CN106987101B - Polymer blend and preparation method thereof - Google Patents
Polymer blend and preparation method thereof Download PDFInfo
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- CN106987101B CN106987101B CN201710193927.5A CN201710193927A CN106987101B CN 106987101 B CN106987101 B CN 106987101B CN 201710193927 A CN201710193927 A CN 201710193927A CN 106987101 B CN106987101 B CN 106987101B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
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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
- C08L2205/24—Crystallisation aids
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Abstract
The present invention relates to a kind of polymer blends and preparation method thereof.The polymer blend is prepared from the following materials: poly terephthalic acid 1,4 cyclohexane dimethanol ester (PCT) resin, glass fibre, nucleating agent A, nucleating agent B, toughener, antioxidant, lubricant, additive.The number-average molecular weight of poly terephthalic acid 1,4 cyclohexane dimethanol ester (PCT) resin is 25000~30000；The nucleating agent A is carboxylic acid sodium salt organic micromolecule nucleating agent, and molecular weight is 100~200g/mol；The nucleating agent B is ionomer salt nucleating agent.Polymer blend crystalline rate of the invention is faster, so that the molding time of material shortens, time cost when finished product processing is saved, and while largely improving crystalline rate, and the comprehensive performances such as impact property, bending property, heat-resistant deforming temperature that can preferably improve material.
Description
Technical field
The present invention relates to Material Fields, more particularly to a kind of polymer blend and preparation method thereof.
Background technique
Polyester is the polymer general name as obtained by polyalcohol and polyacid polycondensation, refers mainly to polyethylene terephthalate
(PET), poly terephthalic acid 1,4- fourth diester (PBT), poly terephthalic acid 1,4 cyclohexane dimethanol ester (PCT), poly- naphthalene two
Acid cyclohexyl alkane diformazan alcohol ester (PCN), polyethylene naphthalate (PEN) and their copolyester.These polyester phases
To cheap, and since their aromatic substances content is higher, there is high glass-transition temperature (Tg), this gives by it
The good heat resistance of manufactured formed article, rigidity and toughness.But since crystalline rate is slow, limit polyester use and
It promotes, especially poly terephthalic acid 1,4-CHDM ester (PCT).
Poly terephthalic acid 1,4-CHDM ester (PCT) is novel engineering resin, it not only has water absorption rate
The advantages of polyester materials such as lower, good stability of the dimension, resistance to chemical reagents be excellent, but also there is the good transparency and resistance to y to penetrate
Linearly, most prominent advantage is that heat resistance is substantially better than PBT, PET engineering plastics, is the highest thermoplastic of current heat resistance
Property polyester, heat resistance can be equal to PPS phase, while it also has crystallization rate and low pitting excellent not available for PPS,
Price is also cheap compared with PPS, therefore, has certain Development volue.But poly terephthalic acid Isosorbide-5-Nitrae-cyclohexane dicarboxylates
(PCT) crystal property is still undesirable, and crystalline rate not only influences the period of its processing and forming, but also it is anti-to directly affect it
The physical mechanical properties such as tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance.
Currently, being some researchs, such as patent CN100577730C to the improvement of crystallizing polyester rate in the prior art
A kind of method for improving poly terephthalic acid diol ester crystalline rate is disclosed, but this method is directed to the crystallization of PET resin
The raising of rate.It is by the isophthalic two containing alkali metal sulfonate substituent group that patent CN101987911A, which is disclosed using strand,
Formic acid replaces the high molecular nucleating agent connected and composed with straight chain type both-end hydroxyl two kinds of structural units of alcohol, to improve poly- 2,6- naphthalene two
The method of formic acid glycol ester crystalline rate.Patent CN103849125A is improved poly- to a certain degree by the way that inorganic nucleator is added
The crystalline rate of ester composition.
Summary of the invention
Based on this, the object of the present invention is to provide one kind to have short molding cycle, crystallization degree height, mechanical performance high, resistance to
Hot high polymer blend, can be applied to high temperature resistant, high optical reflectance electric part in, such as: projection device or lamp
Reflection timbering material of tool etc..
In order to achieve the above objectives, the present invention uses following scheme:
A kind of polymer blend is prepared by the raw material of following parts by weight:
The number-average molecular weight of the poly terephthalic acid 1,4 cyclohexane dimethanol ester resin is 25000~30000.
