CN109081894B - High-fluidity toughening agent and preparation method thereof - Google Patents
High-fluidity toughening agent and preparation method thereof Download PDFInfo
- Publication number
- CN109081894B CN109081894B CN201810806706.5A CN201810806706A CN109081894B CN 109081894 B CN109081894 B CN 109081894B CN 201810806706 A CN201810806706 A CN 201810806706A CN 109081894 B CN109081894 B CN 109081894B
- Authority
- CN
- China
- Prior art keywords
- ethylene
- copolymer
- fluidity
- screw extruder
- acrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012745 toughening agent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title description 6
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims abstract description 22
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims abstract description 20
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- -1 propylene-ethylene Chemical group 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000498 cooling water Substances 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 229920005604 random copolymer Polymers 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 235000012438 extruded product Nutrition 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 13
- 229920001707 polybutylene terephthalate Polymers 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 11
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a high-fluidity toughening agent, which belongs to the technical field of toughening agents and solves the problem that the fluidity of a polyester material is greatly weakened after the toughening agent is added into the polyester material, and the technical scheme is characterized by comprising the following components in percentage by weight: 70-80% of an ethylene-octene copolymer; 8-15% of a propylene-ethylene copolymer; 10-25% of ethylene acrylic acid copolymer; 0.5-1.5% of glycidyl methacrylate; 0.3-2% of 2-hydroxyethyl acrylate; 0.2-0.3% of an initiator; 0.5-1% of crosslinking inhibitor, and the invention can improve the fluidity of the toughening modified polyester system while ensuring the toughening.
Description
Technical Field
The invention belongs to the technical field of toughening agents, and particularly relates to a high-fluidity toughening agent and a preparation method thereof.
Background
The polyester is a general term for a polymer obtained by polycondensation of a polyhydric alcohol and a polybasic acid. Mainly refers to polyethylene terephthalate (PET), and customarily also includes linear thermoplastic resins such as polybutylene terephthalate (PBT) and polyarylate, and is an engineering plastic with excellent performance and wide application.
Among them, polybutylene terephthalate (PBT) is a crystalline linear saturated polyester resin, and thermoplastic polyester resin engineering plastics represented by PBT are another important class of engineering plastics following nylon (PA), oxymethylene Polymer (POM), Polycarbonate (PC), and modified polyphenylene ether (MPPO), and PBT has been industrialized and has taken a leading position in the field of thermoplastic engineering plastics.
The PBT has excellent mechanical, electrical, chemical corrosion resistance, drug resistance, low moisture absorption rate, friction resistance, easy processing and forming and other properties, and has wide application prospects in the fields of automobile industry, electronic information, industrial accessories and the like. However, as a toughness matrix, PBT has higher crack initiation energy and lower crack growth energy, so that unnotched impact strength is very high, notched impact strength is lower, and notched impact sensitivity is high, which severely limits the application range of PBT products, and thus, carrying out toughening modification on PBT is an important part of high-performance research.
Chinese patent CN103881313A introduces a polybutylene terephthalate toughening master batch which takes inorganic filler, matrix resin, coupling agent, dispersant and antioxidant as raw materials and a preparation method thereof, the raw materials are firstly mixed and then prepared by a double-screw extruder to obtain the polybutylene terephthalate toughening master batch, the polybutylene terephthalate toughening master batch has the advantages of low raw material cost, better maintenance of the mechanical properties of the PBT such as tensile strength, bending strength and the like, but small improvement range of the notch impact strength of the polybutylene terephthalate toughening master batch to the PBT, and failure in achieving good toughening effect.
Chinese patent CN1563187A describes a PBT composite material reinforced by glass fiber (wherein the content of the glass fiber is 10-37 wt%). Although the strength, modulus and heat resistance of PBT can be improved to some extent, it has disadvantages in that: the additives are added in relatively large amounts (generally in the range from 10 to 30% by weight), which not only worsens the toughness of the PBT, but also affects its flowability for processing.
Therefore, in the toughening modification process of the polyester material, the toughness of the toughened and modified polyester material is difficult to ensure by the conventional toughening agent (such as an epoxy resin toughening agent), and after the toughening agent is added, the fluidity of most toughened and modified polyester materials is greatly reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a high-fluidity toughening agent which has the effect of improving the fluidity of a toughening modified polyester system.
In order to achieve the purpose, the invention provides the following technical scheme: a high-fluidity toughening agent comprises the following components in percentage by weight:
70-80% of an ethylene-octene copolymer;
8-15% of a propylene-ethylene copolymer;
10-25% of ethylene acrylic acid copolymer;
0.5-1.5% of glycidyl methacrylate;
0.3-2% of 2-hydroxyethyl acrylate;
0.2-0.3% of an initiator;
0.5 to 1% of a crosslinking inhibitor.
By adopting the technical scheme, the ethylene-octene copolymer, the propylene-ethylene copolymer and the ethylene-acrylic acid copolymer are used as base resins, and the high-fluidity toughening agent is obtained by grafting a mixture of glycidyl methacrylate and 2-hydroxyethyl acrylate and adding an initiator, a crosslinking inhibitor and other auxiliary agents.
The ethylene-octene copolymer has lower crystallinity, narrow molecular weight and glass transition temperature, and small density (about 0.87g/cm3), and can play a toughening role after grafting; the propylene-ethylene copolymer has lower crystallinity and glass transition temperature, higher melt index and improved fluidity after grafting; the ethylene acrylic acid copolymer contains COOH groups, the COOH groups are favorable for the combination of grafted products with inorganic matters and metals, and simultaneously, polyester materials such as PBT and PET can be better combined with the inorganic matters such as glass fibers in the subsequent modification.
Both glycidyl methacrylate and 2-hydroxyethyl acrylate contain olefinic double bonds in acrylic acid which, upon opening, can bind to free radicals produced by the ethylene octene copolymer. The addition of the glycidyl methacrylate and the 2-hydroxyethyl acrylate enables the grafted ethylene octene copolymer to contain epoxy active groups contained in the glycidyl methacrylate and ester bonds contained in the 2-hydroxyethyl acrylate, the epoxy groups can enable the grafted product to have good compatibility with polyester materials, and the ester bonds enable the subsequently applied polyester materials to have good compatibility.
The initiator is used for initiating the ethylene-octene copolymer to generate free radicals, so that the free radicals are combined with glycidyl methacrylate, and the grafting rate is improved; and due to the increase of the concentration of the initiator, excessive free radicals can be generated to further initiate crosslinking side reactions (such as PE crosslinking, PP degradation and the like), so that the reaction amount of glycidyl methacrylate can be increased by adding styrene, the excessive free radicals are reduced, and PE crosslinking and PP degradation are effectively inhibited.
In conclusion, the ethylene-octene copolymer, the propylene-ethylene copolymer and the ethylene-acrylic acid copolymer are used as the base resin to be grafted with the mixture of glycidyl methacrylate and 2-hydroxyethyl acrylate, so that the toughness can be ensured, and the flowability of the toughening modified polyester system can be improved.
The invention is further configured to: the propylene-ethylene copolymer is one or two of a propylene-ethylene random copolymer and a propylene-ethylene block copolymer.
By adopting the technical scheme, the propylene-ethylene random copolymer has the characteristics of low crystallinity, good transparency, increased impact strength and reduced characteristic temperature, such as melting temperature, glass transition temperature, brittle temperature and the like, wherein the melting temperature is increased along with the increase of ethylene content; the propylene ethylene block copolymer has a smaller reduction in softening temperature and a larger improvement in brittle temperature than the propylene ethylene random copolymer.
The propylene-ethylene random copolymer and the propylene-ethylene random copolymer have high impact strength, so that the toughening effect of the toughened and modified polyester material is facilitated, and the good low-temperature performance of the toughening agent can be ensured due to the low glass transition temperature.
The invention is further configured to: the initiator is one or two of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and dicumyl peroxide.
By adopting the technical scheme, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and dicumyl peroxide are used as peroxide initiators which can initiate ethylene-octene copolymer to generate free radicals, so that the free radicals are combined with glycidyl methacrylate to realize the grafting reaction process.
The invention is further configured to: the crosslinking inhibitor is one or two of styrene and divinylbenzene.
By adopting the technical scheme, the styrene and the divinylbenzene are bifunctional compounds which can react with generated free radicals, so that the redundant free radicals are reduced, and the grafting rate is improved.
The second purpose of the invention is to provide a preparation method of the high-fluidity toughening agent, which has the advantage of further improving the fluidity of the toughening modified polyester system.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a high-fluidity toughening agent comprises the following steps:
(1) uniformly mixing ethylene acrylic acid copolymer and acrylic acid-2-hydroxyethyl ester according to a formula ratio to obtain a first mixture;
(2) uniformly mixing an initiator and a crosslinking inhibitor according to a formula ratio to obtain a second mixture;
(3) feeding an ethylene octene copolymer, a propylene ethylene copolymer, glycidyl methacrylate, a first mixture and a second mixture into a reactor with an aspect ratio of 52: 1, controlling the rotating speed of the screws in the double-screw extruder (1) at 150-450 r/min, controlling the processing temperature at 190-.
By adopting the technical scheme, after the ethylene-octene copolymer is subjected to melt extrusion by a double-screw extruder, the grafted ethylene-octene copolymer can contain an epoxy active group generated by glycidyl methacrylate and an ester bond generated by 2-hydroxyethyl acrylate, and the initiator and the crosslinking inhibitor are mixed for the purpose of simultaneously reacting to avoid initiating a crosslinking side reaction. Among them, the ethylene octene copolymer has a low crystallinity, a narrow molecular weight and a glass transition temperature, and a small density (about 0.87 g/cm)3) Can be taken off after graftingTo achieve the toughening effect; the propylene-ethylene copolymer has lower crystallinity and glass transition temperature, higher melt index and improved fluidity after grafting; the ethylene acrylic acid copolymer contains COOH groups, the COOH groups are favorable for the combination of grafted products with inorganic matters and metals, and simultaneously, polyester materials such as PBT and PET can be better combined with the inorganic matters, glass fibers and the like in the subsequent modification.
In conclusion, the method adopts the ethylene octene copolymer, the propylene ethylene copolymer and the ethylene acrylic acid copolymer as the base resin to graft with the mixture of the glycidyl methacrylate and the 2-hydroxyethyl acrylate, so that the toughness can be ensured, and the flowability of the toughening modified polyester system can be further improved.
The invention is further configured to: in the step (1) and the step (2), the ethylene acrylic acid copolymer and the acrylic acid-2-hydroxyethyl ester are put into a first reaction kettle with the temperature controlled at 190-200 ℃, the initiator and the crosslinking inhibitor are put into a second reaction kettle with a jacket, and cooling water for controlling the temperature in the mixing process at 25-30 ℃ is filled in the jacket.
By adopting the technical scheme, the ethylene acrylic acid copolymer and the acrylic acid-2-hydroxyethyl ester are put into the first reaction kettle at the temperature of 190-; and the temperature of a second mixture obtained by mixing the initiator and the crosslinking inhibitor is controlled to be 25-30 ℃, so that the second mixture is favorably combined with the glycidyl methacrylate, and the quality of a final product is improved.
The invention is further configured to: in the step (3), the tail end of the double-screw extruder (1) is connected with a screw extruder with the length-diameter ratio of 20: 1, the double-screw extruded product is pressed into a single-screw extruder (2) with the length-diameter ratio of 20: 1 (2) in the single screw extruder, melt extrusion was carried out.
By adopting the technical scheme, the product extruded by the double screws is pressed into the single screw extruder by using nitrogen for melt extrusion, so that the effects of nitrogen protection and air stripping deodorization are achieved.
The invention is further configured to: and a vacuum pump for vacuumizing is arranged at the middle-rear section of the single-screw extruder.
By adopting the technical scheme, the first graft melt can be vacuumized by using the vacuum pump so as to pump away a small part of volatile matters generated by the first graft melt, and the odor of a final product is further reduced.
The invention is further configured to: in the step (3), the tenth section and the eleventh section of the twin-screw extruder are vacuum exhaust ports, and a double vacuum pump for vacuum deashing of a product extruded by the twin-screw extruder is arranged in the vacuum exhaust ports.
By adopting the technical scheme, the vacuum deashing is carried out by utilizing the double vacuum pump, so that the residual graft monomer in the first graft melt can be reduced, namely the smell of the final product can be reduced.
The invention is further configured to: the cooling process in the step (3) comprises a water cooling process of a cooling water tank and an air cooling process of an air cooler.
By adopting the technical scheme, the second graft melt obtained after melt extrusion is thoroughly cooled under the action of the cooling water tank and the air cooler, so that the subsequent processing is facilitated.
In summary, the invention has the following advantages:
1. ethylene octene copolymer, propylene ethylene copolymer and ethylene acrylic acid copolymer are used as base resin to be grafted with glycidyl methacrylate and acrylic acid-2-hydroxyethyl ester, so that the toughness can be ensured, and the fluidity of the toughening modified polyester system can be improved;
2. in the grafting process, the initiator is added to initiate the ethylene-octene copolymer to generate free radicals, so that the free radicals are combined with glycidyl methacrylate, and the grafting rate is improved; and the addition of styrene can improve the reaction amount of glycidyl methacrylate, reduce redundant free radicals and effectively inhibit PE crosslinking and PP degradation.
Drawings
FIG. 1 is a flow chart of the steps for preparing the toughening agent of this example;
FIG. 2 is a schematic diagram of an apparatus layout for preparing the toughening agent.
Description of reference numerals: 1. a twin screw extruder; 2. a single screw extruder; 3. a cooling water tank; 4. an air cooling machine; 5. a granulator; 6. a homogenizing bin; 7. a double vacuum pump; 8. a vacuum pump.
Detailed Description
The following is a description of the technical solutions of the embodiments of the present invention.
The ethylene octene copolymer was POE.8130 (melt index 13g/10min) available from DOW USA.
The propylene ethylene copolymer was POP.8880, available from Exxon, USA.
Ethylene acrylic acid copolymer selected from EAA.3990, available from DuPont, USA.
The crosslinking inhibitor is styrene, and is available from Fujian oil refining chemical Co.
The initiator was 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, available from Aksu Nobel.
Example 1a
A high-fluidity toughening agent is shown in figures 1 and 2 and comprises the following steps:
step1, weighing 11kg of ethylene acrylic acid copolymer and 1.5kg of acrylic acid-2-hydroxyethyl ester, and putting the 11kg of ethylene acrylic acid copolymer and the 1.5kg of acrylic acid-2-hydroxyethyl ester into a first reaction kettle with the temperature controlled at 190 ℃ for primary esterification reaction to obtain a first mixture;
step2, weighing 0.25kg of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.75kg of styrene, putting 0.25kg of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and 0.75kg of styrene into a second reaction kettle with a jacket for mixing, and introducing cooling water into the jacket to control the temperature of the mixing process to be 27 ℃ to obtain a second mixture;
step3, weighing 75kg of ethylene-octene copolymer, 12.5kg of propylene-ethylene copolymer and 1kg of glycidyl methacrylate for later use;
step4, the length-diameter ratio of 52: pumping the tenth section and the eleventh section of the 1 double-screw extruder 1 to the vacuum degree of-0.09 MPa, maintaining the vacuum degree for 2 hours, controlling the screw rotating speed of the 1 double-screw extruder at 150-450 r/min, and controlling the processing temperature at 190-200 ℃;
step5, starting the double-screw extruder 1, putting the first mixture, 75kg of ethylene octene copolymer, 12.5kg of propylene ethylene copolymer and 1kg of glycidyl methacrylate into a first section of the double-screw extruder 1, putting the second mixture into a third section of the double-screw extruder 1, and carrying out melt extrusion to obtain a first graft melt;
step6, vacuumizing the middle and rear sections of the single-screw extruder 2 through a vacuum pump 8, and pressing the melt of the first graft extruded by the double screws into a material with the length-diameter ratio of 20: 1, carrying out melt extrusion in a single-screw extruder 2 to obtain a second graft melt;
and Step7, putting the second graft melt into a cooling water tank 4, cooling and drying the second graft melt by an air cooling machine 5 in sequence, granulating the second graft melt by a granulator 3, and feeding the second graft melt into a homogenizing bin 6 for negative pressure deodorization to obtain the high-fluidity toughening agent.
Examples 1 a-1 e were prepared in the same manner as example 1a, except that the specific components and the specific amounts of the components were different between examples 1 a-1 e and example 1 a.
Examples 1 a-example 1e components are specified in the following table (unit: kg):
the toughening agents prepared in the above examples 1a to 1e were subjected to toughening modification with glass fiber materials and PBT, and tested according to the following criteria:
the tensile strength is tested according to GB/T1040-; the bending strength is tested according to GB/T9341-; the flexural modulus is tested according to the STM D790 standard; the notch impact strength is tested according to GB/T1843-2008; melt finger determination standard: 250 ℃ multiplied by 5 Kg.
The test results are given in the following table:
| test items | Example 1a | Example 1b | Example 1c | Example 1d | Example 1e |
| Tensile Strength (MPa) | 99 | 102 | 102 | 99 | 101 |
| Flexural Strength (MPa) | 155 | 166 | 162 | 154 | 160 |
| Flexural modulus (MPa) | 6012 | 6280 | 6690 | 6350 | 6452 |
| Notched impact strength (J/M) | 160 | 135 | 138 | 134 | 135 |
| Melt index (g/10min) | 44 | 45 | 46 | 42 | 43 |
| Graft ratio (%) | 1.28 | 1.35 | 1.22 | 1.13 | 1.08 |
Comparative example 1a
Comparative example 1a was prepared in the same manner as example 1c except that comparative example 1a did not include the addition of a propylene ethylene copolymer.
Comparative example 1b
Comparative example 1b was prepared identically to example 1c, except that comparative example 1b did not include the addition of an ethylene acrylic acid copolymer.
Comparative example 1c
Comparative example 1c was prepared in the same manner as example 1c except that comparative example 1c did not include the addition of a propylene ethylene copolymer and an ethylene acrylic acid copolymer.
Comparative examples 1a to 1c were also subjected to the above-described tests, and the test results are shown in the following table:
| test items | Example 1a | Example 1b | Example 1c |
| Tensile Strength (MPa) | 94 | 94 | 94 |
| Flexural Strength (MPa) | 151 | 158 | 123 |
| Flexural modulus (MPa) | 6850 | 6433 | 5122 |
| Notched impact strength (J/M) | 118 | 125 | 101 |
| Melt index (g/10min) | 33 | 37 | 25 |
| Graft ratio (%) | 1.23 | 1.15 | 1.18 |
As shown in the table, according to comparative examples 1a to 1c, the melt index is related to the melt index of the base resin, the propylene ethylene copolymer and the ethylene acrylic acid copolymer in the invention are high-melt index materials, and the ethylene acrylic acid copolymer containing COOH groups is beneficial to the combination of the grafted PBT and inorganic matters, and simultaneously, the PBT can be better combined with the inorganic matters and glass fibers in toughening modification. Therefore, if the propylene ethylene copolymer and the ethylene acrylic acid copolymer are not grafted with glycidyl methacrylate as the base resin, the final melt index is greatly reduced.
In conclusion, the tougheners prepared in examples 1a to 1e have good effects in toughening and modifying PBT, the notch impact strength of the tougheners is 18% higher than that of the conventional toughener, and the melt index of the tougheners is 97% higher than that of the conventional toughener, which indicates that the toughener prepared by the invention can greatly improve the toughness and the flowability of PBT.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the design concept of the present invention should be included in the scope of the present invention.
Claims (10)
1. A high-fluidity toughening agent is characterized in that: comprises the following components in percentage by weight:
70-80% of an ethylene-octene copolymer;
8-15% of a propylene-ethylene copolymer;
10-25% of ethylene acrylic acid copolymer;
0.5-1.5% of glycidyl methacrylate;
0.3-2% of 2-hydroxyethyl acrylate;
0.2-0.3% of an initiator;
0.5 to 1% of a crosslinking inhibitor.
2. A high flow toughener according to claim 1, wherein: the propylene-ethylene copolymer is one or two of a propylene-ethylene random copolymer and a propylene-ethylene block copolymer.
3. A high flow toughener according to claim 1, wherein: the initiator is one or two of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and dicumyl peroxide.
4. A high flow toughener according to claim 1, wherein: the crosslinking inhibitor is styrene.
5. A process for preparing a high flow toughener according to any of claims 1-4, characterized in that: the method comprises the following steps:
(1) uniformly mixing ethylene acrylic acid copolymer and acrylic acid-2-hydroxyethyl ester according to a formula ratio to obtain a first mixture;
(2) uniformly mixing an initiator and a crosslinking inhibitor according to a formula ratio to obtain a second mixture;
(3) feeding an ethylene octene copolymer, a propylene ethylene copolymer, glycidyl methacrylate, a first mixture and a second mixture into a reactor with an aspect ratio of 52: 1, controlling the rotating speed of the screws in the double-screw extruder (1) at 150-450 r/min, controlling the processing temperature at 190-.
6. The method for preparing a high-fluidity toughening agent according to claim 5, wherein: in the step (1) and the step (2), the ethylene acrylic acid copolymer and the acrylic acid-2-hydroxyethyl ester are put into a first reaction kettle with the temperature controlled at 190-200 ℃, the initiator and the crosslinking inhibitor are put into a second reaction kettle with a jacket, and cooling water for controlling the temperature in the mixing process at 25-30 ℃ is filled in the jacket.
7. The method for preparing a high-fluidity toughening agent according to claim 5, wherein: in the step (3), the tail end of the double-screw extruder (1) is connected with a screw extruder with the length-diameter ratio of 20: 1, the double-screw extruded product is pressed into a single-screw extruder (2) with the length-diameter ratio of 20: 1 (2) in the single screw extruder, melt extrusion was carried out.
8. The method for preparing a high-fluidity toughening agent according to claim 7, wherein: and a vacuum pump (8) for vacuumizing is arranged at the middle-rear section of the single-screw extruder (2).
9. The method for preparing a high-fluidity toughening agent according to claim 5, wherein: in the step (3), the tenth section and the eleventh section of the twin-screw extruder (1) are vacuum exhaust ports, and a double vacuum pump (7) for performing vacuum devolatilization on a twin-screw extruded product is arranged in the vacuum exhaust ports.
10. The method for preparing a high-fluidity toughening agent according to claim 5, wherein: the cooling process in the step (3) comprises a water cooling process of the cooling water tank (3) and an air cooling process of the air cooler (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810806706.5A CN109081894B (en) | 2018-07-20 | 2018-07-20 | High-fluidity toughening agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810806706.5A CN109081894B (en) | 2018-07-20 | 2018-07-20 | High-fluidity toughening agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109081894A CN109081894A (en) | 2018-12-25 |
| CN109081894B true CN109081894B (en) | 2020-12-15 |
Family
ID=64838455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810806706.5A Active CN109081894B (en) | 2018-07-20 | 2018-07-20 | High-fluidity toughening agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109081894B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457748B (en) * | 2019-09-09 | 2022-06-03 | 王宏亮 | High-toughness low-temperature-resistant powder coating and preparation method thereof |
| CN111217963B (en) * | 2019-11-06 | 2021-12-21 | 宁波能之光新材料科技股份有限公司 | High-fluidity nylon toughening agent and preparation method thereof |
| CN110903486B (en) * | 2019-11-29 | 2021-01-05 | 安徽江淮汽车集团股份有限公司 | Compatilizer, preparation method thereof and PET/inorganic filler composite material |
| CN116178629B (en) * | 2022-12-27 | 2024-05-07 | 广州鹿山新材料股份有限公司 | Hydroxylation modified POE and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4200567A (en) * | 1977-08-22 | 1980-04-29 | Rohm And Haas Company | Synergistic impact modifier system for poly (alkylene terephthalates) |
| US4954568A (en) * | 1985-08-16 | 1990-09-04 | Shell Oil Company | Impact resistant blends of thermoplastic polyesters and modified block copolymers |
| CN1563186A (en) * | 2004-04-15 | 2005-01-12 | 上海普利特复合材料有限公司 | Low warped and high surfaceness PBT composite material enhanced by fiberglass |
| CN101423589A (en) * | 2008-12-12 | 2009-05-06 | 江苏工业学院 | Method for preparing polyethylene/maleic anhydride melt grafting high condensing pre-mixed master batch |
| CN102010483A (en) * | 2010-09-29 | 2011-04-13 | 深圳市科聚新材料有限公司 | POE (Polyethylene Octene Elastomer) graft copolymer and preparation method thereof |
| CN102248733A (en) * | 2011-05-27 | 2011-11-23 | 常州市华星新材料科技有限公司 | Non-natural continuous filament fabric strengthened modified thermoplastic composite sheet material |
| CN102382265A (en) * | 2011-09-21 | 2012-03-21 | 深圳市科聚新材料有限公司 | Polybasic grafted polyethylene and preparation method thereof |
| CN102391432A (en) * | 2011-09-07 | 2012-03-28 | 上海日之升新技术发展有限公司 | High-fluidity ethylene-alpha-octene graft copolymer and preparation method thereof |
| CN103059521A (en) * | 2012-12-27 | 2013-04-24 | 宝天高科（广东）有限公司 | A flame-retardant polyester compound and a preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL214554B1 (en) * | 2010-02-26 | 2013-08-30 | Geo Globe Polska Spolka Z Ograniczona Odpowiedzialnoscia Spolka Komandytowo Akcyjna | Cell geogrids of reduced creep and high resistance to hydrolysis and microbiological activity |
| TW201209087A (en) * | 2010-08-25 | 2012-03-01 | Jin-Fu Chen | Biomass composite material composition and foaming method thereof |
-
2018
- 2018-07-20 CN CN201810806706.5A patent/CN109081894B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4200567A (en) * | 1977-08-22 | 1980-04-29 | Rohm And Haas Company | Synergistic impact modifier system for poly (alkylene terephthalates) |
| US4954568A (en) * | 1985-08-16 | 1990-09-04 | Shell Oil Company | Impact resistant blends of thermoplastic polyesters and modified block copolymers |
| CN1563186A (en) * | 2004-04-15 | 2005-01-12 | 上海普利特复合材料有限公司 | Low warped and high surfaceness PBT composite material enhanced by fiberglass |
| CN101423589A (en) * | 2008-12-12 | 2009-05-06 | 江苏工业学院 | Method for preparing polyethylene/maleic anhydride melt grafting high condensing pre-mixed master batch |
| CN102010483A (en) * | 2010-09-29 | 2011-04-13 | 深圳市科聚新材料有限公司 | POE (Polyethylene Octene Elastomer) graft copolymer and preparation method thereof |
| CN102248733A (en) * | 2011-05-27 | 2011-11-23 | 常州市华星新材料科技有限公司 | Non-natural continuous filament fabric strengthened modified thermoplastic composite sheet material |
| CN102391432A (en) * | 2011-09-07 | 2012-03-28 | 上海日之升新技术发展有限公司 | High-fluidity ethylene-alpha-octene graft copolymer and preparation method thereof |
| CN102382265A (en) * | 2011-09-21 | 2012-03-21 | 深圳市科聚新材料有限公司 | Polybasic grafted polyethylene and preparation method thereof |
| CN103059521A (en) * | 2012-12-27 | 2013-04-24 | 宝天高科（广东）有限公司 | A flame-retardant polyester compound and a preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Toughening of polyethylene terephthalate/amorphous copolyester blends with a maleated thermoplastic elastomer;Yu ZZ，等;《JOURNAL OF APPLIED POLYMER SCIENCE》;20030718;第89卷(第3期);第795-805页 * |
| 环氧官能化弹性体增韧PET的研究;谭志勇，等;《塑料工业》;20130731;第41卷(第7期);第22-26页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109081894A (en) | 2018-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109081894B (en) | High-fluidity toughening agent and preparation method thereof | |
| CN100509953C (en) | Polybutylene terephthalate composite material and preparation method thereof | |
| CN101402793B (en) | Glass fiber-reinforced nylon 6-poly-p-benzene dicarboxylic acid butanediol ester alloy material and method of producing the same | |
| CN109456563B (en) | Special material for UHMWPE alloy compatibilization toughening modified polypropylene corrugated pipe and preparation method thereof | |
| CN101367991A (en) | Method of manufacturing polycarbonate/vinyl cyanide-butadiene-styrol copolymer alloy | |
| CN101195707A (en) | Glass fiber-reinforced nylon 6-polypropylene alloy material | |
| CN105504803B (en) | A kind of high fluidity fiber reinforced nylon composite material and preparation method thereof | |
| CN111040296B (en) | Polyolefin composition with high mechanical property and preparation method thereof | |
| CN102492222A (en) | Polypropylene/fiberglass composite material and preparation method thereof | |
| CN101747600A (en) | Method for preparing polyethylene terephthalate (PET) blend | |
| CN113462141A (en) | High-toughness low-floating-fiber-reinforced PC/PBT alloy material and preparation method thereof | |
| CN111423689B (en) | Modified polypropylene material and preparation method and application thereof | |
| CN105418852A (en) | Low-smell low-radiation glass fiber enhanced polypropylene composition and preparation method therefor | |
| CN111978641A (en) | High-modulus, high-fluidity and high-impact-resistance glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN106939112B (en) | High-gloss HIPS/recycled PET bottle flake composite material and preparation method thereof | |
| CN106893250B (en) | A kind of ABS resin composition being blow molded with high fondant-strength, good appearance | |
| CN112724578B (en) | Polypropylene compound and application and preparation method thereof | |
| CN112778634A (en) | Rigid-tough balance low-density polypropylene composite material and preparation method and application thereof | |
| CN113968940A (en) | Method for preparing low-odor polypropylene grafted maleic anhydride beads under assistance of supercritical carbon dioxide | |
| CN101671420B (en) | PET alloy material, special compatibilizer thereof and preparation method thereof | |
| CN1279115C (en) | Co-fixing polyethylene terephthalate in high tenacity and preparation method | |
| CN111484721A (en) | Low-temperature impact resistant PC/ABS composite material and preparation method thereof | |
| JP2002225011A (en) | Woody composition for molding and its manufacturing method | |
| CN115521535B (en) | High-impact recycled polypropylene resin material and preparation method thereof | |
| CN108530850A (en) | A kind of fire retardant PBT with no halogen/ASA alloys and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: No. 631, 581, tonglong 2nd Road, industrial zone, torch hi tech Zone (Xiang'an), Xiamen City, Fujian Province, 361102 Patentee after: COEs Chemical Co.,Ltd. Address before: Xi Fu Lu Tong An District in Xiamen city of Fujian province 361000 building A No. 131 floor West Patentee before: XIAMEN KEAISI PLASTIC CEMENT TECHNOLOGY Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: The invention relates to a high fluidity toughening agent and a preparation method thereof Effective date of registration: 20220224 Granted publication date: 20201215 Pledgee: Bank of China Limited Xiamen Kaiyuan sub branch Pledgor: COEs Chemical Co.,Ltd. Registration number: Y2022980001793 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20201215 Pledgee: Bank of China Limited Xiamen Kaiyuan sub branch Pledgor: COEs Chemical Co.,Ltd. Registration number: Y2022980001793 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A high fluidity toughening agent and its preparation method Granted publication date: 20201215 Pledgee: Bank of China Limited Xiamen Kaiyuan sub branch Pledgor: COEs Chemical Co.,Ltd. Registration number: Y2024980013985 |