CN110591100A - Ultralow temperature resistant nylon toughening agent and preparation method and application thereof - Google Patents
Ultralow temperature resistant nylon toughening agent and preparation method and application thereof Download PDFInfo
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- CN110591100A CN110591100A CN201910911528.7A CN201910911528A CN110591100A CN 110591100 A CN110591100 A CN 110591100A CN 201910911528 A CN201910911528 A CN 201910911528A CN 110591100 A CN110591100 A CN 110591100A
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- 229920001778 nylon Polymers 0.000 title claims abstract description 102
- 239000004677 Nylon Substances 0.000 title claims abstract description 101
- 239000012745 toughening agent Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 229920013822 aminosilicone Polymers 0.000 claims abstract description 26
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical group 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- RTJGBIGSNVJSDM-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C(C)(C)N=C=O)=C1 RTJGBIGSNVJSDM-UHFFFAOYSA-N 0.000 claims description 2
- GPBUTTSWJNPYJL-UHFFFAOYSA-N 2,2-dimethyloctane Chemical compound CCCCCCC(C)(C)C GPBUTTSWJNPYJL-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 11
- 239000000806 elastomer Substances 0.000 abstract description 7
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 18
- 229920002292 Nylon 6 Polymers 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
-
- 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
- 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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of high polymer materials, and discloses an ultralow temperature resistant nylon toughening agent which comprises a main chain of a polyolefin elastomer and a side chain of a polar monomer, wherein the side chain of the polar monomer is connected with amino silicone oil. Based on the total weight of the nylon flexibilizer, the content of the polyolefin elastomer is 45-70 wt%, the content of the polar monomer is 0.5-5 wt%, and the content of the amino silicone oil is 25-50 wt%; the preparation method of the toughening agent comprises the steps of adding the elastomer, the initiator and the polar monomer into a blending device for melt blending, and then adding the amino silicone oil for continuous blending to prepare the ultralow temperature resistant nylon toughening agent. When the toughening agent is applied to a nylon product, a polar monomer in the toughening agent can react with amino or carboxyl of a nylon chain segment to enhance compatibility, meanwhile, the addition of amino silicone oil can further improve the ultralow-temperature impact resistance and toughness of nylon, and the prepared ultralow-temperature impact resistant nylon has excellent ultralow-temperature impact resistance and can be applied to a plurality of fields such as automobiles, electrical appliances, buildings and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an ultralow temperature resistant nylon toughening agent and a preparation method and application thereof.
Background
Nylon (PA) is an engineering plastic with excellent mechanical properties, solvent resistance, wear resistance, etc., and is widely used in the fields of construction, automobile industry, medical appliances, etc. However, nylon has a low notched impact strength, and particularly, nylon exhibits a disadvantage of poor toughness in a low-temperature environment, which limits further applications of nylon in the industry. Therefore, to meet the needs of industrial development, it is very important to improve the impact resistance of nylon.
At present, nylon toughening has been studied in a great deal and is partially popularized and applied, and the most common methods are two: firstly, the lactam of long chain is introduced in the monomer of nylon as comonomer, reduces the nylon crystallinity, increases the flexible chain segment in the nylon to improve the impact strength of nylon. However, the method needs to start reaction from a polymer monomer, the process conditions are relatively complex, and the residual small molecular monomer is difficult to remove, so that the performance of nylon is influenced, the process is complex, the cost is high, and the method has no universality.
Another method is to use rubber or elastomer as toughening agent of nylon, including ethylene-propylene rubber (EPR), ethylene-propylene-diene copolymer (EPDM), styrene-butadiene-styrene copolymer (SBS), etc. The rubber or the elastomer is dispersed in the nylon matrix by blending with nylon, and when the nylon is impacted by the outside, the rubber or the elastomer can absorb energy and generate porogenesis and yield, and further silver lines and shear bands are initiated by interface transmission, so that a large amount of energy is consumed, and the impact resistance of the nylon is improved. However, these elastomers have high glass transition temperature, and cannot achieve toughening of nylon at ultralow temperature or low temperature, and these elastomers have poor compatibility with nylon, and a large amount of the elastomers added may even cause a decrease in mechanical properties of nylon.
CN 102964822A discloses a nylon resin toughened and modified by silicone rubber and a preparation method thereof, wherein the silicone rubber is uniformly dispersed in nylon, amino silicone oil is added as a compatilizer, and the toughening of the nylon is realized through dynamic vulcanization of the silicone rubber. However, the nylon prepared by the method has unsatisfactory toughening effect, and the compatibility of the silicon rubber and the nylon is not good, so that the impact resistance of the nylon in a low-temperature environment cannot be improved.