The nucleating agent A is carboxylic acid sodium salt organic micromolecule nucleating agent, and molecular weight is 100~200g/mol.
The nucleating agent B is ionomer salt nucleating agent.
The polymer blend is prepared by the raw material of following parts by weight in one of the embodiments:
The toughener is EPDM copolymer rubber (EPDM), Butadiene/Styrene in one of the embodiments,
Block copolymer (SBS), polyolefin thermoelastic (POE) or ethylene-vinyl acetate copolymer.
The antioxidant includes Hinered phenols antioxidant and the phosphorous acid esters antioxygen in one of the embodiments,
Agent.
The Hinered phenols antioxidant is four (β-(3,5- di-tert-butyl-hydroxy phenyl) in one of the embodiments,
Propionic acid) pentaerythritol ester and/or β-(4- hydroxy phenyl -3,5- di-t-butyl) propionic acid n-octadecyl alcohol ester；The phosphite ester
Kind antioxidant is phosphorous acid three (2,4- di-tert-butyl-phenyl) ester.
In one of the embodiments, in parts by weight, the antioxidant includes 0.1~1 part of Hinered phenols antioxidant, with
And 0.1~1 part of phosphite ester antioxidant.
The glass fibre is alkali-free glass fibre in one of the embodiments, which is continuous fine
Dimension and/or chopped strand.
The lubricant is pentaerythritol stearate in one of the embodiments,.
In one of the embodiments, in parts by weight, the additive includes 1~30 part of white pigment and fluorescence
0.03~0.08 part of brightening agent.
The white pigment is Sb in one of the embodiments,2O3、ZnO、TiO2、ZnS、BaSO4、CaCO3One of
Or it is several.
The fluorescent whitening agent is bis- (5 methyl -2- benzoxazolyl) the hexichol second of 4,4- in one of the embodiments,
Alkene.
The present invention also provides the polymer blend preparation methods, include the following steps:
(1) poly terephthalic acid 1,4-CHDM ester (PCT) resin is placed in 100~120 DEG C, drying 4
It is cooling after~12 hours；Poly terephthalic acid 1,4 cyclohexane dimethanol ester (PCT) resin and the toughener after will be cooling
It is added in high-speed mixer and is pre-mixed；
(2) the nucleating agent A, nucleating agent B, antioxidant, lubricant and additive are added to another high-speed mixer
In mixed, then obtained mixture is added in step (1) described high-speed mixer and is mixed；
(3) mixture that step (2) mixes is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder, which is added, carries out melting extrusion, is granulated, technological parameter is as follows: area's temperature is 260
~310 DEG C, two area's temperature: 280~330 DEG C, three area's temperature be 280~330 DEG C, four Qu Wendu: 280~330 DEG C, five Qu Wendu
It is 280~330 DEG C, six Qu Wendu: 280~330 DEG C, die head temperature: 280~325 DEG C, driving screw revolving speed are as follows: 100~
450rpm。
In one of the embodiments, in the step (1), by the poly terephthalic acid 1,4-CHDM ester
(PCT) resin is placed in 110 DEG C, drying 4~6 hours；In the step (3), the technological parameter are as follows: area's temperature be 270~
300 DEG C, two area's temperature: 290~325 DEG C, three area's temperature are 290~325 DEG C, and four Qu Wendu: 290~325 DEG C, five area's temperature are
290~325 DEG C, six Qu Wendu: 290~325 DEG C, die head temperature: 290~325 DEG C, driving screw revolving speed are as follows: 250~450rpm.
The screw configuration of the parallel double-screw extruder is single thread in one of the embodiments,；Spiro rod length L
It is 30~60 with the ratio between diameter D L/D；The screw rod is equipped with more than one gear block area and more than one left-hand thread area.
The ratio between described spiro rod length L and diameter D L/D is 40~55 in one of the embodiments,；The screw rod is equipped with
2 gear block areas and 2 left-hand thread areas.
