CN112708261B - Mixed olefin grafted microsphere reinforced flame-retardant nylon 6 composition and preparation method thereof - Google Patents
Mixed olefin grafted microsphere reinforced flame-retardant nylon 6 composition and preparation method thereof Download PDFInfo
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- CN112708261B CN112708261B CN201911022736.8A CN201911022736A CN112708261B CN 112708261 B CN112708261 B CN 112708261B CN 201911022736 A CN201911022736 A CN 201911022736A CN 112708261 B CN112708261 B CN 112708261B
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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
- 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
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention discloses a mixed olefin grafted microsphere reinforced flame-retardant nylon 6 composition and a preparation method thereof. The nylon 6 composition is prepared by blending the following raw materials: 6100 parts of nylon; 1-10 parts by weight of polyethylene glycol; 1-20 parts by weight of mixed olefin grafted microspheres. The preparation method comprises the following steps: the nylon 6 composition is prepared by melt blending the components according to the dosage. The invention can greatly improve the dispersibility of materials such as glass fiber, flame retardant and the like and polyolefin matrix affinity filler. Therefore, the dispersion of the flame-retardant material and the glass fiber in the polyolefin can be effectively enhanced, and the mechanical property and the flame-retardant effect of the material are improved.
Description
Technical Field
The invention relates to the technical field of nylon, in particular to a mixed olefin grafted microsphere reinforced flame-retardant nylon 6 composition and a preparation method thereof.
Background
The 3D technology is born in the later 90 s of the 20 th century, is based on a digital model and is a high-tech manufacturing technology based on a material accumulation method. The printing machine is basically the same as the common printing working principle, the printing machine is filled with liquid or powder and other printing materials, the printing materials are overlapped layer by layer under the control of a computer after being connected with the computer, and finally, a blueprint on the computer is changed into a real object.
The 3D printing technology uses powder metal or plastic and other bondable materials, integrates mechanical engineering, CAD, reverse revolution technology, layered manufacturing technology, numerical control technology and material science into a whole, and is called as manufacturing technology with industrial revolutionary significance. The technique of forming layer by layer is realized by melting and sintering material powder laid on a worktable or a part in advance selectively layer by layer through high-intensity laser irradiation. The 3D technology has high design flexibility, can produce accurate models and prototypes, can form components with reliable structures that can be used directly, and has short production cycle and simple process, thus being particularly suitable for the development of new products. The molding materials are widely available, including polymers, paraffins, metals, ceramics and their composites. However, the properties and properties of the molding material are important factors for the success of technical sintering, and the molding speed, the molding precision, and the physical and chemical properties and the comprehensive properties of the molded part are directly influenced. Despite the wide variety of suitable molding materials, few polymer powder raw materials are available that can be directly applied to 3D technology and successfully produce moldings with small dimensional errors, regular surfaces and low porosity. The 3D forming mainly comprises various 3D printing technologies including Fused Deposition Modeling (FDM), Selective Laser Sintering (SLS), three-dimensional light solidification modeling (SLA) and the like, so that the material forming method is greatly expanded, and particularly for materials which cannot be formed through fusion processing, the 3D printing forming is a good solution. The 3D printing technology appears as early as the middle of the 90's of the 20 th century, but the technology is immature due to high price, and is not popularized in the early period. After more than 20 years of development, the technology is more skillful and accurate, and the price is reduced. The types of molding materials that can be used in SLS technology are wide, including polymers, paraffins, metals, ceramics, and composites thereof.
Patent CN1250638A discloses a nylon particle toughened polypropylene composite material and its preparation method, the composite material is composed of polypropylene, nylon, interfacial compatilizer (graft of ethylene-4-10 carbon atoms alpha olefin copolymer and polyolefin blend), cross-linking agent (bifunctional epoxy resin or polyfunctional epoxy resin), antioxidant, and lubricant.
Patent CN101195707A discloses a glass fiber reinforced nylon 6-polypropylene alloy material, which is characterized in that nylon 6 and polypropylene are used as matrix resins, and the mechanical properties of the glass fiber reinforced nylon 6 can reach and be superior to those of singly reinforced nylon 6 without adding polypropylene under the condition that the content of a toughening agent (anhydride grafted elastomer and polyethylene or polypropylene polymer) is not changed.
