CN113968939B - Nylon toughening agent and preparation method and application thereof - Google Patents
Nylon toughening agent and preparation method and application thereof Download PDFInfo
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- CN113968939B CN113968939B CN202111356712.3A CN202111356712A CN113968939B CN 113968939 B CN113968939 B CN 113968939B CN 202111356712 A CN202111356712 A CN 202111356712A CN 113968939 B CN113968939 B CN 113968939B
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- 239000004677 Nylon Substances 0.000 title claims abstract description 104
- 229920001778 nylon Polymers 0.000 title claims abstract description 104
- 239000012745 toughening agent Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000004132 cross linking Methods 0.000 claims abstract description 67
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 31
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 30
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- -1 acrylate compound Chemical class 0.000 claims abstract description 8
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 claims description 12
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 10
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 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 4
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 238000012545 processing Methods 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 239000000806 elastomer Substances 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229920001112 grafted polyolefin Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 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
- 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
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)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to the technical field of high polymer materials, in particular to a nylon toughening agent and a preparation method and application thereof. The nylon toughening agent is mainly prepared from the following components: 90-98 parts of polyolefin elastomer, 0.1-1 part of initiator, 1-5 parts of grafting monomer, 0.5-1 part of crosslinking auxiliary agent and 0.5-5 parts of antioxidant; the crosslinking aid comprises a multifunctional acrylate compound. The preparation method of the nylon toughening agent comprises the following steps: carrying out melt extrusion on a mixed material of an initiator, a grafting monomer, a crosslinking auxiliary agent, an antioxidant and part of polyolefin elastomer and the balance of polyolefin elastomer; wherein the mixed material is fed in a main feeding mode, and the rest polyolefin elastomer is fed in a side feeding mode. According to the invention, the specific crosslinking auxiliary agent is introduced, so that micro-crosslinking is generated while the grafting monomer is grafted with the polyolefin elastomer, and the micro-crosslinking and unreacted polyolefin elastomer form a mutually-crossed coating structure, so that the interfacial compatibility, the processing fluidity and the toughening effect can be considered.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a nylon toughening agent and a preparation method and application thereof.
Background
Nylon has excellent properties of high mechanical strength, oil resistance, acid and alkali resistance, easy processing and forming, friction resistance and the like as thermoplastic engineering plastics, and is widely applied to the automobile industry, the electronic and electric appliance industry, the sports equipment industry, the medical equipment industry and the like. However, nylon notch sensitivity is high, toughness is poor in a dry state and at low temperature, the requirement of super-tough polymer materials cannot be met, and meanwhile, due to the existence of amide bonds on a nylon molecular chain, the water absorption rate of nylon is high, the stability of a product is poor, and the further development of nylon is limited. To solve these problems, current researchers have mainly improved by adding toughening agents.
Nylon is mainly toughened by an elastomer grafted or copolymerized with a polar monomer. The elastomer is generally nonpolar and has poor compatibility with nylon, the elastomer needs to be modified, such as initiating grafting polar monomer or copolymerizing polar monomer, and the like, and the polar group is introduced into the molecular chain of the elastomer, so that the interfacial compatibility with the nylon is improved, and the risk of high water absorption rate of the nylon due to the existence of a large number of amide bonds is reduced. When the elastic body is stressed, the stress concentration of the elastic body generates plastic deformation, energy is absorbed, silver grains and a shearing belt are further induced through an interpenetrating interface, the development of the silver grains is stopped when the elastic body meets another elastic body, the shearing belt can also prevent the development of the silver grains, a large amount of energy is consumed, and the impact resistance of the material is improved. The toughness of the material is mainly determined by the interfacial compatibility of the elastomer and the matrix, the dispersion particle size and interval of the elastomer in the matrix, and the like.
In the prior art, the dispersion of the toughening agent in nylon is improved by improving the fluidity of the toughening agent, the toughening effect is maintained or slightly reduced, the grafting reaction is more complicated by introducing the multi-component grafting monomer, the residual quantity is not easy to control, the taste of the toughening agent is larger, and the production controllability is poor.
