CN116875043A - Preparation method of modified polyamide elastomer - Google Patents
Preparation method of modified polyamide elastomer Download PDFInfo
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- CN116875043A CN116875043A CN202310867240.0A CN202310867240A CN116875043A CN 116875043 A CN116875043 A CN 116875043A CN 202310867240 A CN202310867240 A CN 202310867240A CN 116875043 A CN116875043 A CN 116875043A
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- China
- Prior art keywords
- polyborosiloxane
- polyamide elastomer
- modified
- polyvinyl alcohol
- heating
- Prior art date
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 69
- 229920001971 elastomer Polymers 0.000 title claims abstract description 69
- 229920002647 polyamide Polymers 0.000 title claims abstract description 69
- 239000000806 elastomer Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 34
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004327 boric acid Substances 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 15
- 230000006835 compression Effects 0.000 description 10
- 238000007906 compression Methods 0.000 description 10
- 239000003566 sealing material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- -1 polydimethylsiloxane Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention discloses a preparation method of a modified polyamide elastomer, which comprises the following steps: step 1, heating polyborosiloxane and boric acid crosslinked polyvinyl alcohol gel to 95 ℃ together, adding boric acid, heating to 120 ℃ and vacuum dehydrating to obtain polyvinyl alcohol modified polyborosiloxane; step 2, grinding polyvinyl alcohol modified polyborosiloxane into powder by using a mortar; step 3, weighing polyamide elastomer and powdery polyvinyl alcohol modified polyborosiloxane, uniformly blending at normal temperature, and then pouring into an internal mixer for heating to uniformly blend the polyamide elastomer and the polyborosiloxane to prepare a composite material; and 4, taking out the composite material, cooling to normal temperature, crushing, extruding and granulating by using a double-screw extruder to obtain the modified polyamide elastomer.
Description
Technical Field
The invention belongs to the technical field of modified synthetic polyamide elastomer materials, and particularly relates to a preparation method of a modified polyamide elastomer.
Background
Sealing materials have long been developed, and the sealing materials commonly used at the present stage have the following: polyvinyl chloride, ethylene propylene diene monomer rubber and thermoplastic elastomer dynamic vulcanized rubber. However, the polyvinyl chloride sealing material has poor fluidity, is easy to become brittle and crack after long-term use, and has extremely toxicity; the ethylene propylene diene monomer rubber sealing material has high price, is not easy to degrade and has high environmental pressure; thermoplastic elastomeric dynamic vulcanizate seals can be permanently deformed at moderate levels of compression. Therefore, it is an urgent need to develop a sealing material which is environmentally friendly, has low compression set, high rebound resilience, and excellent in fatigue resistance.
The thermoplastic polyamide elastomer is formed by block copolymerization of polyamide hard segments and polyether soft segments. The polyamide soft segment has the properties of elastic materials, has the advantages of high tensile strength and low-temperature impact strength, good flexibility, high elastic recovery rate, good wear resistance, higher fatigue resistance, good thermal stability and the like, and can be used as a new generation of sealing material. However, when the polyamide elastomer is used as a sealing material, the initial modulus of the material is higher due to the existence of hard segments of the polyamide elastomer, and the hard micro-areas of the polyamide elastomer can be rearranged in the process of constant force compression, so that the permanent compression deformation of the polyamide elastomer is higher than that of conventional rubber.
In order to solve the above problems, the present invention proposes a preparation method for improving compression set and impact strength properties of polyamide elastomers. For the hard segment characteristics of polyamide elastomers, all factors contributing to the crystalline structure regularity in the hard domains reduce the compression set of the material. A method for modifying the mechanical properties of nylon 11 by utilizing a polyborosiloxane material is proposed in the Chinese patent of invention, "a preparation method of modified nylon 11" (CN 2023102692491). However, when the method is used for modifying the polyamide elastomer, the polyborosiloxane has extremely poor compatibility with the polyamide elastomer, so that the mechanical property of the material is unstable. In the Chinese patent of the invention of a polyvinyl alcohol modified polyborosiloxane composite material and a preparation method thereof (CN 201911267747.2), the discovery that carbon-carbon chain fragments in polyvinyl alcohol endow the modified polyborosiloxane with good compatibility with an elastomer by using the polyvinyl alcohol modified polyborosiloxane material is provided, and the mechanical property of the composite material is ensured. The invention melt blends the polyborosiloxane material modified by polyvinyl alcohol with the polyamide elastomer, and improves the mechanical property of the polyamide elastomer.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method of a modified polyamide elastomer, and the compression set and the impact strength of the modified polyamide elastomer of a polyborosiloxane/polyvinyl alcohol composite material are obviously superior to those of an unmodified polyamide elastomer and a single polyborosiloxane modified polyamide elastomer by comparing two methods of the polyborosiloxane modified polyamide elastomer and the polyborosiloxane/polyvinyl alcohol composite material modified polyamide elastomer.
