CN112724592B - Super-tough POM composition and preparation method and application thereof - Google Patents
Super-tough POM composition and preparation method and application thereof Download PDFInfo
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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
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/02—Polyacetals containing polyoxymethylene sequences only
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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
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention provides a super-tough POM composition and a preparation method and application thereof. The super-tough POM composition comprises the following components in parts by weight: 100 parts of POM resin; 80-135 parts of polyether block amide elastomer; 15-25 parts of a TPU elastomer; wherein the melt index of the POM resin is 1.9-9 g/10min at 190 ℃ under 2.16 kg; the polyether block amide elastomer consists of PA11 and polyether; the melting point of the polyether block amide elastomer is 150-190 ℃. The notch impact strength of the super-tough POM composition can reach 106kJ/m2The elongation at break can be up to more than 500%.
Description
Technical Field
The invention relates to the field of high polymer materials, and in particular relates to a super-tough POM composition and a preparation method and application thereof.
Background
The Polyformaldehyde (POM) resin has a linear molecular chain configuration, and has the characteristics of high structural symmetry, high regularity and the like, so that the Polyformaldehyde (POM) resin has strong crystallization capacity. Because the POM resin has high crystallinity, the POM resin has high strength, high hardness and sensitivity to gaps, is easy to generate brittle fracture in the using process and greatly limits the application range of the POM resin. Therefore, toughening modification of POM resins is required. However, because the POM molecular chain lacks functional groups and side groups which can react with other polymers, the POM molecule is in weak polarity and has poor compatibility with most toughening agents, so the POM molecule is difficult to toughen.
The toughening modification of the existing POM comprises three types of toughening modification of an elastomer, toughening modification of inorganic rigid particles and alloying toughening modification, while the most common method at present is blending modification of a TPU elastomer and enhancing the toughening effect of the TPU on the POM resin by adding other fillers.
Chinese patent CN103059501A, 5-11% of TPU is added into POM resin as a toughening agent, and the notch impact strength of the prepared POM material is 12-16.3 kJ/m at 23 DEG C2(ii) a Chinese patent CN108976696A selects TPU to cooperate with rigid particle calcium carbonate to toughen and modify POM, and the impact strength of the modified POM resin is 23.6-50.3 kJ/m2The elongation at break is 32.1-81.3%; chinese patent CN109082068A selects Thermoplastic Polyurethane (TPU) as a toughening agent of POM, and lignin is added to improve the toughening effect of the TPU on the POM, so that the impact strength of the prepared POM resin is 14-25 kJ/m2(ii) a According to the Chinese patent CN109880281A, the POM is reinforced, toughened and modified by adding the nano rigid particles, and then the POM is further toughened by adding the toughening agent TPU, so that the notch impact strength of the prepared POM resin is 58-92 kJ/m2。
The toughness of the modified POM resin is 92kJ/m2Hereinafter, the toughness thereof is still to be improved. Therefore, there is a need to develop a super tough POM composition having higher toughness and a simple preparation method.
Disclosure of Invention
The invention aims to overcome the defect of low toughness of POM resin in the prior art and provide a super-tough POM composition. According to the invention, the polyether block amide elastomer is added into the POM resin, and the TPU elastomer is taken as the compatilizer, so that the prepared super-tough POM composition has good toughness, and the notch impact strength of the super-tough POM composition can reach 106kJ/m2The elongation at break can be up to more than 500%.
Another object of the present invention is to provide a process for preparing the super tough POM composition.
Another object of the present invention is to provide the use of said super tough POM composition for the manufacture of toys, gears or automotive parts.
In order to achieve the purpose, the invention adopts the following technical scheme:
the super-tough POM composition comprises the following components in parts by weight:
100 parts of POM resin;
80-135 parts of polyether block amide elastomer;
15-25 parts of a TPU elastomer;
wherein the melt index of the POM resin is 1.9-9 g/10min at 190 ℃ under 2.16 kg;
the polyether block amide elastomer consists of PA11 and polyether;
the melting point of the polyether block amide elastomer is 150-190 ℃.