CN 109880360A discloses a high cold impact resistant nylon composite material and a preparation method thereof, wherein a modified toughening agent and a compound cold-resistant plasticizer are blended with nylon to improve the low-temperature impact resistance of the nylon. The compound cold-resistant plasticizer is a mixture of aromatic plasticizer and aliphatic plasticizer, and the modified plasticizer is a product of rubber or polyurethane elastomer grafted by grafting agent. Although the plasticizer and the toughening agent are adopted to simultaneously toughen and plasticize the nylon, multiple material blending preparation steps are required, the preparation method is complicated in process, and the process is complex.
With the popularization of nylon materials in alpine regions, wider application markets are won, the nylon needs to withstand the test of alpine environments (minus 50 ℃), and the alpine impact strength and toughness of the nylon materials in ultralow temperature environments need to be improved.
Disclosure of Invention
The invention aims to improve the toughness and the impact resistance of nylon in an ultralow temperature environment, the ultralow temperature toughening agent is prepared by taking a polyolefin elastomer as a main chain and amino silicone oil as a branched chain, and the impact resistance of the nylon in the ultralow temperature environment is improved under the condition that the nylon can keep certain strength by adding the ultralow temperature toughening agent into the nylon.
In order to achieve the purpose, the invention adopts the technical scheme that:
an ultra-low temperature resistant nylon toughener comprising: the polyolefin elastomer comprises a main chain of a polyolefin elastomer and a side chain of a polar monomer, wherein the side chain of the polar monomer is connected with amino silicone oil; the total weight of the nylon toughening agent is 45-70 wt% of the polyolefin elastomer, and 0.5-5 wt% of the polar monomer; the content of the amino silicone oil is 25-50 wt%.
The polyolefin elastomer is selected from random ethylene/alpha-olefin copolymer, block ethylene/alpha-olefin copolymer or their mixture.
The polar monomer comprises at least one double bond and at least one polar functional group; the polar functional group is hydroxyl, carboxyl, ether bond, aldehyde group, ester group or cyano. Wherein the double bond and the polyolefin elastomer are copolymerized and grafted, and the polar functional group reacts and is connected with the amino silicone oil.
Further preferably, the polar monomer is selected from one or more of acrylic monomers, maleic anhydride and 3-isopropyl-dimethylbenzyl isocyanate.
The acrylic monomer is one or more selected from acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, hydroxyethyl methacrylate, acrylonitrile and 2-ethylhexyl acrylate.
The polar group in the polar monomer can react with the amino functional group in the amino silicone oil and also react with the terminal carboxyl group and the amino group in the nylon, so that the introduction of the polar monomer can connect the amino silicone oil on one hand and strengthen the action with the nylon on the other hand.
The amino silicone oil comprises at least one amino functional group which reacts with the polar functional group in the polar monomer.
The preparation method of the ultralow temperature resistant nylon toughening agent comprises the following steps: according to the mass parts of the raw materials, 100 parts of polyolefin elastomer, 0.01-0.5 part of initiator and 0.2-10 parts of polar monomer are added into mixing equipment to be melted and blended for 3-15min at the temperature of 160-220 ℃, then 10-150 parts of amino silicone oil are added to be continuously blended for 5-15min, and the ultralow temperature resistant nylon toughening agent is prepared.
In the preparation method, the initiator is a peroxide initiator or an azo initiator.
Further preferably, the peroxide initiator is selected from one or more of dicumyl peroxide, benzoyl peroxide and tert-butyl hexane peroxide; the azo initiator is selected from one or more of azoisobutyronitrile formamide, azodiisobutyronitrile, azodiisovaleronitrile and azodiisoheptanonitrile.
Preferably, the preparation method of the ultralow temperature resistant nylon toughening agent comprises the following steps: according to the mass parts of the raw materials, 100 parts of polyolefin elastomer, 0.01-0.5 part of dicumyl peroxide and 0.2-10 parts of maleic anhydride are added into mixing equipment to be melted and blended for 3-15min at the temperature of 160-220 ℃, 10-150 parts of amino silicone oil is added to be continuously blended for 5-15min, and the nylon toughening agent is prepared, so that the toughening effect is better.
The ultralow temperature resistant nylon toughening agent provided by the invention can be applied to nylon products to prepare ultralow temperature resistant and impact resistant nylon.
The ultralow temperature resistant and impact resistant nylon is prepared by adding 5-20 parts of the nylon toughening agent into every 100 parts of nylon in the processing process of nylon products.
The nylon is selected from one or more of nylon 6, nylon 12, nylon 612, nylon 610, nylon 1010, nylon 66 and nylon 11.
According to the ultralow temperature resistant nylon toughening agent provided by the invention, polar functional groups of polar monomers in the toughening agent can react with amino and carboxyl at the end of a nylon chain to play a role of a compatilizer, so that the dispersibility of the toughening agent in nylon is promoted, and the ultralow temperature impact resistance of nylon is improved; meanwhile, the addition of the amino silicone oil can reduce the glass transition temperature of the polyolefin elastomer and promote the toughness of the ultralow temperature resistant and impact resistant nylon prepared by the toughening agent to be improved.
Compared with the prior art, the invention has the following beneficial effects:
the nylon toughening agent has simple preparation process, no emission and no pollution; when the nylon composite is applied to nylon products, the additive amount is small, the toughness and the impact resistance, especially the impact resistance at ultralow temperature, of the nylon material can be improved while certain strength of the nylon material is maintained, and the nylon composite can be applied to the fields of automobiles, rail transit, electricity, buildings and the like.
Drawings
FIG. 1 is a schematic view of the reaction of polyolefin elastomer, polar monomer and amino silicone oil in the preparation process of the nylon toughening agent of the present invention.
FIG. 2 is an IR spectrum of the ultra low temperature resistant nylon toughener of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
In the present embodiment, the polyolefin elastomer is selected from polyethylene-octene copolymer (POE) with a trademark of exxonmobil 9061, nylon is selected from nylon 6(PA6) with a trademark of japanese ministry 1013B, the initiator is dicumyl peroxide, and other raw materials are commercially available.
As shown in figure 1, in the preparation process of the ultralow temperature resistant nylon toughening agent, a polyolefin elastomer reacts with a polar monomer and amino silicone oil, the polyolefin elastomer serves as a main chain, the polar monomer is grafted on the polyolefin elastomer to serve as a side chain and is connected with the amino silicone oil, so that the ultralow temperature resistant nylon toughening agent is formed.
The test method of the prepared nylon comprises the following steps:
and (3) tensile test: the tensile speed is 10mm/min according to the test of GB 1040-2006 standard.
Low temperature notched impact strength: impact-resistant bars were prepared according to GB/T17037.1-1997 and the samples were left to stand at-50 ℃ for 1h and then removed for notched impact testing.
Drop hammer test: and (3) injection molding a sample to be tested into a baffle seat, standing the baffle seat to be tested at-50 ℃ for 1h, taking out, and testing at the temperature of 23 +/-3 ℃. The impact rod of 6 plus or minus 0.05kg freely falls down from the height of 0.45m, the cross section area of the drop hammer metal rod is 28mm, the impact point is in the middle of the convex edge of the baffle seat to be tested, and the process is repeated for 6 times.
The preparation raw materials of the nylon flexibilizer in the examples 1 to 7 and the comparative example 1 are as follows:
TABLE 1 raw Material composition of Nylon toughener in examples and comparative examples
Examples 1 to 7
Adding POE, dicumyl peroxide and a polar monomer into an internal mixer, melting and blending at the temperature of 200 ℃, wherein the revolution of the internal mixer is 100 r/min, adding amino silicone oil after 5min, continuing blending, and sampling after 8 min to obtain the ultralow temperature resistant nylon toughening agent.
And (3) uniformly blending 15 parts of ultralow temperature resistant nylon toughening agent and 100 parts of PA6, adding into an extruder, carrying out melt blending at the temperature of 200 ℃ and 220 ℃ for 10min, and granulating to obtain the ultralow temperature resistant impact-resistant nylon.
Comparative example 1
Adding POE, dicumyl peroxide and a polar monomer into an internal mixer, melting and blending at the temperature of 200 ℃, wherein the revolution of the internal mixer is 100 r/min, and sampling after 5min to obtain the common nylon toughening agent.
And (3) uniformly blending 15 parts of nylon toughening agent and 100 parts of PA6, adding into an extruder, carrying out melt blending at the temperature of 200 ℃ and 220 ℃ for 10min, and granulating to obtain the common nylon.