In view of this, the present invention has been made.
Disclosure of Invention
The first purpose of the invention is to provide a nylon toughening agent to solve the technical problems of uneven dispersion, poor toughening effect and the like in the prior art.
A second object of the present invention is to provide a method of preparing a nylon toughening agent.
A third object of the present invention is to provide the use of nylon toughening agents in nylon materials.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
The nylon toughening agent is mainly prepared from the following components in parts by weight:
90-98 parts of polyolefin elastomer, 0.1-1 part of initiator, 1-5 parts of grafting monomer, 0.5-1 part of crosslinking auxiliary agent and 0.5-5 parts of antioxidant;
The crosslinking auxiliary agent comprises a polyfunctional acrylate compound.
In particular embodiments of the present invention, the crosslinking aid includes any one or more of dipropylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and ditrimethylolpropane tetraacrylate.
In a specific embodiment of the present invention, the polyolefin elastomer is an ethylene-octene copolymer and/or an ethylene-propylene-nonconjugated diene terpolymer.
In a specific embodiment of the present invention, the initiator comprises any one or more of dibenzoyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, di-t-butyl peroxide, dicumyl peroxide, and di-t-butylcumene peroxide.
In a specific embodiment of the present invention, the grafting monomer comprises any one or more of maleic anhydride, itaconic acid, glycidyl methacrylate, and acrylic acid.
In a specific embodiment of the invention, the antioxidants include Antioxidant 168,168 and Antioxidant 1010,1010. Further, the mass ratio of Antioxidant to Antioxidant 1010 is 2: (2.5-3.5), such as 2:3.
The invention also provides a preparation method of the nylon toughening agent, which comprises the following steps:
carrying out melt extrusion on a mixed material of an initiator, a grafting monomer, a crosslinking auxiliary agent, an antioxidant and part of polyolefin elastomer and the balance of polyolefin elastomer; wherein the mixed material is fed in a main feeding mode, and the balance polyolefin elastomer is fed in a side feeding mode.
In a specific embodiment of the invention, the temperature between the main feed and the side feed is controlled to be 80 ℃ +/-10 ℃ to 190 ℃ +/-10 ℃; the temperature between the side feeding and the tail end is controlled to be 190 ℃ +/-10 ℃ to 180 ℃ +/-10 ℃.
In a specific embodiment of the present invention, the melt extrusion is performed using a twin screw extruder. Further, the double-screw extruder comprises 13 temperature areas, wherein the temperature of a 80℃±10℃、120℃±10℃、170℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃、180℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃, machine head is 180+/-10 ℃ in sequence.
In actual operation, the melt extrusion is carried out in a double-screw extruder, and then the nylon toughening agent is obtained through pelleting, cooling and drying.
In a specific embodiment of the invention, the side feeding is performed in the ninth zone.
In a specific embodiment of the present invention, the mass ratio of the portion of the polyolefin elastomer to the balance of the polyolefin elastomer is 1: (0.8 to 1.2).
In a particular embodiment of the invention, the twin-screw extruder has an aspect ratio of not less than 40, preferably not less than 56.
The invention also provides application of any one of the nylon toughening agents in preparing toughened nylon.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the nylon toughening agent, a specific crosslinking auxiliary agent is introduced, so that micro-crosslinking is generated while grafting monomers and polyolefin elastomers, and a coating structure which is mutually crossed with unreacted polyolefin elastomers is formed; when the modified nylon is blended with nylon, the compatibility of interfaces, the processing fluidity and the toughening effect can be considered;
(2) According to the preparation method of the nylon toughening agent, part of polyolefin elastomer reacts with grafting monomers, crosslinking aids and the like firstly, and micro-crosslinking is generated during grafting; then side feeding the rest polyolefin elastomer, wherein the side feeding polyolefin elastomer and the grafted polyolefin elastomer generate micro-crosslinking to form a mutually-crossed coating structure, and the interface compatibility, the processing fluidity and the toughening effect are taken into consideration; in addition, the coating structure is formed, and meanwhile, the initiator and the grafting monomer can be removed, so that the residue is reduced.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The nylon toughening agent is mainly prepared from the following components in parts by weight:
90-98 parts of polyolefin elastomer, 0.1-1 part of initiator, 1-5 parts of grafting monomer, 0.5-1 part of crosslinking auxiliary agent and 0.5-5 parts of antioxidant;
The crosslinking auxiliary agent comprises a polyfunctional acrylate compound.
