CN113968939A - Nylon toughening agent and preparation method and application thereof - Google Patents
Nylon toughening agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN113968939A CN113968939A CN202111356712.3A CN202111356712A CN113968939A CN 113968939 A CN113968939 A CN 113968939A CN 202111356712 A CN202111356712 A CN 202111356712A CN 113968939 A CN113968939 A CN 113968939A
- Authority
- CN
- China
- Prior art keywords
- parts
- nylon
- polyolefin elastomer
- toughening agent
- antioxidant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004677 Nylon Substances 0.000 title claims abstract description 96
- 229920001778 nylon Polymers 0.000 title claims abstract description 96
- 239000012745 toughening agent Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000004132 cross linking Methods 0.000 claims abstract description 70
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 52
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 15
- -1 acrylate compound Chemical class 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 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
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 8
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000000034 method Methods 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
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 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 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
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 14
- 238000012545 processing Methods 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 22
- 229920001971 elastomer Polymers 0.000 description 9
- 239000000806 elastomer Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229920001112 grafted polyolefin Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000007605 air drying Methods 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
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 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
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 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
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 assistant and 0.5-5 parts of antioxidant; the crosslinking assistant comprises a polyfunctional acrylate compound. The preparation method of the nylon toughening agent comprises the following steps: melting and extruding a mixed material of an initiator, a grafting monomer, a crosslinking assistant, an antioxidant and part of the polyolefin elastomer and the rest of the polyolefin elastomer; wherein, the mixed material is fed by a main feeding mode, and the rest of the polyolefin elastomer is fed by a side feeding mode. According to the invention, by introducing the specific crosslinking assistant, micro-crosslinking is generated while grafting the grafting monomer and the polyolefin elastomer, and an intercrossed coating structure is formed with the unreacted polyolefin elastomer, so that the interfacial compatibility, the processing fluidity and the toughening effect can be considered at the same time.
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 as a thermoplastic engineering plastic has excellent properties of high mechanical strength, oil resistance, acid and alkali resistance, easy processing and forming, friction resistance and the like, and is widely applied to the automobile industry, the electronic and electrical industry, the sports equipment industry, the medical equipment industry and the like. However, nylon has high notch sensitivity and poor toughness in a dry state and at a low temperature, and cannot meet the requirement of a super-tough polymer material, and due to the existence of amido bonds on a nylon molecular chain, the nylon has high water absorption rate and poor product stability, so that the further development of nylon is limited. To solve these problems, researchers mainly improve the problems by adding a toughening agent.
Nylon is mainly toughened by an elastomer grafted or copolymerized with a polar monomer. The elastomer is generally non-polar and has poor compatibility with nylon, and the elastomer needs to be modified, such as initiating grafting of polar monomers or copolymerization of polar monomers and the like, and introducing polar groups on the molecular chain of the elastomer, so that the interface compatibility with nylon is improved, and the risk of high water absorption of nylon due to the existence of a large number of amido bonds is reduced. When the elastic body is stressed, the elastic body is subjected to stress concentration to generate plastic deformation and absorb energy, and further, crazes and shear zones are initiated through the mutually-permeated interface, the crazes are stopped when the crazes develop and meet another elastic body, the shear zones can also prevent the crazes from developing, a large amount of energy is consumed, and the impact resistance of the material is improved. The toughness of the material mainly depends on the interfacial compatibility of the elastomer and the matrix, the dispersed particle size and the spacing of the elastomer in the matrix, and the like.
In the prior art, the dispersion of the toughening agent in nylon is improved mainly by improving the fluidity of the toughening agent and the like, the toughening effect is maintained or slightly reduced, the introduced multi-component grafting monomer enables the grafting reaction to be more complex, the residual quantity is difficult to control, the taste of the toughening agent is larger, and the production controllability is poor.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a nylon toughening agent to solve the technical problems of uneven dispersion, poor toughening effect and the like in the prior art.
The second purpose of the invention is to provide a preparation method of the nylon toughening agent.
The third purpose of the invention is to provide the application of the nylon toughening agent in the nylon material.
In order to achieve the above purpose of the present invention, the following technical solutions are 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 assistant and 0.5-5 parts of antioxidant;
the crosslinking assistant comprises a multifunctional acrylate compound.