Comparative example 2
100 parts of PA6 is added into an extruder, and the mixture is melted and blended for 10min at the temperature of 200 ℃ and 220 ℃, and then the common nylon is obtained after granulation.
TABLE 2 mechanical Properties of nylons in examples and comparative examples
The IR spectra before and after POE grafting are shown in FIG. 2, which shows that the grafted POE is obtained by Maleic Anhydride (MAH)After graft modification, at 1782cm-1Characteristic peaks of MAH appear nearby. When further reacted with amino silicone oil, at 1100cm-1An absorption peak of a siloxane bond on the amino silicone oil is obviously appeared nearby.
As can be seen from the data in Table 2, the drop weight test results of examples 1-7 compared with comparative example 2 show that the addition of the ultralow temperature resistant nylon toughening agent of the present invention to PA6 can significantly improve the low temperature impact resistance of PA 6. Comparing examples 1-7 with comparative example 1, it can be seen that the toughness of PA6 can be further improved by the amino silicone oil grafted into the toughening agent, compared with the ordinary nylon toughening agent without grafted amino silicone oil.
Claims (10)
1. An ultra-low temperature resistant nylon toughening agent, which is characterized by comprising: the polyolefin elastomer comprises a main chain of a polyolefin elastomer and a side chain of a polar monomer, wherein the side chain of the polar monomer is connected with amino silicone oil; based on the total weight of the nylon toughening agent, the content of the polyolefin elastomer is 45-70 wt%, and the content of the polar monomer is 0.5-5 wt%; the content of the amino silicone oil is 25-50 wt%.
2. The ultra low temperature resistant nylon toughener of claim 1, wherein the polar monomer comprises at least one double bond and at least one polar functional group;
the polar functional group is hydroxyl, carboxyl, ether bond, aldehyde group, ester group or cyano.
3. The ultra-low temperature resistant nylon toughener according to claim 1 or 2, wherein the polar monomer is selected from one or more of acrylic monomers, maleic anhydride, and 3-isopropyl-dimethylbenzyl isocyanate.
4. The ultra-low temperature resistant nylon toughener of claim 3, wherein the acrylic monomer is selected from one or more of acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, hydroxyethyl methacrylate, acrylonitrile, and 2-ethylhexyl acrylate.
5. The ultra-low temperature resistant nylon toughener of claim 1, wherein the amino silicone oil contains at least one amino functional group.
6. The preparation method of the nylon toughening agent according to any one of claims 1 to 5, wherein 100 parts by mass of the polyolefin elastomer, 0.01 to 0.5 part by mass of the initiator and 0.2 to 10 parts by mass of the polar monomer are added into a mixing device to be melt-blended at 220 ℃ for 3 to 15min, and then 10 to 150 parts by mass of the amino silicone oil are added to be continuously blended for 5 to 15min, so as to prepare the nylon toughening agent resistant to ultralow temperature.
7. The method for preparing nylon toughening agent according to claim 6, wherein the initiator is peroxide initiator or azo initiator.
8. The method for preparing nylon toughening agent according to claim 7, wherein the peroxide initiator is selected from one or more of dicumyl peroxide, benzoyl peroxide and tert-butyl hexane peroxide;
the azo initiator is selected from one or more of azoisobutyronitrile formamide, azodiisobutyronitrile, azodiisovaleronitrile and azodiisoheptanonitrile.
9. The method for preparing nylon toughening agent according to claim 6, wherein the initiator is dicumyl peroxide; the polar monomer is maleic anhydride.
10. An ultra-low temperature resistant and impact resistant nylon, which is characterized in that 5 to 20 parts of the nylon toughening agent of any one of claims 1 to 5 is added into every 100 parts of nylon during the processing of nylon products to prepare the ultra-low temperature resistant and impact resistant nylon.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910911528.7A CN110591100B (en) | 2019-09-25 | 2019-09-25 | Ultralow temperature resistant nylon toughening agent and preparation method and application thereof |
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| CN201910911528.7A CN110591100B (en) | 2019-09-25 | 2019-09-25 | Ultralow temperature resistant nylon toughening agent and preparation method and application thereof |
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| CN110591100A true CN110591100A (en) | 2019-12-20 |
| CN110591100B CN110591100B (en) | 2020-08-04 |
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| CN201910911528.7A Active CN110591100B (en) | 2019-09-25 | 2019-09-25 | Ultralow temperature resistant nylon toughening agent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023082277A1 (en) * | 2021-11-15 | 2023-05-19 | Dow Global Technologies Llc | Toughened polyamide |
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