According to the nylon toughening agent, a specific crosslinking auxiliary agent is introduced, and micro-crosslinking is generated when a grafting monomer is grafted with the polyolefin elastomer, so that a micro-crosslinking structure plays a role of a bridge, a better compatible interface can be formed with nylon, and physical entanglement can be generated between the nylon toughening agent and an uncrosslinked polyolefin elastomer molecular chain; when the cross-linked polyolefin elastomer is blended with nylon, the uncrosslinked polyolefin elastomer molecular chain is endowed with good fluidity, the micro-crosslinked structure can ensure compatibility, and meanwhile, the compatibility is further improved on one hand by matching with intermolecular acting force between ester bonds in the cross-linking auxiliary agent and amide bonds in the nylon, and on the other hand, the occurrence of multiple silver marks can be ensured to be easily initiated when the cross-linked polyolefin elastomer molecular chain is stressed, so that the toughening effect is improved.
In various embodiments, the nylon toughening agent may comprise the following components:
The polyolefin elastomer may be used in an amount of 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, etc.;
The initiator may be used in an amount of 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, etc.;
The amount of grafting monomer may be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc.;
The crosslinking aid may be used in an amount of 0.5 parts, 0.55 parts, 0.6 parts, 0.65 parts, 0.7 parts, 0.75 parts, 0.8 parts, 0.85 parts, 0.9 parts, 1 part, etc.;
the antioxidant may be used in an amount of 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc.
In the specific embodiment of the invention, the nylon toughening agent is mainly prepared from the following components in parts by weight: 95 to 98 parts of polyolefin elastomer, 0.1 to 0.5 part of initiator, 1 to 3 parts of grafting monomer, 0.5 to 0.8 part of crosslinking auxiliary agent and 0.5 to 2 parts of antioxidant. Preferably, the nylon toughening agent is mainly prepared from the following components in parts by weight: 96-98 parts of polyolefin elastomer, 0.1-0.3 part of initiator, 1-2 parts of grafting monomer, 0.5-0.6 part of crosslinking auxiliary agent and 0.5-1 part of antioxidant.
In a specific embodiment of the present invention, the polyfunctional acrylate has a functionality of 2 to 4, such as 2 or 3 or 4, preferably 4.
In particular embodiments of the present invention, the crosslinking aid includes any one or more of dipropylene glycol diacrylate (DPGDA), trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate (3-EO-TMPTA), and ditrimethylolpropane tetraacrylate (Di-TMPTA).
Intermolecular forces can be generated between the ester bonds in the crosslinking auxiliary agent and the amide bonds in the nylon, so that the interfacial compatibility is improved, and meanwhile, silver streaks are also facilitated to be generated under stress, and the toughening effect is improved.
In a specific embodiment of the present invention, the polyolefin elastomer is an ethylene-octene copolymer and/or an ethylene-propylene-nonconjugated diene terpolymer.
In a specific embodiment of the present invention, the initiator comprises any one or more of dibenzoyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, di-t-butyl peroxide, dicumyl peroxide, and di-t-butylcumene peroxide.
In a specific embodiment of the present invention, the grafting monomer comprises any one or more of maleic anhydride, itaconic acid, glycidyl methacrylate, and acrylic acid.
In a specific embodiment of the invention, the antioxidants include Antioxidant 168,168 and Antioxidant 1010,1010. Further, the mass ratio of Antioxidant to Antioxidant 1010 is 2:3.
The invention also provides a preparation method of the nylon toughening agent, which comprises the following steps:
carrying out melt extrusion on a mixed material of an initiator, a grafting monomer, a crosslinking auxiliary agent, an antioxidant and part of polyolefin elastomer and the balance of polyolefin elastomer; wherein the mixed material is fed in a main feeding mode, and the balance polyolefin elastomer is fed in a side feeding mode.
The invention makes partial polyolefin elastomer react with grafting monomer and crosslinking assistant to produce micro crosslinking while grafting; and then the balance polyolefin elastomer is laterally fed, the laterally fed polyolefin elastomer and the grafted and micro-crosslinked polyolefin elastomer form a mutually-crossed coating structure, the laterally fed polyolefin elastomer endows the toughening agent with better fluidity, the micro-crosslinked structure plays a role of bridging, a better compatible interface is formed with nylon, meanwhile, physical entanglement and the like are generated with the laterally fed polyolefin elastomer molecular chain, the interface compatibility is improved, and multiple silver lines are easily generated when stressed, so that the toughening effect is improved, and higher processing fluidity is maintained.
According to the preparation method, the molecular weight of the polyolefin elastomer in the nylon toughening agent is not limited completely, the dispersibility of the toughening agent in a nylon matrix is improved by part of movable molecular chains, three types of combinations are promoted by a micro-crosslinking structure, the intermolecular acting force between an ester bond in a crosslinking auxiliary agent and an amide bond in nylon is further matched, the interface compatibility is greatly improved, the toughness of the nylon is further improved together, and the high processing fluidity is maintained.
In addition, the preparation method disclosed by the invention has the advantages of one-step molding, short production period and strong controllability, can greatly reduce the residues of the initiator and the monomer, improves the product quality, and is suitable for industrial production.
In a specific embodiment of the present invention, the preparation of the mixture comprises: mixing initiator, grafting monomer, cross-linking assistant, antioxidant and part of polyolefin elastomer in a high-speed mixer for 1-2 min.
In a specific embodiment of the invention, the temperature between the main feed and the side feed is controlled to be 80 ℃ +/-10 ℃ to 190 ℃ +/-10 ℃; the temperature between the side feeding and the tail end is controlled to be 190 ℃ +/-10 ℃ to 180 ℃ +/-10 ℃.
In a specific embodiment of the present invention, the melt extrusion is performed using a twin screw extruder. Further, the double-screw extruder is a homodromous double-screw extruder. Further, the twin-screw extruder comprises 13 temperature areas, and the temperature of the 80℃±10℃、120℃±10℃、170℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃、180℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃, machine heads is 180+/-10 ℃ in sequence.
In actual operation, the melt extrusion is carried out in a double-screw extruder, and then the nylon toughening agent is obtained through pelleting, cooling and drying.
The invention adopts a double-screw extruder, realizes grafting and crosslinking at the front section of the screw to generate a microstructure, and mixes the high-viscosity structure and the low-viscosity structure at the rear section to form a coating structure to obtain the nylon toughening agent. The high-viscosity structure and the low-viscosity structure are combined to form the coating structure by utilizing the double-screw extruder, so that the coating structure is easy to disperse in nylon on one hand, and can form interfacial permeation with a nylon matrix on the other hand; when being stressed, the polymer in the penetration area forms fine microfibers to form silver grains, so that the toughening effect is improved.
In a specific embodiment of the invention, the side feeding is performed in the ninth zone. Wherein, the grafting crosslinking is melted and plasticized in the area of 1 to 9, and the cladding structure is formed in the area of 10 to 13, and the residual initiator and grafting monomer can be removed.
In a specific embodiment of the present invention, the mass ratio of the partial polyolefin elastomer to the residual polyolefin elastomer is 1: (0.8 to 1.2), preferably 1:1.
As in the various embodiments, the mass ratio of the portion of the polyolefin elastomer to the balance of the polyolefin elastomer in the blend may be 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, etc.
In a specific embodiment of the invention, the twin-screw extruder has an aspect ratio of not less than 40, preferably not less than 56, such as an aspect ratio of 56.
In a specific embodiment of the present invention, the rotation speed ratio of the main feed to the side feed is 1:1.
The invention also provides application of any one of the nylon toughening agents in preparing toughened nylon.
In a specific embodiment of the present invention, the nylon toughening agent is used in an amount of 10wt% to 20wt%, preferably 15wt%, of the mass of the nylon matrix.
When the nylon toughening agent prepared by the invention is used for toughening nylon matrixes such as PA6, the toughness of the toughened nylon material is obviously improved, the IZOD notch impact strength is more than or equal to 60KJ/m 2, and the IZOD notch impact strength can be as high as 71.3KJ/m 2; meanwhile, the melt mass flow rate (190 ℃ C., 2.16 kg) of the nylon toughening agent is more than or equal to 0.1g/10min, and more preferably more than or equal to 0.15g/10min.
Example 1
The embodiment provides a preparation method of a nylon toughening agent, which comprises the following steps:
(1) 98 parts of an ethylene-octene copolymer (Dow POE 8150), 0.15 part of an initiator (dicumyl peroxide (DCP)), 1.5 parts of a grafting monomer (maleic anhydride (MAH)), 0.5 parts of a crosslinking auxiliary (dipropylene glycol diacrylate (DPGDA)) and 0.5 parts of an antioxidant (168:1010=2:3) are weighed according to parts by weight.
(2) Mixing the initiator, the grafting monomer, the crosslinking auxiliary agent, the antioxidant and half of ethylene-octene copolymer (49 parts) in the step (1) in a high-speed mixer for 1.5min, feeding the mixture to a double-screw extruder with the length-diameter ratio of 56, the temperature of the extruder from zone 1 to zone 13 is set at 80 ℃, 120 ℃, 170 ℃, 190 ℃ and 190 DEG 190 ℃, 180 ℃, 190 ℃, the machine head is 180 ℃, a side feed is arranged in a ninth zone, the rest ethylene-octene copolymer (49 parts) is fed, the ratio of the side feed rotating speed to the main feed rotating speed is 1:1, and the extrudate is pelletized under water, cooled, centrifugally dehydrated and air-blown to be dried, so that the nylon toughening agent is obtained.
Example 2
The preparation method of the nylon toughening agent of reference example 1 in this example only differs in that:
The crosslinking auxiliary was different in kind, and the crosslinking auxiliary dipropylene glycol diacrylate DPGDA in example 1 was replaced with equal parts by weight of trimethylolpropane triacrylate TMPTA.
Example 3
The preparation method of the nylon toughening agent of reference example 1 in this example only differs in that:
The crosslinking auxiliary agent DPGDA in example 1 was replaced with an equal weight part of ethoxylated trimethylolpropane triacrylate 3-EO-TMPTA.
Example 4
The preparation method of the nylon toughening agent of reference example 1 in this example only differs in that:
The crosslinking auxiliary agent DPGDA in example 1 was replaced with equal parts by weight of ditrimethylolpropane tetraacrylate Di-TMPTA.
Example 5
The preparation method of the nylon toughening agent of reference example 4 in this example only differs in that:
The amounts of crosslinking assistants vary. The crosslinking aid ditrimethylolpropane tetraacrylate Di-TMPTA of example 5 was used in an amount of 0.8 parts.
Example 6
Example 6 the method of making the nylon toughening agent of reference example 4 differs only in:
The amounts of crosslinking assistants vary. The crosslinking aid ditrimethylolpropane tetraacrylate Di-TMPTA of example 6 was used in an amount of 1 part.
Example 7
The preparation method of the nylon toughening agent of reference example 4 in this example only differs in that:
Step (2) is different.
Step (2) of example 7 comprises: mixing the initiator, the grafting monomer, the crosslinking auxiliary agent, the antioxidant and half of the ethylene-octene copolymer (49 parts) in the step (1) in a high-speed mixer for 1.5min, then discharging the mixture to a double-screw extruder with the length-diameter ratio of 40, setting the temperature of the extruder from 1 area to 9 areas to 80 ℃, 120 ℃, 170 ℃, 190 ℃, 180 ℃, 190 ℃ and 180 ℃ at the head, setting side feeding in a fifth area, feeding the rest of the ethylene-octene copolymer (49 parts), wherein the ratio of the side feeding rotating speed to the main feeding rotating speed is 1:1, and granulating the extrudate under water, cooling, centrifugally dewatering and air drying to obtain the nylon toughening agent.
Comparative example 1
Comparative example 1 the preparation method of the nylon toughening agent of reference example 1 is different in that:
The crosslinking auxiliary was varied, and the crosslinking auxiliary DPGDA in example 1 was replaced with triallyl isocyanurate TAIC in an equal weight portion.
Comparative example 2
Comparative example 2 the preparation method of the nylon toughening agent of reference example 1 is different in that:
comparative example 2 does not add a crosslinking auxiliary species.
Comparative example 3
Comparative example 3 the preparation method of the nylon toughening agent of reference example 4 is different in that:
The amounts of crosslinking assistants vary. The amount of the crosslinking aid ditrimethylolpropane tetraacrylate Di-TMPTA of comparative example 4 was 0.3 part.
Comparative example 4
Comparative example 4 the preparation method of the nylon toughening agent of reference example 4 is only different in that:
Step (2) is different.
Step (2) of comparative example 4 includes: mixing the initiator, the grafting monomer, the crosslinking auxiliary agent, the antioxidant and the ethylene-octene copolymer in the step (1) in a high-speed mixer for 1.5min, then feeding the mixture to a double-screw extruder with the length-diameter ratio of 56, the temperature of the extruder from zone 1 to zone 13 is set at 80 ℃, 120 ℃, 170 ℃,190 ℃ and 190 DEG 190 ℃, the machine head is at 180 ℃, and the extrudate is pelletized under water, cooled, centrifugally dehydrated and air-blown to be dried, thus obtaining the nylon toughening agent.
Comparative example 5
Comparative example 5 the preparation method of the nylon toughening agent of reference example 4 is only different in that:
Step (2) is different.
Step (2) of comparative example 5 includes: mixing the initiator, the grafting monomer, the crosslinking auxiliary agent, the antioxidant and the ethylene-octene copolymer in the step (1) in a high-speed mixer for 1.5min, then discharging to a double-screw extruder with the length-diameter ratio of 40, setting the temperature of the extruder from 1 area to 9 areas to 80 ℃,120 ℃,170 ℃, 190 ℃ and 180 ℃ of the machine head, and performing underwater pelleting, cooling, centrifugal dehydration and forced air drying on the extrudate to obtain the nylon toughening agent.
Experimental example
In order to verify the toughening effect of the nylon toughening agents prepared in different examples and comparative examples on nylon, the nylon toughening agents prepared in different examples and comparative examples are applied to PA6 (Yueyang petrochemical PA6 BL 3280H), the addition amount of each group of nylon toughening agents is 15wt% of the mass of PA6, the PA6 and the nylon toughening agents are mixed in a mixer and then added into a double screw extruder, the extrusion temperature is 80 ℃, 150 ℃, 190 ℃, 210 ℃, 230 ℃, 240 ℃, and the machine head temperature is 230 ℃, and the toughened nylon is obtained through extrusion, granulation, cooling and drying. The nylon toughening effect of the toughened nylon obtained in each group was tested, and the test results are shown in table 1 (wherein the test objects of melt mass flow rate, grafting rate and yellow index are nylon toughening agents, and the test object of IZOD notch impact strength is toughened nylon).
TABLE 1 different sets of test results
From the test results, the cross-linking auxiliary agent is not added in the comparative example 2, an effectively mutually crossed coating structure is not formed under the same process, the toughening effect is not obvious, the cross-linking auxiliary agent is added in each of the examples 1-4 and the comparative example 1 to form a mutually crossed micro-crosslinked coating structure, part of movable molecular chains provide better fluidity, so that the molecular chains are uniformly dispersed in nylon, the micro-crosslinked structure plays a bridge role, forms an interpenetrating interface with the nylon, and is physically entangled with adjacent elastomers, multiple silver lines are induced when stressed, and the toughness is greatly improved. Meanwhile, the acrylic ester cross-linking auxiliary agent can be combined with nylon to form intermolecular acting force, so that the compatibility of the toughening agent and nylon is improved, the toughness is further improved, and the degree of cross-linking is improved and the toughness is improved along with the increase of the polyfunctional group number of the cross-linking auxiliary agent.
It is clear from the combination of examples 4,5, 6 and 3 that the maximum value of the crosslinking assistant increases and the system decreases, because the crosslinking assistant exceeds a certain amount, the crosslinking degree of the system increases, the molecular chain movement is limited, and the toughening effect decreases due to the inability to uniformly disperse.
It is evident from the combination of examples 4, 7, 4 and 5 that neither comparative example 4 nor comparative example 5 is side-fed with POE, the system is mainly crosslinked, the viscosity is increased, the system cannot be uniformly dispersed in nylon matrix, and the toughening effect is poor; the screw in the embodiment 7 has shorter length-diameter ratio, insufficient crosslinking, namely POE (polyolefin elastomer) is introduced into the screw, the formed coating structure is limited, the toughening effect is not ideal, the subsequent volatilization of an initiator and a grafting monomer is not facilitated, and the odor is large.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (14)
1. The nylon toughening agent is characterized by being prepared from 90-98 parts by weight of polyolefin elastomer, 0.1-1 part by weight of initiator, 1-5 parts by weight of grafting monomer, 0.5-1 part by weight of crosslinking auxiliary agent and 0.5-5 parts by weight of antioxidant;
The cross-linking auxiliary agent comprises a polyfunctional acrylate compound;
the preparation method of the nylon toughening agent comprises the following steps:
The initiator, the grafting monomer, the crosslinking auxiliary agent, the antioxidant and a part of polyolefin elastomer are mixed and extruded with the rest of polyolefin elastomer in a melting way; wherein the mixed material is fed in a main feeding mode, and the balance polyolefin elastomer is fed in a side feeding mode.
2. The nylon toughening agent according to claim 1, which is mainly prepared from the following components in parts by weight: 95-98 parts of polyolefin elastomer, 0.1-0.5 part of initiator, 1-3 parts of grafting monomer, 0.5-0.8 part of crosslinking auxiliary agent and 0.5-2 parts of antioxidant.
3. The nylon toughening agent according to claim 1, which is mainly prepared from the following components in parts by weight: 96-98 parts of polyolefin elastomer, 0.1-0.3 part of initiator, 1-2 parts of grafting monomer, 0.5-0.6 part of crosslinking auxiliary agent and 0.5-1 part of antioxidant.
4. The nylon toughening agent according to claim 1, wherein the crosslinking aid comprises any one or more of dipropylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and ditrimethylolpropane tetraacrylate.
5. The nylon toughening agent according to any one of claims 1 to 4, wherein the polyolefin elastomer is an ethylene-octene copolymer and/or an ethylene-propylene-non-conjugated diene terpolymer;
And/or the initiator comprises any one or more of dibenzoyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, di-t-butyl peroxide, dicumyl peroxide, and di-t-butylcumene peroxide;
and/or the grafting monomer comprises any one or more of maleic anhydride, itaconic acid, glycidyl methacrylate and acrylic acid;
And/or the antioxidants include Antioxidant, 168 and Antioxidant, 1010.
6. The nylon toughening agent according to claim 1, wherein the temperature between the main feed and the side feed is controlled to be 80 ℃ ± 10 ℃ -190 ℃ ± 10 ℃; the temperature between the side feeding and the tail end is controlled to be 190+/-10 ℃ to 180+/-10 ℃.