Patent CN101538388A discloses a preparation method of beta-crystal polypropylene/nylon alloy, which improves the effective concentration of nucleating agent in polypropylene by controlling crystallization temperature, increases nucleation efficiency, and forms high-content beta-crystal polypropylene/nylon alloy. The rigidity of the material is obviously improved, the toughness of the material is obviously reduced, and the use limit in the market is large.
In the above-mentioned published patents, all are blends of several components, and the grafted material is prepared by adding ethylene to react and extrude to be used as a compatible auxiliary agent.
In the traditional glass fiber reinforced flame-retardant nylon 6 material, because the compatibility of glass fibers, a flame retardant and a nylon matrix resin material is poor, the third component and the fourth component are added to increase the melting between the materials during the preparation of the flame-retardant nylon material, so that the function of a compatilizer is achieved. The nylon 6 material has higher viscosity, so that the material mixing is usually accompanied with the increase of energy consumption, and the torque value of equipment is obviously increased.
Disclosure of Invention
In order to solve the problem that the dispersion of a flame retardant and glass fiber in nylon 6 matrix resin is poor in the prior art, the invention provides a mixed olefin grafted microsphere reinforced flame-retardant nylon 6 composition and a preparation method thereof. The maleic anhydride graft polymer is added when mixing olefin, which can greatly improve the dispersibility of materials such as glass fiber, flame retardant and the like and polyolefin matrix affinity filler. Therefore, the dispersion of the flame-retardant material and the glass fiber in the polyolefin can be effectively enhanced, and the mechanical property and the flame-retardant effect of the material are improved.
One of the purposes of the invention is to provide a flame-retardant nylon 6 composition reinforced by mixed olefin grafted microspheres.
The nylon 6 composition is prepared by blending the following raw materials:
the components are counted by weight part, and the weight percentage is,
6100 parts by weight of nylon;
1-10 parts by weight of polyethylene glycol; preferably 3 to 6 parts by weight;
1-20 parts by weight of mixed olefin grafted microspheres; preferably 5 to 10 parts by weight.
The raw materials of the nylon 6 composition also comprise: glass fiber, flame retardant or antioxidant.
Based on 100 parts by weight of nylon 6,
5 to 35 parts by weight, preferably 10 to 30 parts by weight of a glass fiber.
10-20 parts of flame retardant, preferably 13-16 parts.
The mixed olefin grafted microsphere is prepared according to the method comprising the following steps:
carrying out copolymerization reaction on the mixed olefin and maleic anhydride in the presence of nitrogen, an initiator and an organic solvent, and separating, washing and drying to obtain the mixed olefin grafted microspheres;
the mixed olefin is at least two of trans-2-butene, cis-2-butene, n-butene, isobutene, isoprene, cyclopentadiene, 1, 4-pentadiene and piperylene; n-butenes and isobutene are preferred. The ratio of the amounts of the olefins in the mixed olefin is not particularly limited, and can be adjusted by the skilled person according to the actual situation. When the mixed olefin is n-butene and isobutene, the mixing ratio of the n-butene and the isobutene is more preferably (0.5-2): 1.
the initiator is an azo initiator or a peroxide initiator;
among them, the azo initiator is preferably Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (ABVN), and more preferably azobisisoheptonitrile; the peroxide initiator is preferably at least one of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate, and more preferably dibenzoyl peroxide.
The organic solvent is at least one of organic acid alkyl ester, a mixture of the organic acid alkyl ester and alkane, and a mixture of the organic acid alkyl ester and aromatic hydrocarbon; the organic acid alkyl esters include, but are not limited to: at least one of methyl formate, ethyl formate, methyl propyl formate, methyl butyl ester, methyl isobutyl formate, pentyl formate, methyl acetate, ethyl ester, propylene acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate.
The weight ratio of the mixed olefin to the maleic anhydride is (0.5-5): 1; preferably (3-5): 1.
the concentration of the maleic anhydride in the organic solvent is 15-30 wt%; preferably 20 to 30 wt%.
The dosage of the initiator is 1 to 5 weight percent of the weight of the maleic anhydride.
The copolymerization reaction temperature is 60-100 ℃, and preferably 80-95 ℃; the copolymerization reaction pressure is 0.2-2 MPa, preferably 0.5-1 MPa; the copolymerization reaction time is 5-8 hours.
The raw materials of the nylon 6 composition also comprise: at least one of glass fiber, flame retardant and antioxidant.
The flame retardant is an organic phosphorus flame retardant, preferably at least one of triphenyl phosphate and its oligomer, resorcinol-bis (diphenyl phosphate), bisphenol-a-bis (diphenyl phosphate), resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ], hexaphenoxycyclotriphosphazene.
The antioxidant is a conventional antioxidant in the art, such as: 1010. 168, 1098, BX225, etc., in conventional amounts, which can be adjusted by the skilled person according to the actual circumstances.
The nylon 6 composition of the present invention may further comprise other conventional additives, such as an internal lubricant, a chain extender, etc., and the amount of the additives is also conventional, and the additives can be added by a skilled person according to actual situations.
The invention also aims to provide a preparation method of the flame-retardant nylon 6 composition reinforced by the mixed olefin grafted microspheres.
The method comprises the following steps:
the nylon 6 composition is prepared by melt blending the components according to the dosage.
Among them, preferred are:
the melting temperature is 230-250 ℃.
In the preparation process of the material, the polyethylene glycol and the mixed olefin-maleic anhydride copolymer microspheres are added to play a role of a compatilizer and also play a good role in material lubrication, so that the friction between the material and a machine barrel material is reduced, the torque value is reduced, and the energy consumption is reduced. The dispersion performance of glass fiber, flame retardant and the like in the nylon 6 material is improved.
In the preparation process, the polyethylene glycol material is added to reduce the torque value of the mixture, so that the lubricating property of the material is achieved. The mixed olefin-maleic anhydride copolymer microsphere grafted polypropylene GFPA6 has good compatibility, and the maleic anhydride grafted polymer is added when the olefin is mixed, so that the dispersibility of materials such as glass fiber, flame retardant and the like and polyolefin matrix affinity filler can be greatly improved. Therefore, the dispersion of the flame-retardant material and the glass fiber in the polyolefin can be effectively enhanced, and the mechanical property and the flame-retardant property of the material are improved.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The present invention will be further described with reference to the following examples.
Raw materials:
polypropylene: trademark T30, China petrochemical Yanshan mountain petrochemical
Nylon 6: 3200, manufactured by the company Zhongpetrochemical Balng.
Glass fiber: high strength alkali-free glass fiber, Mount Taishan, Inc
Flame retardant, commercially available
Maleic anhydride: experimental grade, New Acciao Beijing, New Kogyo
Polyethylene glycol: trade name 6000, DuPont Corp
The mixed olefin-maleic anhydride copolymer microsphere is produced by petrochemical north chemical industry.
Firstly, preparing mixed olefin grafting microspheres:
mixed olefin graft microspheres A
The copolymer microspheres are copolymer microspheres of maleic anhydride, n-butene and isobutene, and the mixed olefin graft copolymer microspheres A are prepared by copolymerization of the maleic anhydride, the n-butene and the isobutene in the presence of nitrogen, an Azobisisobutyronitrile (AIBN) initiator and an organic solvent; the ratio of n-butenes to isobutene was 1: 1.
the weight ratio of the mixed C4 to the maleic anhydride is 3: 1.
the concentration of maleic anhydride in the organic solvent of the isoamyl acetate is 20 wt%;
the amount of the initiator is 1 percent of the weight of the maleic anhydride;
the copolymerization reaction temperature is 80 ℃; the copolymerization reaction pressure is 1 MPa; the copolymerization time was 6 hours.
The particle size of the microspheres is in the range of 5-8 microns.
