CN111217963A - High-fluidity nylon toughening agent and preparation method thereof - Google Patents
High-fluidity nylon toughening agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of high polymer materials, and discloses a high-fluidity nylon toughening agent and a preparation method thereof. The nylon toughening agent comprises the following raw materials in parts by weight: 20-90 parts of propenyl elastomer, 10-80 parts of vinyl elastomer, 0.3-5 parts of first grafting monomer, 0.1-5 parts of second grafting monomer, 0.01-0.5 part of initiator and 0.1-2 parts of diluent. The preparation method of the nylon toughening agent comprises the following steps: mixing the propenyl elastomer, the vinyl elastomer, the first grafting monomer, the second grafting monomer, the initiator and the diluent, adding into an extruder, melting and plasticizing, reacting and extruding, granulating, cooling and drying to obtain the high-fluidity nylon toughening agent. The nylon toughening agent has good toughening effect and high fluidity, can improve the notch impact strength of a nylon product and simultaneously keep the processing fluidity of the nylon product to a large extent, has a simple preparation method, a short production period and strong controllability, and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-fluidity toughening agent for toughening nylon and a preparation method thereof.
Background
The nylon is one of five general engineering plastics, has high yield, wide application, excellent mechanical strength, heat resistance, oil resistance, weak acid resistance, alkali resistance and common solvents, no toxicity, no odor, good electrical insulation property and good weather resistance. The nylon has the defects that the notch impact performance is general, the product needs post-conditioning treatment to improve the toughness, meanwhile, the water absorption of the nylon is high, the dimensional stability of the product is influenced, the production cost is increased, and the application of the nylon is greatly limited. In order to solve the problem of insufficient toughness of nylon, the toughness is generally improved by adding a toughening agent.
The toughening of nylon is mainly elastomer toughening at present. Because the compatibility between the nonpolar elastomer molecules and the polar nylon molecules is poor, the interface bonding force is low, and the mechanical property of the material is difficult to improve, the compatibility between the nonpolar elastomer molecules and the polar nylon molecules needs to be improved by utilizing a grafting monomer, namely, a functional monomer which can generate chemical reaction with the nylon molecules or has equivalent polarity is grafted on the soft polyolefin elastomer molecules by a grafting chemical modification method, so that the polyolefin elastomer is uniformly dispersed in a nylon matrix in the form of tiny particles and forms a firm interface layer with the nylon. When the material is impacted by the outside, the soft polyolefin elastomer firstly absorbs energy to generate voiding and yielding, and then silver lines and shear bands are initiated through interface transmission, so that a large amount of energy is consumed, and the effect of improving the impact strength of the material is achieved macroscopically. However, the elastomer toughening agent in the current market has higher viscosity, greatly reduces the processing fluidity of the material while improving the toughness of nylon, and is not beneficial to the subsequent processing of large or complex-shaped workpieces.
Chinese patent literature (publication number: CN108129833A, published: 2018, 6 and 8) discloses a toughening agent of polyolefin grafted maleic anhydride for low-temperature-resistant nylon and a preparation method thereof, wherein the toughening agent comprises the following raw materials in parts by weight: 100 parts of polyolefin elastomer, 0.3-1.5 parts of maleic anhydride, 2-6 parts of ionic polymer, 1.0-2.0 parts of polypropylene powder, 0.05-0.15 part of grafted polypropylene, 0.05-0.25 part of lubricant, 0.1-0.3 part of plasticizer, 0.05-0.2 part of initiator and 0.1-0.3 part of antioxidant. Wherein, the polypropylene powder has the functions of: the polypropylene has large melt index, good fluidity and more convenient processing process, and ensures that various reaction raw materials are well dispersed. The nylon toughening agent can effectively improve the low-temperature impact property of the nylon material, but the flowability of the toughening agent is almost unchanged compared with that of a common toughening agent, and the influence of the toughening agent on the processing flowability of the nylon material cannot be reduced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-fluidity nylon toughening agent and a preparation method thereof. The nylon toughening agent has good toughening effect and high fluidity, and can keep the processing fluidity of the nylon product to a large extent while improving the notch impact strength of the nylon product.
