of 5 minutes, to obtain an ester-functionalized polyolefin elastomer having an ester-functionalized monomer content of 8.5% by weight, which was used in example 8.

Preparation example 5

The master batch preparation step comprises the following steps: 67 parts of polyolefin elastomer particles, 30 parts of fumaric acid ester, 1 part by weight of t-butyl perbenzoate, 2 parts by weight of OILOB55 paraffin oil were mixed with a high speed mixer at 1000rpm for 5 minutes to obtain a master batch.

Preparation of ester group functionalized polyolefin elastomer: 50 parts of the master batch prepared above and 50 parts of polyolefin elastomer were dry-mixed at room temperature, and the dry mixture was placed in a twin-screw extruder for reaction extrusion granulation at a temperature of 120 to 160℃in each stage of the extruder for a material residence time of 5 minutes, to obtain an ester-functionalized polyolefin elastomer having an ester-functionalized monomer content of 11.7% by weight, which was used in example 9.

Preparation example 6

The master batch preparation step comprises the following steps: 61 parts of polyolefin elastomer particles, 36 parts of fumaric acid ester, 1 part by weight of t-butyl perbenzoate, 2 parts by weight of OILOB55 paraffin oil were mixed with a high speed mixer at 1000rpm for 5 minutes to obtain a master batch.

Preparation of ester group functionalized polyolefin elastomer: 50 parts of the master batch prepared above and 50 parts of polyolefin elastomer were dry-mixed at room temperature, and the dry mixture was placed in a twin-screw extruder for reaction extrusion granulation at a temperature of 120 to 160℃in each stage of the extruder for a material residence time of 5 minutes, to obtain an ester-functionalized polyolefin elastomer having an ester-functionalized monomer content of 14.4% by weight, which was used in example 10.

Example 1

85.7 parts of polyethylene terephthalate (brand Zhejiang Hengyi petrochemical HYW01, the same applies below) and 14 parts of ester-functionalized polyolefin elastomer (the content of ester-functionalized monomer is 8.1 wt%) are mixed for 5min by a high-speed mixer at a rotating speed of 2000rpm, then the mixture is uniformly mixed with 0.3 part of antioxidant 7070 and then added into a hopper of a double-screw extruder, the feeding frequency is 5Hz, the rotating speed of the screw is 80r/min, the temperature of each section of the extruder is 130-260 ℃, the temperature of a machine head is 255 ℃, the extruded materials are cooled in water at 30 ℃, and the final product (namely, the polyester composite material) is obtained by cutting and granulating and drying for 5h at 115 ℃.

Example 2

Mixing 80.7 parts of polyethylene terephthalate and 19 parts of ester-functionalized polyolefin elastomer (the content of ester-functionalized monomer is 8.1 wt%) for 5min by a high-speed mixer at a rotating speed of 2000rpm, uniformly mixing the mixture with 0.3 part of antioxidant 7070, adding the mixture into a hopper of a double-screw extruder, wherein the feeding frequency is 5Hz, the rotating speed of the screw is 80r/min, the temperature of each section of the extruder is 130-260 ℃, the temperature of a machine head is 255 ℃, extruding materials, cooling in water at 30 ℃, cutting and granulating, and drying at 115 ℃ for 5h to obtain a final product (namely the polyester composite material).

Example 3

75.7 parts of polyethylene terephthalate and 24 parts of ester-functionalized polyolefin elastomer (the content of ester-functionalized monomer is 8.1 weight percent) are mixed for 5 minutes by a high-speed mixer at a rotating speed of 2000rpm, then the mixture and 0.3 part of antioxidant 7070 are uniformly mixed and added into a hopper of a double-screw extruder, the feeding frequency is 5Hz, the rotating speed of the screw is 80r/min, the temperature of each section of the extruder is 130-260 ℃, the temperature of a machine head is 255 ℃, the materials are extruded, the materials are cooled in water at 30 ℃, cut and granulated, and the materials are dried for 5 hours at 115 ℃ to obtain the final product (namely the polyester composite material).

Example 4

69.7 parts of polyethylene terephthalate and 30 parts of ester-functionalized polyolefin elastomer (the content of ester-functionalized monomer is 8.1 weight percent) are mixed for 5 minutes by a high-speed mixer at the rotating speed of 2000rpm, then the mixture and 0.3 part of antioxidant 7070 are uniformly mixed and added into a hopper of a double-screw extruder, the feeding frequency is 5Hz, the rotating speed of the screw is 80r/min, the temperature of each section of the extruder is 130-260 ℃, the temperature of a machine head is 255 ℃, the materials are extruded, the materials are cooled in water at 30 ℃, cut and granulated, and the materials are dried for 5 hours at 115 ℃ to obtain the final product (namely the polyester composite material).