In the existing modification of the toughness of the POM resin, TPU is mostly adopted as a main toughening agent, and can be used for improving the modification effect of the TPU on the POM resin by cooperating with other fillers, but the toughening effect of the TPU as the toughening agent is limited, and at present, the highest toughening effect can only reach 92kJ/m2And the use with higher toughness requirement cannot be met. On the other hand, since POM resins are incompatible with most polymeric tougheners, the space available for selection is limited.
Polyether block amide elastomers consisting of PA11 and a polyether are frequently used as UV protection additives. The inventors have surprisingly found that the addition of a relatively large amount of polyether block amide elastomer to the POM resin further improves the toughness of the POM resin. Meanwhile, in order to solve the problem of compatibility of the POM resin and the polyether block amide elastomer, the TPU elastomer is added as a compatilizer, so that the super-tough POM composition with higher toughness can be successfully prepared.
The selection of the POM resin with the proper melt index is beneficial to the material to have better toughness, the melt index is too high, the POM has too large fluidity in the processing process, the melt index is too low, the fluidity is poor, and the too large or poor fluidity can influence the dispersion of the polyether block amide elastomer and the compatilizer in the resin, thereby influencing the toughness of the material. The melting temperature of the polyether block amide elastomer is too high, so that the POM resin is difficult to plasticize in the processing process or is decomposed at a higher processing temperature; the melting temperature of the polyether block amide elastomer is too low, so that the dispersibility of the polyether block amide elastomer in the POM resin is poor, and the toughness of the material is influenced.
Further preferably, the super tough POM composition comprises the following components in parts by weight:
100 parts of POM resin;
100-120 parts of polyether block amide elastomer;
20-22 parts of TPU elastomer.
Preferably, the POM resin is one or a combination of POM 100P, POM 25-44 or POM 90-44.
Preferably, the polyether block amide elastomer is one or a combination of more of PEBAX55R53, PEBAX 70R53 or PEBAX 30R 51.
Preferably, the TPU elastomer is one or a combination of polyester type TPU elastomer or polyether type TPU elastomer.
The toughness of the material can be influenced by the hardness of the TPU elastomer, and the toughness of the material can be reduced due to the excessively high hardness; the hardness is too low to uniformly disperse the polyether block amide elastomer in the POM resin, and the toughness of the material is deteriorated.
Preferably, the Shore hardness of the TPU elastomer is 80-90A.
Further preferably, the shore hardness of the TPU elastomer is 85A.
Preferably, the super-tough POM composition further comprises an auxiliary agent, wherein the auxiliary agent is one or a combination of more of a main antioxidant, an auxiliary antioxidant, allantoin or EBS.
The preparation method of the super-tough POM composition comprises the steps of uniformly mixing POM resin, polyether block amide elastomer, TPU elastomer and auxiliary agent, and then extruding, cooling and granulating at 150-210 ℃ to obtain the super-tough POM composition.
Preferably, the temperature of the mixing is 150-210 ℃.
Preferably, the extrusion can be carried out using a twin-screw extruder.
Preferably, the screw temperatures of the twin-screw extruder from the feed port to the head are respectively: 150-180 deg.C, 170-210 deg.C, 170-200 deg.C, 170-210 deg.C.
Preferably, the rotating speed of the double-screw extruder is 250-350 r/min.
Preferably, the feeding amount of the double-screw extruder is 50-200 kg/h.
Preferably, the vacuum degree of the double-screw extruder is-0.1-0 MPa.
