CN109081894A - A kind of high fluidity toughener and preparation method thereof - Google Patents
A kind of high fluidity toughener and preparation method thereof Download PDFInfo
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- CN109081894A CN109081894A CN201810806706.5A CN201810806706A CN109081894A CN 109081894 A CN109081894 A CN 109081894A CN 201810806706 A CN201810806706 A CN 201810806706A CN 109081894 A CN109081894 A CN 109081894A
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- toughener
- high fluidity
- ethylene
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- 239000012745 toughening agent Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims abstract description 21
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims abstract description 19
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 17
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 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
- 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 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 14
- 230000002262 irrigation Effects 0.000 abstract 1
- 238000003973 irrigation Methods 0.000 abstract 1
- 230000003313 weakening effect Effects 0.000 abstract 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 11
- -1 polyethylene terephthalate Polymers 0.000 description 10
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 5
- 229920005604 random copolymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920006351 engineering plastic Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002253 acid 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
- 150000002148 esters Chemical class 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001877 deodorizing effect 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
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- XSMJZKTTXZAXHD-UHFFFAOYSA-N ethene;2-methylprop-2-enoic acid Chemical group C=C.CC(=C)C(O)=O XSMJZKTTXZAXHD-UHFFFAOYSA-N 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002978 peroxides Chemical group 0.000 description 1
- 229920000058 polyacrylate Polymers 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
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 238000007348 radical reaction Methods 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
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of high fluidity toughener, belong to toughener technical field, it solves after polyester material is added in toughener, the problem of weakening the mobility of polyester material significantly, drip irrigation device includes the component of following weight percent content: ethylene octene copolymer 70~80%；Propylene ethylene copolymers 8~15%；Ethylene acrylic acid co polymer 10~25%；Glycidyl methacrylate 0.5~1.5%；2-hydroxyethyl acrylate 0.3~2%；Initiator 0.2~0.3%；Cross-linked inhibitor 0.5~1%, the present invention can improve the mobility of toughening modifying polyester system while guaranteeing increasing tougheness.
Description
Technical field
The invention belongs to toughener technical fields, and more specifically it is related to a kind of high fluidity toughener and its preparation side
Method.
Background technique
Polyester, the polymer general name as obtained by polyalcohol and polyacid polycondensation.Refer mainly to polyethylene terephthalate
(PET), also include traditionally linear thermoplastics' resins such as polybutylene terephthalate (PBT) and polyarylate, be a kind of performance
Excellent, widely used engineering plastics.
Wherein, polybutylene terephthalate (PBT) (PBT) is a kind of crystal type line style saturated polyester resin, using PBT as generation
The thermoplastic polyester engineering plastics of table are after nylon (PA), yuban (POM), polycarbonate (PC) and polyphenylene oxide
The important engineering plastics of the later another class of modifier (MPPO), PBT have been carried out industrialization, account in thermoplastic engineering plastics field
There is leading position.
PBT has low excellent mechanics, electricity, resistant to chemical etching, drug-resistant, hydroscopicity, rub resistance, easy processing molding etc.
Performance has wide practical use in fields such as auto industry, electronic information, industry accessories.But PBT has as tough matrix
There is higher crackle to cause energy and lower crack growth energy, so its unnotched impact strength is very high, and notch impact strength
Lower, notch shock sensibility is big, and this severely limits the use scopes of PBT product, therefore carries out toughening modifying always to PBT
It is the pith of its high performance research.
Chinese patent CN103881313A describes one kind with inorganic filler, matrix resin, coupling agent, dispersing agent and antioxygen
Agent is the polybutylene terephthalate (PBT) plasticizing mother particle and preparation method thereof of raw material, and raw material first passes through mixing and passes through twin-screw again
Prepared by extruder, obtain polybutylene terephthalate (PBT) plasticizing mother particle, its advantage is that cost of material is low, can preferably protect
The mechanical properties such as tensile strength, the bending strength of PBT are held, but it is little to the notch impact strength promotion amplitude of PBT, fails to reach
To good toughening effect.
Chinese patent CN1563187A describes one kind, and with fiber glass reinforced PBT composite material, (wherein glass fiber content is 10-
37wt%).Although to a certain extent, can improve the intensity, modulus and heat resistance of PBT, it has the disadvantage that addition
The additive amount of agent is larger (generally in 10-30wt%), this not only makes the degraded toughness of PBT, but also influences the mobility of its processing.