In a specific embodiment of the present invention, the crosslinking assistant comprises any one or more of dipropylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and ditrimethylolpropane tetraacrylate.
In a particular embodiment of the 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-butylperoxycumene.
In a specific embodiment of the present invention, the grafting monomer includes any one or more of maleic anhydride, itaconic acid, glycidyl methacrylate and acrylic acid.
In a specific embodiment of the present invention, the Antioxidant comprises aniioxidant 168 and aniioxidant 1010. Further, the mass ratio of the Antioxidant 168 to the Antioxidant 1010 is 2: 2.5 to 3.5, such as 2: 3.
The invention also provides a preparation method of the nylon toughening agent, which comprises the following steps:
melting and extruding a mixed material of an initiator, a grafting monomer, a crosslinking assistant, an antioxidant and part of the polyolefin elastomer and the rest of the polyolefin elastomer; wherein, the mixed material is fed by a main feeding mode, and the rest polyolefin elastomer is fed by a side feeding mode.
In a specific embodiment of the invention, the temperature between the main feed and the side feed is controlled at 80 ℃ + -10 ℃ to 190 ℃ + -10 ℃; the temperature between the side feeding and the tail end is controlled to be 190 +/-10-180 +/-10 ℃.
In a specific embodiment of the present invention, the melt extrusion is performed using a twin-screw extruder. Further, the twin-screw extruder comprises 13 temperature zones, the temperature is 80 ℃ +/-10 ℃, 120 ℃ +/-10 ℃, 170 ℃ +/-10 ℃, 190 ℃ +/-10 ℃, 180 ℃ +/-10 ℃, 190 ℃ +/-10 ℃ and 180 ℃ +/-10 ℃ in sequence, and the temperature of a machine head is 180 ℃ +/-10 ℃.
In actual operation, the melt extrusion is carried out in a double-screw extruder, and then granulation, cooling and drying are carried out to obtain the nylon toughening agent.
In a particular embodiment of the invention, the side feeding is carried out in the ninth zone.
In a specific embodiment of the present invention, the mass ratio of the partial polyolefin elastomer to the rest of the polyolefin elastomer is 1: 0.8 to 1.2.
In a particular embodiment of the invention, the twin-screw extruder has a length/diameter ratio of 40 or more, preferably 56 or more.
The invention also provides application of any one of the nylon toughening agents in preparation of 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, micro-crosslinking is generated while a grafting monomer is grafted with a polyolefin elastomer, and an intercrossed coating structure is formed with the unreacted polyolefin elastomer; when the material is blended with nylon, the interface compatibility, the processing fluidity and the toughening effect can be considered;
(2) the preparation method of the nylon toughening agent of the invention firstly reacts part of the polyolefin elastomer with the grafting monomer, the crosslinking assistant and the like to generate micro-crosslinking during grafting; then the polyolefin elastomer with the allowance is fed laterally, the polyolefin elastomer fed laterally and the grafted polyolefin elastomer which generates micro-crosslinking form an intercrossed coating structure, and the interfacial compatibility, the processing fluidity and the toughening effect are considered; in addition, the initiator and the graft monomer can be removed while forming the coating structure, thereby reducing the residue.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
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 assistant and 0.5-5 parts of antioxidant;
the crosslinking assistant comprises a multifunctional acrylate compound.
According to the nylon toughening agent, a specific crosslinking auxiliary agent is introduced, micro-crosslinking is generated while a grafting monomer is grafted with a polyolefin elastomer, and a micro-crosslinking structure plays a role of a bridge, so that a better compatible interface can be formed with nylon, and physical entanglement can be generated with a molecular chain of the polyolefin elastomer which is not crosslinked; when the polyolefin elastomer is blended with nylon, the molecular chain of the uncrosslinked polyolefin elastomer is endowed with better fluidity, the micro-crosslinked structure can ensure compatibility, and meanwhile, the intermolecular force between an ester bond in a crosslinking auxiliary agent and an amido bond in the nylon is matched, so that the compatibility is further improved, and the generation of multiple silver stripes is easily caused when stress is applied, thereby improving the toughening effect.
In the raw material components of the nylon toughening agent, as in different embodiments, the amounts of the components can be respectively as follows:
polyolefin elastomers may be used in amounts of 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, and the like;
the initiator may be used in amounts of 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, etc.;
the graft monomer may be used in an amount of 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 assistant 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, and the like.
