CN118164849A - Transparent nylon composite resin and preparation method and application thereof - Google Patents
Transparent nylon composite resin and preparation method and application thereof Download PDFInfo
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- CN118164849A CN118164849A CN202410564409.XA CN202410564409A CN118164849A CN 118164849 A CN118164849 A CN 118164849A CN 202410564409 A CN202410564409 A CN 202410564409A CN 118164849 A CN118164849 A CN 118164849A
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- 239000004677 Nylon Substances 0.000 title claims abstract description 107
- 229920001778 nylon Polymers 0.000 title claims abstract description 107
- 239000000805 composite resin Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 58
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 51
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 42
- 239000001361 adipic acid Substances 0.000 claims description 30
- 235000011037 adipic acid Nutrition 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 230000035484 reaction time Effects 0.000 claims description 17
- 150000008064 anhydrides Chemical class 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 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 4
- GQXRTXAQSDUAEY-UHFFFAOYSA-N 2-methylidenehexanedioic acid Chemical compound OC(=O)CCCC(=C)C(O)=O GQXRTXAQSDUAEY-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- CSNDXHSGSSAWOF-UHFFFAOYSA-L disodium;ethenyl phosphate Chemical compound [Na+].[Na+].[O-]P([O-])(=O)OC=C CSNDXHSGSSAWOF-UHFFFAOYSA-L 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- 239000004952 Polyamide Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- -1 aliphatic diamine Chemical class 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229920000577 Nylon 6/66 Polymers 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- PTORSGGOWTZSMO-UHFFFAOYSA-N [PH2](O)=O.C(CCC(=O)O)(=O)O Chemical compound [PH2](O)=O.C(CCC(=O)O)(=O)O PTORSGGOWTZSMO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- FHESUNXRPBHDQM-UHFFFAOYSA-N diphenyl benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OC=2C=CC=CC=2)=CC=1C(=O)OC1=CC=CC=C1 FHESUNXRPBHDQM-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/22—Tricarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a transparent nylon composite resin and a preparation method and application thereof, and belongs to the technical field of high polymer materials. According to the invention, the functional monomer containing metal ions with a specific structure is introduced to a molecular chain segment of the nylon resin in a specific addition amount, so that the transparent nylon composite resin with high metal ion content and activity is prepared, and the transparent nylon composite resin has high transparency and excellent mechanical property.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a transparent nylon composite resin and a preparation method and application thereof.
Background
Polyamide (nylon) is a thermoplastic resin containing repeated amide groups-NHCO-on the molecular main chain, and has huge yield and wide application. However, because of the presence of amide groups, strong hydrogen bonds exist between nylon molecular chains, and molecules are easily aligned to generate crystallization, so that the common polyamide resins such as PA6, PA66 and the like generally have a non-transparent or milky color. The crystallization behavior of the polyamide chain can be regulated and controlled through the molecular structure design of the polyamide or the action of an auxiliary agent, so that the polyamide chain becomes amorphous or forms microcrystals with the size smaller than 400-700nm of visible light wavelength, and the polyamide macroscopically presents a transparent state, and the material is called transparent nylon; transparent nylon has excellent transparency, toughness, thermal stability and good solubility resistance, and is widely applied to the fields of household articles, electronic equipment, precise optical instruments, sports equipment, medical care, automobile industry and the like; thus, transparent modification of nylon is a hotspot of current research.