The specific technical scheme of the invention is as follows:
a high-fluidity nylon toughening agent comprises the following raw materials in parts by weight: 20-90 parts of propenyl elastomer, 10-80 parts of vinyl elastomer, 0.3-5 parts of first grafting monomer, 0.1-5 parts of second grafting monomer, 0.01-0.5 part of initiator and 0.1-2 parts of diluent.
When preparing the toughening agent, the grafting monomer is grafted to the elastomer under the action of the initiator. When the nylon material is treated by the toughening agent, the grafting monomer is connected with nylon molecules through chemical reaction, so that the elastomer is uniformly dispersed in a nylon matrix and forms a firm interface layer with the nylon. When the material is impacted by the outside, the soft polyolefin elastomer firstly absorbs energy to generate voiding and yielding, and further silver lines and shear bands are initiated through interface transmission, so that impact energy is dispersed and a large amount of energy is consumed, and the effect of improving the impact strength of the material is achieved macroscopically. The diluent acts to dissolve the initiator, allowing it to disperse uniformly into the elastomer and graft monomer, thereby ensuring a uniform chemical structure of the graft reaction product.
The invention innovatively adopts the combination of the propenyl elastomer and the vinyl elastomer as the matrix material of the toughening agent. In the process of double-screw chemical reaction extrusion, under the attack of free radicals generated by the decomposition of an initiator, the molecular chain breaking of the propenyl elastomer is generated to change the propenyl elastomer into a shorter chain, the molecular weight is reduced, and the fluidity is increased, so that the nylon toughening agent with better fluidity can be obtained. In terms of toughening effect, the ethylene-based elastomer is superior to the propylene-based elastomer, the toughening effect of the propylene-based elastomer is obviously reduced in a low-temperature environment, and the ethylene-based elastomer has better low-temperature resistance. Therefore, the toughening agent and the toughening agent are combined for use, so that the toughening effect is ensured, and meanwhile, the fluidity of the toughening agent is increased, so that the modified nylon material keeps better processing fluidity.
Preferably, the propylene-based elastomer is a propylene-ethylene copolymer or a propylene-octene copolymer with 84-96% of propylene content produced by metallocene catalysis.
The polypropylene is hard and can reduce the crystallinity of the polypropylene by copolymerizing with ethylene, thereby reducing the hardness and ensuring better toughening effect.
Preferably, the vinyl elastomer is a copolymer elastomer mainly composed of ethylene.
Preferably, the ethylene-based elastomer is at least one of ethylene-octene copolymer (POE), ethylene-butene copolymer, ethylene-propylene-diene monomer (EPDM), ethylene-vinyl acetate copolymer (EVA), and ethylene-acrylic ester copolymer (e.g., ethylene-methyl acrylate copolymer (EMA), ethylene-methacrylic acid copolymer (EMAA), ethylene-butyl acrylate copolymer (EBA)).
Preferably, the first grafting monomer is at least one of maleic anhydride, maleic acid, fumaric acid, acrylic acid, phthalic anhydride and glycidyl methacrylate; the second grafting monomer is at least one of styrene, pyridine and caprolactam.
The first grafting monomer has the function of reacting with nylon molecules to improve the compatibility between elastomer molecules and the nylon molecules; the second grafting monomer is used for promoting the reaction of the first grafting monomer and the elastomer and improving the grafting speed and the grafting rate.
Preferably, the initiator is at least one of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, dicumyl peroxide (DCP), dibenzoyl peroxide (BPO), bis (2-t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-butylperoxide, t-amyl perbenzoate, 2-bis (t-amylperoxy) -butane, di-t-amylperoxide, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3, 5, 5-trimethylhexanoate, and dibenzoyl peroxide.
An important principle in the choice of initiator is that it has a half-life which is matched to the residence time of the material in the processing temperature range. If the half-life is too long, the grafting rate is reduced, the initiator cannot be completely utilized, material waste is caused, and the performance of the final product can be influenced by the residual initiator; if the half-life is too short, the initiator will initially decompose to produce a higher concentration of free radicals, increasing the likelihood of di-radical termination, and the grafting rate will be limited by the rate of diffusion of monomer to the reaction site.
Preferably, the diluent is at least one of acetone, butanone, ethanol and ethyl acetate.
A preparation method of a high-fluidity nylon toughening agent comprises the following steps: uniformly mixing the propenyl elastomer, the vinyl elastomer, the first grafting monomer, the second grafting monomer, the initiator and the diluent, adding into an extruder, melting and plasticizing, reacting and extruding, granulating, cooling and drying to obtain the high-fluidity nylon toughening agent.
The invention carries out melt grafting reaction by reactive extrusion, and the principle is that an initiator is decomposed at high temperature to generate primary free radicals, and the primary free radicals and an elastomer main chain carry out hydrogen absorption reaction to form macromolecular free radicals, thereby carrying out grafting reaction. Compared with other grafting methods such as a monomer polymerization method, a solution method, a radiation method, a solid phase method and the like, the grafting method of the melting method has the advantages of high grafting rate, simple operation, low production cost, continuous operation and benefit for environmental protection.
Preferably, the temperature in the extruder is 80-195 ℃.
In reactive extrusion processes, the processing temperature has a significant influence on the quality of the final product: too low extrusion temperature can result in low decomposition rate of the initiator, low concentration of generated free radicals and low reactivity of elastomer molecular chains, thus being not beneficial to grafting reaction, and simultaneously, low temperature is not beneficial to mixing and processing of materials; when the extrusion temperature is too high, the rate of side reactions such as radical termination and induced decomposition of primary radicals generated by the decomposition of the initiator increases, and the graft ratio decreases. The temperature in the extruder is controlled to be 80-195 ℃, so that the obtained toughening agent has higher grafting rate.
Preferably, the extruder is a twin-screw extruder, and the temperatures of zones 1 to 14 of the extruder are set to 80 + -10 ℃, 160 + -10 ℃, 180 + -10 ℃, 190 + -10 ℃, 195 + -10 ℃, 190 + -10 ℃, 180 + -10 ℃ and 190 + -10 ℃ at the head.
Compared with a single-screw extruder, the double-screw extruder has the advantages of uniform material mixing, no local overheating of the material, effective control of the retention time of the material, uniform chemical structure of the product and the like.
The invention has the following beneficial effects:
the nylon toughening agent has a good toughening effect, can effectively improve the notch impact strength of a nylon product, has high fluidity, can reduce the influence of the toughening agent on the fluidity of nylon, and can be applied to the modification of nylon with high requirements on toughness and processing fluidity.
The preparation method of the high-fluidity nylon toughening agent is simple to operate, short in production period, strong in controllability and suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Weighing the following raw materials in parts by weight: 90 parts of propylene-ethylene copolymer with the propylene content of 84 percent; 10 parts of vinyl elastomer (Dow POE, 8150); the first grafting monomer is maleic anhydride, 2 parts; the second grafting monomer is styrene, 1 part; 0.1 part of dicumyl peroxide serving as an initiator; the diluent is acetone, 1 part.
Mixing the above materials in a low speed blender for 20min, adding into a double screw extruder, setting the temperature of zone 1 to zone 14 of the extruder at 80 deg.C, 160 deg.C, 180 deg.C, 190 deg.C, 195 deg.C, 190 deg.C, 180 deg.C, and 190 deg.C. And carrying out melt plasticization, kneading and mixing, extruding by a machine head, granulating by a water ring, cooling, dehydrating, and drying by air blasting to obtain the product.
Example 2
Weighing the following raw materials in parts by weight: the propylene-based elastomer is a propylene-ethylene copolymer with the propylene content of 92 percent, and 70 parts; vinyl elastomer (dow EPDM, 3745P), 30 parts; the first grafting monomer is maleic anhydride, 2 parts; the second grafting monomer is caprolactam, 1 part; the initiator consists of 0.15 part of dibenzoyl peroxide and 0.15 part of dicumyl peroxide in a mass ratio of 1: 2; the diluent is butanone and 1.5 portions.
Mixing the above materials in a low speed blender for 20min, adding into a double screw extruder, setting the temperature of zone 1 to zone 14 of the extruder at 80 deg.C, 160 deg.C, 180 deg.C, 190 deg.C, 195 deg.C, 190 deg.C, 180 deg.C, and 190 deg.C. And carrying out melt plasticization, kneading and mixing, extruding by a machine head, granulating by a water ring, cooling, dehydrating, and drying by air blasting to obtain the product.
Example 3
Weighing the following raw materials in parts by weight: the propylene-based elastomer is a propylene-octene copolymer with the propylene content of 88 percent, and 60 parts; ethylene-based elastomer (acoma EMA, 28MA07), 40 parts; the first grafting monomer is glycidyl methacrylate, and 5 parts; the second grafting monomer is styrene, 2.5 parts; the initiator is 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, and 0.4 part; the diluent is ethanol and 2 parts.
Mixing the above materials in a low speed blender for 20min, adding into a double screw extruder, setting the temperature of zone 1 to zone 14 of the extruder at 80 deg.C, 160 deg.C, 180 deg.C, 190 deg.C, 195 deg.C, 190 deg.C, 180 deg.C, and 190 deg.C. And carrying out melt plasticization, kneading and mixing, extruding by a machine head, granulating by a water ring, cooling, dehydrating, and drying by air blasting to obtain the product.
Example 4
Weighing the following raw materials in parts by weight: the propylene-based elastomer is a propylene-ethylene copolymer with the propylene content of 94 percent, and 20 parts; vinyl elastomer (dow EPDM, 3745P), 80 parts; the first grafting monomer is maleic anhydride, 2 parts; the second grafting monomer is caprolactam, 1 part; the initiator consists of 0.15 part of dibenzoyl peroxide and 0.15 part of dicumyl peroxide in a mass ratio of 1: 2; the diluent is butanone and 1.5 portions.
Mixing the above materials in a low speed blender for 20min, adding into a double screw extruder, setting the temperature of zone 1 to zone 14 of the extruder at 80 deg.C, 160 deg.C, 180 deg.C, 190 deg.C, 195 deg.C, 190 deg.C, 180 deg.C, and 190 deg.C. And carrying out melt plasticization, kneading and mixing, extruding by a machine head, granulating by a water ring, cooling, dehydrating, and drying by air blasting to obtain the product.
Comparative example 1
Weighing the following raw materials in parts by weight: vinyl elastomer (POE, 8150), 100 parts; the grafting monomer is maleic anhydride, 2 parts; 0.1 part of dicumyl peroxide serving as an initiator; the diluent is acetone, 1 part; 0.2 portion of white oil.
Mixing the above materials in a low speed blender for 20min, adding into a double screw extruder, setting the temperature of zone 1 to zone 14 of the extruder at 80 deg.C, 160 deg.C, 180 deg.C, 190 deg.C, 195 deg.C, 190 deg.C, 180 deg.C, 170 deg.C, 160 deg.C, and the head at 150 deg.C. And carrying out melt plasticization, kneading and mixing, extruding by a machine head, bracing, cooling, granulating and drying on the mixed material to obtain the product.
Comparative example 2
Weighing the following raw materials in parts by weight: 60 parts of polypropylene powder; ethylene-based elastomer (acoma EMA, 28MA07), 40 parts; the first grafting monomer is glycidyl methacrylate, and 5 parts; the second grafting monomer is styrene, 2.5 parts; the initiator is 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, and 0.4 part; the diluent is ethanol and 2 parts.
