An ultrahigh-barrier high-strength TPEE composite material and a preparation method and application thereof

Abstract

The application discloses a kind of superhigh barrier high-strength TPEE composite material and its preparation method and application.The composite material is composed of modified TPEE elastomer and high-density polyethylene, and the modified TPEE elastomer is measured by weight parts, including the following components: TPEE resin 50 parts, antistatic agent 2-4 parts, hydrophilic agent 1-3 parts;The polyether content of TPEE elastomer is 10-20wt%;The weight average molecular weight of high-density polyethylene is 200-400 thousand.By optimizing the TPEE material with higher polyether addition amount on the basis of the existing high-hygroscopic TPEE material, and being compounded with high-density polyethylene fiber, the TPEE composite film has better strength and moisture permeability, and the material is made into TPEE film, which has good barrier property and better moisture absorption, and is suitable for higher grade medical packaging and high-grade food packaging field.

Description

Technical Field

[0001] The present invention relates to the field of polyester elastomer (TPEE) materials, and in particular to an ultra-high barrier and high-strength TPEE composite material, a preparation method thereof, and applications thereof. Background Art

[0002] Polyetherester (TPEE) is a polybutylene terephthalate-polyethylene oxide-polypropylene oxide thermoplastic elastomer (TPEE). It is a block copolymer derived from the co-condensation of dimethyl terephthalate, butanediol, polyethylene oxide glycol, and / or polypropylene oxide glycol. It exhibits excellent flexibility and mechanical properties. TPEE materials are widely used in membranes due to their excellent mechanical and processing properties. However, current protective membrane materials struggle to achieve ideal moisture permeability, strength, and hydrostatic pressure. Therefore, a protective membrane material with high moisture permeability, strength, and hydrostatic pressure is urgently needed. Summary of the Invention

[0003] In response to the deficiencies in the prior art, the present invention proposes an ultra-high barrier and high-strength TPEE composite material, its preparation method, and application. By optimizing a TPEE material with a higher polyether addition content based on the existing high-moisture-permeable TPEE material and compounding it with high-density polyethylene fiber, the TPEE composite film itself has better strength and moisture permeability. The material is made into a TPEE film, which has good barrier properties and better hygroscopicity, and can be widely used in higher-grade medical packaging and high-grade food packaging fields.

[0004] The present invention provides a TPEE composite material, comprising a modified TPEE elastomer and high-density polyethylene;

[0005] The modified TPEE elastomer is 53-57 parts by weight;

[0006] The high-density polyethylene is 45-55 parts by weight;

[0007] Wherein, the modified TPEE elastomer comprises the following components in parts by weight:

[0008] 50 parts of TPEE resin;

[0009] 2-4 parts of antistatic agent;

[0010] 1-3 parts of hydrophilic agent;

[0011] The polyether content of the TPEE elastomer is 10-20wt%; preferably 12-18%. The polyether content is determined by the mass ratio of polyester to polyether in the raw material feed. The higher the polyether content, the more hydrophilic the ether-containing component is, and thus the better the moisture permeability of the material, and the more comfortable the fabric is. However, if the polyether content is too high, the mechanical properties of the material itself will be worse, affecting the hydrostatic pressure and tensile properties of the material. The weight-average molecular weight of high-density polyethylene is 200,000-400,000. The larger the molecular weight of HDPE, the higher the fiber tensile properties, but the higher the molecular weight, the worse the spinning performance of the material. Experiments have confirmed that the molecular weight range of 200,000-400,000 is the preferred range for the material molecular weight.

[0012] The weight average molecular weight of the high-density polyethylene is 200,000-400,000; the use of high-density polyethylene fibers has better moisture permeability and can maintain good mechanical strength. In comparison, low-density PE and PP do not have the same mechanical strength while maintaining the same moisture permeability.

[0013] The TPEE composite material includes a TPEE moisture-permeable layer and a high-density polyethylene fiber mesh, which are composited together by thermal bonding.

[0014] Furthermore, the antistatic agent is isohexanol polyoxyethylene ether and / or polyethylene oxide. The antistatic effect of isohexanol polyoxyethylene ether and / or polyethylene oxide is more lasting than other small molecule antistatic agents. At the same time, its addition to TPEE material provides better compatibility for subsequent composite of fabric and HDPE non-woven material.

[0015] Furthermore, the hydrophilic agent is one or more of methanesulfonic acid, octylphenol polyoxyethylene ether, or acetylene glycol ethoxylates, preferably octylphenol polyoxyethylene ether. Octylphenol polyoxyethylene ether has more similar functional groups to TPEE and HDPE, and has better compatibility when the two are compounded.

[0016] Furthermore, the modified TPEE elastomer also includes an antioxidant, and the antioxidant is 0.3-1 parts by weight.

[0017] Furthermore, the surface density of the TPEE moisture permeable layer is 45±5g / m 2 ;The surface density of high-density polyethylene fiber mesh is 45±5g / m 2 .

[0018] Furthermore, the surface density of the TPEE composite material is 89-92 g / m 2 .

[0019] The present invention also provides a method for preparing the TPEE elastomer, comprising the following steps:

[0020] S1: Weigh each component by weight, and add the remaining components except high-density polyethylene into a high-pressure mixer to mix and obtain a premix;

[0021] S2: The premix is ​​melt-extruded through a twin-screw extruder, small molecular substances are extracted by vacuum, and the TPEE elastomer is obtained by cooling and granulation.

[0022] Furthermore, the mixing time in S1 is 1 to 3 minutes, and the rotation speed is 1000 to 2000 rpm.

[0023] Furthermore, the temperature of each zone of the screw in S2 is 190-230° C., and the vacuum pressure is below -0.06 MPa.

[0024] The present invention also provides a method for preparing an ultra-high barrier and high-strength TPEE composite material, comprising the following steps:

[0025] (1) melt-extruding the prepared elastomer and drawing it into a film; melt-spinning the high-density polyethylene material, laying a web, and hot-rolling;

[0026] (2) melt-spinning a high-density polyethylene material to obtain a fiber with a diameter of 5-20 μm, and evenly laying the fiber to obtain an HDPE fiber fabric, which is then hot-rolled to obtain an HDPE fiber fabric;

[0027] (3) TPEE and high-density polyethylene fiber fabric are hot-rolled to obtain the ultra-high barrier and high-strength TPEE composite material.

[0028] The present invention also provides the use of the ultra-high barrier and high-strength TPEE composite material in the preparation of medical packaging or food packaging.

[0029] In summary, compared with the prior art, the present invention achieves the following technical effects:

[0030] (1) The present invention uses a preferred TPEE material to modify the TPEE and composite it with a preferred HDPE material, which significantly improves the barrier properties and strength of the material, enabling it to be widely used in the field of high-risk medical packaging;

[0031] (2) By selecting and compounding different high-density polyethylene and TPEE, the breaking strength and barrier capacity of the material are greatly improved, making the material have a better wrapping effect in metal medical packaging;

[0032] (3) The present invention uses common TPEE and high-density polyethylene as the base material, and the method of obtaining the same is economical and has broad application prospects in the fields of medical packaging, food packaging, etc. DETAILED DESCRIPTION

[0033] In order to help those skilled in the art better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making any creative efforts should fall within the scope of protection of the present invention.

[0034] Example

[0035] The present invention is further illustrated below with reference to specific examples and comparative examples. The following specific examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the following examples, and are particularly not limited to the types of the various component raw materials used in the following specific examples.

[0036] 1. The raw materials used for each component are as follows:

[0037] TPEE resin: TPEE#1: polyether molar content of 15%, brand 4056, purchased from DuPont, USA;

[0038] TPEE resin: TPEE#2: polyether molar content of 20%, brand VT7812, purchased from DSM;

[0039] TPEE resin: TPEE#3: polyether molar content of 10%, brand VT3108, purchased from DSM;

[0040] TPEE resin: TPEE#4: polyether molar content of 7%, brand VT3104, purchased from DSM;

[0041] TPEE resin: TPEE#5: polyether molar content of 25%, brand VT3118, purchased from DSM;

[0042] High-density polyethylene: HDPE#1, weight-average molecular weight Mw of 200,000, brand HDPE8008, purchased from Sinopec; the weight-average molecular weight was measured by high-temperature GPC at a temperature of 150°C, a flow rate of 1 mL / min, and an injection volume of 200 μL, the same below.

[0043] High-density polyethylene: HDPE#2, weight-average molecular weight Mw 300,000, brand BH500, purchased from Asahi Kasei;

[0044] High-density polyethylene: HDPE#3, weight-average molecular weight Mw 400,000, brand T0504F, purchased from Sinopec;

[0045] High-density polyethylene: HDPE#4, weight-average molecular weight Mw 500,000, brand T0604F, purchased from Sinopec;

[0046] High-density polyethylene: HDPE#5, weight-average molecular weight Mw of 150,000, brand HDPE 5000S, purchased from Sinopec;

[0047] Low-density polyethylene: LDPE, weight-average molecular weight Mw is 300,000, commercially available;

[0048] Antistatic agent #1: polyoxyethylene isohexyl alcohol ether, brand TF-481, Zhejiang Chuanhua Co., Ltd., the same substance was used in parallel experiments;

[0049] Antistatic agent #2: polyethylene oxide, brand WS308, Dow Chemical, USA;

[0050] Hydrophilic agent #1: octylphenol polyoxyethylene ether, purchased from Shengxu Energy, the same substance was used in parallel experiments;

[0051] Hydrophilic agent #2: octadecyltrimethylammonium chloride, brand GX80, Guangzhou Diaoling Fine Chemicals;

[0052] Antioxidant: Hindered phenolic antioxidant 1010, commercially available, the same substance was used in parallel experiments.

[0053] The preparation method of ultra-high barrier and high-strength TPEE composite material is as follows: (1) Weigh each component (except HDPE) according to the weight parts in Table 1 and Table 2, add it to a high-speed mixer and mix it for 1 to 3 minutes at a speed of 1000 to 2000 rpm to obtain a premix; (2) The premix is ​​melt-extruded through a twin-screw extruder, the temperature of each zone of the screw is 190 to 230°C, and small molecular substances are vacuum-extracted. The vacuum pressure is below -0.06MPa, and the TPEE elastomer is obtained by vacuum granulation. (3) The prepared TPEE elastomer is added to the screw extruder and melt-extruded, and then passes through the material path and metering pump to enter the casting die. The melt meets the high-speed hot air at the outlet of the melt-blown die and is stretched and homogenized into a film under the action of the high-speed hot air. After cooling and winding, the surface density is 45±5g / m 2 (4) melt spinning high-density polyethylene material to obtain fibers with a diameter of 5-20 μm, and evenly laying the fibers to obtain HDPE fiber fabrics, which are then hot-rolled to obtain a fabric with a surface density of 45±5 g / m 2 (5) TPEE and high-density polyethylene fiber fabric are hot-rolled to obtain TPEE / HDPE composite fabric with a surface density of 89-92g / m 2 .

[0054] 2. Product performance test standards and conditions

[0055] Test the surface density, hydrostatic pressure, breaking strength and other properties of TPEE / HDPE composite fabric samples.

[0056] (1) Areal density is tested according to GB / T24218.1-2009 standard, and the testing instrument is an electronic balance;

[0057] (2) Hydrostatic pressure was tested according to ENISO811:2018 standard, with a pressure increase rate of 60 cm H2O / min;

[0058] (3) Breaking strength is tested according to GB / T 3923.1-1997 standard, sample size 50*150mm, tensile speed 100mm / min.