The principle of the present invention and advantage are as follows:
The nucleation of high polymer includes primary nucleation and secondary nucleation.Wherein primary nucleation be divided into again homogeneous nucleation and out-phase at
Two kinds of core, general polymerization object exists simultaneously both mechanism of nucleation.Homogeneous nucleation is generated by itself warm-up movement of molecular melt segment
As nucleus, nucleus is continuously generated the chain bundle or folded chain of ordered arrangement in the whole process, therefore the nucleus developed into
It is not of uniform size, required temperature is usually relatively low.Heterogeneous nucleation impurity next other than being, polymer crystals, artificial be added are divided
Centered on scattered small particles or chamber wall, adsorpting polymerization object segment makees ordered arrangement and forms nucleus, and heterogeneous nucleation is by temperature shadow
Sound is smaller, can occur at a higher temperature.So to improve crystalline rate, it is necessary to increase its heterogeneous nucleation ability.
The present invention is by selecting reasonable ionomer and small organic molecule nucleating agent, and both interworkings content uses, and obtains
Obtained poly terephthalic acid 1,4-CHDM ester (PCT) resin material of more highly crystalline rate.To prepare molding
The preferable engineering polyester plasticses of comprehensive performances such as the time is short, its good mechanical performance, heat resistance height.Wherein, small organic molecule
The mechanism of nucleation of nucleating agent is mainly related with its chemical structure, and PCT and carboxylic acid sodium salt can occur chemical anti-when squeezing out at high temperature
It answers, generates PCT-COONa substance, will form ion cluster between the PCT melt with ionic end groups, ion cluster will become nucleation
Agent plays nucleation, the regular arrangement rapid crystallization of strand in the melt.Ionomer, that is, ionomer is common one
Kind high molecular nucleating agent refers to that main component is by non-ionic skeleton with a small amount of ionogen on high polymer main chain
The chain and component containing ion is constituted on a small quantity.Compared with small organic molecule nucleating agent, ionomer nucleating agent is having ionic end groups
Macromolecular while generate, there are also the PCT-R flexible group of organic nucleating agent (R be) to generate, due to R strand ratio PCT points
Subchain is flexible more preferable, plays the role of promotor again in system, its introducing promotes the molecular motion of PCT, reduces point
Subchain diffuses into the free energy of lattice.When the two is used in compounding, small organic molecule nucleating agent plays main nucleation, and
Ionomer nucleating agent reduces the free energy help nucleus growth that strand diffuses into lattice, the two by introducing flexible group
Reach synergistic effect, further increases the crystalline rate of PCT.
Compared with prior art, the invention has the following beneficial effects:
1, polymer blend crystalline rate of the invention faster, so that the molding time of material shortens, saves finished product
Time cost when processing, and largely improve crystalline rate while, and can preferably improve material impact property,
The comprehensive performances such as bending property, heat-resistant deforming temperature.
2, above-mentioned polymer blend is prepared using the preparation method of polymer blend of the invention, simple process is easy to
Control, not high to equipment requirement, used equipment is general polymer-processing equipment, and investment is not high, and due to preferable
Dispersibility make material settling out performance high.
Detailed description of the invention
Fig. 1 is the preparation technology flow chart of polymer blend described in one embodiment of the invention.
Specific embodiment
To further understand the features of the present invention, technological means and specific purposes achieved, function, parse this hair
Bright advantage and spirit, by following embodiment, the present invention is further elaborated.
The reaction mechanism is as follows for polymer blend of the present invention:
Raw material used in the embodiment of the present invention is as follows, and preparation technology flow chart is see Fig. 1:
Poly terephthalic acid 1,4-CHDM ester (PCT) resin, number-average molecular weight is about 28000, is selected from the U.S.
Yisiman Chemical Company；
Nucleating agent A is carboxylic acid sodium salt, and it is a kind of small organic molecule nucleating agent that molecular weight, which is 100~200g/mol, choosing
From Chinese medicines group Solution on Chemical Reagents in Shanghai Co., Ltd；
Nucleating agent B is ionomer8920, it is a kind of sodium-ion type thermoplasticity ionomer, is selected from the U.S.