Mixed olefin grafted microspheres B
The copolymer microsphere is a copolymer microsphere of maleic anhydride, isoprene and isobutene, and the mixed olefin graft copolymer microsphere B is prepared by copolymerization reaction of the maleic anhydride, a methyl formate solvent, the isoprene and the isobutene under the existence of nitrogen and Azodiisobutyronitrile (AIBN) as an initiator and an organic solvent; the weight ratio of mixed C4 to maleic anhydride was (4: 1), and the ratio of isoprene to isobutylene was 0.5: 1;
the concentration of maleic anhydride in the organic solvent is preferably 30 wt.%;
the amount of the initiator is 3 percent of the weight of the maleic anhydride;
the copolymerization reaction temperature is 95 ℃; the copolymerization reaction pressure is 2 MPa; the copolymerization time was 5 hours.
The particle size of the microspheres is in the range of 5-8 microns.
Mixed olefin grafted microspheres C
The copolymer microsphere of maleic anhydride, n-butene and isobutene is subjected to copolymerization reaction in the presence of nitrogen, dibenzoyl peroxide thermal initiator and organic solvent to prepare a mixed olefin graft copolymer microsphere C; the weight ratio of the mixed C4 to the maleic anhydride is (5: 1); the ratio of n-butenes to isobutene is 2: 1.
the concentration of maleic anhydride in the organic solvent ethyl acetate is preferably 30% by weight;
the amount of the initiator is 5 percent of the weight of the maleic anhydride;
the copolymerization reaction temperature is 100 ℃, and the copolymerization reaction pressure is 1 MPa; the copolymerization time was 8 hours.
The particle size of the microspheres is in the range of 5-8 microns.
Preparation of mixed olefin grafted microsphere reinforced flame-retardant nylon 6 composition
Example 1
The nylon 6 composition is prepared by melt blending the components according to the using amounts.
The melting temperature was 230 ℃.
Example 2
The nylon 6 composition is prepared by melt blending the components according to the dosage.
The melting temperature was 235 ℃.
Example 3
The nylon 6 composition is prepared by melt blending the components according to the using amounts.
The melting temperature was 235 ℃.
Example 4
The nylon 6 composition is prepared by melt blending the components according to the dosage.
The melting temperature was 245 ℃.
Example 5
The nylon 6 composition is prepared by melt blending the components according to the dosage.
The melting temperature was 245 ℃.
Example 6
The nylon 6 composition is prepared by melt blending the components according to the dosage.
The melting temperature was 245 ℃.
Comparative example 1
The nylon 6 composition is prepared by melt blending the components according to the using amounts.
The melting temperature is 230 DEG C
Comparative example 2
The nylon 6 composition is prepared by melt blending the components according to the using amounts.
The melting temperature was 230 ℃.
Comparative example 3
The nylon 6 composition is prepared by melt blending the components according to the dosage.
The melting temperature was 230 ℃.
The torque values for the comparative example and example 1 are shown in table 1.
TABLE 1
As can be seen from table 1, the torque value of the nylon 6 composition prepared in example 1 of the present application was reduced by 10% to 20% compared to the comparative example. In the extrusion process of the double-screw extruder, the components of the nylon 6, the glass fiber and the flame retardant are changed, the friction strength of the material to a machine barrel is high, the torque value of equipment is increased, and the energy consumption of material production is increased, so that a polyethylene glycol lubricant is required to be added, and the torque resistance can be reduced to a certain extent (comparative examples 1-3), but the nylon 6 composition is not ideal. After the mixed olefin grafted microspheres are added, the dispersibility of materials such as glass fiber, flame retardant and the like and polyethylene glycol can be greatly improved, so that the torque value is obviously reduced, and the energy consumption is saved.
The mechanical properties of the examples and comparative examples are shown in Table 2;
TABLE 2 mechanical properties of the examples and comparative examples
As can be seen from the data in Table 2, the nylon 6 compositions prepared by the invention have better mechanical properties than the comparative examples, and have excellent mechanical properties.