The application of the super-tough POM composition in preparing toys, gears or automobile parts is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the polyether block amide elastomer is added into the POM resin, and the TPU elastomer is taken as the compatilizer, so that the prepared super-tough POM composition has good toughness, and the notch impact strength of the super-tough POM composition can reach 106kJ/m2The elongation at break can be up to more than 500%.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
The embodiment of the invention selects the following raw materials:
POM resin: POM 100P, melt index 1.9g/10min, available from DuPont, Inc., USA;
POM resin: POM 25-44, melt index 2.5g/10min, available from DuPont Inc., USA;
POM resin: POM 90-44, melt index 9g/10min, purchased from Sun Patch;
POM resin: POM M270-44, melt index 27g/10min, purchased from the Japanese treasures;
POM resin: POM 500P, 15g/10min melt index, available from DuPont, Inc., USA;
polyether block amide elastomer: PEBAX55R53, melting point 167 deg.C, available from Ashoma group, France;
polyether block amide elastomer: PEBAX 70R53, melting point 186 ℃, available from Ashoma group, France;
polyether block amide elastomer: PEBAX 30R51, melting point 150 deg.C, available from Ashoma group, France;
polyether block amide elastomer: PEBAX 35R53, melting point 135 deg.C, available from Ashoma group, France;
TPU elastomer: polyether type, 85A (shore hardness), purchased from bayer, germany;
TPU elastomer: polyester type, 85A (shore hardness), purchased from bayer, germany;
TPU elastomer: polyether type, 80A (shore hardness), purchased from bayer, germany;
TPU elastomer: polyether type, 90A (shore hardness), purchased from bayer, germany;
TPU elastomer: polyether type, 75A (shore hardness), purchased from bayer, germany;
TPU elastomer: polyether type, 95A (shore hardness), purchased from bayer, germany;
EBS: vinyl bis stearamide, available from Kyoto chemical Co., Ltd;
main antioxidant: antioxidant 245, available from basf (china) ltd;
auxiliary antioxidant: antioxidant 168, available from basf (china) ltd;
allantoin: available from Shanghai Michelin Biochemical technology, Inc.
Examples 1 to 12
According to the formula in table 1, the POM resin, the polyether block amide elastomer, the TPU elastomer and the auxiliary agent are added into a mixer to be uniformly mixed, and then are added into a double-screw extruder with the feeding amount of 50-200 kg/h, wherein the temperatures of all cylinders from a feeding port of the double-screw extruder to a machine head are respectively as follows: 150-180 ℃, 170-210 ℃, 170-200 ℃, the rotating speed of a double screw extruder is 250-350 r/min, the vacuum degree is-0.1-0 MPa, and the super-tough POM composition is obtained through extrusion, cooling and granulation.
TABLE 1 raw material formulation (parts by weight)
Comparative example 1
This comparative example is different from example 1 in that the POM resin was replaced with POM M270-44 having a higher melt index.
Comparative example 2
This comparative example is different from example 1 in that the POM resin was replaced with POM 500P having a higher melt index.
Comparative example 3
This comparative example is compared to example 1, except that the polyether block amide elastomer was replaced with a lower melting PEBAX 35R 53.
Comparative example 4
This comparative example compares to example 1 with the difference that the TPU elastomer was replaced with a polyether TPU, 75A, which has a lower hardness.
Comparative example 5
This comparative example is compared to example 1, except that the TPU elastomer was replaced with a higher durometer polyether type, 95A.
Comparative example 6
This comparative example is compared to example 1, except that the polyether block amide elastomer PEBAX55R53 was replaced with the polyether type, 85A, i.e., a TPU elastomer was selected as the toughening agent.
The toughness of the POM compositions prepared in the above examples and comparative examples was tested, and the specific test items and test methods were as follows:
1. notched impact strength: according to ISO 180: 2019, wherein the notch type is A-type notch, Zwick/Roell;
2. elongation at break: according to ISO 527: 2019. the standard is tested at 23 ℃, and it should be noted that the maximum breaking elongation detectable by the electronic universal tester (UTM4104, Shenzhen Sansi longitudinal and transverse technology) is 500%.