Example 5

64.7 parts of polyethylene terephthalate and 35 parts of ester-functionalized polyolefin elastomer (the content of ester-functionalized monomer is 8.1 weight percent) are mixed for 5 minutes by a high-speed mixer at a rotating speed of 2000rpm, then the mixture and 0.3 part of antioxidant 7070 are uniformly mixed and added into a hopper of a double-screw extruder, the feeding frequency is 5Hz, the rotating speed of the screw is 80r/min, the temperature of each section of the extruder is 130-260 ℃, the temperature of a machine head is 255 ℃, the materials are extruded, the materials are cooled in water at 30 ℃, cut and granulated, and the materials are dried for 5 hours at 115 ℃ to obtain the final product (namely the polyester composite material).

Example 6

72.7 parts of polyethylene terephthalate and 27 parts of ester-functionalized polyolefin elastomer (the content of ester-functionalized monomer is 3.2 weight percent) are mixed for 6 minutes by a high-speed mixer at the rotation speed of 1800rpm, then the mixture and 0.3 part of antioxidant 1098 are mixed uniformly and added into a hopper of a double-screw extruder, the feeding frequency is 6Hz, the rotation speed of the screw is 90r/min, the temperature of each section of the extruder is 130-260 ℃, the temperature of a machine head is 250 ℃, the materials are extruded, the materials are cooled in water at 25 ℃, cut and granulated, and the materials are dried for 4 hours at 120 ℃ to obtain the final product (namely the polyester composite material).

Example 7

72.7 parts of polyethylene terephthalate and 27 parts of ester-functionalized polyolefin elastomer (the content of ester-functionalized monomer is 5.3 weight percent) are mixed for 6 minutes by a high-speed mixer at the rotation speed of 1800rpm, then the mixture and 0.3 part of antioxidant 1098 are mixed uniformly and added into a hopper of a double-screw extruder, the feeding frequency is 6Hz, the rotation speed of the screw is 90r/min, the temperature of each section of the extruder is 130-260 ℃, the temperature of a machine head is 250 ℃, the materials are extruded, the materials are cooled in water at 25 ℃, cut and granulated, and the materials are dried for 4 hours at 120 ℃ to obtain the final product (namely the polyester composite material).

Example 8

72.7 parts of polyethylene terephthalate and 27 parts of ester-functionalized polyolefin elastomer (the content of ester-functionalized monomer is 8.5 wt%) are mixed for 6min by a high-speed mixer at the rotation speed of 1800rpm, then the mixture and 0.3 part of antioxidant 1098 are uniformly mixed and added into a hopper of a double-screw extruder, the feeding frequency is 6Hz, the rotation speed of the screw is 90r/min, the temperature of each section of the extruder is 130-260 ℃, the temperature of a machine head is 250 ℃, the materials are extruded, the materials are cooled in water at 25 ℃, cut and granulated, and the materials are dried for 4h at 120 ℃ to obtain the final product (namely the polyester composite material).

Example 9

72.7 parts of polyethylene terephthalate and 27 parts of ester-functionalized polyolefin elastomer (the content of ester-functionalized monomer is 11.7 wt%) are mixed for 6min by a high-speed mixer at the rotation speed of 1800rpm, then the mixture and 0.3 part of antioxidant 1098 are uniformly mixed and added into a hopper of a double-screw extruder, the feeding frequency is 6Hz, the rotation speed of the screw is 90r/min, the temperature of each section of the extruder is 130-260 ℃, the temperature of a machine head is 250 ℃, the materials are extruded, the materials are cooled in water at 25 ℃, cut and granulated, and the materials are dried for 4h at 120 ℃ to obtain the final product (namely the polyester composite material).

Example 10

72.7 parts of polyethylene terephthalate and 27 parts of ester-functionalized polyolefin elastomer (the content of ester-functionalized monomer is 14.4 weight percent) are mixed for 6 minutes by a high-speed mixer at the rotation speed of 1800rpm, then the mixture and 0.3 part of antioxidant 1098 are mixed uniformly and added into a hopper of a double-screw extruder, the feeding frequency is 6Hz, the rotation speed of the screw is 90r/min, the temperature of each section of the extruder is 130-260 ℃, the temperature of a machine head is 250 ℃, the materials are extruded, the materials are cooled in water at 25 ℃, cut and granulated, and the materials are dried for 4 hours at 120 ℃ to obtain the final product (namely the polyester composite material).

Comparative example 1

99.7 parts of polyethylene terephthalate and 0.3 part of antioxidant 7070 are uniformly mixed and then added into a hopper of a double-screw extruder, the feeding frequency is 5Hz, the screw rotating speed is 80r/min, the temperature of each section of the extruder is 130-260 ℃, the temperature of a machine head is 255 ℃, the materials are extruded, the materials are cooled in water at 30 ℃, cut and granulated, and the materials are dried at 115 ℃ for 5 hours to obtain the final product (namely the polyester composite material).