The current transparent modification means of nylon are divided into physical modification and chemical modification, wherein the chemical modification comprises aliphatic transparent nylon, semi-aromatic and aromatic transparent nylon and transparent nylon with complex structure. (1) The aliphatic transparent nylon is a transparent material obtained by polycondensation of aliphatic dibasic acid and aliphatic diamine, ring-opening polymerization of lactam or polycondensation of amino fatty acid. The polymerized monomer can be a straight-chain monomer or a monomer containing alicyclic, the regularity of a polyamide chain segment is greatly reduced by introducing the alicyclic, the crystallization capability is weakened, the transparency is enhanced, or a high polymer with very low crystallinity or non-crystallization is obtained by multi-element random copolycondensation, so that the transparent nylon material is prepared; such as PACM12, PACP-9/6, BMACM14, PA6/66, PA6/12, and PA11/12, etc. However, the method is limited in domestic sources and has higher price due to the need of adding alicyclic-containing monomers; the method is generally used for transparent modification of nylon with long carbon chains, and if the method is used for transparent modification of PA66, the mechanical properties can be greatly reduced; the random copolymerization method of the multi-element straight-chain aliphatic monomer is high in synthesis process difficulty, and the mechanical property of the random copolymer is obviously reduced compared with that of PA66 due to no crystallization, so that the use value is low. (2) Semi-aromatic transparent nylon is generally prepared by copolymerizing aliphatic diamine and aromatic diamine or aliphatic diamine and aromatic diamine and other monomers; such as PA6T/6I, PA10I/10T, PA6-3-T, MXD6, etc. The method greatly improves the heat resistance and mechanical property of the material and reduces the water absorption rate due to the introduction of the aromatic ring in the molecular chain, but the synthesis process is difficult to control. (3) The wholly aromatic transparent nylon is prepared from aromatic dibasic acid and aromatic diamine, wherein the main chain has higher proportion of rigid aromatic rings, and the polymer has good crystallinity, heat resistance and solvent resistance, such as transparent nylon synthesized by taking 2-amino-6- (4-aminobenzene) -6-methylheptane and diphenyl isophthalate as monomers; however, this method has a high melting temperature and extremely severe requirements for molding equipment, so that the wholly aromatic transparent polyamide is not industrially produced. (4) The transparent nylon material with a complex structure breaks the regularity of nylon molecules by introducing special heteroatoms or heterocycles such as trifluoromethyl phenoxy, tert-butyl cyclohexyl, xanthene, sulfone groups and the like into a main chain, thereby realizing transparent modification and obtaining the corresponding functions of the introduced groups. However, the method adopts a complex monomer structure, has limited sources and is mainly a laboratory research product at present. The main method of physical modification is to add a nucleating agent to obtain a product with smaller crystal area size. PACM12 transparent polyamides as developed by merkle et al and Trogamid CX7323 and CX970l transparent polyamides developed by Creanova; however, the method has certain requirements on the nylon base material, needs the nylon base material to have lower crystallinity, and has high requirements on the nylon processing and molding process, so that the application range of the method is narrower.
Aiming at the problems existing in the transparent modification process of nylon, development of a nylon composite resin with high transparency and excellent mechanical properties is an important point of research in the field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a transparent nylon composite resin, a preparation method and application thereof, wherein the transparent nylon composite resin has high transparency and excellent mechanical properties.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
In a first aspect, the invention provides an application of a functional monomer containing metal ions in transparent nylon, wherein the structural formula of the functional monomer containing metal ions is shown as follows:
、/>、/>。
As a preferred embodiment of the application of the metal ion-containing functional monomer in transparent nylon, the preparation method of the metal ion-containing functional monomer comprises the following steps: adding unsaturated metal salt into an organic solvent, heating to 80-100 ℃, then adding unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride, and reacting for 3-6h at 130-160 ℃ to obtain the functional monomer containing metal ions.
As a more preferred embodiment of the use of the metal ion-containing functional monomer of the present invention in transparent nylon, the unsaturated metal salt is selected from at least one of lithium acrylate, disodium vinylphosphate, and sodium methallyl sulfonate.
In the invention, the preparation method of the lithium acrylate comprises the following steps: mixing acrylic acid and lithium hydroxide in a molar ratio of 1:1, heating to 58-62 ℃, reacting for 1-1.5h to obtain lithium acrylate aqueous solution, and freezing and recrystallizing to obtain lithium acrylate crystals.
As a more preferred embodiment of the use of the metal ion-containing functional monomer of the present invention in transparent nylon, the unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride is at least one selected from maleic acid (anhydride), itaconic acid (anhydride), and methylene adipic acid (anhydride).
