CN116854885A - Toughening modifier for PET resin, modified PET resin and application - Google Patents
Toughening modifier for PET resin, modified PET resin and application Download PDFInfo
- Publication number
- CN116854885A CN116854885A CN202310865292.4A CN202310865292A CN116854885A CN 116854885 A CN116854885 A CN 116854885A CN 202310865292 A CN202310865292 A CN 202310865292A CN 116854885 A CN116854885 A CN 116854885A
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- China
- Prior art keywords
- toughening modifier
- pet
- toughening
- diisocyanate
- latex
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- 239000003607 modifier Substances 0.000 title claims abstract description 76
- 229920005989 resin Polymers 0.000 title claims abstract description 55
- 239000011347 resin Substances 0.000 title claims abstract description 55
- 239000004814 polyurethane Substances 0.000 claims abstract description 78
- 229920002635 polyurethane Polymers 0.000 claims abstract description 78
- 239000004816 latex Substances 0.000 claims abstract description 41
- 229920000126 latex Polymers 0.000 claims abstract description 41
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 239000000839 emulsion Substances 0.000 claims description 64
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 claims description 28
- FSEJJKIPRNUIFL-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-octadecanoyloxypropyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)COC(=O)CCCCCCCCCCCCCCCCC FSEJJKIPRNUIFL-UHFFFAOYSA-N 0.000 claims description 26
- 150000002825 nitriles Chemical class 0.000 claims description 26
- 239000003995 emulsifying agent Substances 0.000 claims description 24
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 21
- 229920000570 polyether Polymers 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 21
- 229920001451 polypropylene glycol Polymers 0.000 claims description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 20
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 20
- -1 pentaerythritol ester Chemical class 0.000 claims description 20
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 19
- 125000005442 diisocyanate group Chemical group 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 19
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 18
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 18
- 238000010559 graft polymerization reaction Methods 0.000 claims description 18
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 18
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 239000004970 Chain extender Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 230000001804 emulsifying effect Effects 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 3
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- XIYYCJIGAOLCPV-UHFFFAOYSA-N S1SCC=C1.C(CCCCCCC)[Sn]CCCCCCCC Chemical compound S1SCC=C1.C(CCCCCCC)[Sn]CCCCCCCC XIYYCJIGAOLCPV-UHFFFAOYSA-N 0.000 claims description 3
- FWCDLNRNBHJDQB-UHFFFAOYSA-N [2-(hydroxymethyl)-3-octadecanoyloxy-2-(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC FWCDLNRNBHJDQB-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 239000002131 composite material Substances 0.000 abstract description 7
- 229920000728 polyester Polymers 0.000 abstract description 3
- 230000003014 reinforcing effect Effects 0.000 abstract description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 95
- 239000005020 polyethylene terephthalate Substances 0.000 description 95
- 239000008367 deionised water Substances 0.000 description 26
- 229910021641 deionized water Inorganic materials 0.000 description 26
- 238000001035 drying Methods 0.000 description 20
- 239000012948 isocyanate Substances 0.000 description 20
- 150000002513 isocyanates Chemical class 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 239000012745 toughening agent Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 238000001914 filtration Methods 0.000 description 13
- DSROZUMNVRXZNO-UHFFFAOYSA-K tris[(1-naphthalen-1-yl-3-phenylnaphthalen-2-yl)oxy]alumane Chemical compound C=1C=CC=CC=1C=1C=C2C=CC=CC2=C(C=2C3=CC=CC=C3C=CC=2)C=1O[Al](OC=1C(=C2C=CC=CC2=CC=1C=1C=CC=CC=1)C=1C2=CC=CC=C2C=CC=1)OC(C(=C1C=CC=CC1=C1)C=2C3=CC=CC=C3C=CC=2)=C1C1=CC=CC=C1 DSROZUMNVRXZNO-UHFFFAOYSA-K 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 11
- 239000003365 glass fiber Substances 0.000 description 11
- 229960001545 hydrotalcite Drugs 0.000 description 11
- 229910001701 hydrotalcite Inorganic materials 0.000 description 11
- 125000003700 epoxy group Chemical group 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 125000005219 aminonitrile group Chemical group 0.000 description 4
- 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
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- DQQIUVCNBOJDGF-UHFFFAOYSA-N 2-aminobutanenitrile Chemical compound CCC(N)C#N DQQIUVCNBOJDGF-UHFFFAOYSA-N 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229940124277 aminobutyric acid Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 238000009864 tensile test 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The invention provides a toughening modifier for PET resin, modified PET resin and application thereof. The toughening modifier for PET resin has a core-shell structure, and comprises a core structure of polyurethane latex and a shell structure of amino-terminated butyronitrile latex. The toughening modifier can be used in various composite systems, is applied to toughening of PET resin, has good toughening/reinforcing effects, and is suitable for modifying and applying polyester materials such as PET.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a toughening modifier of PET resin, modified PET resin and application.