In a specific embodiment of the invention, the nylon toughening agent 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 assistant and 0.5-2 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 assistant and 0.5-1 part of antioxidant.
In a specific embodiment of the present invention, in the multifunctional acrylate compound, the functionality is 2 to 4, such as 2 or 3 or 4, and preferably 4.
In a specific embodiment 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 acting force can be generated between an ester bond in the crosslinking assistant and an amido bond in the nylon, so that the interfacial compatibility is improved, the generation of silver streaks is also facilitated when the stress is applied, and the toughening effect is improved.
In a particular embodiment of the 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-butylperoxycumene.
In a specific embodiment of the present invention, the grafting monomer includes any one or more of maleic anhydride, itaconic acid, glycidyl methacrylate and acrylic acid.
In a specific embodiment of the present invention, the Antioxidant comprises aniioxidant 168 and aniioxidant 1010. Further, the mass ratio of the Antioxidant 168 to the Antioxidant 1010 is 2: 3.
The invention also provides a preparation method of the nylon toughening agent, which comprises the following steps:
melting and extruding a mixed material of an initiator, a grafting monomer, a crosslinking assistant, an antioxidant and part of the polyolefin elastomer and the rest of the polyolefin elastomer; wherein, the mixed material is fed by a main feeding mode, and the rest polyolefin elastomer is fed by a side feeding mode.
In the invention, part of polyolefin elastomer is firstly reacted with grafting monomer, crosslinking auxiliary agent and the like to generate micro-crosslinking during grafting; and then the polyolefin elastomer is fed laterally, the polyolefin elastomer fed laterally and the grafted polyolefin elastomer which generates micro-crosslinking form an intercrossed coating structure, the polyolefin elastomer fed laterally endows the toughening agent with better fluidity, and the micro-crosslinking structure plays a role of a bridge, not only forms a better compatible interface with nylon, but also physically entangles with the molecular chain of the polyolefin elastomer fed laterally and the like, improves the interface compatibility, and is easy to cause multiple silver stripes to be generated when stressed, so that the toughening effect is improved, and higher processing fluidity is maintained.
According to the preparation method disclosed by the invention, the molecular weight of the polyolefin elastomer in the nylon toughening agent is not completely limited, part of the active molecular chains improve the dispersibility of the toughening agent in a nylon matrix, the micro-crosslinking structure promotes the combination of the three, and the intermolecular force between an ester bond in the crosslinking assistant and an amide bond in the nylon is further matched, so that the interface compatibility is greatly improved, the toughness of the nylon is further improved together, and the high processing fluidity is kept.
In addition, the preparation method provided by the invention is formed in one step, has a short production period and strong controllability, can greatly reduce 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 mixed material comprises: and mixing the initiator, the grafting monomer, the crosslinking assistant, the antioxidant and part of the 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 at 80 ℃ + -10 ℃ to 190 ℃ + -10 ℃; the temperature between the side feeding and the tail end is controlled to be 190 +/-10-180 +/-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 co-rotating double-screw extruder. Further, the twin-screw extruder comprises 13 temperature zones, the temperature is 80 ℃ +/-10 ℃, 120 ℃ +/-10 ℃, 170 ℃ +/-10 ℃, 190 ℃ +/-10 ℃, 180 ℃ +/-10 ℃, 190 ℃ +/-10 ℃ and the head temperature is 180 ℃ +/-10 ℃.
In actual operation, the melt extrusion is carried out in a double-screw extruder, and then granulation, cooling and drying are carried out to obtain the nylon toughening agent.
According to the invention, a double-screw extruder is adopted, grafting crosslinking is realized at the front section of a screw to generate a microstructure, and a high-viscosity structure and a low-viscosity structure are mixed at the rear section to form a coating structure, so that the nylon toughening agent is obtained. According to the invention, the high-viscosity structure and the low-viscosity structure are combined to form the coating structure by using the double-screw extruder, so that the coating structure is easy to disperse in nylon on one hand, and can form interface permeation with a nylon substrate on the other hand; when the stress is applied, the absorption capacity is subjected to plastic shear deformation, and meanwhile, the polymer in the penetration area forms fine microfibers to form silver lines, so that the toughening effect is improved.
