CN111100449A - Polyamide composition and preparation method thereof - Google Patents
Polyamide composition and preparation method thereof Download PDFInfo
- Publication number
- CN111100449A CN111100449A CN201911221379.8A CN201911221379A CN111100449A CN 111100449 A CN111100449 A CN 111100449A CN 201911221379 A CN201911221379 A CN 201911221379A CN 111100449 A CN111100449 A CN 111100449A
- Authority
- CN
- China
- Prior art keywords
- polyamide composition
- zone
- temperature
- agent
- polyamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polyamide composition and a preparation method thereof, wherein the polyamide composition comprises the following components in percentage by weight: 27-51% of type 6 polyamide resin, 2.5-10% of toughening agent, 45-65% of glass fiber, 0.2-1% of coupling agent, 1-1.5% of auxiliary agent and 600ppm of inorganic phosphoric acid. The polyamide composition provided by the invention can obviously improve the injection molding appearance of the material through reasonable matching of different components, and can maintain the melt fluidity and tensile strength of the material to a certain extent.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyamide composition.
Background
The 6 type polyamide resin has good comprehensive properties including mechanical property, heat resistance, abrasion resistance, chemical resistance and self-lubricity, low friction coefficient, certain flame retardance, easy processing and the like, and is widely applied to daily production and life. In order to improve the mechanical properties of type 6 polyamides, various modifiers are frequently added, glass fibers being the most common additive, and sometimes toughening agents, such as EPDM, are also added to improve impact resistance.
Since the type 6 polyamide resin has a strong moisture absorption property, it is necessary to pay special attention to the humidity in the space during injection drying. When the type 6 polyamide resin is processed and injected into large or complex products, the melt viscosity affects the injection molding appearance of the final product, the melt flowability of the type 6 polyamide resin is relatively weak, and the application range of the type 6 polyamide resin is greatly limited, so that the polyamide composition consisting of the type 6 polyamide resin with high flowability and low crystallization temperature and other additives is urgently needed on the premise of keeping the mechanical property and the processability of the material.
Disclosure of Invention
In view of the above, the present invention aims to provide a polyamide composition having good melt flowability while maintaining mechanical properties, and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the polyamide composition comprises the following components in percentage by weight: 27-51% of 6 type polyamide resin, 2.5-10% of toughening agent, 45-65% of glass fiber, 1-1.5% of auxiliary agent, 0.2-1% of coupling agent and 100-600ppm of inorganic phosphoric acid.
Further, the type 6 polyamide resin comprises at least 90% by weight of caprolactam.
Further, the polyamide has an apparent melt viscosity of 400-1300Pa.s according to the standardISO11443 shear Rate 1000s-1And a temperature of 250 ℃.
Further, the glass fiber is preferably alkali-free glass, and the preferred length range of the glass fiber is 1.5-6 mm.
Further, the toughening agent is ethylene-propylene-diene copolymer (EPDM); the diene monomer in the ethylene-propylene-diene copolymer (EPDM) is at least one of non-conjugated diene, cyclic diene and alkenyl norbornene.
Further, the non-conjugated diene is at least one of 1, 4-pentadiene, 1, 4-hexadiene, 2, 5-dimethyl-1, 5-hexadiene and 1, 4-octadiene.
Further, the cyclic diene is at least one of cyclopentadiene, cyclohexadiene and dicyclopentadiene.
Further, the alkenyl norbornene is preferably at least one of 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene and 5-vinyl-5-norbornene.
Further, the diene monomer in the ethylene-propylene-diene copolymer (EPDM) is preferably at least one of 1, 4-pentadiene, 5-vinyl-5-norbornene and cyclopentadiene.
Further, the auxiliaries are additives generally used for processing polyamide compositions, and are selected from one or more of plasticizers, nucleating agents, light stabilizers, heat stabilizers, antioxidants, antistatic agents, compatibilizers, lubricants and dispersants.
Further, the coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) -gamma-aminopropyltriethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, N- β - (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane and aniline methyltriethoxysilane.
The invention also provides a preparation method of the flame-retardant polyamide composition, which comprises the following steps:
(1) uniformly mixing inorganic phosphoric acid, a coupling agent, polyamide resin, glass fiber, a toughening agent and an auxiliary agent in a high-speed mixer:
(2) and extruding, cooling, drying and granulating the mixed material by a double-screw extruder to obtain a composition product. Wherein the temperature of the first zone of the double-screw extruder is 210-230 ℃, the temperature of the second zone is 220-240 ℃, the temperature of the third zone is 220-240 ℃, the temperature of the fourth zone is 220-240 ℃, the temperature of the fifth zone is 230-250 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 230-250 ℃, the temperature of the eighth zone is 220-240 ℃ and the temperature of the ninth zone is 200-220 ℃; the residence time is 150 seconds, and the rotation speed of the main engine is 200 and 350 revolutions per minute.
Compared with the prior art, the polyamide composition has the following advantages:
according to the polyamide composition disclosed by the invention, in the injection molding process, materials need to be heated, the 6-type polyamide resin is in a molten state in the heating process, and in the molten state, the addition of the inorganic phosphoric acid can degrade a part of molecular chain segments in the 6-type polyamide resin, so that the movement capacity of the molecular chain segments is improved, the viscosity of the 6-type polyamide resin is reduced, the melt flowability of the composition is improved, and the injection molding appearance of a product is improved.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
The polyamide compositions were prepared by mixing the components in the weight percentages shown in Table 1 and processing the mixture according to the steps (1) to (2) described above.
The obtained polyamide composition was subjected to a performance test by a method comprising: the tensile strength is tested according to GB/T1040.4-2006, the melt flow rate is tested according to GB/T3682.1-2000, and the injection molding appearance is tested according to GB/T2828.1-2003.
The formulation compositions and performance test results of the examples and comparative examples are shown in table 1.
TABLE 1 Polyamide composition Components and Performance test results (in the Table, the component contents are in weight percent)
TABLE 1
As can be seen from Table 1, the polyamide powder composition of the present invention has a significant effect of improving the injection molding appearance when the inorganic phosphoric acid is added in an amount of 100-600ppm by weight as compared with the non-inorganic phosphoric acid, and also can achieve a balance between the melt flowability and the tensile strength of the material (at least at the same level as that when the inorganic phosphoric acid is not added), because: during the injection molding process, the material is heated, the 6-type polyamide resin is in a molten state, the added inorganic phosphoric acid is uniformly distributed around the 6-type polyamide resin under the action of the silane coupling agent, partial molecular chain segments of the 6-type polyamide resin are degraded, the viscosity of the 6-type polyamide resin is further reduced, the melt flowability of the composition is improved, and the injection molding appearance of the product is finally improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The polyamide composition is characterized by comprising the following components in percentage by weight: 27-51% of 6 type polyamide resin, 2.5-10% of toughening agent, 45-65% of glass fiber, 1-1.5% of auxiliary agent, 0.2-1% of coupling agent and 100-600ppm of inorganic phosphoric acid.
2. The polyamide composition of claim 1, characterized in that: the polyamide has an apparent melt viscosity of 400-1300Pa · s; the type 6 polyamide resin comprises at least 90% by weight of caprolactam.
3. The polyamide composition of claim 1, characterized in that: the glass fiber is alkali-free glass, and the preferred length range of the glass fiber is 1.5-6 mm.
4. The polyamide composition of claim 1, characterized in that: the toughening agent is an ethylene-propylene-diene copolymer (EPDM).
5. Polyamide composition according to claim 4, characterized in that: the diene monomer in the ethylene-propylene-diene copolymer (EPDM) is at least one of non-conjugated diene, cyclic diene and alkenyl norbornene.
6. Polyamide composition according to claim 5, characterized in that: the non-conjugated diene is at least one of 1, 4-pentadiene, 1, 4-hexadiene, 2, 5-dimethyl-1, 5-hexadiene and 1, 4-octadiene; the cyclic dienes are at least one of cyclopentadiene, cyclohexadiene and dicyclopentadiene; the alkenyl norbornene is preferably at least one of 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene and 5-vinyl-5-norbornene.
7. The polyamide composition of claim 6, characterized in that: the diene monomer in the ethylene-propylene-diene copolymer (EPDM) is at least one of 1, 4-pentadiene, 5-vinyl-5-norbornene and cyclopentadiene.
8. The polyamide composition of claim 1, characterized in that: the auxiliary agent is one or more of a plasticizer, a nucleating agent, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a compatilizer, a lubricant, a dispersing agent or other conventional additives.
9. The polyamide composition as claimed in claim 1, wherein the coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) -gamma-aminopropyltriethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, N- β - (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, and anilinomethyltriethoxysilane.
10. Process for the preparation of a polyamide composition according to any one of claims 1 to 9, characterized in that it comprises the following steps:
s1: adding inorganic phosphoric acid, a coupling agent, 6-type polyamide resin, glass fiber, a toughening agent and an auxiliary agent into a high-speed mixer, and uniformly mixing:
s2: extruding the mixed material by a double-screw extruder, cooling, drying and granulating to obtain a composition product; wherein the temperature of the first zone of the double-screw extruder is 210-230 ℃, the temperature of the second zone is 220-240 ℃, the temperature of the third zone is 220-240 ℃, the temperature of the fourth zone is 220-240 ℃, the temperature of the fifth zone is 230-250 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 230-250 ℃, the temperature of the eighth zone is 220-240 ℃, and the temperature of the ninth zone is 200-220 ℃; the residence time is 150 seconds, and the rotation speed of the main engine is 200 and 350 revolutions per minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911221379.8A CN111100449A (en) | 2019-12-03 | 2019-12-03 | Polyamide composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911221379.8A CN111100449A (en) | 2019-12-03 | 2019-12-03 | Polyamide composition and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111100449A true CN111100449A (en) | 2020-05-05 |
Family
ID=70421229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911221379.8A Pending CN111100449A (en) | 2019-12-03 | 2019-12-03 | Polyamide composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111100449A (en) |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101296992A (en) * | 2005-10-28 | 2008-10-29 | 伊士曼化工公司 | Polyester compositions which comprise cyclobutanediol and at least one phosphorus compound |
| CN101921475A (en) * | 2010-09-07 | 2010-12-22 | 厦门建霖工业有限公司 | Metal-like engineering plastic composite material and preparation method thereof |
| CN102153857A (en) * | 2011-03-16 | 2011-08-17 | 金发科技股份有限公司 | High-filled modified-surface strengthened polyamide composition |
| CN103013099A (en) * | 2012-12-03 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | High-flowability long glass fiber reinforced nylon 6 material and preparation method thereof |
| CN103282434A (en) * | 2010-12-23 | 2013-09-04 | 拜耳知识产权有限责任公司 | Antistatic polycarbonate molding compounds |
| CN103597033A (en) * | 2011-05-31 | 2014-02-19 | 阿克马法国公司 | Method for increasing the reusability of a polyamide used in sintering |
| CN105153689A (en) * | 2015-09-23 | 2015-12-16 | 南京聚隆科技股份有限公司 | Polyamide 6 composite and preparation method thereof |
| CN106164141A (en) * | 2014-04-09 | 2016-11-23 | 旭化成株式会社 | Amilan polyamide resin composition |
| CN106317867A (en) * | 2015-06-18 | 2017-01-11 | 合肥杰事杰新材料股份有限公司 | Low-fiber exposure hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and preparation method thereof |
| CN106916445A (en) * | 2017-04-21 | 2017-07-04 | 金旸（厦门）新材料科技有限公司 | One kind exempts from spraying transparent glass fiber reinforced nylon resin material and preparation method thereof |
| CN106928697A (en) * | 2017-04-14 | 2017-07-07 | 广州市聚赛龙工程塑料股份有限公司 | Nylon material and its preparation method and application |
| CN107057339A (en) * | 2017-06-02 | 2017-08-18 | 杭州本松新材料技术股份有限公司 | A kind of activeness and quietness nylon material and its preparation method and application |
| CN107603210A (en) * | 2017-09-22 | 2018-01-19 | 杭州本松新材料技术股份有限公司 | A kind of flame-retardant polyamide composition and its preparation method and application |
| CN109206899A (en) * | 2018-09-03 | 2019-01-15 | 杭州本松新材料技术股份有限公司 | A kind of multiple-effect compound type resin additive and composite material |
| CN109385079A (en) * | 2017-08-11 | 2019-02-26 | 科莱恩塑料和涂料有限公司 | Fire-resistant polyamide composite and application thereof |
| CN109467923A (en) * | 2017-09-07 | 2019-03-15 | 科莱恩塑料和涂料有限公司 | With the high fire-resistant polyamide composite of resistance to heat distorsion and application thereof |
-
2019
- 2019-12-03 CN CN201911221379.8A patent/CN111100449A/en active Pending
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101296992A (en) * | 2005-10-28 | 2008-10-29 | 伊士曼化工公司 | Polyester compositions which comprise cyclobutanediol and at least one phosphorus compound |
| CN101921475A (en) * | 2010-09-07 | 2010-12-22 | 厦门建霖工业有限公司 | Metal-like engineering plastic composite material and preparation method thereof |
| CN103282434A (en) * | 2010-12-23 | 2013-09-04 | 拜耳知识产权有限责任公司 | Antistatic polycarbonate molding compounds |
| CN102153857A (en) * | 2011-03-16 | 2011-08-17 | 金发科技股份有限公司 | High-filled modified-surface strengthened polyamide composition |
| CN103597033A (en) * | 2011-05-31 | 2014-02-19 | 阿克马法国公司 | Method for increasing the reusability of a polyamide used in sintering |
| CN103013099A (en) * | 2012-12-03 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | High-flowability long glass fiber reinforced nylon 6 material and preparation method thereof |
| CN106164141A (en) * | 2014-04-09 | 2016-11-23 | 旭化成株式会社 | Amilan polyamide resin composition |
| CN106317867A (en) * | 2015-06-18 | 2017-01-11 | 合肥杰事杰新材料股份有限公司 | Low-fiber exposure hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and preparation method thereof |
| CN105153689A (en) * | 2015-09-23 | 2015-12-16 | 南京聚隆科技股份有限公司 | Polyamide 6 composite and preparation method thereof |
| CN106928697A (en) * | 2017-04-14 | 2017-07-07 | 广州市聚赛龙工程塑料股份有限公司 | Nylon material and its preparation method and application |
| CN106916445A (en) * | 2017-04-21 | 2017-07-04 | 金旸（厦门）新材料科技有限公司 | One kind exempts from spraying transparent glass fiber reinforced nylon resin material and preparation method thereof |
| CN107057339A (en) * | 2017-06-02 | 2017-08-18 | 杭州本松新材料技术股份有限公司 | A kind of activeness and quietness nylon material and its preparation method and application |
| CN109385079A (en) * | 2017-08-11 | 2019-02-26 | 科莱恩塑料和涂料有限公司 | Fire-resistant polyamide composite and application thereof |
| CN109467923A (en) * | 2017-09-07 | 2019-03-15 | 科莱恩塑料和涂料有限公司 | With the high fire-resistant polyamide composite of resistance to heat distorsion and application thereof |
| CN107603210A (en) * | 2017-09-22 | 2018-01-19 | 杭州本松新材料技术股份有限公司 | A kind of flame-retardant polyamide composition and its preparation method and application |
| CN109206899A (en) * | 2018-09-03 | 2019-01-15 | 杭州本松新材料技术股份有限公司 | A kind of multiple-effect compound type resin additive and composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103102684B (en) | A kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide composite and preparation method thereof | |
| CN106317867A (en) | Low-fiber exposure hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and preparation method thereof | |
| CN110183849B (en) | Halogen-free flame-retardant reinforced PA66 composite material and preparation method thereof | |
| CN107778853A (en) | A kind of heat oxygen aging resistance hydrolysis continuous glass-fiber reinforced polyamide composite and preparation method thereof | |
| CN109486013B (en) | Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polypropylene and preparation method thereof | |
| CN113061303A (en) | Glass fiber reinforced polypropylene material and preparation method thereof | |
| CN112143103A (en) | Cage-type silsesquioxane modified polypropylene composite material and preparation method thereof | |
| CN112679947A (en) | Heat insulation strip and preparation method thereof | |
| CN113980459A (en) | High-rigidity glass fiber reinforced nylon composite material and preparation method thereof | |
| CN112852149A (en) | Flame-retardant antistatic glass fiber reinforced nylon 6 composite material and preparation method thereof | |
| CN109370210B (en) | Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of nylon 6 and preparation method thereof | |
| CN107778652B (en) | Mica glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN103980707A (en) | Toughened polyether-imide composite material and preparation method thereof | |
| CN111100449A (en) | Polyamide composition and preparation method thereof | |
| CN104448825A (en) | Polyphenylene sulfide composite material and preparation method thereof | |
| CN112812562A (en) | Low-fiber-floating low-warpage high-glass-fiber-content reinforced polyphenylene sulfide composite material and preparation method thereof | |
| CN111117237A (en) | Polyamide composite material and preparation method thereof | |
| CN112745642A (en) | Low-mold-fouling flame-retardant reinforced PBT (polybutylene terephthalate) composite material as well as preparation method and application thereof | |
| CN112480644A (en) | Insulating self-lubricating polyphenyl ether composite material and preparation method thereof | |
| CN109535559B (en) | Efficient enhanced flame-retardant functional master batch for direct injection molding of polypropylene and preparation method thereof | |
| CN111073269B (en) | Flame-retardant polyamide composition and preparation method thereof | |
| CN106046777A (en) | Glass fiber reinforced polyamide compound material and preparation method thereof | |
| CN115819962A (en) | Halogen-free flame-retardant glass fiber reinforced PA6 material with high CTI value and preparation method thereof | |
| KR20160060907A (en) | Glass fiber reinforced PBT high flow resin composition and injection molding product | |
| CN111690254B (en) | Long-term heat-resistant modified polyamide composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200505 |
|
| RJ01 | Rejection of invention patent application after publication |