E.I.Du Pont Company；
Glass fibre, diameter is at 12~23 μm, including continuous fiber and chopped strand, public selected from U.S.'s OWENS CORNING
Department；
White pigment, average grain diameter is in 0.2~0.3um, and D50 is less than 0.25um, is selected from DuPont Corporation；
Toughener, Butadiene/Styrene block copolymer (SBS), styrene specific gravity are selected from yueyang, hunan 30~50%
Petrochemical industry；
Four (β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters (antioxidant 1010), as main antioxygen
Agent is selected from Ciba, Switzerland；
Phosphorous acid three (2,4- di-tert-butyl-phenyl) ester (irgasfos 168) is selected from Switzerland's vapour Bagong as auxiliary antioxidant
Department；
Pentaerythritol stearate (lubricant) is selected from U.S.'s Clariant Corporation；
4,4- bis- (5 methyl -2- benzoxazolyl) talan (fluorescent whitening agent) are selected from U.S.'s Clariant Corporation.
Embodiment 1:
A kind of polymer blend of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned polycarbonate compositions, comprising the following steps:
(1) the PCT resin is placed in 110 DEG C, it is cooling after 6 hours dry, by PCT resin after cooling and described
Toughener is added in high-speed mixer and is pre-mixed；
(2) by the white pigment, nucleating agent A, nucleating agent B, Hinered phenols antioxidant, phosphite ester antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another high-speed mixer and are mixed, and obtained mixture is then added to step
(1) it is mixed in high-speed mixer described in；
(3) mixture that step (2) mixes is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder, which is added, carries out melting extrusion, is granulated, technological parameter is as follows: area's temperature is 300
DEG C, two area's temperature: 310 DEG C, three area's temperature be 310 DEG C, four Qu Wendu: 310 DEG C, five area's temperature be 310 DEG C, six Qu Wendu: 310
DEG C, die head temperature: 310 DEG C, driving screw revolving speed are as follows: 350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 45,
The screw rod is equipped with 2 gear block areas and 2 left-hand thread areas.
Embodiment 2:
A kind of polymer blend of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned polycarbonate compositions, comprising the following steps:
(1) the PCT resin is placed in 110 DEG C, it is cooling after 6 hours dry, by PCT resin after cooling and described
Toughener is added in high-speed mixer and is pre-mixed；
(2) by white pigment, nucleating agent A, nucleating agent B, Hinered phenols antioxidant, phosphite ester antioxidant, lubricant
And fluorescent whitening agent is added in another high-speed mixer and is mixed, and obtained mixture is then added to step (1)
Described in mixed in high-speed mixer；
(3) mixture that step (2) mixes is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder, which is added, carries out melting extrusion, is granulated, technological parameter is as follows: area's temperature is 295
DEG C, two area's temperature: 310 DEG C, three area's temperature be 310 DEG C, four Qu Wendu: 315 DEG C, five area's temperature be 315 DEG C, six Qu Wendu: 315
DEG C, die head temperature: 310 DEG C, driving screw revolving speed are as follows: 400rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 55,
The screw rod is equipped with 2 gear block areas and 2 left-hand thread areas.
Embodiment 3:
A kind of polymer blend of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned polycarbonate compositions, comprising the following steps:
(1) the PCT resin is placed in 110 DEG C, after 6 hours dry, cooling, by PCT resin after cooling and toughening
Agent is added in high-speed mixer and is pre-mixed；
(2) by the white pigment, nucleating agent A, nucleating agent B, Hinered phenols antioxidant, phosphite ester antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another high-speed mixer and are mixed, and obtained mixture is then added to step
(1) it is mixed in high-speed mixer described in；
(3) mixture that step (2) mixes is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder, which is added, carries out melting extrusion, is granulated, technological parameter is as follows: area's temperature is 300
DEG C, two area's temperature: 310 DEG C, three area's temperature be 310 DEG C, four Qu Wendu: 310 DEG C, five area's temperature be 310 DEG C, six Qu Wendu: 310
DEG C, die head temperature: 310 DEG C, driving screw revolving speed are as follows: 350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is equipped with 2 gear block areas and 2 left-hand thread areas.