In a particular embodiment of the invention, the side feeding is carried out in the ninth zone. Wherein, the melt plasticizing grafting cross-linking is carried out in the 1-9 area, the melt forming coating structure is carried out in the 10-13 area, and the residual initiator and the grafting monomer can be removed.
In a specific embodiment of the present invention, the mass ratio of the partial polyolefin elastomer to the rest polyolefin elastomer is 1: 0.8 to 1.2, preferably 1: 1.
As in the different embodiments, the mass ratio of the partial polyolefin elastomer to the remaining polyolefin elastomer in the mixed material can be 1: 0.8, 1: 0.9, 1: 1, 1: 1.1, 1: 1.2, etc.
In a particular embodiment of the invention, the twin-screw extruder has a length to diameter ratio of 40 or more, preferably 56 or more, such as 56.
In a particular embodiment of the 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 preparation of toughened nylon.
In a specific embodiment of the present invention, the amount of the nylon toughening agent is 10 wt% to 20 wt%, preferably 15 wt%, of the mass of the nylon matrix.
When the nylon toughening agent prepared by the invention is used for toughening nylon substrates such as PA6, the toughness of the nylon material subjected to toughening treatment is remarkably improved, and the IZOD notch impact strength is more than or equal to 60KJ/m2And can be as high as 71.3KJ/m2(ii) a Meanwhile, the melt mass flow rate (190 ℃, 2.16kg) of the nylon toughening agent is more than or equal to 0.1g/10min, and more preferably more than or equal to 0.15g/10 min.
Example 1
The embodiment provides a preparation method of a nylon toughening agent, which comprises the following steps:
(1) 98 parts of ethylene-octene copolymer (Dow POE 8150), 0.15 part of initiator (dicumyl peroxide DCP), 1.5 parts of grafting monomer (maleic anhydride MAH), 0.5 part of crosslinking aid (dipropylene glycol diacrylate DPGDA) and 0.5 part of antioxidant (168: 1010: 2: 3) are weighed according to parts by weight.
(2) Mixing the initiator, the grafting monomer, the crosslinking assistant, 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 to a double-screw extruder with the length-diameter ratio of 56, setting the temperatures of zones 1 to 13 of the extruder to be 80 ℃, 120 ℃, 170 ℃, 190 ℃, 180 ℃, side feeding in a ninth zone, feeding the rest of the ethylene-octene copolymer (49 parts), setting the ratio of the side feeding rotation speed to the main feeding rotation speed to be 1: 1, and carrying out underwater granulation, cooling, centrifugal dehydration and air blast drying on the extrudate to obtain the nylon toughening agent.
Example 2
This example refers to the preparation of the nylon toughener of example 1, with the only difference that:
the crosslinking assistant used in example 1 was replaced with the same amount by weight of trimethylolpropane triacrylate TMPTA, although the crosslinking assistant used was different in kind.
Example 3
This example refers to the preparation of the nylon toughener of example 1, with the only difference that:
the crosslinking assistant used in example 1 was replaced with an equal part by weight of ethoxylated trimethylolpropane triacrylate 3-EO-TMPTA, although the crosslinking assistant used was DPGDA.
Example 4
This example refers to the preparation of the nylon toughener of example 1, with the only difference that:
the crosslinking assistant used in example 1 was replaced with the same amount by weight of Di-trimethylolpropane tetraacrylate Di-TMPTA, but the type of the crosslinking assistant varied.
Example 5
This example refers to the preparation of the nylon toughener of example 4, with the only difference that:
the amount of crosslinking aid used is different. The crosslinking assistant ditrimethylolpropane tetraacrylate Di-TMPTA of example 5 was used in an amount of 0.8 parts.
Example 6
Example 6 reference is made to the preparation of the nylon toughener of example 4, except that:
the amount of crosslinking aid used is different. The crosslinking aid Di-trimethylolpropane tetraacrylate Di-TMPTA of example 6 was used in an amount of 1 part.
Example 7
This example refers to the preparation of the nylon toughener of example 4, with the only difference that:
the step (2) is different.
Step (2) of example 7 comprises: mixing the initiator, the grafting monomer, the crosslinking assistant, 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 to a double-screw extruder with the length-diameter ratio of 40, setting the temperatures of regions 1 to 9 of the extruder at 80 ℃, 120 ℃, 170 ℃, 190 ℃, 180 ℃, 190 ℃ and setting a side feeding in a fifth region, 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 performing underwater granulation, cooling, centrifugal dehydration and blast drying on the extrudate to obtain the nylon toughening agent.