Mixing the above materials in a low speed blender for 20min, adding into a double screw extruder, setting the temperature of zone 1 to zone 14 of the extruder at 80 deg.C, 160 deg.C, 180 deg.C, 190 deg.C, 195 deg.C, 190 deg.C, 180 deg.C, and 190 deg.C. And carrying out melt plasticization, kneading and mixing, extruding by a machine head, granulating by a water ring, cooling, dehydrating, and drying by air blasting to obtain the product.
Comparative example 3
Weighing the following raw materials in parts by weight: 95 parts of propylene-ethylene copolymer with the propylene content of 84 percent; vinyl elastomer (Dow POE, 8150), 5 parts; the first grafting monomer is maleic anhydride, 2 parts; the second grafting monomer is styrene, 1 part; 0.1 part of dicumyl peroxide serving as an initiator; the diluent is acetone, 1 part.
Mixing the above materials in a low speed blender for 20min, adding into a double screw extruder, setting the temperature of zone 1 to zone 14 of the extruder at 80 deg.C, 160 deg.C, 180 deg.C, 190 deg.C, 195 deg.C, 190 deg.C, 180 deg.C, and 190 deg.C. And carrying out melt plasticization, kneading and mixing, extruding by a machine head, granulating by a water ring, cooling, dehydrating, and drying by air blasting to obtain the product.
Comparative example 4
Weighing the following raw materials in parts by weight: 10 parts of propylene-ethylene copolymer with the propylene content of 94 percent; ethylene-based elastomer (dow EPDM, 3745P), 90 parts; the first grafting monomer is maleic anhydride, 2 parts; the second grafting monomer is caprolactam, 1 part; the initiator consists of 0.15 part of dibenzoyl peroxide and 0.15 part of dicumyl peroxide in a mass ratio of 1: 2; the diluent is butanone and 1.5 portions.
Mixing the above materials in a low speed blender for 20min, adding into a double screw extruder, setting the temperature of zone 1 to zone 14 of the extruder at 80 deg.C, 160 deg.C, 180 deg.C, 190 deg.C, 195 deg.C, 190 deg.C, 180 deg.C, and 190 deg.C. And carrying out melt plasticization, kneading and mixing, extruding by a machine head, granulating by a water ring, cooling, dehydrating, and drying by air blasting to obtain the product.
The toughening agents prepared in examples 1 to 4 and comparative examples 1 to 4 were applied to PA6 (Nissan department of Japan, 1013B), 15 parts of the toughening agents prepared in examples 1 to 4 and comparative examples 1 to 4 were added to PA6, and the performances of pure PA6 and modified PA6 are shown in Table 1.
TABLE 1
From the comparison of the data, the IZOD notch impact strength of the PA6 material modified by the nylon toughening agent prepared in the embodiments 1-4 is obviously improved, which shows that the nylon toughening agent has a better toughening effect. Compared with the common nylon toughening agent prepared in the comparative example 1, the PA6 modified by the nylon toughening agent prepared in the examples 1-4 has a significantly higher melt mass flow rate, which indicates that the nylon toughening agent can keep better processing fluidity of the nylon material. In conclusion, compared with the common toughening agent, the nylon toughening agent provided by the invention can effectively improve the toughness of nylon, obviously reduce the reduction of the processing fluidity of nylon materials, and can be applied to the modification of nylon with high requirements on toughness and processing fluidity.
In the prior art (Chinese patent publication No. CN 108129833A), a small amount of polypropylene powder is added into a toughening agent raw material, and various reaction raw materials are well dispersed by utilizing the characteristic of good fluidity of polypropylene, but the processing fluidity of nylon is hardly influenced due to the small amount of the polypropylene powder. If the addition amount of the polypropylene powder is increased, the propylene-based elastomer in example 3 is replaced by the same weight part of the polypropylene powder as in comparative example 2, and the result shows that the IZOD notched impact strength of the nylon material in comparative example 2 is greatly reduced without significantly increasing the fluidity compared to example 3, which is limited by the amount of the initiator, but if the amount of the initiator is increased, the cost is greatly increased, and the small molecules generated by the decomposition of the initiator negatively affect the toughening effect.