The test results are shown in table 2.
TABLE 2 results of performance test of each composition in examples and comparative examples
As can be seen from the results in table 2, the POM resins of comparative examples 1 and 2 have a higher melt index and too high flowability, resulting in agglomeration of the compatibilizer, and thus lower notched impact strength and elongation at break of the prepared POM compositions; comparative example 3 because the melting point of the polyether block amide elastomer is too low, the dispersibility of the polyether block amide elastomer in the POM resin is deteriorated at the processing temperature, and the notched impact strength and elongation at break of the prepared POM composition are low; comparative example 4 selects a TPU elastomer with lower hardness as a compatibilizer, which causes poor dispersibility of the polyether block amide elastomer in the POM resin, and further causes lower notched impact strength and elongation at break of the prepared POM composition; comparative example 5 selects a TPU elastomer with higher hardness, too high hardness, resulting in lower notched impact strength and elongation at break of the POM composition; comparative example 6 the prepared POM composition had lower notched impact strength and elongation at break by selecting the TPU elastomer as the toughening agent.
The notch impact strength of the super tough POM compositions prepared in examples 1-12 can be as high as 106kJ/m2The elongation at break is more than 500%, and the steel has excellent toughness.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The super-tough POM composition is characterized by comprising the following components in parts by weight:
100 parts of POM resin;
80-135 parts of polyether block amide elastomer;
15-25 parts of a TPU elastomer;
wherein the melt index of the POM resin is 1.9-9 g/10min at 190 ℃ under 2.16 kg;
the polyether block amide elastomer consists of PA11 and polyether;
the melting point of the polyether block amide elastomer is 150-190 ℃;
the Shore hardness of the TPU elastomer is 80-90A.
2. The super tough POM composition of claim 1 comprising the following components in parts by weight:
100 parts of POM resin;
100-120 parts of polyether block amide elastomer;
20-22 parts of TPU elastomer.
3. The super tough POM composition of claim 1, wherein the POM resin is one or a combination of POM 100P, POM 25-44, or POM 90-44.
4. The super tough POM composition of claim 1, wherein the polyether block amide elastomer is one or a combination of PEBAX55R53, PEBAX 70R53, or PEBAX 30R 51.
5. The super tough POM composition of claim 1, wherein the TPU elastomer is 85A shore hardness.
6. The super tough POM composition of claim 1 wherein the TPU elastomer is one or a combination of polyester TPU elastomers or polyether TPU elastomers.
7. The super tough POM composition of claim 1, further comprising an auxiliary agent, wherein the auxiliary agent is one or a combination of primary antioxidant, secondary antioxidant, allantoin, or EBS.
8. The preparation method of the super-tough POM composition according to any one of claims 1 to 7, wherein the super-tough POM composition is obtained by uniformly mixing the POM resin, the polyether block amide elastomer, the TPU elastomer and the auxiliary agent, and then extruding, cooling and granulating the mixture at 150 to 210 ℃.
9. Use of the super tough POM composition of any one of claims 1 to 7 in the manufacture of toys, gears or automotive parts.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5043399A (en) * | 1987-09-22 | 1991-08-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyacetal composition |
| CN111635613A (en) * | 2020-05-11 | 2020-09-08 | 天津金发新材料有限公司 | Super-tough and wear-resistant POM/TPU composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10237884A1 (en) * | 2002-08-19 | 2004-03-11 | Ticona Gmbh | Impact-resistant polyoxymethylene molding compositions, their use and molded articles made therefrom |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5043399A (en) * | 1987-09-22 | 1991-08-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyacetal composition |
| CN111635613A (en) * | 2020-05-11 | 2020-09-08 | 天津金发新材料有限公司 | Super-tough and wear-resistant POM/TPU composition and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 永久抗静电聚甲醛的研究;詹延辉;《塑料工业》;20131231;第41卷(第12期);第79-82段 * |
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