Comparative example 1
Comparative example 1 reference example 1 a method of preparing the nylon toughening agent of example 1, except that:
the crosslinking aid DPGDA of example 1 was replaced with an equal part by weight of triallyl isocyanurate TAIC, depending on the kind of the crosslinking aid.
Comparative example 2
Comparative example 2 reference example 1 a nylon toughener preparation process, except that:
comparative example 2 no crosslinking assistant species were added.
Comparative example 3
Comparative example 3 the nylon toughener of example 4 was prepared with the following differences:
the amount of crosslinking aid used is different. The crosslinking assistant ditrimethylolpropane tetraacrylate Di-TMPTA of comparative example 4 was used in an amount of 0.3 part.
Comparative example 4
Comparative example 4 the nylon toughener of example 4 was prepared with the only difference that:
the step (2) is different.
Step (2) of comparative example 4 includes: mixing the initiator, the grafting monomer, the crosslinking assistant, the antioxidant and the ethylene-octene copolymer in the step (1) in a high-speed mixer for 1.5min, then blanking to a double-screw extruder with the length-diameter ratio of 56, setting the temperature of zones 1 to 13 of the extruder to be 80 ℃, 120 ℃, 170 ℃, 190 ℃ and 180 ℃ at the machine head, and carrying out underwater granulation, cooling, centrifugal dehydration and air drying on the extrudate to obtain the nylon toughening agent.
Comparative example 5
Comparative example 5 the nylon toughener of example 4 was prepared with the following differences:
the step (2) is different.
Step (2) of comparative example 5 includes: and (2) mixing the initiator, the grafting monomer, the crosslinking assistant, 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 region to 9 region at 80 ℃, 120 ℃, 170 ℃, 190 ℃, 180 ℃ at the head, and carrying out underwater granulation, cooling, centrifugal dehydration and air blast drying on the extrudate to obtain the nylon toughening agent.
Examples of the experiments
In order to verify the toughening effect of the nylon toughening agent prepared in different embodiments and comparative examples on nylon, the nylon toughening agent prepared in different embodiments and comparative examples is applied to PA6 (Yueyangyanpetrochemical PA6 BL3280H), the addition amount of each group of nylon toughening agent is 15 wt% of the mass of PA6, the PA6 and the nylon toughening agent are mixed in a mixer and then added into a double-screw extruder, the extrusion temperature is 80 ℃, 150 ℃, 190 ℃, 210 ℃, 230 ℃, 240 ℃, 230 ℃, granulation, cooling and drying are carried out, and the toughened nylon is obtained. In the toughened nylon obtained in each group, the toughening effect of nylon was tested, and the test results are shown in table 1 (wherein the test objects of melt mass flow rate, grafting ratio and yellow index are nylon toughening agents, and the test object of IZOD notch impact strength is toughened nylon).
TABLE 1 results of different groups of tests
From the test results, the crosslinking assistant is not added in the comparative example 2, an effective intercrossed coating structure is not formed under the same process, and the toughening effect is not obvious, while the crosslinking assistant is added in the examples 1 to 4 and the comparative example 1 to form an intercrossed micro-crosslinked coating structure, a part of movable molecular chains provide better fluidity, so that the intercrossed micro-crosslinked coating structure is dispersed in nylon more uniformly, the micro-crosslinked coating structure plays a role of a bridge, forms an interpenetration interface with the nylon, and is physically entangled with an adjacent elastomer, so that multiple silver streaks are caused when stress is applied, and the toughness is greatly improved. Meanwhile, the acrylate crosslinking assistant can be combined with nylon to form intermolecular acting force, so that the compatibility of the toughening agent and the nylon is improved, the toughness is further improved, and the crosslinking degree is increased and the toughness is improved along with the increase of the number of polyfunctional groups of the crosslinking assistant.
It is known from the combination of examples 4, 5, 6 and 3 that the maximum value of the system decreases with the increase of the content of the crosslinking aid, because the crosslinking degree of the system increases and the molecular chain movement is limited due to the increase of the crosslinking aid in a certain amount, and the toughening effect decreases due to the failure of uniform dispersion.