The weight parts of the propenyl elastomer and the vinyl elastomer are respectively 20-90 parts and 10-80 parts, wherein the influence of the toughening agent on the processing fluidity of the nylon material can be reduced by the excess propenyl elastomer, but the negative influence on the toughening effect can be caused; the vinyl elastomer can enhance the toughening effect when being in excess, but the impact of the toughening agent on the processing flowability of the nylon material is large. Comparative examples 3 and 4 can demonstrate this: in comparative example 3, 95 parts and 5 parts of propylene-based elastomer and 5 parts of ethylene-based elastomer, respectively, the melt mass flow rate of the comparative example was increased as compared with example 1 (90 parts and 10 parts of propylene-based elastomer and 10 parts of ethylene-based elastomer, respectively), but the IZOD notched impact strength was significantly reduced and the toughening effect of the toughening agent was not good; in comparative example 4, 10 parts and 90 parts of propylene-based elastomer and ethylene-based elastomer, respectively, whereas the IZOD notched impact strength of this comparative example was increased but the melt mass flow rate was significantly reduced as compared with example 4 (20 parts and 80 parts of propylene-based elastomer and ethylene-based elastomer, respectively).
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The high-fluidity nylon toughening agent is characterized by comprising the following raw materials in parts by weight: 20-90 parts of propenyl elastomer, 10-80 parts of vinyl elastomer, 0.3-5 parts of first grafting monomer, 0.1-5 parts of second grafting monomer, 0.01-0.5 part of initiator and 0.1-2 parts of diluent.
2. The high-flowability nylon toughening agent of claim 1, wherein the propylene-based elastomer is a propylene-ethylene copolymer or a propylene-octene copolymer with 84-96% of propylene content produced by metallocene catalysis.
3. The toughening agent of claim 1, wherein the vinyl elastomer is a copolymer elastomer based on ethylene.
4. The toughening agent of claim 3, wherein the vinyl elastomer is at least one of ethylene-octene copolymer, ethylene-butene copolymer, ethylene-propylene-diene monomer, ethylene-vinyl acetate copolymer, and ethylene-acrylate copolymer.
5. The high flow nylon toughener of claim 1 wherein the first grafting monomer is at least one of maleic anhydride, maleic acid, fumaric acid, acrylic acid, phthalic anhydride, glycidyl methacrylate; the second grafting monomer is at least one of styrene, pyridine and caprolactam.
6. The high flow nylon toughening agent of claim 1, the initiator is at least one of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, dicumyl peroxide, dibenzoyl peroxide, bis (2-tert-butylperoxyisopropyl) benzene, tert-butylcumyl peroxide, di-tert-butyl peroxide, tert-amyl perbenzoate, 2-bis (tert-amylperoxy) -butane, di-tert-amyl peroxide, tert-butylperoxy benzoate, tert-butylperoxy-2-ethyl hexanoate, tert-butylperoxy-3, 5, 5-trimethyl hexanoate and dibenzoyl peroxide.
7. The toughening agent of claim 1, wherein the diluent is at least one of acetone, butanone, ethanol, and ethyl acetate.
8. A method for preparing a high-fluidity nylon toughening agent according to any one of claims 1 to 7, which comprises the following steps: uniformly mixing the propenyl elastomer, the vinyl elastomer, the first grafting monomer, the second grafting monomer, the initiator and the diluent, adding into an extruder, melting and plasticizing, reacting and extruding, granulating, cooling and drying to obtain the high-fluidity nylon toughening agent.
9. The method for preparing the high-fluidity nylon toughening agent according to claim 8, wherein the temperature in the extruder is 80-195 ℃.
10. The method of claim 8, wherein the extruder is a twin screw extruder, and the temperatures of the zones 1 to 14 of the extruder are set to 80 ± 10 ℃, 160 ± 10 ℃, 180 ± 10 ℃, 190 ± 10 ℃, 195 ± 10 ℃, 190 ± 10 ℃, 180 ± 10 ℃ and 190 ± 10 ℃ at the head.
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