Background
Polyethylene terephthalate (PET) is a common thermoplastic engineering plastic, and because a continuous ester group exists on the PET main chain, a rigid molecular chain is formed, so that the PET has high rigidity and high mechanical strength. However, PET has high brittleness and is easy to break, so that the PET has certain limit on production application. In the actual production process, an elastomer toughening agent and other inorganic fillers are generally added to toughen and modify the PET resin. The reasons for the poor toughness of the modified PET are mainly the toughness of the PET resin itself, the interfacial compatibility of the resin and the filler, and the like. In the Chinese patent application with publication number of CN113788914A, a method for toughening PET resin by using polystyrene-poly (ethylene-butylene) -polystyrene block copolymer/aluminum titanate (SEBS/AT) as a composite toughening agent is disclosed, when the dosage of the composite toughening agent is 1.5%, compared with the PET resin without the toughening agent, the impact resistance of the resin is improved by 125%, but the tensile strength is reduced by 18%. The addition of the toughening agent can effectively improve the toughness of PET and reduce the tensile strength of PET. How to enhance the impact toughness of a material without significantly reducing the tensile strength of the material is an urgent technical problem to be solved.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. The invention mainly designs and prepares a reactive toughening modifier from the high elastic structure and interface compatibility required by the toughening agent, synthesizes a polyurethane chain segment by polyether glycol and diisocyanate, regulates and controls the soft and hard proportion of polyurethane by the reaction and chain extension of hydroxyl groups of hydrophilic chain extenders such as dimethylolpropionic acid, carboxyl groups, polyurethane isocyanate groups and glycol hydroxyl groups, and further enhances the stability of the aqueous core polyurethane emulsion. Finally, the shell layer coverage is completed through the blocked isocyanate grafted amino-terminated nitrile rubber.
The toughening modifier provided by the invention can be used for toughening and modifying PET resin, on one hand, through the toughening effect of polyurethane regulation and control, a large number of polyurethane chain segments in a toughening agent system have high elasticity, and in the process of toughening PET resin, the toughening modifier can better absorb energy brought by impact, so that the toughness of PET resin is greatly improved. On the other hand, an epoxy resin (e.g., diglycidyl phthalate) is added to the shell layer, and the nitrile latex is cured by the reaction of the epoxy group with the aminonitrile. In addition, certain pentaerythritol ester (such as pentaerythritol distearate) is added into the system, so that the compatibility of the toughening agent and PET can be improved. Hydroxyl in the molecular structure of pentaerythritol ester can participate in the reaction of isocyanate in polyurethane core, and also can participate in the reaction of shell layer and epoxy group.
Finally, when the modified polymer is applied to a PET resin modified system, the compatibility is further improved by electrostatic attraction between positive charges carried by shell layer terminal amino groups and negative charges carried by surfaces of glass fibers and hydrotalcite, and the glass fibers and the hydrotalcite can improve the tensile strength and heat resistance stability of the resin. Experiments prove that the prepared toughening modifier is applied to toughening of PET resin, has good toughening/reinforcing effects, and is suitable for modifying and applying polyester materials such as PET.
Specifically, the invention provides the following technical scheme:
in a first aspect, the present invention provides a toughening modifier for PET resins, the toughening modifier having a core shell structure, the modifier comprising a core structure of polyurethane latex and a shell structure of an amino terminated nitrile latex.
According to an embodiment of the present invention, the toughening modifier for PET resin described above may further include the following technical features:
according to the embodiment of the invention, the mass ratio of the polyurethane latex core structure to the amino-terminated nitrile latex shell structure is 5: (1-2).