Combining example 4, example 7, comparative example 4 and comparative example 5, it is clear that the POE is not fed to the side of comparative example 4 and comparative example 5, the system is mainly crosslinked, the viscosity is increased, the uniform dispersion in the nylon matrix is not realized, and the toughening effect is not good; in the embodiment 7, the long diameter of the screw is short, the POE is introduced into the side feeding process when the crosslinking is not sufficient, the formed coating structure is limited, the toughening effect is not ideal, the subsequent volatilization of the initiator and the grafting monomer is not facilitated, and the odor is large.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The nylon toughening agent is characterized by mainly comprising, by weight, 90-98 parts of a polyolefin elastomer, 0.1-1 part of an initiator, 1-5 parts of a grafting monomer, 0.5-1 part of a crosslinking assistant and 0.5-5 parts of an antioxidant;
the crosslinking assistant comprises a multifunctional acrylate compound.
2. The nylon toughening agent of claim 1, which is 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 assistant and 0.5-2 parts of antioxidant;
preferably, the adhesive 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 assistant and 0.5-1 part of antioxidant.
3. The nylon toughener of claim 1, wherein the crosslinking coagent comprises any one or more of dipropylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and ditrimethylolpropane tetraacrylate.
4. The nylon toughener of any one of claims 1-3, wherein the polyolefin elastomer is an ethylene-octene copolymer and/or an ethylene-propylene-nonconjugated diene terpolymer;
and/or the initiator comprises any one or more of dibenzoyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, di-tert-butyl peroxide, dicumyl peroxide and di-tert-butyl cumyl peroxide;
and/or the grafting monomer comprises any one or more of maleic anhydride, itaconic acid, glycidyl methacrylate and acrylic acid;
and/or the Antioxidant comprises Antioxidant 168 and Antioxidant 1010.
5. A method for preparing a nylon toughening agent according to any one of claims 1 to 4, comprising the steps of:
melting and extruding a mixed material of an initiator, a grafting monomer, a crosslinking assistant, an antioxidant and part of the polyolefin elastomer and the rest of the polyolefin elastomer; wherein, the mixed material is fed by a main feeding mode, and the rest polyolefin elastomer is fed by a side feeding mode.
6. The preparation method of the nylon toughening agent according to claim 5, wherein 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 +/-10-180 +/-10 ℃.
7. The method for preparing nylon toughening agent according to claim 5, wherein the melt extrusion is performed by using a twin-screw extruder;
preferably, the twin-screw extruder comprises 13 temperature zones, the temperature is 80 ℃ +/-10 ℃, 120 ℃ +/-10 ℃, 170 ℃ +/-10 ℃, 190 ℃ +/-10 ℃, 180 ℃ +/-10 ℃, 190 ℃ +/-10 ℃, 180 ℃ +/-10 ℃ and the head temperature is 180 ℃ +/-10 ℃;
preferably, the side feeding is performed in the ninth zone.
8. The preparation method of the nylon toughening agent according to claim 7, wherein the length-diameter ratio of the twin-screw extruder is not less than 40;
preferably, the length-diameter ratio of the double-screw extruder is more than or equal to 56.
9. The method of claim 5, wherein the mass ratio of the partial polyolefin elastomer to the residual polyolefin elastomer is 1: 0.8 to 1.2;
preferably, the mass ratio of the partial polyolefin elastomer to the rest of the polyolefin elastomer is 1: 1.