Therefore, during the toughening modifying of polyester material, existing toughener (such as epoxy resin toughener) is difficult to protect
The toughness of polyester material after demonstrate,proving toughening modifying, and the polyester material after using the toughener is added, after most toughening modifying
Mobility all reduce significantly.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of high fluidity toughener, has and mention
The effect of the mobility of high toughening modifying polyester system.
To achieve the above object, the present invention provides the following technical scheme that a kind of high fluidity toughener, including it is following heavy
Measure the component of degree:
Ethylene octene copolymer 70~80%；
Propylene ethylene copolymers 8~15%；
Ethylene acrylic acid co polymer 10~25%；
Glycidyl methacrylate 0.5~1.5%；
2-hydroxyethyl acrylate 0.3~2%；
Initiator 0.2~0.3%；
Cross-linked inhibitor 0.5~1%.
By using above-mentioned technical proposal, with ethylene octene copolymer, propylene ethylene copolymers and ethylene-acrylic acid copolymer
Object as basic resin, and by the mixture of graft glycidyl methacrylate and 2-hydroxyethyl acrylate and
The auxiliary agents such as initiator, cross-linked inhibitor are added and obtain the toughener of high fluidity.
Ethylene octene copolymer has lower crystallinity, narrow molecular-weight and glass transition temperature, and small (the about 0.87g/ of density
Cm3), toughening effect can be played after grafting；Propylene ethylene copolymers have lower crystallinity and glass transition temperature, and
Melt index with higher, can be improved mobility after grafting；Ethylene acrylic acid co polymer contains COOH group, COOH base
The presence of group has conducive to the combination of product and inorganic matter and metal after grafting, while the polyester materials such as PBT, PET can be made rear
Continue the combination in modified preferably with inorganic matter, such as glass fibre.
Glycidyl methacrylate and 2-hydroxyethyl acrylate are containing the olefinic double bonds in acrylic acid, double
Key can be in conjunction with the free radical that ethylene octene copolymer generates after opening.Wherein, glycidyl methacrylate and propylene
The addition of acid -2- hydroxyethyl ester can make the ethylene octene copolymer after grafting contain what glycidyl methacrylate contained
The ester bond that epoxy-reactive group and 2-hydroxyethyl acrylate contain, epoxy group can allow grafting after product and polyester material
Material has preferable compatible role, and the presence of ester bond can make the polyester material of subsequent applications have preferable compatibility.
The effect of initiator is to cause ethylene octene copolymer to generate free radicals, and keeps free radical sweet with Glycidyl methacrylate
Grease combines, and improves grafting rate；And due to the increase of initiator concentration, excessive free radical can be generated, and then it is secondary to cause crosslinking
Reaction (such as PE crosslinking, PP degradation), so that the reacting dose of glycidyl methacrylate can be made by the way that styrene is added
It improves, reduces extra free radical, effectively inhibit PE crosslinking and PP degradation.
To sum up, using ethylene octene copolymer, propylene ethylene copolymers and ethylene acrylic acid co polymer as basic resin
It is grafted with the mixture of glycidyl methacrylate and 2-hydroxyethyl acrylate, can guarantee increasing tougheness
Meanwhile improving the mobility of toughening modifying polyester system.
The present invention is further arranged to: the propylene ethylene copolymers are that propylene-ethylene random copolymer and propylene and ethylene are embedding
Section copolymer one of which or two kinds.
By using above-mentioned technical proposal, the characteristics of propylene-ethylene random copolymer is that crystallinity is low, and the transparency is good, impact
Intensity increases, and characteristic temperature is declined, such as melting temperature, glass transition temperature, brittle temperature, and melting temperature is with second
The increase of alkene content and increase；Compared with propylene-ethylene random copolymer, softening temperature reduces very propylene ethylene block copolymer
It is few, and brittle temperature improvement is larger.
Wherein, since the impact strength of propylene-ethylene random copolymer and propylene-ethylene random copolymer itself is big, thus
Be conducive to the toughening effect of polyester material after toughening modifying, and lower glass transition temperature can guarantee that toughener is good
Cryogenic property.
The present invention is further arranged to: the initiator is bis- (tert-butyl peroxy base) hexanes of 2,5- dimethyl -2,5- and mistake
Aoxidize diisopropylbenzene (DIPB) one of which or two kinds.
By using above-mentioned technical proposal, bis- (tert-butyl peroxy base) hexanes of 2,5- dimethyl -2,5- and peroxidating diisopropyl
Benzene is peroxide initiator, can cause ethylene octene copolymer and generate free radicals, make free radical and methacrylic acid
Ethylene oxidic ester combines, and realizes process of grafting.
The present invention is further arranged to: the cross-linked inhibitor be styrene and divinylbenzene one of which or two kinds.
By using above-mentioned technical proposal, styrene and divinylbenzene are bifunctional compound, can be with generation
Radical reaction, reduce extra free radical, improve grafting rate.
The second object of the present invention is to provide a kind of preparation method of high fluidity toughener, the advantage is that further
Improve the mobility of toughening modifying polyester system.
To achieve the above object, the present invention provides the following technical scheme that a kind of preparation method of high fluidity toughener,
The following steps are included:
(1) ethylene acrylic acid co polymer and 2-hydroxyethyl acrylate are uniformly mixed by formula rate, obtain the first mixing
Object；
(2) initiator and cross-linked inhibitor are uniformly mixed by formula rate, obtain the second mixture；
(3) by ethylene octene copolymer, propylene ethylene copolymers, glycidyl methacrylate, the first mixture and
Two mixtures are put into the double screw extruder (1) that draw ratio is 52:1, and screw speed is controlled in 150~450r/min,
Processing temperature is in 190-200 DEG C of control, after twin-screw melting extrusion, to get a kind of high flowing after cooling, drying, granulation
Property toughener.
Ethylene by using above-mentioned technical proposal, after the melting extrusion of double screw extruder, after grafting can be made
What the epoxy-reactive group and 2-hydroxyethyl acrylate that octene copolymer contains glycidyl methacrylate generation generated
Ester bond, and initiator and the purpose of cross-linked inhibitor mixing are to make the two that can avoid causing crosslinking side reaction with simultaneous reactions.Its
In, ethylene octene copolymer has lower crystallinity, narrow molecular-weight and glass transition temperature, and small (the about 0.87g/cm of density3),
Toughening effect can be played after grafting；Propylene ethylene copolymers have lower crystallinity and glass transition temperature, and have
Higher melt index, can be improved mobility after grafting；Ethylene acrylic acid co polymer contains COOH group, COOH group
There are the combinations for being conducive to product and inorganic matter and metal after being grafted, while the polyester materials such as PBT, PET can be made to change subsequent
In property preferably with inorganic matter, the combination of glass fibre etc..
To sum up, the above method uses ethylene octene copolymer, propylene ethylene copolymers and ethylene acrylic acid co polymer conduct
The mixture of base resin and glycidyl methacrylate and 2-hydroxyethyl acrylate is grafted, and can guaranteed
While increasing tougheness, the mobility of toughening modifying polyester system is further increased.
The present invention is further arranged to: in step (1) and step (2), by ethylene acrylic acid co polymer and acrylic acid -2- hydroxyl
Ethyl ester puts into temperature control in 190-200 DEG C of the first reaction kettle, and initiator and cross-linked inhibitor investment are had collet
The second reaction kettle in, the cooling water for making the temperature control of mixed process at 25~30 DEG C is connected in the collet.
By using above-mentioned technical proposal, ethylene acrylic acid co polymer and 2-hydroxyethyl acrylate are put into temperature control
It makes in 190-200 DEG C of the first reaction kettle, ethylene acrylic acid co polymer can be made to be completely melt, become liquid, after being conducive to
Continuous and graft combination；And the temperature for the second mixture for being mixed to get initiator and cross-linked inhibitor is controlled 25~30
DEG C, be conducive in conjunction with glycidyl methacrylate, improve the quality of final product.
The present invention is further arranged to: in step (3), the tail end of the double screw extruder (1) is connected with draw ratio and is
The single screw extrusion machine (2) of 20:1, the product of twin-screw extrusion are pressed into the single screw extrusion machine (2) of draw ratio 20:1 by nitrogen
In, carry out melting extrusion.
By using above-mentioned technical proposal, will be carried out in the product indentation single screw extrusion machine of twin-screw extrusion using nitrogen
Melting extrusion, to play the role of nitrogen protection and air lift taste removal.
The present invention is further arranged to: the posterior segment of the single screw extrusion machine is provided with the vacuum pump for vacuumizing.
By using above-mentioned technical proposal, the first graft melt can be vacuumized using vacuum pump, to take away
The volatile matter that small part the first graft melt generates, is further reduced the smell of final product.
The present invention is further arranged to: in step (3), the protelum of the double screw extruder and the 11st section are vacuum
Exhaust outlet is provided with double vacuum pumps that vacuum deliming is carried out for the product to twin-screw extrusion in the vaccum exhaust outlet.
By using above-mentioned technical proposal, vacuum deliming is carried out using double vacuum pumps, can reduce by the first graft melt
In remaining graft monomer, the smell of final product can be reduced.
The present invention is further arranged to: the cooling procedure in step (3) includes the cold process of cooling water tank and Air cooler
Air-cooled process.
By using above-mentioned technical proposal, the second graft melt for obtaining after melting extrusion is in cooling trough and air-cooled
It is thoroughly cooled down under the action of machine, is convenient for subsequent processing.
In conclusion the invention has the following advantages that
1, using ethylene octene copolymer, propylene ethylene copolymers and ethylene acrylic acid co polymer as basic resin and methyl-prop
Olefin(e) acid ethylene oxidic ester and 2-hydroxyethyl acrylate are grafted, and can improve toughening modifying while guaranteeing increasing tougheness
The mobility of polyester system；
2, ethylene octene copolymer can be caused and generate free radicals by initiator being added in grafting process, make free radical and methyl-prop
Olefin(e) acid ethylene oxidic ester combines, and improves grafting rate；And styrene, which is added, can make the reacting dose of glycidyl methacrylate
It improves, and reduces extra free radical, effectively inhibit PE crosslinking and PP degradation.
Detailed description of the invention
Fig. 1 is the preparation step flow chart of toughener in the present embodiment；
Fig. 2 is the device layout schematic diagram for preparing toughener.
Description of symbols: 1, double screw extruder；2, single screw extrusion machine；3, cooling trough；4, Air cooler；5, it is granulated
Machine；6, homogenizing bin；7, double vacuum pumps；8, vacuum pump.
Specific embodiment
It is that the technical solution of the embodiment of the present invention is described below.
Ethylene octene copolymer selects POE.8130 (melting means 13g/10min), is purchased from U.S. DOW.
Propylene ethylene copolymers select POP.8880, are purchased from american exxon.
Ethylene acrylic acid co polymer selects EAA.3990, is purchased from Dupont.
Cross-linked inhibitor is styrene, is purchased from Fujian Oil-Refining Chemical Co., Ltd..
Initiator is bis- (tert-butyl peroxy base) hexanes of 2,5- dimethyl -2,5-, is purchased from Akzo Nobel N.V..
Embodiment 1a
A kind of high fluidity toughener, as shown in Figure 1, 2, comprising the following steps:
Step1, first weighs the ethylene acrylic acid co polymer of 11kg and the 2-hydroxyethyl acrylate of 1.5kg, then by 11kg ethylene
Acrylic copolymer and the investment temperature control of 1.5kg 2-hydroxyethyl acrylate carry out preliminary in 190 DEG C of the first reaction kettle
Esterification obtains the first mixture；
Step2 first weighs the styrene of 2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexanes and 0.75kg of 0.25kg, then
By 0.25kg2, the styrene investment second with collet of bis- (tert-butyl peroxy base) hexanes of 5- dimethyl -2,5- and 0.75kg are anti-
It answers in kettle and is mixed, and be passed through the cooling water for making the temperature control of mixed process at 27 DEG C in collet, obtain the second mixture；
Step3 weighs the methacrylic acid contracting of the ethylene octene copolymer of 75kg, the propylene ethylene copolymers of 12.5kg and 1kg
Water glyceride, for use；
Draw ratio is evacuated to vacuum by double vacuum pumps 7 for the protelum of 52:1 double screw extruder 1 and the 11st section by Step4
Degree is -0.09MPa and keeps the vacuum degree 2 hours, and the screw speed of double screw extruder 1 is controlled in 150~450r/
Min, processing temperature is in 190-200 DEG C of control；
Step5 starts double screw extruder 1, by the first mixture, the ethylene octene copolymer of 75kg, the propylene second of 12.5kg
The glycidyl methacrylate of alkene copolymer and 1kg are put into the first segment of double screw extruder 1, then second is mixed
Object is put into the third section of double screw extruder 1, is carried out melting extrusion, is obtained the first graft melt；
Step6 is vacuumized by vacuum pump 8 in the posterior segment of single screw extrusion machine 2, recycles nitrogen by twin-screw extrusion
The first graft melt indentation draw ratio 20:1 single screw extrusion machine 2 in, carry out melting extrusion, it is molten to obtain the second graft
Body；
Step7 accesses the second graft melt in cooling trough 4, and successively cooling through Air cooler 5, dry, and pelletizer 3 is made
After grain, it is sent into homogenizing bin 6 and carries out negative pressure deodorizing, obtain high fluidity toughener.
Embodiment 1a- embodiment 1e is identical as the preparation method of embodiment 1a, and difference is only that, embodiment 1a- is implemented
Concrete component and concrete content between example 1e and embodiment 1a have differences.
Embodiment 1a- embodiment 1e component specifically see the table below (unit: kg):
Toughener made from above embodiments 1a- embodiment 1e and glass fiber material and PBT are subjected to toughening modifying, and by following
Standard is tested:
Tensile strength is tested by GB/T 1040-2006；Bending strength is tested by GB/T 9341-2000；Bending modulus presses STM
D790 standard is tested；Notch impact strength is tested by GB/T 1843-2008；Melting means measurement standard: 250 DEG C × 5Kg.
Test result see the table below:
| Test item | Embodiment 1a | Embodiment 1b | Embodiment 1c | Embodiment 1d | Embodiment 1e |
| Tensile strength (MPa) | 99 | 102 | 102 | 99 | 101 |
| Bending strength (MPa) | 155 | 166 | 162 | 154 | 160 |
| Bending modulus (MPa) | 6012 | 6280 | 6690 | 6350 | 6452 |
| Notch impact strength (J/M) | 160 | 135 | 138 | 134 | 135 |
| Melt index (g/10min) | 44 | 45 | 46 | 42 | 43 |
| Grafting rate (%) | 1.28 | 1.35 | 1.22 | 1.13 | 1.08 |
Comparative example 1a
Comparative example 1a is identical as the preparation method of embodiment 1c, and difference is only that comparative example 1a does not add propylene ethylene copolymer
Object.
Comparative example 1b
Comparative example 1b is identical as the preparation method of embodiment 1c, and difference is only that, it is total that comparative example 1b does not add ethylene acrylic
Polymers.
Comparative example 1c
Comparative example 1c is identical as the preparation method of embodiment 1c, and difference is only that comparative example 1c does not add propylene ethylene copolymer
Object and ethylene acrylic acid co polymer.
Comparative example 1a- comparative example 1c is equally subjected to above-mentioned test, test result see the table below:
| Test item | Embodiment 1a | Embodiment 1b | Embodiment 1c |
| Tensile strength (MPa) | 94 | 94 | 94 |
| Bending strength (MPa) | 151 | 158 | 123 |
| Bending modulus (MPa) | 6850 | 6433 | 5122 |
| Notch impact strength (J/M) | 118 | 125 | 101 |
| Melt index (g/10min) | 33 | 37 | 25 |
| Grafting rate (%) | 1.23 | 1.15 | 1.18 |
As shown above, according to comparative example 1a- comparative example 1c it is found that melt index and the melt index of base resin itself have
It closes, the propylene ethylene copolymers and ethylene acrylic acid co polymer in the present invention are high melting means material, and contain COOH group
Ethylene acrylic acid co polymer be conducive to grafting after PBT and inorganic matter combination, while can make PBT in toughening modifying preferably
With inorganic matter, glass fibre is combined.Therefore, if lacking propylene ethylene copolymers and ethylene acrylic acid co polymer as basic resin
With glycidyl methacrylate graft, final melt index will be substantially reduced.