According to an embodiment of the present invention, the core structure of the polyurethane latex is that of an isocyanate-terminated polyurethane latex, and the toughening modifier is obtained by emulsifying the isocyanate-terminated polyurethane latex and an amino-terminated nitrile latex, an epoxy resin, and a pentaerythritol ester, and performing graft polymerization. On one hand, the polyurethane has high elasticity through regulating and controlling the toughening effect of polyurethane, and a large number of polyurethane chain segments in the toughening modifier system can better absorb energy brought by impact in the process of toughening PET resin, so that the toughness of the PET resin is greatly improved. On the other hand, an epoxy resin (e.g., diglycidyl phthalate) is added to the shell layer, and the nitrile latex is cured by the reaction of the epoxy group with the aminonitrile. In addition, certain pentaerythritol ester (such as pentaerythritol distearate) is added into the system, so that the compatibility of the toughening agent and PET can be improved. Hydroxyl in the molecular structure of pentaerythritol ester can participate in the reaction of isocyanate in polyurethane core, and also can participate in the reaction of shell layer and epoxy group.
According to the embodiment of the invention, the mass of the epoxy resin is 10-20% of the mass of the amino-terminated nitrile latex.
According to the embodiment of the invention, the mass of the pentaerythritol ester is 150-200% of the mass of the epoxy resin.
According to the embodiment of the invention, the time for emulsification is 20-60 minutes, the temperature for grafting polymerization is 60-90 ℃, and the time for grafting polymerization is 1-3 hours.
According to an embodiment of the invention, the epoxy resin is selected from at least one of triglycidyl isophthalate, diglycidyl phthalate, preferably diglycidyl phthalate.
According to the embodiment of the invention, the mass of the diglycidyl phthalate is 10-20% of the mass of the amino-terminated butyronitrile latex.
According to an embodiment of the present invention, the pentaerythritol ester is selected from at least one of pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, preferably pentaerythritol distearate.
According to the embodiment of the invention, the mass of the pentaerythritol distearate is 150-200% of the mass of the diglycidyl phthalate.
According to the embodiment of the invention, the core structure of the polyurethane emulsion is obtained by mixing and emulsifying polyether glycol, diisocyanate, a chain extender, a catalyst and an emulsifier serving as a disperse phase and water serving as a continuous phase.
According to an embodiment of the invention, the volume fraction of the dispersed phase is 74% to 90%, preferably 80% to 85%.
According to an embodiment of the present invention, the polyether glycol is one of PPG200, PPG330, PPG400, preferably PPG200.
According to an embodiment of the present invention, the diisocyanate is one of isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and preferably hexamethylene diisocyanate;
according to an embodiment of the invention, the chain extender is dimethylolpropionic acid, dimethylolbutyric acid, sodium 1, 4-butanediol-2-sulfonate, preferably dimethylolpropionic acid;
according to an embodiment of the invention, the catalyst is one of dibutyltin dilaurate, dioctyltin dithiol, preferably dibutyltin dilaurate;
according to an embodiment of the invention, the emulsifier is a mixture of sodium lauryl sulfate, an addition polymer of polypropylene glycol and ethylene oxide (F127);
according to an embodiment of the invention, the mass ratio of sodium dodecyl sulfate and addition polymer of polypropylene glycol and ethylene oxide (F127) is 1:3, a step of;
according to an embodiment of the invention, the emulsifier is used in an amount of 1 to 3% by mass of the polyether glycol and the diisocyanate.
According to an embodiment of the invention, the molar ratio of the polyether diol and the diisocyanate is 1:1.5, wherein the chain extender is 10-25% of the mass of the nuclear monomer (polyether glycol and diisocyanate), and the catalyst is 1% of the mass of the nuclear monomer (polyether glycol and diisocyanate).
In a second aspect the invention provides the use of the toughening modifier of the first aspect in the preparation of a PET resin.
A third aspect of the invention provides a PET resin comprising PET and a toughening modifier according to any of the first aspects of the invention;
according to an embodiment of the invention, the mass ratio of the toughening modifier to the PET is 10:100.
the beneficial effects obtained by the invention are as follows:
(1) The toughening modifier can be applied to various composite systems such as PET/glass fiber/hydrotalcite, on one hand, the toughening effect is regulated and controlled through polyurethane, and a large number of polyurethane chain segments in the toughening agent system have high elasticity, and can better absorb energy brought by impact in the process of toughening PET resin, so that the toughness of the PET resin is greatly improved. On the other hand, an epoxy resin (e.g., diglycidyl phthalate) is added to the shell layer, and the nitrile latex is cured by the reaction of the epoxy group with the aminonitrile. In addition, certain pentaerythritol ester (such as pentaerythritol distearate) is added into the system, so that the compatibility of the toughening agent and PET can be improved. Hydroxyl in the molecular structure of pentaerythritol ester can participate in the reaction of isocyanate in polyurethane core, and also can participate in the reaction of shell layer and epoxy group. Finally, the electrostatic attraction between the positive charges carried by the shell layer terminal amino groups and the negative charges carried by the surfaces of the glass fiber and the hydrotalcite is beneficial to further improving the compatibility, and the glass fiber and the hydrotalcite can improve the tensile strength and the heat-resistant stability of the resin. Experiments prove that the prepared toughening modifier is applied to toughening of PET resin, has good toughening/reinforcing effects, and is suitable for modifying and applying polyester materials such as PET.
Detailed Description
The following detailed description of embodiments of the invention, it should be noted that the listed embodiments are intended to be illustrative of the invention and should not be construed as limiting the invention.
The invention provides a toughening modifier for PET resin, which has a core-shell structure, and comprises a core structure of polyurethane latex and a shell structure of amino-terminated butyronitrile latex.
According to an embodiment of the invention, the mass ratio of the polyurethane latex core structure to the amino-terminated nitrile latex shell structure is 5: (1-2).
According to an embodiment of the present invention, the core structure of the polyurethane latex is that of an isocyanate-terminated polyurethane latex, and the toughening modifier is obtained by emulsifying the isocyanate-terminated polyurethane latex with an aminobutyric acid latex, an epoxy resin, and pentaerythritol ester, and performing graft polymerization. On one hand, the toughening agent system has high elasticity through the polyurethane regulation and control toughening effect, and a large number of polyurethane chain segments in the toughening agent system can better absorb energy brought by impact in the process of toughening PET resin, so that the toughness of the PET resin is greatly improved. On the other hand, an epoxy resin (e.g., diglycidyl phthalate) is added to the shell layer, and the nitrile latex is cured by the reaction of the epoxy group with the aminonitrile. In addition, certain pentaerythritol ester (such as pentaerythritol distearate) is added into the system, so that the compatibility of the toughening agent and PET can be improved. Hydroxyl in the molecular structure of pentaerythritol ester can participate in the reaction of isocyanate in polyurethane core, and also can participate in the reaction of shell layer and epoxy group.
According to a specific embodiment, the mass of the epoxy resin is 10% -20% of the mass of the amino terminated nitrile latex, for example 10%, 15%, 20%.
According to a specific embodiment, the mass of the pentaerythritol ester is 150% -200%, such as 150%, 160%, 170%, 180%, 190%, 200% of the mass of the epoxy resin.
According to an embodiment of the present invention, the time for emulsification is 20 to 60 minutes, the temperature for graft polymerization is 60 to 90 degrees celsius, and the time for graft polymerization is 1 to 3 hours.
According to an embodiment of the invention, the epoxy resin is selected from at least one of triglycidyl isophthalate, diglycidyl phthalate, preferably diglycidyl phthalate.
According to the embodiment of the invention, the consumption of the diglycidyl phthalate is 10-20% of the mass of the terminated amino butyronitrile latex.
According to an embodiment of the present invention, the pentaerythritol ester is selected from at least one of pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, preferably pentaerythritol distearate.
According to an embodiment of the present invention, the mass of pentaerythritol distearate is 150% to 200% of the mass of diglycidyl phthalate.
According to an embodiment of the present invention, the core structure of the polyurethane emulsion is obtained by mixing and emulsifying polyether glycol, diisocyanate, chain extender, catalyst and emulsifier as a dispersed phase and water as a continuous phase.
According to an embodiment of the invention, the volume fraction of the dispersed phase is 74% to 90%, preferably 80% to 85%.
According to an embodiment of the present invention, the polyether glycol is one of PPG200, PPG330, PPG400, preferably PPG200.
According to an embodiment of the present invention, the diisocyanate is one of isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, preferably hexamethylene diisocyanate;
according to an embodiment of the invention, the chain extender is dimethylolpropionic acid, dimethylolbutyric acid, sodium 1, 4-butanediol-2-sulfonate, preferably dimethylolpropionic acid;
according to an embodiment of the invention, the catalyst is one of dibutyl tin dilaurate and dioctyl tin dithiol, preferably dibutyl tin dilaurate;
according to an embodiment of the invention, the emulsifier is a mixture of sodium lauryl sulfate, an addition polymer of polypropylene glycol and ethylene oxide (F127);
according to the examples of the invention, the ratio of sodium lauryl sulfate and addition polymer of polypropylene glycol and ethylene oxide (F127) is 1:3, a step of;
according to a specific embodiment, the emulsifier is used in an amount of 1% to 3% of the mass of the core monomer (the total mass of the polyether diol and the diisocyanate).
According to a specific embodiment, the molar ratio of the polyether glycol core diisocyanate is 1:1.5, wherein the chain extender is 10-25% of the mass of the nuclear monomer (the total mass of the polyether glycol and the diisocyanate), and the catalyst is 1% of the mass of the nuclear monomer (the total mass of the polyether glycol and the diisocyanate).
The invention provides a reactive toughening modifier which can be used for toughening modification of polyethylene terephthalate (PET). According to the specific embodiment of the invention, the provided toughening modifier adopts a concentrated emulsion step-by-step polymerization method, a monomer mixture of polyether glycol, diisocyanate, a chain extender, a catalyst and the like is taken as a disperse phase, water and an emulsifier are taken as a continuous phase, and the mixture is mixed to obtain a concentrated emulsion, and the concentrated emulsion reacts for 1h at 50 ℃ to obtain a polyurethane emulsion core structure; and adding amino-terminated butyronitrile latex, epoxy resin and pentaerythritol ester, emulsifying for 30min at a high speed, heating to 70 ℃ for reacting for 2h, washing and drying to obtain the toughening modifier. The polyurethane emulsion blocked by isocyanate is prepared through the reactions of polyether glycol, isocyanate, chain extender, catalyst and the like, then the amino-terminated liquid nitrile emulsion is grafted, the epoxy resin is added to cure the nitrile emulsion, and the pentaerythritol stearate is added to improve the compatibility of the toughening agent and PET. The reactive PET toughening modifier is obtained by washing and drying, and is added into PET resin, so that the toughness of the PET resin is effectively improved, and the rigidity of the resin is enhanced to a certain extent. The composite latex is obtained through two-step polymerization, isocyanate end-capped polyurethane latex is prepared through polymerization, and then the modified toughening agent is obtained through grafting amino end-capped liquid nitrile latex. The obtained PET toughening modifier can be compounded with glass fiber and hydrotalcite to be added into PET resin, so that the toughness of the PET resin is effectively improved, and the rigidity of the resin is also enhanced to a certain extent. According to a specific embodiment, the present invention also provides a modified PET resin comprising 100 parts of polybutylene terephthalate resin (PET); 10 parts of toughening modifier; 30 parts of glass fiber; and 15 parts of hydrotalcite.
According to a specific embodiment, the emulsifier in the continuous phase mentioned is a mixture of sodium lauryl sulfate, an addition polymer of polypropylene glycol and ethylene oxide. According to the specific embodiment, the PET toughening modifier can be obtained by drying for 5 hours at 80 ℃ by using a forced air drying oven.
Example 1
Example 1 a PET toughening modifier was prepared by the following method:
into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 35g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
The polyurethane emulsion is reacted for 1h at 50 ℃ to obtain isocyanate end-capped polyurethane emulsion, and then 50g of amino-terminated liquid nitrile emulsion (ATBN 1300X35 of Shenzhen Jiadieda new material technology Co., ltd.), 10g of diglycidyl phthalate and 20g of pentaerythritol distearate are added, and the mixture is emulsified for 30min at a high speed and heated to 70 ℃ for 2h to complete graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Example 2
Example 2 a PET toughening modifier was prepared by the following method:
into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 50g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
The polyurethane emulsion is reacted for 1h at 50 ℃ to obtain isocyanate end-capped polyurethane emulsion, and then 50g of amino-terminated liquid butyronitrile emulsion (ATBN 1300X35 of Shenzhen Jiadieda new material technology Co., ltd.), 10g of diglycidyl phthalate and 20g of pentaerythritol distearate are added, the emulsion is emulsified for 30min at a high speed, and the temperature is raised to 70 ℃ for 2h to complete graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Example 3
Example 3 a PET toughening modifier was prepared by the following method:
into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 20g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
The polyurethane emulsion is reacted for 1h at 50 ℃ to obtain isocyanate end-capped polyurethane emulsion, and then 50g of amino-terminated liquid butyronitrile emulsion (ATBN 1300X35 of Shenzhen Jiadieda new material technology Co., ltd.), 10g of diglycidyl phthalate and 20g of pentaerythritol distearate are added, the emulsion is emulsified for 30min at a high speed, and the temperature is raised to 70 ℃ for 2h to complete graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Example 4
Example 4a PET toughening modifier was prepared by the following method:
into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 35g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
The polyurethane emulsion is reacted for 1h at 50 ℃ to obtain isocyanate end-capped polyurethane emulsion, and then 80g of amino-terminated liquid butyronitrile emulsion (ATBN 1300X35 of Shenzhen Jiadieda new material technology Co., ltd.), 10g of diglycidyl phthalate and 20g of pentaerythritol distearate are added, and the mixture is emulsified for 30min at a high speed and heated to 70 ℃ for 2h to complete graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Example 5
Example 5 a PET toughening modifier was prepared by the following method, example 5 being compared to example 1 without the addition of diglycidyl phthalate.
Into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 35g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
The polyurethane emulsion is reacted for 1h at 50 ℃ to obtain isocyanate end-capped polyurethane emulsion, and then 50g of amino-terminated liquid nitrile emulsion (ATBN 1300X35 of Shenzhen Jiadieda new material technology Co., ltd.) and 20g of pentaerythritol distearate are added, emulsified for 30min at high speed and heated to 70 ℃ for 2h of reaction to complete graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Example 6
Example 6 a PET toughening modifier was prepared by the following method, example 6 compared to example 1 without pentaerythritol distearate added.
Into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 35g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
The polyurethane emulsion is reacted for 1h at 50 ℃ to obtain isocyanate end-capped polyurethane emulsion, and then 50g of amino-terminated liquid butyronitrile emulsion (ATBN 1300X35 of Shenzhen Jiadieda new material technology Co., ltd.) and 10g of diglycidyl phthalate are added, and the mixture is emulsified for 30min at a high speed and heated to 70 ℃ for 2h to complete graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Example 7
Example 7 a PET toughening modifier was prepared by the following method, example 7 differing from example 1 in the lower amount of amino terminated liquid nitrile latex added.
Into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 35g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
The polyurethane emulsion is reacted for 1h at 50 ℃ to obtain isocyanate end-capped polyurethane emulsion, and then 20g of amino-terminated liquid nitrile emulsion (ATBN 1300X35 of Shenzhen Jiadieda new material technology Co., ltd.), 10g of diglycidyl phthalate and 20g of pentaerythritol distearate are added, and the mixture is emulsified for 30min at a high speed and heated to 70 ℃ for 2h to complete the graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Example 8
Example 8 a PET toughening modifier was prepared by the following method, example 8 being distinguished from example 1 by the higher content of the added amino terminated liquid nitrile latex.
Into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 35g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
The polyurethane emulsion is reacted for 1h at 50 ℃ to obtain isocyanate end-capped polyurethane emulsion, and then 100g of amino-terminated liquid nitrile emulsion (ATBN 1300X35 of Shenzhen Jiadieda new material technology Co., ltd.), 10g of diglycidyl phthalate and 20g of pentaerythritol distearate are added, and the mixture is emulsified for 30min at a high speed and heated to 70 ℃ for 2h to complete graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Example 9
Example 9 a PET toughening modifier was prepared by the following method, with less diglycidyl phthalate being added in example 9 compared to example 1.
Into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 35g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
The polyurethane emulsion is reacted for 1h at 50 ℃ to obtain isocyanate end-capped polyurethane emulsion, and then 50g of amino-terminated liquid nitrile emulsion (ATBN 1300X35 of Shenzhen Jiadieda new material technology Co., ltd.), 5g of diglycidyl phthalate and 20g of pentaerythritol distearate are added, and the mixture is emulsified for 30min at a high speed and heated to 70 ℃ for 2h to complete graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Example 10
Example 10 a PET toughening modifier was prepared by the following method, example 10 having more diglycidyl phthalate added than example 1:
into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 35g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
The polyurethane emulsion is reacted for 1h at 50 ℃ to obtain isocyanate end-capped polyurethane emulsion, and then 50g of amino-terminated liquid nitrile emulsion (ATBN 1300X35 of Shenzhen Jiadieda new material technology Co., ltd.), 20g of diglycidyl phthalate and 20g of pentaerythritol distearate are added, and the mixture is emulsified for 30min at a high speed and heated to 70 ℃ for 2h to complete graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Example 11
Example 11 a PET toughening modifier was prepared by the following method, with example 11 having a reduced amount of pentaerythritol distearate added compared to example 1.
Into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 35g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
The polyurethane emulsion is reacted for 1h at 50 ℃ to obtain isocyanate end-capped polyurethane emulsion, and then 50g of amino-terminated liquid nitrile emulsion (ATBN 1300X35 of Shenzhen Jiadieda new material technology Co., ltd.), 10g of diglycidyl phthalate and 10g of pentaerythritol distearate are added, and the mixture is emulsified for 30min at a high speed and heated to 70 ℃ for 2h to complete the graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Example 12
Example 12 a PET toughening modifier was prepared by the following method, example 12 differing from example 1 in the higher pentaerythritol distearate addition.
Into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 35g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
The polyurethane emulsion is reacted for 1h at 50 ℃ to obtain isocyanate end-capped polyurethane emulsion, and then 50g of amino-terminated liquid nitrile emulsion (ATBN 1300X35 of Shenzhen Jiadieda new material technology Co., ltd.), 10g of diglycidyl phthalate and 30g of pentaerythritol distearate are added, and the mixture is emulsified for 30min at a high speed and heated to 70 ℃ for 2h to complete graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Comparative example 1
Comparative example 1 a PET toughening modifier was prepared by the following method, comparative example 1 differing from example 1 in that: no amino terminated liquid nitrile latex was added to comparative example 1.
Into a 500ml three-necked flask, 50ml of deionized water, 1.5g of sodium dodecyl sulfate as an emulsifier, and 4.5g of an addition polymer (F127) of polypropylene glycol and ethylene oxide were charged as a continuous phase. 110g of hexamethylene diisocyanate, 90g of PPG200, 35g of dimethylolpropionic acid and 2g of dibutyltin dilaurate are weighed and uniformly mixed to obtain a disperse phase, and the disperse phase is added into the continuous phase and stirred and mixed to obtain the polyurethane emulsion.
Reacting the polyurethane emulsion for 1h at 50 ℃ to obtain isocyanate-terminated polyurethane emulsion, adding 10g of diglycidyl phthalate and 20g of pentaerythritol distearate, emulsifying for 30min at a high speed, and heating to 70 ℃ to react for 2h to complete graft polymerization. Washing with deionized water, filtering and drying to obtain the PET toughening modifier.
Taking the reactive toughening modifier prepared in examples 1-12 and comparative example 1, wherein the reactive toughening modifier comprises PET resin in mass ratio: toughening modifier: glass fiber: hydrotalcite = 100:10:30:15, uniformly mixing a toughening modifier, hydrotalcite and PET resin according to a proportion, feeding from a feed opening, feeding glass fibers from a vacuum opening, setting the temperature of each temperature zone of an extruder to 260-280 ℃, carrying out water cooling granulation by a double screw extruder bracing water trough, drying the obtained resin particles at 110 ℃ for 8 hours, and carrying out injection molding by an injection molding machine to obtain standard test sample strips, wherein the injection molding temperature is 270-290 ℃, and placing the sample strips in a drying dish for 12 hours to be tested.
Comparative example 2
The pure PET resin is taken, and the PET resin is prepared from the following components in percentage by mass: glass fiber: hydrotalcite=100:30:15, uniformly mixing hydrotalcite and PET resin according to a proportion, feeding from a feed opening, feeding glass fibers from a vacuum opening, setting the temperature of each temperature zone of an extruder to 260-280 ℃, carrying out water cooling granulation by a double screw extruder bracing water trough, drying the obtained resin particles at 110 ℃ for 8 hours, and carrying out injection molding by an injection molding machine to obtain standard test bars, wherein the injection molding temperature is 270-290 ℃, and placing the bars in a drying dish for 12 hours to be tested.
In order to verify the technical effect of the reactive toughening modifier, the following test is carried out:
the bars obtained by injection molding of examples 1-5 and comparative examples 1-2 were each subjected to the following test:
tensile strength/elongation at break: the test was performed according to ASTM D-638, with a universal tester performing a tensile test at a speed of 20 mm/min.
Flexural strength/modulus: the test was performed according to ASTM D-790, standard cut specimens having a cross section of 3.2X12.7 mm 2 The rate was 5mm/min.
Notched impact strength: the notched impact test was performed according to ASTM D-256 with a sample size of 64X 12X 3.2mm 3 The notch machining radius is 0.25mm, the notch depth is 2.5mm, and the angle is 45 degrees.
The test results are shown in Table 1 below.
Table 1 material property test of examples and comparative examples
As can be seen from the comparison of examples 1 to 12 and comparative example 2 (no toughening modifier is added in comparative example 2), the toughening modifier of PET resin according to the present invention can effectively improve the impact toughness of PET, and is characterized by a significant improvement in both elongation at break and notched impact strength. As can be seen from comparison of example 1, example 4 and comparative example 1, the shell nitrile rubber part of the toughening modifier of the PET resin has obvious improvement on the breaking elongation and the notch impact strength of the PET material. From comparison of examples 1, 5, 9 and 10, the addition of the epoxy resin has a certain enhancement effect on the tensile strength and the bending strength of the PET material; too high an amount of addition reduces the impact strength of the PET material and too low results in a decrease in tensile strength. From comparison of examples 1, 6, 11 and 12, the addition of pentaerythritol also improves the elongation at break and notched impact strength of PET by a small extent; the tensile strength and impact strength of the PET composite material which is excessively low or not added are reduced to a small extent, and the impact strength of the PET composite material is slightly influenced only by the fact that the performance is not obviously influenced by the excessively high addition amount.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A toughening modifier for PET resin, wherein the toughening modifier has a core-shell structure, and the toughening modifier comprises a core structure of polyurethane latex and a shell structure of amino-terminated butyronitrile latex.
2. The toughening modifier according to claim 1, wherein the mass ratio of the polyurethane latex core structure to the amino terminated nitrile latex shell structure is 5: (1-2).
3. The toughening modifier according to claim 1, wherein the core structure of the polyurethane latex is that of an isocyanate-terminated polyurethane latex, which is obtained by emulsifying the isocyanate-terminated polyurethane latex and an amino-terminated nitrile latex, an epoxy resin and a pentaerythritol ester, and performing graft polymerization.
4. A toughening modifier according to claim 3, wherein the epoxy resin is at least one selected from triglycidyl isophthalate and diglycidyl phthalate.
5. The toughening modifier according to claim 4, wherein the pentaerythritol ester is at least one selected from pentaerythritol monostearate, pentaerythritol distearate and pentaerythritol tristearate.
6. The toughening modifier according to claim 1, wherein the polyurethane emulsion is obtained by mixing and emulsifying polyether glycol, diisocyanate, chain extender and catalyst as a dispersed phase, water and an emulsifier as a continuous phase.
7. The toughening modifier according to claim 6, wherein,
the polyether glycol is selected from at least one of PPG200, PPG330 and PPG 400;
the diisocyanate is at least one selected from isophorone diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate;
the chain extender is at least one selected from dimethylolpropionic acid, dimethylolbutyric acid and 1, 4-butanediol-2-sodium sulfonate;
the catalyst is at least one selected from dibutyl tin dilaurate and dioctyl tin dithiol;
the emulsifier is a mixture of sodium dodecyl sulfate, an addition polymer of polypropylene glycol and ethylene oxide (F127); the mass ratio of the sodium dodecyl sulfate to the addition polymer (F127) of polypropylene glycol and ethylene oxide is 1:3, a step of;
the dosage of the emulsifier is 1-3% of the total mass of the polyether glycol and the diisocyanate.
8. The toughening modifier according to claim 7, wherein the molar ratio of the polyether glycol to the diisocyanate is 1:1.5, wherein the chain extender is 10-25% of the total mass of the polyether glycol and the diisocyanate, and the catalyst is 1% of the total mass of the polyether glycol and the diisocyanate.
9. Use of the toughening modifier of any one of claims 1 to 8 in the preparation of PET resins.
10. A PET resin comprising PET and the toughening modifier of any one of claims 1 to 8.
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| CN117603565A (en) * | 2024-01-24 | 2024-02-27 | 无锡富盛阀业有限公司 | Hydrolysis-resistant polyester material, sealing gasket and application thereof in ball gasket of floating ball valve |
| CN117603565B (en) * | 2024-01-24 | 2024-04-02 | 无锡富盛阀业有限公司 | Hydrolysis-resistant polyester material, sealing gasket and application thereof in ball gasket of floating ball valve |
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