As a still further preferred embodiment of the use of the metal ion-containing functional monomer of the present invention in transparent nylon, the unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride is maleic acid, itaconic acid or methyleneadipic acid.
As a more preferable embodiment of the application of the metal ion-containing functional monomer in transparent nylon, the mass ratio of the unsaturated metal salt to the unsaturated dicarboxylic acid or the unsaturated dicarboxylic anhydride is as follows: unsaturated metal salt: unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride=1:1-1.2.
In a second aspect, the present invention provides a transparent nylon composite resin, wherein the structural formula of the transparent nylon composite resin is one of the following:
、/>、。
The transparency of such polymeric materials as PA66 is primarily affected by the chain structure of the material, and if the grain size is greater than the wavelength of visible light, the light will not pass through the material after the polymeric material has crystallized, thus making the material opaque; in addition, the refractive index of the crystalline region and the amorphous region of the material is different, and light can be refracted when passing through the material, so that the material is opaque; the improvement of the transparency of nylon materials is therefore currently mainly initiated from two aspects: on one hand, the crystallinity of the nylon is reduced, so that the nylon can be transparent when the nylon is amorphous; on the other hand, the size of the crystal area of nylon is reduced, which is smaller than the wavelength of visible light; in addition, structurally, both the nitrogen atom and the oxygen atom in the polyamide group of the nylon resin have lone pair electrons, and from the broad acid-base theory, both have the capability of giving electrons, belong to Lewis base, and can interact with Lewis acid, and the occurrence of the interaction inevitably changes the aggregation state structure of the polyamide; in the prior art, caCl 2, liCl, trimethyl borate, tributyl borate and the like are introduced in a blending mode, so that complexing can be formed with a nylon molecular chain, the crystallinity of the nylon material is obviously changed, and when the adding amount of the complexing agent reaches a certain degree, the nylon can be changed into an amorphous state, so that the transparent nylon material is prepared; however, the transparent nylon material prepared by the method is unstable, and dissolution, precipitation and the like of the complexing agent can be generated during storage and use, so that the transparency is reduced.
The invention introduces metal ions into the molecular chain segment of PA66 through the functional monomer containing metal ions, and has the following advantages: (1) The metal ions on the molecular chain and the metal ions and the amide groups have stronger interaction, so that the movement of the molecular chain is inhibited in the forming process, the crystallinity of the molecular chain is reduced, and the transparency of the final product is enhanced; (2) Through molecular structure design, the transparency of the product is realized by adopting a Li or Na metal ion complexing mechanism, and meanwhile, the problem of transparency reduction caused by complexing agent precipitation is solved.
The inventor has unexpectedly found that the mechanical properties of the modified nylon composite resin are not obviously reduced, and the mechanical properties of the modified nylon composite resin are improved to a certain extent.
In a third aspect, the present invention provides a method for preparing a transparent nylon composite resin, the method comprising the steps of:
S1, adding the functional monomer containing metal ions, adipic acid and hexamethylenediamine in the first aspect into water, and stirring at 25-60 ℃ to obtain uniform and stable dispersion liquid, wherein the mass ratio of the functional monomer containing metal ions to the adipic acid is (6-20): 100;
S2, carrying out prepolymerization reaction on the dispersion liquid obtained in the step S1 under the protection of nitrogen at a high temperature and high pressure, wherein the reaction temperature is 230-250 ℃, the reaction time is 2-3h, and the reaction pressure is 1.5-2.0MPa;
S3, decompressing the product obtained after the prepolymerization reaction in the step S2 to normal pressure, then heating to 260-280 ℃ to perform polycondensation reaction, wherein the reaction time is 1-2h, the reaction pressure is-0.06-0.1 MPa, and the product obtained after the reaction is the transparent nylon composite resin.
The inventor finds that when the mass ratio of the functional monomer containing metal ions to adipic acid is (6-20): 100, the prepared nylon composite resin has better mechanical property and transparency; because of the difference of chemical structures, the reactivity of the functional monomer containing metal ions and adipic acid is different, the functional monomer containing metal ions has a certain inhibition effect on the polymerization of nylon resin, and the molecular chain growth can be influenced only in a certain amount range; when the addition amount of the functional monomer containing metal ions is too large, the molecular chain growth is rapidly stopped, so that the molecular weight is low, the relative viscosity is low, the material is weak and brittle, the molding processing is difficult, and the use value is hardly increased; and when the content of the functional monomer containing metal ions is too low, the improvement of the transparency of the product is not obvious.
As a preferred embodiment of the method for preparing the transparent nylon composite resin of the present invention, in the step S1, the mass ratio of adipic acid to hexamethylenediamine is adipic acid: hexamethylenediamine=1:1-1.04.
In a fourth aspect, the present invention provides the use of the transparent nylon composite resin according to the second aspect for preparing a transparent nylon material.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, the functional monomer containing metal ions with a specific structure is introduced to a molecular chain segment of the nylon resin in a specific addition amount, so that the transparent nylon composite resin with high metal ion content and activity is prepared, and the transparent nylon composite resin has high transparency and excellent mechanical property.
Drawings
FIG. 1 is an infrared spectrum of a functional monomer containing metal ions according to an embodiment of the present invention;
FIG. 2 is an infrared spectrum of a transparent nylon composite resin according to an embodiment of the present invention;
FIG. 3 is a graph of thermal weight loss of the transparent nylon composite resin of FIG. 2;
FIG. 4 is an infrared spectrum of a functional monomer containing metal ions according to an embodiment of the present invention;
FIG. 5 is an infrared spectrum of a transparent nylon composite resin according to an embodiment of the present invention;
FIG. 6 is a graph of thermal weight loss of the transparent nylon composite resin of FIG. 5;
FIG. 7 is an infrared spectrum of a functional monomer containing metal ions according to an embodiment of the present invention;
FIG. 8 is an infrared spectrum of a transparent nylon composite resin according to an embodiment of the present invention;
FIG. 9 is a graph of thermal weight loss of the transparent nylon composite resin of FIG. 8.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
Example 1
The preparation method of the functional monomer containing metal ions in the embodiment 1 of the invention comprises the following steps: adding lithium acrylate into N, N-Dimethylformamide (DMF), heating to 80 ℃, stirring for dissolution, and then adding maleic acid which is equimolar with the lithium acrylate for reaction, wherein the reaction temperature is 130-160 ℃, and the reaction time is 3-6h; then adding ethanol for precipitation and suction filtration to obtain the functional monomer containing metal ions, wherein the reaction formula is shown in the following formula, and an infrared spectrogram of the functional monomer containing metal ions is shown in figure 1:
（1）
The lithium acrylate in this embodiment is self-made, and the preparation method is as follows: mixing acrylic acid and lithium hydroxide in a molar ratio of 1:1, heating to 60 ℃, reacting for 1h to obtain lithium acrylate aqueous solution, and freezing and recrystallizing to obtain lithium acrylate crystals.
The preparation method of the transparent nylon composite resin comprises the following steps:
S1, adding the functional monomer containing metal ions in the formula (1), adipic acid and hexamethylenediamine into water, and stirring for 10min at 25-60 ℃ to obtain uniform and stable dispersion liquid, wherein the mass ratio of the functional monomer containing metal ions to the adipic acid is 10:100, and the mass ratio of the adipic acid to the hexamethylenediamine is adipic acid: hexamethylenediamine=1:1.04;
S2, carrying out prepolymerization reaction on the dispersion liquid obtained in the step S1 under the protection of nitrogen at a high temperature and high pressure, wherein the reaction temperature is 230 ℃, the reaction time is 3 hours, and the reaction pressure is 1.5MPa;
S3, decompressing the product obtained after the prepolymerization reaction in the step S2 to normal pressure, then heating to 260 ℃ for polycondensation reaction, wherein the reaction time is 1h, the reaction pressure is-0.1 MPa, discharging and granulating after the reaction, and obtaining the product, namely the transparent nylon composite resin, wherein the infrared spectrogram of the transparent nylon composite resin is shown in FIG. 2, the thermogravimetric analysis is shown in FIG. 3, and the chemical formula of the transparent nylon composite resin is shown as follows:
。
Example 2
The preparation method of the metal ion-containing functional monomer in the embodiment 2 comprises the following steps: adding disodium vinylphosphate into DMF, heating to 100 ℃, stirring for dissolution, and then adding itaconic acid which is equimolar with the disodium vinylphosphate for reaction, wherein the reaction temperature is 130-160 ℃ and the reaction time is 3-6h; then adding ethanol for precipitation and suction filtration to obtain the functional monomer containing metal ions, which is shown in the following reaction formula, wherein the infrared spectrogram of the functional monomer containing metal ions is shown in figure 4:
（2）
the preparation method of the transparent nylon composite resin comprises the following steps:
S1, adding the functional monomer containing metal ions in the formula (2), adipic acid and hexamethylenediamine into water, and stirring for 10min at 25-60 ℃ to obtain uniform and stable dispersion liquid, wherein the mass ratio of the functional monomer containing metal ions to the adipic acid is 6:100, and the mass ratio of the adipic acid to the hexamethylenediamine is adipic acid: hexamethylenediamine=1:1.02;
s2, carrying out prepolymerization reaction on the dispersion liquid obtained in the step S1 under the protection of nitrogen at a high temperature and high pressure, wherein the reaction temperature is 230 ℃, the reaction time is 3 hours, and the reaction pressure is 1.7MPa;
S3, decompressing the product obtained after the prepolymerization reaction in the step S2 to normal pressure, then heating to 268 ℃ for polycondensation reaction, wherein the reaction time is 1h, the reaction pressure is-0.1 MPa, discharging and granulating after the reaction, and the obtained product is transparent nylon composite resin, wherein the chemical formula of the transparent nylon composite resin is shown as the following formula, the infrared spectrogram of the transparent nylon composite resin is shown in fig. 5, and the thermal weight loss analysis is shown in fig. 6:
。
Example 3
The preparation method of the metal ion-containing functional monomer in the embodiment 3 comprises the following steps: adding sodium methallyl sulfonate into DMF, heating to 100 ℃, stirring and dissolving, and then adding methylene adipic acid which is equimolar with the sodium methallyl sulfonate for reaction, wherein the reaction temperature is 130-160 ℃, and the reaction time is 3-6h; then adding ethanol for precipitation and suction filtration to obtain the functional monomer containing metal ions, wherein the reaction formula is shown in the following formula, and an infrared spectrogram of the functional monomer containing metal ions is shown in fig. 7:
（3）
the preparation method of the transparent nylon composite resin comprises the following steps:
s1, adding the functional monomer containing metal ions in the formula (3), adipic acid and hexamethylenediamine into water, and stirring for 10min at 25-60 ℃ to obtain uniform and stable dispersion liquid, wherein the mass ratio of the functional monomer containing metal ions to the adipic acid is 20:100, and the mass ratio of the adipic acid to the hexamethylenediamine is adipic acid: hexamethylenediamine=1:1.04;
S2, carrying out prepolymerization reaction on the dispersion liquid obtained in the step S1 under the protection of nitrogen at a high temperature and high pressure, wherein the reaction temperature is 230 ℃, the reaction time is 3 hours, and the reaction pressure is 1.5MPa;
s3, decompressing the product obtained after the prepolymerization reaction in the step S2 to normal pressure, then heating to 260 ℃ for polycondensation reaction, wherein the reaction time is 1.5h, the reaction pressure is-0.8 MPa, discharging and granulating after the reaction, and obtaining the product, namely the transparent nylon composite resin, wherein the chemical formula of the transparent nylon composite resin is shown in the following formula, the infrared spectrogram of the transparent nylon composite resin is shown in fig. 8, and the thermal weight loss analysis is shown in fig. 9:
。
comparative example 1
The difference between this comparative example and example 1 is that: functional monomers without metal ions are added; the preparation method of the nylon resin comprises the following steps:
S1, adding adipic acid and hexamethylenediamine into water, and stirring for 10min at 25-60 ℃ to obtain uniform and stable dispersion liquid, wherein the mass ratio of the adipic acid to the hexamethylenediamine is as follows: hexamethylenediamine=1:1.02;
S2, carrying out prepolymerization reaction on the dispersion liquid obtained in the step S1 under the protection of nitrogen at a high temperature and high pressure, wherein the reaction temperature is 230 ℃, the reaction time is 3 hours, and the reaction pressure is 1.5MPa;
s3, decompressing the product obtained after the prepolymerization reaction in the step S2 to normal pressure, then heating to 270 ℃ to perform polycondensation reaction, wherein the reaction time is 1.5h, the reaction pressure is-0.8 MPa, discharging and granulating after the reaction, and obtaining the product, namely nylon resin, wherein the chemical formula of the nylon resin is shown as follows:
。
Comparative example 2
The difference between this comparative example and example 1 is that: the functional monomer containing metal ions is sodium phenyl hypophosphite succinic acid, and the preparation method of the nylon material comprises the following steps:
S1, adding sodium 2, 3-dicarboxypropyl (phenyl) hypophosphite and adipic acid and hexamethylenediamine into water, and stirring for 10min at 25-60 ℃ to obtain uniform and stable dispersion, wherein the mass ratio of the functional monomer containing metal ions to the adipic acid is 20:100, and the mass ratio of the adipic acid to the hexamethylenediamine is adipic acid: hexamethylenediamine=1:1.02;
S2, carrying out prepolymerization reaction on the dispersion liquid obtained in the step S1 under the protection of nitrogen at a high temperature and high pressure, wherein the reaction temperature is 230 ℃, the reaction time is 3 hours, and the reaction pressure is 1.5MPa;
S3, decompressing the product obtained after the prepolymerization reaction in the step S2 to normal pressure, then heating to 270 ℃ to perform polycondensation reaction, wherein the reaction time is 1.5h, the reaction pressure is-0.8 MPa, discharging and granulating after the reaction, and obtaining the product, namely the nylon composite resin, wherein the chemical formula of the nylon composite resin is shown as follows:
。
Comparative example 3
The difference between this comparative example and the method for producing a transparent nylon composite resin of example 2 is that in step S1, the mass ratio of the functional monomer containing metal ions to adipic acid is 4:100, and the remainder is the same as example 2.
Comparative example 4
The difference between this comparative example and the method for producing a transparent nylon composite resin of example 2 is that in step S1, the mass ratio of the functional monomer containing metal ions to adipic acid is 30:100, and the remainder is the same as example 2.
Comparative example 5
In the comparative example, the nylon resin in the comparative example 1 and CaCl 2 are melt-blended to prepare a nylon composite material, and the preparation method comprises the following steps: the nylon resin described in comparative example 1 and CaCl 2 were mixed, and the mass ratio of CaCl 2 to nylon resin was: and 6:100, blending processing is carried out in an extruder at the temperature of 260 ℃, and the nylon composite resin is obtained after granulating.
Performance testing
1. Tensile strength and flexural strength: tensile strength was tested according to ISO 527 standard, equipment test conditions were: the stretching speed is 50mm/min, the tension sensor 20000N and the gauge length is 75mm; 5 samples were tested for each sample, and the results averaged; the bending strength is tested according to the ISO178 standard, and the equipment test conditions are as follows: the test rate was 2mm/min, 3 samples were measured for each sample, and the results were averaged.
2. Transparency: adopting a light transmittance detector to test; cutting the plastic material into small pieces of the same size and cleaning the surface to ensure the accuracy of the test results; placing the sample in a testing device, adjusting the heights and angles of the light source and the receiver to ensure that the incidence and emergent angles of the light are correct, and recording test data: the transmitted light intensity through the sample was recorded and the transparency calculated using the following formula:
Transparency = transmitted light intensity/incident light intensity
3. Melting temperature: testing with a Differential Scanning Calorimeter (DSC); the nylon composite resin and the reference sample of the examples and the comparative examples were placed in two independent furnace chambers of DSC, respectively, the heating rate was set to 10 ℃/min, the cut-off temperature was set to 300 ℃, and the endothermic peak of the nylon composite resin occurring during melting of the examples and the comparative examples was observed by the heat capacity change of the nylon composite resin and the reference sample of the comparative examples and the comparative examples, and the melting temperature of the sample was determined from the peak temperature.
The test results are shown in table 1 below:
TABLE 1
As can be seen from the results of Table 1, the transparent nylon composite resin according to examples 1 to 3 of the present invention has a tensile strength of 80MPa or more, a flexural strength of 126MPa or more, a transparency of 90% or more, and no change in transparency for 90 days. The nylon resin in comparative example 1 is less transparent and is milky white because the functional monomer containing metal ions is not added; the functional monomer containing metal ions used in the nylon composite resin of comparative example 2 was not within the range provided by the present invention, and the transparency of the final material was not as good as that of the examples; in comparative example 3, the functional monomer containing metal ions is added in an excessively small amount, so that the transparency of the final nylon composite resin is semitransparent, and the mechanical properties are also reduced to different degrees; in comparative example 4, the excessive addition of the functional monomer containing metal ions causes excessive viscosity of the product, so that the product is difficult to be fed and the mechanical property of the product cannot be measured; comparative example 5, which adopts the prior art melting method, can improve the transparency of nylon material, but has poor storability and transparency stability.
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 scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The application of the functional monomer containing the metal ions in the transparent nylon is characterized in that the structural formula of the functional monomer containing the metal ions is one of the following formulas:
、/>、/>。
2. the use according to claim 1, wherein the preparation method of the functional monomer containing metal ions comprises the following steps: adding unsaturated metal salt into an organic solvent, heating to 80-100 ℃, then adding unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride, and reacting for 3-6h at 130-160 ℃ to obtain the functional monomer containing metal ions.
3. The use according to claim 2, characterized in that the unsaturated metal salt is selected from at least one of lithium acrylate, disodium vinylphosphate, sodium methallyl sulfonate.
4. The use according to claim 2, characterized in that the unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride is selected from at least one of maleic acid (anhydride), itaconic acid (anhydride), methylene adipic acid (anhydride).
5. The use according to claim 2, characterized in that the mass ratio of the unsaturated metal salt to the unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride is: unsaturated metal salt: unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride=1:1-1.2.
6. The transparent nylon composite resin is characterized by comprising one of the following structural formulas:
、/>、。
7. the method for preparing the transparent nylon composite resin according to claim 6, which comprises the following steps:
S1, adding the functional monomer containing metal ions, adipic acid and hexamethylenediamine into water, and stirring at 25-60 ℃ to obtain uniform and stable dispersion, wherein the mass ratio of the functional monomer containing metal ions to adipic acid is (6-20): 100;
S2, carrying out prepolymerization reaction on the dispersion liquid obtained in the step S1 under the protection of nitrogen at a high temperature and high pressure, wherein the reaction temperature is 230-250 ℃, the reaction time is 2-3h, and the reaction pressure is 1.5-2.0MPa;
S3, decompressing the product obtained after the prepolymerization reaction in the step S2 to normal pressure, then heating to 260-280 ℃ to perform polycondensation reaction, wherein the reaction time is 1-2h, the reaction pressure is-0.06-0.1 MPa, and the product obtained after the reaction is the transparent nylon composite resin.
8. The method according to claim 7, wherein in the step S1, the mass ratio of adipic acid to hexamethylenediamine is adipic acid: hexamethylenediamine=1:1-1.04.
9. The use of the transparent nylon composite resin of claim 6 in the preparation of transparent nylon materials.
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