To sum up, good effect can be played in the toughening modifying of PBT by toughener prepared by embodiment 1a- embodiment 1e
Fruit, notch impact strength is higher than conventional toughener by 18%, and melt index is higher than conventional toughener by 97%, shows that the present invention is made
Standby toughener can greatly improve the toughness and mobility of PBT.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to restrict the invention, all in design structure of the invention
Within think of, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of high fluidity toughener, it is characterised in that: the component including following weight percent content:
Ethylene octene copolymer 70~80%；
Propylene ethylene copolymers 8~15%；
Ethylene acrylic acid co polymer 10~25%；
Glycidyl methacrylate 0.5~1.5%；
2-hydroxyethyl acrylate 0.3~2%；
Initiator 0.2~0.3%；
Cross-linked inhibitor 0.5~1%.
2. a kind of high fluidity toughener according to claim 1, it is characterised in that: the propylene ethylene copolymers are third
The one of which of alkene ethylene atactic copolymer and propylene ethylene block copolymer or two kinds.
3. a kind of high fluidity toughener according to claim 1, it is characterised in that: the initiator is 2,5- diformazan
The one of which of bis- (tert-butyl peroxy base) hexanes of base -2,5- and cumyl peroxide or two kinds.
4. a kind of high fluidity toughener according to claim 1, it is characterised in that: the cross-linked inhibitor is styrene
With the one of which of divinylbenzene or two kinds.
5. a kind of preparation method of high fluidity toughener according to claim 1-4, it is characterised in that: including
Following steps:
(1) ethylene acrylic acid co polymer and 2-hydroxyethyl acrylate are uniformly mixed by formula rate, obtain the first mixing
Object；
(2) initiator and cross-linked inhibitor are uniformly mixed by formula rate, obtain the second mixture；(3) ethylene octene is total to
Polymers, propylene ethylene copolymers, glycidyl methacrylate, the first mixture and the second mixture investment draw ratio are
In the double screw extruder (1) of 52:1, and by screw speed control in 150~450r/min, processing temperature is in control 190-200
DEG C, after twin-screw melting extrusion, to get a kind of high fluidity toughener after cooling, drying, granulation.
6. a kind of preparation method of high fluidity toughener according to claim 5, it is characterised in that: step (1) and step
Suddenly in (2), ethylene acrylic acid co polymer and 2-hydroxyethyl acrylate investment temperature control is first anti-at 190-200 DEG C
It answers in kettle, by initiator and cross-linked inhibitor investment in the second reaction kettle of collet, being connected in the collet makes to mix
Cooling water of the temperature control of journey at 25~30 DEG C.
7. a kind of preparation method of high fluidity toughener according to claim 5, it is characterised in that: in step (3), institute
The tail end for stating double screw extruder (1) is connected with the single screw extrusion machine (2) that draw ratio is 20:1, the product of twin-screw extrusion by
Nitrogen is pressed into the single screw extrusion machine (2) of draw ratio 20:1, carries out melting extrusion.
8. a kind of preparation method of high fluidity toughener according to claim 7, it is characterised in that: the single screw rod is squeezed
The posterior segment of machine (2) is provided with the vacuum pump (8) for vacuumizing out.
9. a kind of preparation method of high fluidity toughener according to claim 5, it is characterised in that: in step (3), institute
The protelum and the 11st section for stating double screw extruder (1) are vaccum exhaust outlet, be provided in the vaccum exhaust outlet for pair
The product of twin-screw extrusion carries out double vacuum pumps (7) of vacuum deliming.
10. a kind of preparation method of high fluidity toughener according to claim 5, it is characterised in that: in step (3)
Cooling procedure includes the Cooling Process of cooling trough (3) and the air-cooled process of Air cooler (4).
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| CN116178629A (en) * | 2022-12-27 | 2023-05-30 | 广州鹿山新材料股份有限公司 | Hydroxylation modified POE and preparation method and application thereof |
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| CN116178629A (en) * | 2022-12-27 | 2023-05-30 | 广州鹿山新材料股份有限公司 | Hydroxylation modified POE and preparation method and application thereof |
| CN116178629B (en) * | 2022-12-27 | 2024-05-07 | 广州鹿山新材料股份有限公司 | Hydroxylation modified POE and preparation method and application thereof |
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