7. The nylon toughening agent according to claim 1, wherein the melt extrusion is performed using a twin screw extruder.
8. The nylon toughening agent according to claim 7, wherein the twin screw extruder comprises 13 temperature zones, the temperature being 80℃±10℃、120℃±10℃、170℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃、180℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃、190℃±10℃, die temperatures of 180 ℃ ± 10 ℃.
9. The nylon toughening agent according to claim 8, wherein the side feeding is performed in a ninth zone.
10. The nylon toughening agent according to claim 7, wherein the aspect ratio of the twin screw extruder is not less than 40.
11. The nylon toughening agent according to claim 10, wherein the aspect ratio of the twin screw extruder is not less than 56.
12. The nylon toughening agent according to claim 1, wherein the mass ratio of the part of polyolefin elastomer to the rest of polyolefin elastomer is 1: (0.8 to 1.2).
13. The nylon toughening agent according to claim 12, wherein the mass ratio of the portion of polyolefin elastomer to the balance of polyolefin elastomer is 1:1.
14. Use of the nylon toughening agent of any of claims 1 to 13 in the preparation of toughened nylon.
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| PCT/CN2022/087179 WO2023087614A1 (en) | 2021-11-16 | 2022-04-15 | Nylon toughening agent, and preparation method therefor and use thereof |
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| CN116102882B (en) * | 2022-12-22 | 2023-10-13 | 沈阳工业大学 | A low-temperature, high-toughness, low-water-absorption bio-based PA56 alloy and its preparation method |
| CN116178629B (en) * | 2022-12-27 | 2024-05-07 | 广州鹿山新材料股份有限公司 | Hydroxylation modified POE and preparation method and application thereof |
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| WO1994012575A1 (en) * | 1992-11-20 | 1994-06-09 | Exxon Chemical Patents Inc. | Toughened thermoplastic nylon compositions |
| CN1480489A (en) * | 2002-09-03 | 2004-03-10 | 中国石油化工股份有限公司 | Toughening polyamide combination and prepn method |
| CN103073880A (en) * | 2012-12-25 | 2013-05-01 | 广州鹿山新材料股份有限公司 | Toughened nylon composite and preparation method thereof |
| CN106750347A (en) * | 2017-03-09 | 2017-05-31 | 山东省科学院能源研究所 | A kind of nylon toughener and its preparation method and application |
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| DE3436362A1 (en) * | 1984-10-04 | 1986-04-10 | Basf Ag, 6700 Ludwigshafen | IMPACT TOOL POLYAMIDE MOLDS WITH REDUCED TENSION RISK |
| EP0740688B1 (en) * | 1994-01-21 | 2002-08-28 | E.I. Du Pont De Nemours & Company Incorporated | Blowmoldable nylon compositions |
| US20110207838A1 (en) * | 2010-02-25 | 2011-08-25 | E.I. Du Pont De Nemours And Company | Recycled thermoplastic with toughener |
| CN113968939B (en) * | 2021-11-16 | 2024-05-28 | 广州鹿山新材料股份有限公司 | Nylon toughening agent and preparation method and application thereof |
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| JPS6454062A (en) * | 1987-05-18 | 1989-03-01 | Mitsui Petrochemical Ind | Polyamide resin composition |
| WO1994012575A1 (en) * | 1992-11-20 | 1994-06-09 | Exxon Chemical Patents Inc. | Toughened thermoplastic nylon compositions |
| CN1480489A (en) * | 2002-09-03 | 2004-03-10 | 中国石油化工股份有限公司 | Toughening polyamide combination and prepn method |
| CN103073880A (en) * | 2012-12-25 | 2013-05-01 | 广州鹿山新材料股份有限公司 | Toughened nylon composite and preparation method thereof |
| CN106750347A (en) * | 2017-03-09 | 2017-05-31 | 山东省科学院能源研究所 | A kind of nylon toughener and its preparation method and application |
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