10. Use of a nylon toughening agent according to any one of claims 1 to 4 in the preparation of a toughened nylon.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111356712.3A CN113968939A (en) | 2021-11-16 | 2021-11-16 | Nylon toughening agent and preparation method and application thereof |
| PCT/CN2022/087179 WO2023087614A1 (en) | 2021-11-16 | 2022-04-15 | Nylon toughening agent, and preparation method therefor and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111356712.3A CN113968939A (en) | 2021-11-16 | 2021-11-16 | Nylon toughening agent and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113968939A true CN113968939A (en) | 2022-01-25 |
Family
ID=79590028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111356712.3A Pending CN113968939A (en) | 2021-11-16 | 2021-11-16 | Nylon toughening agent and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113968939A (en) |
| WO (1) | WO2023087614A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102882A (en) * | 2022-12-22 | 2023-05-12 | 沈阳工业大学 | Low-temperature high-toughness low-water-absorption bio-based PA56 alloy and preparation method thereof |
| WO2023087614A1 (en) * | 2021-11-16 | 2023-05-25 | 广州鹿山新材料股份有限公司 | Nylon toughening agent, and preparation method therefor and use thereof |
| CN116178629A (en) * | 2022-12-27 | 2023-05-30 | 广州鹿山新材料股份有限公司 | Hydroxylation modified POE and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20110207838A1 (en) * | 2010-02-25 | 2011-08-25 | E.I. Du Pont De Nemours And Company | Recycled thermoplastic with toughener |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113968939A (en) * | 2021-11-16 | 2022-01-25 | 广州鹿山新材料股份有限公司 | Nylon toughening agent and preparation method and application thereof |
-
2021
- 2021-11-16 CN CN202111356712.3A patent/CN113968939A/en active Pending
-
2022
- 2022-04-15 WO PCT/CN2022/087179 patent/WO2023087614A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20110207838A1 (en) * | 2010-02-25 | 2011-08-25 | E.I. Du Pont De Nemours And Company | Recycled thermoplastic with toughener |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023087614A1 (en) * | 2021-11-16 | 2023-05-25 | 广州鹿山新材料股份有限公司 | Nylon toughening agent, and preparation method therefor and use thereof |
| CN116102882A (en) * | 2022-12-22 | 2023-05-12 | 沈阳工业大学 | Low-temperature high-toughness low-water-absorption bio-based PA56 alloy and preparation method thereof |
| CN116102882B (en) * | 2022-12-22 | 2023-10-13 | 沈阳工业大学 | Low-temperature high-toughness low-water-absorption bio-based PA56 alloy and preparation method thereof |
| CN116178629A (en) * | 2022-12-27 | 2023-05-30 | 广州鹿山新材料股份有限公司 | Hydroxylation modified POE and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023087614A1 (en) | 2023-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113968939A (en) | Nylon toughening agent and preparation method and application thereof | |
| CN102391431B (en) | Nylon toughener and preparation method and application thereof | |
| CN102115591B (en) | Toughened nylon blend and preparation method thereof | |
| CN106750347A (en) | A kind of nylon toughener and its preparation method and application | |
| CN104292821A (en) | Nylon toughening masterbatch and preparation method thereof | |
| CN109181281B (en) | Alloy toughening agent for nylon toughening | |
| CN101591416B (en) | Environmental-friendly polypropylene compatilizer preparation method | |
| CN113563593B (en) | Core-shell toughening agent, preparation method thereof and toughened nylon applied by core-shell toughening agent | |
| US6426389B2 (en) | Functionalized polypropylenes and process for production | |
| CN110041470B (en) | Functionalized olefin block copolymer antioxidant masterbatch and preparation method thereof | |
| CN111825801B (en) | Toughening agent composition and preparation method thereof | |
| CN108623893A (en) | The technique that one-time prilling method prepares toughening nylon plasticising master batch | |
| CN1957032B (en) | Modifiers for thermoplastic alloys and alloys produced using such modifiers | |
| JPS63305148A (en) | Glass fiber-reinforced polyamide composition | |
| AU693484B2 (en) | Free radical grafting of monomers onto polypropylene resins | |
| CN108342012B (en) | mLLDPE resin composition for plastic greenhouse film and preparation method thereof | |
| CN109337016B (en) | Process for controlling cross-linking side reaction generated in grafting reaction process | |
| CN106928624A (en) | A kind of nucleocapsid nylon toughener and preparation method and application based on extruder technique | |
| JP2837909B2 (en) | Fiber reinforced resin composition | |
| JP4068162B2 (en) | Process for producing polyacrylate / polyolefin blends | |
| JPS59145242A (en) | Impact resistance improved propylene copolymer | |
| CN108239232A (en) | It is a kind of for heat resisting flexibilizer of nylon and preparation method thereof | |
| CN115521566B (en) | Nylon toughening agent and preparation method and application thereof | |
| CN110591100B (en) | Ultralow temperature resistant nylon toughening agent and preparation method and application thereof | |
| WO1996006871A1 (en) | Polymeric blends based on polypropylene and polybutylene terephthalate resins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |