CN111057352A - Polyester type thermoplastic elastomer composition and preparation method and application thereof - Google Patents
Polyester type thermoplastic elastomer composition and preparation method and application thereof Download PDFInfo
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- CN111057352A CN111057352A CN201911358116.1A CN201911358116A CN111057352A CN 111057352 A CN111057352 A CN 111057352A CN 201911358116 A CN201911358116 A CN 201911358116A CN 111057352 A CN111057352 A CN 111057352A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention discloses a polyester type thermoplastic elastomer composition, a preparation method and application thereof, wherein the polyester type thermoplastic elastomer composition is prepared from 60-87 parts of TPEE, 10-25 parts of plasticizer, 0-5 parts of filler, 0.2-1 part of lubricant, 1-4 parts of deodorant, 1-2 parts of scratch-resistant agent, 0.3-0.5 part of antioxidant and 0.2-0.5 part of weather-resistant agent according to parts by weight. The polyester type thermoplastic elastomer composition of the present invention has low odor and high fluidity, and is very suitable for injection molding processes.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a polyester type thermoplastic elastomer composition, and a preparation method and application thereof.
Background
Polyester thermoplastic elastomers (TPEE), also known as polyester rubbers, are a class of linear block copolymers containing PBT (polybutylene terephthalate) polyester hard segments and aliphatic polyester or polyether soft segments. TPEE has excellent elasticity of rubber and easy processability of thermoplastic plastics, has adjustable hardness and free design, and is a new variety which is concerned by the thermoplastic elastomer.
The existing automotive upholstery adopts soft touch feeling and low emission, matte materials gradually become the pursuit target of middle-high-end vehicle types, the traditional soft materials such as PVC and TPU have the defects of large smell, high temperature resistance, cold resistance and the like, at present, a slush molding process is used on the forming process of part of the existing TPU or PVC materials, and the slush molding process has the problems of long period, insufficient productivity and high energy consumption. The existing injection molding process has the advantages of fast molding, short processing time and the like, can well avoid the problems of low efficiency and the like of the slush molding process, but the injection molding process requires a material with high fluidity, which is a difficult problem in the development of the injection molding process.
Disclosure of Invention
In view of the above, the present invention provides a polyester thermoplastic elastomer composition, and a preparation method and an application thereof, wherein the polyester thermoplastic elastomer composition uses TPEE as a matrix, a plasticizer and a deodorant as main components, and is matched with other additives, so that the polyester thermoplastic elastomer composition has low odor and high fluidity, is very suitable for an injection molding process, solves the problem of large odor of the existing PVC soft skin, and solves the problem of long slush molding process period.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the invention provides a polyester type thermoplastic elastomer composition, which is prepared from the following components in parts by weight:
A) 60 to 87 portions of TPEE,
B) 10-25 parts of a plasticizer,
C) 0 to 5 parts of a filler,
D) 0.2 to 1 portion of lubricant,
E) 1-4 parts of a smell removing agent,
F) 1-2 parts of scratch-resistant agent,
G) 0.3 to 0.5 portion of antioxidant,
H) 0.2 to 0.5 portion of weather resistant agent.
Further, the Shore hardness of the TPEE is 28D-35D, and the melt index under the condition of 230 ℃/2.16kg is 20-35g/10 min.
Further, the plasticizer is one of an ester plasticizer and an epoxy plasticizer. It is understood that ester plasticizers, such as SH1012, TOTM, etc., and epoxy plasticizers, such as UltraLITE 513, etc., may be used as conventional plasticizers in this field.
Further, the filler is a mineral filler, which may be conventionally selected in the art, and specific examples thereof include, but are not limited to, at least one of calcium carbonate, zinc oxide, titanium dioxide, and silica.
Further, the lubricant comprises at least one of an acidified polyethylene wax and a stearic acid-based lubricant. Among them, examples that may be mentioned of the stearic acid-based lubricant include, but are not limited to, sodium stearate, calcium stearate, pentaerythritol stearate, and the like.
Further, the smell removing agent is a porous inorganic adsorbent, and the specific surface area of the porous inorganic adsorbent is more than or equal to 350m2G, pore volume is more than or equal to 0.6cm3Examples which may be mentioned are nanosilica and the like.
Furthermore, the scratch-resistant agent is silicone master batch taking TPEE as a carrier.
Further, the antioxidant used in the present invention may be conventionally selected in the art and will not be described in detail herein, and preferably, in some embodiments of the present invention, the antioxidant comprises at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 3- (dodecylthio) -2, 2-bis [ (3- (dodecylthio) -propionyloxy) methyl ] -1, 3-propanediol.
Further, the weather-resistant agent is at least one of an ultraviolet light absorber and a hindered amine light stabilizer. The ultraviolet light absorber and hindered amine light stabilizer may be conventional in the art and are not described in detail herein.
The second aspect of the present invention provides a method for preparing the polyester type thermoplastic elastomer composition according to the first aspect of the present invention, comprising the steps of:
heating and stirring TPEE, a plasticizer, an antioxidant and a weather resisting agent according to the proportion to obtain a first mixed material; in some embodiments of the present invention, the heating and stirring described herein is stirring at 80-130 ℃ for 10-20 h.
Uniformly mixing the first mixed material with a filler, a lubricant, a deodorant and a scratch-resistant agent to obtain a second mixed material;
and adding the second mixed material into a double-screw extruder, and carrying out melting, extrusion and grain cutting to obtain the polyester type thermoplastic elastomer composition, wherein the temperature of a charging barrel of the double-screw extruder is 200-240 ℃, the rotating speed of a screw is 300-400 r/min, and the vacuum degree is-0.04-0.1 MPa.
A third aspect of the present invention provides the use of the polyester-based thermoplastic elastomer composition according to the first aspect of the present invention for preparing an automotive interior skin or an automotive instrument panel skin.
According to the polyester type thermoplastic elastomer composition, the ultrahigh-surface-area porous inorganic adsorbent is particularly good in adsorption effect on polar molecules, the ester plasticizer or the ester epoxy plasticizer can be well absorbed by satin in the polyester type thermoplastic elastomer, the absorption efficiency is high, the absorption capacity is large, the material can achieve high fluidity, in addition, the calcium carbonate has weak alkalinity, the fluidity can be properly improved under the condition that the performances such as strength are met by properly controlling the addition amount of the calcium carbonate, and the fluidity of the polyester type thermoplastic elastomer composition can achieve high fluidity.
The polyester type thermoplastic elastomer composition has the excellent characteristics of low odor and high fluidity, the odor grade of the composition passes through general grade 6, the TVOC is less than 10000, the fluidity is high, the melt index is 230 ℃/2.16kg and can reach 280g/10min at most, and the composition can be used as an ideal material for automobile interior trim skins and automobile instrument panel skins in the field of automobiles.
The raw materials used in the invention are commercially available and widely available, and the polyester type thermoplastic elastomer composition can meet the injection molding requirement of automobile skin parts, and meets the general and popular odor grade, and has lower VOC and TVOC.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The following examples and comparative examples have the respective components:
and (2) component A: TPEE, No. 35DLG, shore hardness 35D, purchased from jiang yin and chuang ltd;
component B
B1: dodecyl p-hydroxybenzoate, trade name: SH1012, available from Jiangsu Senhe chemical Co., Ltd;
b2: cardanol epoxy plasticizer, brand No.: ultra LITE 513 from Kadeli chemical (Zhuhai) Inc.;
b3: tris (2-ethylhexyl) trimellitate, grade: TOTM-D, available from Toyo plasticizers, Inc., Korea;
and (3) component C: calcium carbonate, grade: NC-60A, available from Asahon powder materials Co., Ltd, Quanzhou;
and (3) component D: acidified polyethylene wax, grade: PED521, available from Klien, Inc. of Germany;
component E
E1: porous calcium silicate odor adsorbent, brand: DSX-650, available from Shandong de Sheng New Material science and technology Co., Ltd;
e2: inorganic odor removal master batch, brand: LPV9020, available from Fertilizer-in-place Innovation lightweight materials, Inc.;
and (3) component F: silicone masterbatch, brand: LYSI-03, available from Dow Sirkac, Inc.;
component G
G1: antioxidant 1010, brand No.: irganox 1010, available from Pasteur, Germany;
g2: thermal stabilizer 412S, grade: naugard 412s, available from Asia-Van, USA;
component H
H1: ultraviolet light absorber, designation Tinuvin326, available from basf, germany;
h2: hindered amine light stabilizers, designated Chimssorb 944, were purchased from Pasteur, Germany.
The preparation methods of the polyester type thermoplastic elastomer compositions in the examples and comparative examples were:
adding TPEE, a plasticizer, an antioxidant and a weather resisting agent into a heating tank according to the mixture ratio in the table 1 or the table 2, heating to 100 ℃, and mixing and stirring for 12 hours to obtain a first mixed material;
uniformly mixing the first mixed material with a filler, a lubricant, a deodorant and a scratch-resistant agent in a mixing pot, and carrying out melting, extrusion and granulation to obtain the polyester thermoplastic elastomer composition, wherein the temperature of a charging barrel of the double-screw extruder is respectively as follows: the first zone is 180 ℃, the second zone is 230 ℃ to the fifth zone, the sixth zone is 220 ℃ to the eighth zone, the head is 230 ℃, the rotating speed of the screw is 400r/min, and the vacuum degree is-0.1 MPa. Since the twin-screw extruder has little effect on the properties of the composition within the defined protective range, it is only possible to carry out this with the parameters specified as preferred.
Table 1 examples of the raw materials and the amounts (parts by weight)
| Composition of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 |
| A | 87 | 74 | 60 | 87 | 74 | 60 | 87 | 74 | 60 |
| B1 | 10 | 20 | 25 | ||||||
| B2 | 10 | 20 | 25 | ||||||
| B3 | 10 | 20 | 25 | ||||||
| C | 3 | 5 | 3 | 5 | 3 | 5 | |||
| D | 0.2 | 0.5 | 1 | 0.2 | 0.5 | 1 | 0.2 | 0.5 | 1 |
| E1 | 1 | 0.5 | 2 | 1 | 0.5 | 2 | 1 | 0.5 | 2 |
| E2 | 1 | 2 | 1 | 2 | 1 | 2 | |||
| F | 1 | 1.5 | 2 | 1 | 1.5 | 2 | 1 | 1.5 | 2 |
| G1 | 0.1 | 0.2 | 0.2 | 0.1 | 0.2 | 0.2 | 0.1 | 0.2 | 0.2 |
| G2 | 0.2 | 0.2 | 0.3 | 0.2 | 0.2 | 0.3 | 0.2 | 0.2 | 0.3 |
| H1 | 0.1 | 0.1 | 0.2 | 0.1 | 0.1 | 0.2 | 0.1 | 0.1 | 0.2 |
| H2 | 0.1 | 0.2 | 0.3 | 0.1 | 0.2 | 0.3 | 0.1 | 0.2 | 0.3 |
TABLE 2 comparative examples the raw materials and the amounts (parts by weight)
| Composition of | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| A | 87 | 74 | 60 |
| C | 3 | 5 | |
| D | 0.2 | 0.5 | 1 |
| F | 1 | 1.5 | 2 |
| G1 | 0.1 | 0.2 | 0.2 |
| G2 | 0.2 | 0.2 | 0.3 |
| H1 | 0.1 | 0.1 | 0.2 |
| H2 | 0.1 | 0.2 | 0.3 |
The polyester type thermoplastic elastomer compositions prepared in examples 1 to 9 and comparative examples 1 to 3 were respectively tested for tensile strength, elongation at break, melt flow rate, general odor grade, and the test standards and the performance test results thereof are shown in tables 3 and 4, respectively.
Table 3 results of property test of the polyester type thermoplastic elastomer composition in examples
TABLE 4 results of the Performance test of the polyester type thermoplastic elastomer composition in the comparative example
Note: the test standards for each test item in tables 3 and 4 are
(1) Tensile strength: DIN 53504;
(2) elongation at break: DIN 53504;
(3) melt flow rate: ASTM-D1238-04;
(4) general odor rating: GME 60276.
As can be seen from table 3, the polyester thermoplastic elastomer compositions prepared in embodiments 1 to 9 of the present invention have a high melt flow rate, a high odor level (general odor standard), and a high tensile strength and elongation at break, and are very suitable for automotive interiors such as skin injection of automobile instrument panels, thin-wall soft touch materials, and the like, which can greatly shorten the processing and molding time, help to save the cost, and improve the productivity.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The polyester type thermoplastic elastomer composition is characterized by being prepared from the following components in parts by weight:
A) 60 to 87 portions of TPEE,
B) 10-25 parts of a plasticizer,
C) 0 to 5 parts of a filler,
D) 0.2 to 1 portion of lubricant,
E) 1-4 parts of a smell removing agent,
F) 1-2 parts of scratch-resistant agent,
G) 0.3 to 0.5 portion of antioxidant,
H) 0.2 to 0.5 portion of weather resistant agent.
2. The polyester thermoplastic elastomer composition according to claim 1, wherein the TPEE has a shore hardness of 28D to 35D and a melt index of 20 to 35g/10min at 230 ℃/2.16 kg.
3. The polyester thermoplastic elastomer composition according to claim 1, wherein the plasticizer is one of an ester plasticizer and an epoxy plasticizer.
4. The polyester thermoplastic elastomer composition according to claim 1, wherein the filler is a mineral filler comprising at least one of calcium carbonate, zinc oxide, titanium dioxide and silica.
5. The polyester thermoplastic elastomer composition of claim 1, wherein the lubricant comprises at least one of an acidified polyethylene wax, a stearic-based lubricant.
6. The polyester thermoplastic elastomer composition according to claim 1, wherein the deodorant is a porous inorganic adsorbent having a specific surface area of 350m or more2G, pore volume is more than or equal to 0.6cm3/g。
7. The polyester thermoplastic elastomer composition according to claim 1, wherein the scratch resistant agent is a silicone masterbatch with TPEE as a carrier.
8. The polyester thermoplastic elastomer composition according to claim 1, wherein the antioxidant comprises at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 3- (dodecylthio) -2, 2-bis [ (3- (dodecylthio) -propionyloxy) methyl ] -1, 3-propanediol ester;
the weather resisting agent is at least one of an ultraviolet light absorber and a hindered amine light stabilizer.
9. A process for producing a polyester type thermoplastic elastomer composition according to any one of claims 1 to 8, which comprises the steps of:
heating and stirring TPEE, a plasticizer, an antioxidant and a weather resisting agent according to the proportion to obtain a first mixed material;
uniformly mixing the first mixed material with a filler, a lubricant, a deodorant and a scratch-resistant agent to obtain a second mixed material;
and adding the second mixed material into a double-screw extruder, and carrying out melting, extrusion and grain cutting to obtain the polyester type thermoplastic elastomer composition, wherein the temperature of a charging barrel of the double-screw extruder is 200-240 ℃, the rotating speed of a screw is 300-400 r/min, and the vacuum degree is-0.04 to-0.1 MPa.
10. Use of the polyester type thermoplastic elastomer composition according to any one of claims 1 to 8 for preparing an automotive interior skin or an automotive instrument panel skin.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724348A (en) * | 2020-12-28 | 2021-04-30 | 会通新材料(上海)有限公司 | Heat-resistant high-viscosity polyether ester elastomer composition and preparation method thereof |
| CN112759896A (en) * | 2021-01-22 | 2021-05-07 | 会通新材料股份有限公司 | Thermoplastic elastomer material and preparation method thereof |
| CN113699617A (en) * | 2021-09-02 | 2021-11-26 | 杨柏容 | Synthetic yarn of thermoplastic elastomer and preparation method thereof |
| CN116120716A (en) * | 2022-12-16 | 2023-05-16 | 重庆会通科技有限公司 | Scratch-resistant and wear-resistant thermoplastic polyester elastomer material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724348A (en) * | 2020-12-28 | 2021-04-30 | 会通新材料(上海)有限公司 | Heat-resistant high-viscosity polyether ester elastomer composition and preparation method thereof |
| CN112759896A (en) * | 2021-01-22 | 2021-05-07 | 会通新材料股份有限公司 | Thermoplastic elastomer material and preparation method thereof |
| CN113699617A (en) * | 2021-09-02 | 2021-11-26 | 杨柏容 | Synthetic yarn of thermoplastic elastomer and preparation method thereof |
| CN116120716A (en) * | 2022-12-16 | 2023-05-16 | 重庆会通科技有限公司 | Scratch-resistant and wear-resistant thermoplastic polyester elastomer material and preparation method thereof |
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