CN106280299A - A kind of glass fiber reinforced flame retardant PET/PC resin combination of high fluidity and preparation method thereof - Google Patents
A kind of glass fiber reinforced flame retardant PET/PC resin combination of high fluidity and preparation method thereof Download PDFInfo
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- CN106280299A CN106280299A CN201610637903.XA CN201610637903A CN106280299A CN 106280299 A CN106280299 A CN 106280299A CN 201610637903 A CN201610637903 A CN 201610637903A CN 106280299 A CN106280299 A CN 106280299A
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
Glass fiber reinforced flame retardant PET/PC resin combination that the invention discloses a kind of high fluidity and preparation method thereof, said composition includes component: low-melting point PET resin 10 parts 75.9 parts；PC resin 5 parts 70.9 parts；Toughener 0 part 15 parts；Brominated flame-retardant 10 parts 20 parts；Fire retarding synergist 3 parts 5 parts；Glass fibre 5 parts 50 parts；0.6 part of antioxidant；Ester exchange inhibitor 0.5 part, wherein low-melting point PET resin is that a kind of fusing point is 190 230 DEG C of special PET resin.The present invention is by preferred PC resin, low-melting point PET resin, toughener, fire retardant and the kind of glass fibre and consumption, and the glass fiber reinforced flame retardant PET/PC resin combination prepared has the feature of high fluidity, can be widely applied in injection-molded item.
Description
Technical field
The present invention relates to engineering plastics technical field, be specifically related to the glass fiber reinforced flame retardant PET/ of a kind of high fluidity
PC resin combination and preparation method thereof.
Background technology
Conventional polybutylene terephthalate (PBT) (PET) is the engineering plastics of a kind of hemicrystalline, and it has good
Mechanical property, electrical property, thermostability and chemical resistance etc., be widely used in the industries such as automobile, electronics, electrical equipment；Also in polyester bottles, fine
Dimension, the field such as thin film is widely used.But at injection molding art, owing to PET resin can crystallize in melting process, it cools down knot
Brilliant speed is relatively slow, and cool time is longer, limits its application.
By polymerization process introduces copolymerization units, it is possible to reduce the cold crystallization of PET and crystallizing power, even synthesize amorphous
PET resin, this resin has relatively low fusing point.As patent CN103102473 A discloses a kind of by introducing 10-30%
M-phthalic acid, the crystallization modifier of 5-29% and the branched regulator of 0.03-2%, finally synthesized low melting point, transparent
PET resin.Patent CN 103102646 A discloses a kind of fusing point regulator by introducing 5-10% and the crystallization of 7-20%
Accelerator, has synthesized a kind of low melting point, the PET resin of high crystallization temperature.And patent CN 104987498 A discloses a kind of logical
Cross introducing 2-methyl isophthalic acid, ammediol (MPO) and M-phthalic acid, synthesized low melting point PTT and
Polyethylene terephthalate, its melting range is between 190 DEG C to 250 DEG C.
Copolyester with low melting point application currently mainly is textile industry, and it can carry out composite spinning with conventional polyester,
The core-skin composite fiber of gained can be used for and wool blended the worn performance improving worsted fabric；And copolyester with low melting point is also
Wide application prospect is had in non-woven fabrics, hot-melt prepreg machine, building materials and paint field.
The PET resin of low melting point and the alloy of PC resin, compared to traditional PET and PC alloy, in processing fluidity side
There is significant advantage in face, particularly glass fiber reinforced flame retardant PET/PC alloy, and the advantage of its mobility is more aobvious prominent.Therefore,
This patent develops the glass fiber reinforced flame retardant PET/PC resin alloy of high fluidity, can solve some glass fibre at present
Strengthen Flame-retardant PET/PC alloy problem in terms of injection.
Summary of the invention
The purpose of the present invention, it is simply that provide the glass fiber reinforcement resistance of a kind of high fluidity in order to solve the problems referred to above
Combustion PET/PC resin combination and preparation method thereof.
The object of the present invention is achieved like this:
A kind of glass fiber reinforced flame retardant PET/PC resin combination of the high fluidity of the present invention, this PET/PC resin group
Compound includes following components and weight portion content:
The glass fiber reinforced flame retardant PET/PC resin combination of above-mentioned a kind of high fluidity, wherein low-melting point PET tree
The repetitive of fat is made up of following components:
Component A: account for the dicarboxylic acid units of the repetitive 45-55mol% of resin；
Component B: account for the diol units that carbon number is 2～14 of the repetitive 45-55mol% of resin；
Wherein, described component A is by accounting for terephthalic acid units A1 of its 80-100mol% and accounting between its 0-20mol%
Phthalic acid or O-phthalic acid unit A2 composition；Wherein, described component B by account for its 80-100mol% ethylene glycol unit B 1,
Account for the aliphatic diol that carbon number is 2～9 of its 0-20mol% or cycloaliphatic diol units B2 group that carbon number is 2～9
Become；And meet in component A or component B at least any one component, comprise two or more different unit.
The glass fiber reinforced flame retardant PET/PC resin combination of above-mentioned a kind of high fluidity, low-melting point PET resin its
Melting range is between 190-230 DEG C, between preferably 210-230 DEG C, between most preferably 215-225 DEG C.Described low melting point
PET resin, its intrinsic viscosity is between 0.55-0.95ml/g, between preferably 0.65-0.85ml/g, most preferably 0.7-
Between 0.8ml/g.
The glass fiber reinforced flame retardant PET/PC resin combination of above-mentioned a kind of high fluidity, wherein PC resin is selected from virtue
At least one in fragrant adoption carbonic ester, fatty poly-ester carbonate, aromatic-aliphatic Merlon, branching polycarbonate；Excellent
Elect aromatic copolycarbonate as；Described aromatic copolycarbonate is selected from the aromatic polycarbonate of viscosity-average molecular weight 13000-40000
Ester, the preferably aromatic copolycarbonate of viscosity-average molecular weight 16000-28000, most preferably viscosity-average molecular weight 17000-24000
Aromatic copolycarbonate.
The glass fiber reinforced flame retardant PET/PC resin combination of above-mentioned a kind of high fluidity, wherein toughener is second
Alkene-vinylacetate, ethylene-methyl acrylate, ethylene-ethylacrylate, Ethylene-butyl acrylate, Low Density Polyethylene, horse
Maleic anhydride grafted ethylene-octene copolymer, ethylene-ethylacrylate-glycidyl ester copolymer, Ethylene-butyl acrylate-contracting
At least one in water glyceride copolymer
The glass fiber reinforced flame retardant PET/PC resin combination of above-mentioned a kind of high fluidity, wherein brominated flame-retardant is
At least one in brominated Polystyrene, TDE, brominated polycarbonate, brominated epoxy etc..
The glass fiber reinforced flame retardant PET/PC resin combination of above-mentioned a kind of high fluidity, wherein fire retarding synergist is
At least one in antimony containing compounds, preferably antimony oxide or sodium antimonate.
The glass fiber reinforced flame retardant PET/PC resin combination of above-mentioned a kind of high fluidity, wherein glass fibre is nothing
Alkali short glass fiber or continuously alkali-free glass fibre, wherein glass fiber diameter is 10～25 μm.
The glass fiber reinforced flame retardant PET/PC resin combination of above-mentioned a kind of high fluidity, wherein antioxidant is season penta
Four alcohol esters and phosphite ester, the two weight ratio is 1:1.
The glass fiber reinforced flame retardant PET/PC resin combination of above-mentioned a kind of high fluidity, wherein ester exchange inhibitor
For Sodium Acid Pyrophosphate.
Present invention also offers the glass fiber reinforced flame retardant PET/PC resin combination of a kind of high fluidity, including following
Step:
(1) according to following components and weight portion content preparation raw material:
(2) by PC resin, PET resin, toughener, brominated flame-retardant, fire retarding synergist, antioxidant and ester exchange inhibitor
Uniformly enter double screw extruder after mixing, in an extruder between position add glass fibre, processing technique is as follows: district's temperature
220-230 DEG C, two district's temperature 230-240 DEG C, three district's temperature 240-250 DEG C, four district's temperature 240-250 DEG C, five district's temperature 240-
250 DEG C, six district's temperature 245-255 DEG C, seven district's temperature 245-255 DEG C, eight district's temperature 245-255 DEG C, nine district's temperature 240-250
℃；Engine speed 300-400 rev/min.
(3) discharging, cools down after extrusion, is dried, pelletizing, and the glass fibre that can prepare high fluidity of the present invention increases
Strong Flame-retardant PET/PC resin combination.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
The material that the embodiment of the present invention and comparative example are used is as follows:
Low-melting point PET resin: intrinsic viscosity is 0.71ml/g, the trade mark is HS550, SINOPEC's asset management
Engineering plastics factory of Yizheng branch company of company limited；Wherein, terephthalic acid units content is 39mol% ratio, M-phthalic acid
Unit content is 11mol% ratio, and ethylene glycol unit content is 50mol% ratio；
Conventional PET resin: intrinsic viscosity is 0.68ml/g, and the trade mark is SB500, and SINOPEC's asset management has
Engineering plastics factory of Yizheng branch company of limit company；
PC resin: viscosity-average molecular weight is about 25000, and the trade mark is 1300-10, LG chemical company of Korea S；
Toughener: Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer, the trade mark is PTW, and the U.S. shuts out
Company of nation；Maleic anhydride grafted ethene-octene copolymer (MPOE), the trade mark is N493D, du pont company；
Short glass fiber: the trade mark is ECS 303H-3, a diameter of 10 μm, Chongqing Polycomp International Co., Ltd.
Continuous glass fibre: the trade mark is ER14-2000-988A, diameter 13 μm, megalith group of China.
Brominated flame-retardant: the trade mark is PBS-64HW, brominated polystyrene, U.S.'s Chemtura；The trade mark is BC-52, and bromination is gathered
Carbonic ester, U.S.'s Chemtura；
Fire retarding synergist: the trade mark is S-05N, antimony oxide, Hu'nan Chenzhou Mining Co., Ltd.；
Antioxidant: four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propanoic acid] pentaerythritol ester, Irganox 1010,
Ciba fine chemicals.Three [2.4-di-tert-butyl-phenyl] phosphite ester, Irganox168, Ciba fine chemicals；Two
Person's ratio of weight and number is 1:1；
Ester exchange inhibitor: Sodium Acid Pyrophosphate (SAPP), Sichuan Jin Diyamei Science and Technology Ltd..
Embodiment 1～12 and comparative example 1～3:
By table 1 formula, by PC resin, PET resin, toughener, brominated flame-retardant and other auxiliary agents etc. in mixed at high speed
In machine, mixing obtains premix material for 1-2 minute, and premix material is through double screw extruder, and glass fibre adds in the middle part of extruder, 210
Melt extrude at DEG C-250 DEG C, cool down, pelletize and get final product.
The performance test results is as shown in table 1.
The component (weight portion) of table 1 embodiment 1-12 and comparative example 1-3 and the performance test results
*: fusing point uses DSC method test；
Knowable to embodiment 1-12 of table 1 and the comparison of comparative example 1-3, the present invention is by preferred PC resin, low melting point
PET resin and toughener, use different brominated flame-retardants and glass fibre, it is possible to preparation has the glass fibre of high fluidity
Strengthening Flame-retardant PET/PC resin combination, this novel resin combination will be well used at Injection Industry.
Above example is used for illustrative purposes only, rather than limitation of the present invention, about the technology people of technical field
Member, without departing from the spirit and scope of the present invention, it is also possible to make various conversion or modification, the most all equivalents
Technical scheme also should belong to scope of the invention, should be limited by each claim.
Claims (12)
1. the glass fiber reinforced flame retardant PET/PC resin combination of a high fluidity, it is characterised in that described high flowing
The glass fiber reinforced flame retardant PET/PC resin combination of property includes the component of following parts by weight:
The glass fiber reinforced flame retardant PET/PC resin combination of a kind of high fluidity the most as claimed in claim 1, its feature
Being, the repetitive of described low-melting point PET resin is made up of following components:
Component A: account for the dicarboxylic acid units of the repetitive 45-55mol% of resin；
Component B: account for the diol units that carbon number is 2-14 of the repetitive 45-55mol% of resin；
Wherein, described component A is by accounting for terephthalic acid units A1 of its 80-100mol% and accounting for the isophthalic two of its 0-20mol%
Formic acid or O-phthalic acid unit A2 composition；Wherein, described component B is by accounting for the ethylene glycol unit B 1 of its 80-100mol%, accounting for it
The carbon number of 0-20mol% is aliphatic diol or the cycloaliphatic diol units B2 composition of 2-9；And meet component A or component B
At least in any one component, comprise two or more different unit.
The glass fiber reinforced flame retardant PET/PC resin combination of a kind of high fluidity the most as claimed in claim 1, its feature
Being, described its melting range of low-melting point PET resin is between 190-230 DEG C, between preferably 210-230 DEG C, most preferably
Between 215-225 DEG C.
The glass fiber reinforced flame retardant PET/PC resin combination of a kind of high fluidity the most as claimed in claim 1, its feature
Being, described low-melting point PET resin, its intrinsic viscosity is between 0.55-0.95ml/g, between preferably 0.65-0.85ml/g,
Between most preferably 0.7-0.8ml/g.
The glass fiber reinforced flame retardant PET/PC resin combination of a kind of high fluidity the most as claimed in claim 1, its feature
Being, described PC resin is selected from aromatic copolycarbonate, fatty poly-ester carbonate, aromatic-aliphatic Merlon, branched
At least one in Merlon；It is preferably aromatic copolycarbonate；Described aromatic copolycarbonate is selected from viscosity-average molecular weight
The aromatic copolycarbonate of 13000-40000, preferably the aromatic copolycarbonate of viscosity-average molecular weight 16000-28000, more excellent
Elect the aromatic copolycarbonate of viscosity-average molecular weight 17000-24000 as.
The glass fiber reinforcement PET/PC resin combination of a kind of high fluidity the most as claimed in claim 1, it is characterised in that
Described toughener is ethylene-vinyl acetate, ethylene-methyl acrylate, ethylene-ethylacrylate, ethylene-acrylic acid fourth
Ester, Low Density Polyethylene, maleic anhydride grafted ethene-octene copolymer, ethylene-ethylacrylate-glycidyl ester copolymer,
At least one in Ethylene-butyl acrylate-glycidyl ester copolymer etc..
The glass fiber reinforcement PET/PC resin combination of a kind of high fluidity the most as claimed in claim 1, it is characterised in that
Described brominated flame-retardant is at least in brominated Polystyrene, TDE, brominated polycarbonate, brominated epoxy etc.
Kind.
The glass fiber reinforcement PET/PC resin combination of a kind of high fluidity the most as claimed in claim 1, it is characterised in that
Described fire retarding synergist is at least one in a kind of antimony containing compounds, preferably antimony oxide or sodium antimonate.
The glass fiber reinforced flame retardant PET/PC resin combination of a kind of high fluidity the most as claimed in claim 1, its feature
Being, described glass fibre is alkali-free short glass fiber or continuous alkali-free glass fibre, and wherein glass fiber diameter is
10-25 μm.
The glass fiber reinforced flame retardant PET/PC resin combination of a kind of high fluidity the most as claimed in claim 1, its feature
Being, described antioxidant is pentaerythritol ester and phosphite ester, and parts by weight ratio is 1:1.
The glass fiber reinforced flame retardant PET/PC resin combination of 11. a kind of high fluidities as claimed in claim 1, its feature
Being, described ester exchange inhibitor is Sodium Acid Pyrophosphate.
The preparation of the glass fiber reinforced flame retardant PET/PC resin combination of 12. a kind of high fluidities as claimed in claim 1
Method, it is characterised in that comprise the following steps:
(1) according to following components and weight portion content preparation raw material:
(2) by uniform to PC resin, PET resin, toughener, brominated flame-retardant, fire retarding synergist, antioxidant and ester exchange inhibitor
After mixing enter double screw extruder, in an extruder between position add glass fibre, processing technique is as follows: district's temperature 220-
230 DEG C, two district's temperature 230-240 DEG C, three district's temperature 240-250 DEG C, four district's temperature 240-250 DEG C, five district's temperature 240-250
DEG C, six district's temperature 245-255 DEG C, seven district's temperature 245-255 DEG C, eight district's temperature 245-255 DEG C, nine district's temperature 240-250 DEG C；Main
Machine rotating speed 300-400 rev/min.
(3) discharging, cools down after extrusion, is dried, pelletizing, can prepare the glass fiber reinforcement resistance of high fluidity of the present invention
Combustion PET/PC resin combination.
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| CN201610637903.XA CN106280299A (en) | 2016-08-05 | 2016-08-05 | A kind of glass fiber reinforced flame retardant PET/PC resin combination of high fluidity and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276751A (en) * | 2017-12-26 | 2018-07-13 | 浙江普利特新材料有限公司 | A kind of high-impact high fire-retardance PC-ABS composite material and preparation methods |
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|---|---|---|---|---|
| CN101410443A (en) * | 2006-01-27 | 2009-04-15 | 沙伯基础创新塑料知识产权有限公司 | Molding compositions containing polycarbonate and modified polybutylene terephthalate(PBT) random copolymers derived from polyethylene terephthalate (PET) |
| CN101410442A (en) * | 2006-01-27 | 2009-04-15 | 沙伯基础创新塑料知识产权有限公司 | Articles derived from compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET) |
-
2016
- 2016-08-05 CN CN201610637903.XA patent/CN106280299A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101410443A (en) * | 2006-01-27 | 2009-04-15 | 沙伯基础创新塑料知识产权有限公司 | Molding compositions containing polycarbonate and modified polybutylene terephthalate(PBT) random copolymers derived from polyethylene terephthalate (PET) |
| CN101410442A (en) * | 2006-01-27 | 2009-04-15 | 沙伯基础创新塑料知识产权有限公司 | Articles derived from compositions containing modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalate (PET) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276751A (en) * | 2017-12-26 | 2018-07-13 | 浙江普利特新材料有限公司 | A kind of high-impact high fire-retardance PC-ABS composite material and preparation methods |
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