Comparative example 2

72.7 parts of polyethylene terephthalate and 27 parts of polyolefin elastomer (the insertion rate of the ester-based functional monomer is 0 wt%) are mixed for 6min by a high-speed mixer at the rotation speed of 1800rpm, then the mixture is uniformly mixed with 0.3 part of antioxidant 1098 and then added into a hopper of a double-screw extruder, the feeding frequency is 6Hz, the rotation speed of the screw is 90r/min, the temperature of each section of the extruder is 130-260 ℃, the temperature of a machine head is 250 ℃, the materials are extruded, the materials are cooled in water at 25 ℃, cut and granulated, and the final product (namely the polyester composite material) is obtained after drying for 4h at 120 ℃.

Performance testing

The products obtained in examples 1 to 5 and comparative example 1 were tested for mechanical properties by the following method:

room temperature tensile testing was performed using a universal material tester (Zwick/Roell Z020, zwick company, germany) according to GB/T528-2009 test method at a 20mm/min tensile rate. Room temperature cantilever impact test was performed using a pendulum impact instrument (CE Λst, world (hong kong) technology limited) according to GBT 1843-1996 test method, with a pendulum maximum impact energy of 5.5J. All samples were tested for tensile and impact of 5 or more bars and the test results averaged.

The test results are shown in table 1 below:

TABLE 1

As can be seen from the comparison of the data in examples 1-5 and comparative example 1 in Table 1, the ester-functionalized polyolefin elastomer toughened polyester composites provided by the present invention have outstanding performance advantages over pure polyester materials. And along with the increase of the content of the ester group functionalized polyolefin elastomer in the composite material, the polyester composite material obviously increases the toughness of the material while maintaining the better strength of the polyester material, and achieves the good balance between the strength and the toughness.

The products obtained in examples 6 to 10 and comparative example 2 were subjected to mechanical properties test, and the test method was referred to above.

The test results are shown in table 2 below:

TABLE 2

As can be seen from the comparison of the data of examples 6-10 and comparative example 2 in Table 2, the ester-based functionalized polyolefin elastomer toughened polyester composite material provided by the invention has very obvious mechanical property advantages compared with the common polyolefin elastomer toughened polyester composite material, and the ester-based functionalized polyolefin elastomer toughened polyester composite material is superior to the common polyolefin elastomer toughened polyester composite material in terms of strength and toughness of the material. And, as the content of the ester-functional monomer in the ester-functional polyolefin elastomer increases, the toughening effect of the material is more remarkable.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The polyester composite material toughened by the ester-functionalized polyolefin elastomer is characterized by comprising, by weight, 60-86 parts of polyester, 14-40 parts of the ester-functionalized polyolefin elastomer and 0-1 part of an antioxidant;

the ester-functionalized polyolefin elastomer is prepared from a polyolefin elastomer and a master batch;

the master batch is a mixture of polyolefin elastomer, ester-based functional monomer, free radical initiator and coating;

the ester functional monomer is selected from any one or more of maleate, fumarate or dimethyl itaconate.

2. The polyester composite according to claim 1, wherein the content of the ester-functional monomer in the ester-functional polyolefin elastomer is 3 to 15wt%.

3. The polyester composite according to claim 1, wherein the polyester composite comprises, by weight, 65 to 81 parts of polyester, 19 to 35 parts of an ester-based functionalized polyolefin elastomer, and 0.1 to 0.8 part of an antioxidant.

4. The polyester composite according to claim 1, wherein the ester-functionalized polyolefin elastomer is prepared from 50 to 90 parts by weight of polyolefin elastomer and 10 to 50 parts by weight of master batch.

5. The polyester composite according to claim 1, wherein the masterbatch is a mixture of 5 to 89 parts by weight of the polyolefin elastomer, 10 to 40 parts by weight of the ester-functional monomer, 0.5 to 2 parts by weight of the radical initiator, and 1 to 3 parts by weight of the coating.

6. The polyester composite of claim 1, wherein the polyolefin elastomer is an ethylene/α -olefin random copolymer;

the weight average molecular weight of the ethylene/alpha-olefin random copolymer is 150000 ～ 250000, and the molecular weight distribution index is 1.5-2.5.

7. The polyester composite of claim 6, wherein the ethylene/α -olefin random copolymer has an α -olefin content of 20 to 35wt%;

the alpha-olefin in the ethylene/alpha-olefin random copolymer is selected from any one or more of 1-butene, 1-hexene or 1-octene.

8. The polyester composite according to claim 1, wherein the polyester is selected from any one or more of polyethylene terephthalate, polypropylene terephthalate, or polybutylene terephthalate;

the free radical initiator is selected from any one or more of benzoyl peroxide, cumene peroxide or tert-butyl perbenzoate;

the coating is selected from paraffin oil and/or microcrystalline wax;

the antioxidant is selected from any one or more of antioxidant BHT, antioxidant 1098 and antioxidant 7070.

9. A process for the preparation of a polyester composite material as claimed in any one of claims 1 to 8, comprising the steps of:

and uniformly mixing the polyester and the ester-functionalized polyolefin elastomer, uniformly mixing the obtained mixture with an optional antioxidant, extruding, and granulating to obtain the polyester composite material.

10. The method of claim 9, wherein the extrusion temperature is 130-260 ℃.