A method for preparing a modified polyamide elastomer, comprising the steps of:
step 1, heating polyborosiloxane and boric acid crosslinked polyvinyl alcohol gel to 95 ℃ together, adding boric acid, heating to 120 ℃ and vacuum dehydrating to obtain polyvinyl alcohol modified polyborosiloxane;
step 2, weighing the polyvinyl alcohol modified polyborosiloxane obtained in the step 1, and grinding the polyborosiloxane into powder by using a mortar;
step 3, weighing polyamide elastomer and powdery polyvinyl alcohol modified polyborosiloxane, uniformly blending at normal temperature, pouring into an internal mixer, and heating to 235 ℃ to uniformly blend the polyamide elastomer and the polyborosiloxane to prepare a composite material;
and 4, taking out the composite material prepared in the step 3, reducing the temperature to normal temperature, crushing, and extruding and granulating at 190 ℃ by using a double-screw extruder to obtain the modified polyamide elastomer.
Further, the molar ratio of silicon atoms to boron atoms in the polyborosiloxane in the step 1 is 15.1:1-5.3:1.
Further, the mass ratio of the polyborosiloxane to the polyvinyl alcohol in the step 1 is 95:5-75:35.
Further, the ratio of the powdery polyvinyl alcohol modified polyborosiloxane to the polyamide elastomer in the step 3 is 1:200-3:17.
The invention has the beneficial effects that:
the polyborosiloxane material with good compatibility is prepared by blending polyborosiloxane and polyvinyl alcohol, and after the modified polyborosiloxane and the polyamide elastomer are fused and blended, si-O-B weak bonds in the polyborosiloxane react with polyamide hard segments, and when the material is impacted or compressed, the Si-O-B weak bonds can be spontaneously broken and reconnected, so that the mechanical property of the material is stably improved.
Detailed Description
The invention is described in further detail below in connection with the specific embodiments using E55 from the winning specialty chemical as the polyamide elastomer substrate.
Example 1
The material provided by the invention is prepared from the following raw materials in percentage by mass:
100 parts of E55 polyamide elastomer
0.5 part of powdery polyvinyl alcohol modified polyborosiloxane
Placing the powdery polyvinyl alcohol modified polyborosiloxane and the E55 polyamide elastomer into an internal mixer for banburying for 15min at 235 ℃ to ensure that the materials are uniformly mixed, and granulating the mixture in a double-screw extruder.
Example 2
The material provided by the invention is prepared from the following raw materials in percentage by mass:
100 parts of E55 polyamide elastomer
1.5 parts of powdery polyvinyl alcohol modified polyborosiloxane
Placing the powdery polyvinyl alcohol modified polyborosiloxane and the E55 polyamide elastomer into an internal mixer for banburying for 15min at 235 ℃ to ensure that the materials are uniformly mixed, and granulating the mixture in a double-screw extruder.
Example 3
The material provided by the invention is prepared from the following raw materials in percentage by mass:
100 parts of E55 polyamide elastomer
2 parts of powdery polyvinyl alcohol modified polyborosiloxane
Placing the powdery polyvinyl alcohol modified polyborosiloxane and the E55 polyamide elastomer into an internal mixer for banburying for 15min at 235 ℃ to ensure that the materials are uniformly mixed, and granulating the mixture in a double-screw extruder.
Example 4
The material provided by the invention is prepared from the following raw materials in percentage by mass:
100 parts of E55 polyamide elastomer
2.5 parts of powdery polyvinyl alcohol modified polyborosiloxane
Placing the powdery polyvinyl alcohol modified polyborosiloxane and the E55 polyamide elastomer into an internal mixer for banburying for 15min at 235 ℃ to ensure that the materials are uniformly mixed, and granulating the mixture in a double-screw extruder.
Example 5
The material provided by the invention is prepared from the following raw materials in percentage by mass:
100 parts of E55 polyamide elastomer
3 parts of powdery polyvinyl alcohol modified polyborosiloxane
Placing the powdery polyvinyl alcohol modified polyborosiloxane and the E55 polyamide elastomer into an internal mixer for banburying for 15min at 235 ℃ to ensure that the materials are uniformly mixed, and granulating the mixture in a double-screw extruder.
Comparative examples the following methods were used to compare with the inventive examples.
The E55 polyamide elastomer is modified by the polyborosiloxane material, which comprises the following steps:
step 1, stirring polydimethylsiloxane and boric acid in a vacuum kneader, heating to 80 ℃, adding boric acid, and heating to 120 ℃ to obtain a polyborosiloxane material;
step 2, weighing the polyborosiloxane obtained in the step 1, and grinding the polyborosiloxane into powder by using a mortar;
step 3, weighing the polyamide elastomer and the powdery polyborosiloxane, wherein the proportion of the powdery polyborosiloxane to the polyamide elastomer is 1:200-3:100, uniformly blending at normal temperature, pouring into an internal mixer, and heating to 235 ℃ to uniformly blend the components to prepare the composite material;
and 4, taking out the composite material prepared in the step 3, reducing the temperature to normal temperature, crushing, and extruding and granulating at 190 ℃ by using a double-screw extruder to obtain the modified polyamide elastomer.