Claims (14)
1. The flame-retardant nylon 6 composition reinforced by the mixed olefin grafted microspheres is characterized by being prepared by blending the following raw materials:
the components are counted by weight part, and the weight percentage is,
6100 parts by weight of nylon;
1-10 parts by weight of polyethylene glycol;
1-20 parts by weight of mixed olefin grafted microspheres;
the nylon 6 composition also comprises the following raw materials: at least one of glass fiber, flame retardant and antioxidant;
the particle size range of the mixed olefin microspheres is 1-20 microns;
the mixed olefin grafted microsphere is prepared according to the method comprising the following steps:
carrying out copolymerization reaction on the mixed olefin and maleic anhydride in the presence of nitrogen, an initiator and an organic solvent, and separating, washing and drying to obtain the mixed olefin grafted microspheres;
the mixed olefin is at least two of trans-2-butene, cis-2-butene, n-butene, isobutene, isoprene, cyclopentadiene, 1, 4-pentadiene and piperylene;
the weight ratio of the mixed olefin to the maleic anhydride is (0.5-5): 1.
2. the nylon 6 composition of claim 1, wherein:
the components are calculated according to the parts by weight,
6100 parts by weight of nylon;
3-6 parts of polyethylene glycol;
5-10 parts of mixed olefin grafted microspheres;
the particle size range of the mixed olefin microspheres is 5-15 microns.
3. The nylon 6 composition of claim 2, wherein:
the particle size range of the mixed olefin microspheres is 5-8 microns.
4. The nylon 6 composition of claim 1, wherein:
based on 100 parts by weight of nylon-6,
5-35 parts of glass fiber.
5. The nylon 6 composition of claim 4, wherein:
based on 100 parts by weight of nylon 6,
10-30 parts of glass fiber.
6. The nylon 6 composition of claim 1, wherein:
based on 100 parts by weight of nylon 6,
10-20 parts of a flame retardant;
the flame retardant is at least one of triphenyl phosphate and its oligomer, resorcinol-bis (diphenyl phosphate), bisphenol A-bis (diphenyl phosphate), resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ], and hexaphenoxycyclotriphosphazene.
7. The nylon 6 composition of claim 1, wherein:
based on 100 parts by weight of nylon 6,
13-16 parts of flame retardant.
8. The nylon 6 composition of claim 1, wherein:
the initiator is an azo initiator or a peroxide initiator; the amount of the initiator is 1-5 wt% of the weight of the maleic anhydride.
9. The nylon 6 composition of claim 1, wherein:
the weight ratio of the mixed olefin to the maleic anhydride is (3-5): 1;
the concentration of the maleic anhydride in the organic solvent is 15wt% -30 wt%.
10. The nylon 6 composition of claim 9, wherein:
the concentration of the maleic anhydride in the organic solvent is 20wt% -30 wt%.
11. The nylon 6 composition of claim 1, wherein:
the temperature of the copolymerization reaction is 60-100 ℃; the copolymerization reaction pressure is 0.2-2 MPa; the copolymerization reaction time is 5-8 hours.
12. The nylon 6 composition of claim 11, wherein:
the copolymerization reaction temperature is 80-95 ℃; the copolymerization reaction pressure is 0.5-1 MPa.
13. A process for preparing a nylon 6 composition according to any of claims 1 to 12, comprising:
the nylon 6 composition is prepared by melt blending the components according to the dosage.
14. A process for preparing a nylon 6 composition according to claim 13, characterized in that:
the melting temperature is 230-250 ℃.
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| CN201911022736.8A CN112708261B (en) | 2019-10-25 | 2019-10-25 | Mixed olefin grafted microsphere reinforced flame-retardant nylon 6 composition and preparation method thereof |
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| CN104774447A (en) * | 2015-04-16 | 2015-07-15 | 苏州靖羽新材料有限公司 | Long fiber reinforced nylon plastic and preparation method thereof |
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2019
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| US5543452A (en) * | 1988-03-15 | 1996-08-06 | Asahi Kasei Kogyo Kabushiki Kaisha | Flame-resistant polyamide resin compositions and flame retardants therefor |
| CN104774447A (en) * | 2015-04-16 | 2015-07-15 | 苏州靖羽新材料有限公司 | Long fiber reinforced nylon plastic and preparation method thereof |
| CN109721813A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | Polypropylene modification composition and modified polypropene |
| CN110256843A (en) * | 2019-06-25 | 2019-09-20 | 平顶山市科隆新材料有限公司 | A kind of flame-retardant and anti-static nylon material and preparation method thereof |
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