[0059] Table 1 Example technical solutions and effects (parts by weight)

[0060]

[0061] Table 2 Comparative Example Technical Scheme and Effects (Parts by Weight)

[0062] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 TPEE#1 100 50 50 50 TPEE#4 50 TPEE#5 50 HDPE#1 100 50 50 HDPE#4 50 HDPE#5 50 LDPE 50 antioxidants 1 1 1 1 1 1 1 Antistatic Agent #1 3 3 3 3 3 3 3 Hydrophilic Agent #1 2 2 2 2 2 2 2 <![CDATA[Areal density (g / m 2 )]]> 91 89 90 90 89 89 89 <![CDATA[Hydrostatic pressure (60 cm H2O / min)]]> 223 336 234 256 72 156 178 Breaking strength (N) 235 321 226 168 56 113 145

[0063] From Examples 1 to 9, it can be seen that the TPEE composite material has good strength, barrier and hygroscopicity through the formulation and preparation method of the present invention. The surface density is 89-92g / m 2 , hydrostatic pressure is 979-1234 (60cm H2O / min), and breaking strength is 328-421N.

[0064] Comparative Examples 1 to 7 all have a single variable similar to Example 1. Comparative Example 1 contains only TPEE without HDPE; Comparative Example 2 contains only HDPE without TPEE; the weight-average molecular weight of the HDPE used in Comparative Example 3 is outside the range of 200,000-400,000; the polyether content of the TPEE used in Comparative Example 4 is less than 10 wt%; Comparative Example 5 replaces the high-density polyethylene with low-density polyethylene, the polyether content of the TPEE used in Comparative Example 6 is greater than 20 wt%, and the molecular weight of the HDPE used in Comparative Example 7 is less than 200,000. None of the above comparative examples can simultaneously meet the requirements of strength, barrier properties, and hygroscopicity.

[0065] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A TPEE composite material, characterized in that: Including modified TPEE elastomer and high-density polyethylene; The modified TPEE elastomer is 53-57 parts by weight; The high-density polyethylene is 45-55 parts by weight; Wherein, the modified TPEE elastomer comprises the following components in parts by weight: 50 parts of TPEE resin; 2-4 parts of antistatic agent; 1-3 parts of hydrophilic agent; The polyether content of the TPEE elastomer is 10-20wt%; The weight average molecular weight of the high-density polyethylene is 200,000-400,000; The TPEE composite material includes a TPEE moisture-permeable layer and a high-density polyethylene fiber mesh, which are composited together by thermal bonding.

2. The TPEE composite material according to claim 1, characterized in that The antistatic agent is isohexanol polyoxyethylene ether and / or polyethylene oxide.

3. The TPEE composite material according to claim 1, characterized in that The hydrophilic agent is octylphenol polyoxyethylene ether.

4. The TPEE composite material according to claim 1, characterized in that The modified TPEE elastomer further comprises an antioxidant, and the antioxidant is 0.3-1 parts by weight.

5. The TPEE composite material according to claim 1, characterized in that The surface density of the TPEE moisture permeable layer is 45±5g / m 2 ;The surface density of high-density polyethylene fiber mesh is 45±5g / m 2 .

6. The TPEE composite material according to claim 1, wherein The surface density of the TPEE composite material is 89-92 g / m 2 .

7. The method for preparing the TPEE composite material according to any one of claims 1 to 6, characterized in that: The steps include: S1: Weigh each component by weight, and add the remaining components except high-density polyethylene into a high-pressure mixer to mix and obtain a premix; S2: The premix is ​​melted and extruded through a twin-screw extruder, small molecules are extracted by vacuum, and the modified TPEE elastomer is obtained by cooling and granulation; S3: melt-extrude the modified TPEE elastomer and draw it into a film to prepare a TPEE moisture-permeable layer; S4: melt-spinning a high-density polyethylene material to obtain fibers with a diameter of 5-20 μm, evenly laying the fibers, and hot-rolling the fibers to obtain a high-density polyethylene fiber web; S5: hot-rolling the TPEE moisture-permeable layer and the high-density polyethylene fiber mesh to obtain the TPEE composite material.

8. The preparation method according to claim 7, characterized in that The mixing time in S1 is 1 to 3 minutes, and the rotation speed is 1000 to 2000 rpm.

9. The preparation method according to claim 7, characterized in that The temperature of each zone of the screw in S2 is 190-230° C., and the vacuum pressure is below -0.06 MPa.

10. Use of the TPEE composite material according to any one of claims 1 to 6 in the preparation of medical packaging or food packaging.

Images