Comparative example 1
Unmodified E55 polyamide elastomer
Comparative example 2
100 parts of E55 polyamide elastomer
0.5 part of polyborosiloxane
The polyborosiloxane and the E55 polyamide elastomer are put into an internal mixer for internal mixing for 15min at 235 ℃ to ensure that the materials are uniformly mixed, and the mixture is granulated in a double-screw extruder.
Comparative example 3
100 parts of E55 polyamide elastomer
1.5 parts of polyborosiloxane
The polyborosiloxane and the E55 polyamide elastomer are put into an internal mixer for internal mixing for 15min at 235 ℃ to ensure that the materials are uniformly mixed, and the mixture is granulated in a double-screw extruder.
Comparative example 4
100 parts of E55 polyamide elastomer
2.5 parts of polyborosiloxane
The polyborosiloxane and the E55 polyamide elastomer are put into an internal mixer for internal mixing for 15min at 235 ℃ to ensure that the materials are uniformly mixed, and the mixture is granulated in a double-screw extruder.
Comparative example 5
100 parts of E55 polyamide elastomer
3 parts of polyborosiloxane
The polyborosiloxane and the E55 polyamide elastomer are put into an internal mixer for internal mixing for 15min at 235 ℃ to ensure that the materials are uniformly mixed, and the mixture is granulated in a double-screw extruder.
The above examples and comparative examples were each tested for compression set (national standard GB/T7759.1-2015) and impact strength (GB/T1843-2008) of the materials.
Table 1 comparison of mechanical properties of examples and comparative examples
Table 2 comparison of mechanical properties of examples and comparative examples
| Sample of | Impact strength (MPa) |
| Comparative example 1 | 62P* |
| Comparative example 2 | 62P* |
| Comparative example 3 | 78P* |
| Comparative example 4 | 72P* |
| Comparative example 5 | 76P* |
| Example 1 | 67P* |
| Example 2 | 71P* |
| Example 3 | 75P* |
| Example 4 | 82P* |
| Example 5 | 88P* |
The comparative experiment shows that the compression set of the polyborosiloxane modified polyamide elastomer is reduced compared with that of the unmodified polyamide elastomer, the impact strength is improved, the performance of the modified polyamide elastomer is extremely unstable, and the compression set and the impact performance of the composite material blended with the polyamide elastomer after the polyborosiloxane is modified by the polyvinyl alcohol are stably improved along with the increase of the content of the polyborosiloxane modified by the polyvinyl alcohol.
The above description of the present invention is only a part of the embodiments, but the present invention is not limited to the above embodiments. The above embodiments are illustrative and not limiting. All specific extensions fall within the scope of the present invention when materials and methods of the present invention are employed without departing from the spirit of the invention and the scope of the claims.
Claims (4)
1. A method for preparing a modified polyamide elastomer, comprising the steps of:
step 1, heating polyborosiloxane and boric acid crosslinked polyvinyl alcohol gel to 95 ℃ together, adding boric acid, heating to 120 ℃ and vacuum dehydrating to obtain polyvinyl alcohol modified polyborosiloxane;
step 2, weighing the polyvinyl alcohol modified polyborosiloxane obtained in the step 1, and grinding the polyborosiloxane into powder by using a mortar;
step 3, weighing polyamide elastomer and powdery polyvinyl alcohol modified polyborosiloxane, uniformly blending at normal temperature, pouring into an internal mixer, and heating to 235 ℃ to uniformly blend the polyamide elastomer and the polyborosiloxane to prepare a composite material;
and 4, taking out the composite material prepared in the step 3, reducing the temperature to normal temperature, crushing, and extruding and granulating at 190 ℃ by using a double-screw extruder to obtain the modified polyamide elastomer.
2. The method for producing a modified polyamide elastomer according to claim 1, wherein the molar ratio of silicon atoms to boron atoms in the polyborosiloxane in step 1 is 15.1:1 to 5.3:1.
3. The method for producing a modified polyamide elastomer as claimed in claim 1, wherein the mass ratio of the polyborosiloxane to the polyvinyl alcohol in step 1 is 95:5 to 75:35.
4. The method of producing a modified polyamide elastomer according to claim 1, wherein the ratio of the powdery polyvinyl alcohol-modified polyborosiloxane to the polyamide elastomer in step 3 is 1:200 to 3:17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310867240.0A CN116875043A (en) | 2023-07-14 | 2023-07-14 | Preparation method of modified polyamide elastomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310867240.0A CN116875043A (en) | 2023-07-14 | 2023-07-14 | Preparation method of modified polyamide elastomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116875043A true CN116875043A (en) | 2023-10-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310867240.0A Pending CN116875043A (en) | 2023-07-14 | 2023-07-14 | Preparation method of modified polyamide elastomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116875043A (en) |
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2023
- 2023-07-14 CN CN202310867240.0A patent/CN116875043A/en active Pending
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