Embodiment 4:
A kind of polymer blend of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned polycarbonate compositions, comprising the following steps:
(1) the PCT resin is placed in 110 DEG C, it is cooling after 6 hours dry, by PCT resin after cooling and described
Toughener is added in high-speed mixer and is pre-mixed；
(2) by the white pigment, nucleating agent A, nucleating agent B, Hinered phenols antioxidant, phosphite ester antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another high-speed mixer and are mixed, and obtained mixture is then added to step
(1) it is mixed in high-speed mixer described in；
(3) mixture that step (2) mixes is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder, which is added, carries out melting extrusion, is granulated, technological parameter is as follows: area's temperature is 295
DEG C, two area's temperature: 310 DEG C, three area's temperature be 310 DEG C, four Qu Wendu: 315 DEG C, five area's temperature be 315 DEG C, six Qu Wendu: 315
DEG C, die head temperature: 310 DEG C, driving screw revolving speed are as follows: 400rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is equipped with 2 gear block areas and 2 left-hand thread areas.
Embodiment 5:
A kind of polymer blend of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned polycarbonate compositions, comprising the following steps:
(1) the PCT resin is placed in 110 DEG C, it is cooling after 6 hours dry, by PCT resin after cooling and described
Toughener is added in high-speed mixer and is pre-mixed；
(2) by the white pigment, nucleating agent A, nucleating agent B, Hinered phenols antioxidant, phosphite ester antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another high-speed mixer and are mixed, and obtained mixture is then added to step
(1) it is mixed in high-speed mixer described in；
(3) mixture that step (2) mixes is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder, which is added, carries out melting extrusion, is granulated, technological parameter is as follows: area's temperature is 300
DEG C, two area's temperature: 310 DEG C, three area's temperature be 310 DEG C, four Qu Wendu: 310 DEG C, five area's temperature be 310 DEG C, six Qu Wendu: 310
DEG C, die head temperature: 310 DEG C, driving screw revolving speed are as follows: 350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 45,
The screw rod is equipped with 2 gear block areas and 2 left-hand thread areas.
Comparative example 1:
A kind of polymer blend of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned polycarbonate compositions, comprising the following steps:
(1) the PCT resin is placed in 110 DEG C, it is cooling after 6 hours dry, by PCT resin after cooling and described
Toughener is added in high-speed mixer and is pre-mixed；
(2) by the white pigment, nucleating agent A, nucleating agent B, Hinered phenols antioxidant, phosphite ester antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another high-speed mixer and are mixed, and obtained mixture is then added to step
(1) it is mixed in high-speed mixer described in；
(3) mixture that step (2) mixes is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder, which is added, carries out melting extrusion, is granulated, technological parameter is as follows: area's temperature is 300
DEG C, two area's temperature: 310 DEG C, three area's temperature be 310 DEG C, four Qu Wendu: 310 DEG C, five area's temperature be 310 DEG C, six Qu Wendu: 310
DEG C, die head temperature: 310 DEG C, driving screw revolving speed are as follows: 350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is equipped with 2 gear block areas and 2 left-hand thread areas.
Comparative example 2:
A kind of polymer blend of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned polycarbonate compositions, comprising the following steps:
(1) the PCT resin is placed in 110 DEG C, it is cooling after 6 hours dry, by PCT resin after cooling and described
Toughener is added in high-speed mixer and is pre-mixed；
(2) by the white pigment, nucleating agent A, nucleating agent B, Hinered phenols antioxidant, phosphite ester antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another high-speed mixer and are mixed, and obtained mixture is then added to step
(1) it is mixed in high-speed mixer described in；
(3) mixture that step (2) mixes is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder, which is added, carries out melting extrusion, is granulated, technological parameter is as follows: area's temperature is 300
DEG C, two area's temperature: 310 DEG C, three area's temperature be 310 DEG C, four Qu Wendu: 310 DEG C, five area's temperature be 310 DEG C, six Qu Wendu: 310
DEG C, die head temperature: 310 DEG C, driving screw revolving speed are as follows: 350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is equipped with 2 gear block areas and 2 left-hand thread areas.
Comparative example 3:
A kind of polymer blend of this comparative example, is prepared from the following raw materials:
The preparation method of above-mentioned polycarbonate compositions, comprising the following steps:
(1) the PCT resin is placed in 110 DEG C, it is cooling after 6 hours dry, by PCT resin after cooling and described
Toughener is added in high-speed mixer and is pre-mixed；
(2) by the white pigment, nucleating agent A, nucleating agent B, Hinered phenols antioxidant, phosphite ester antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another high-speed mixer and are mixed, and obtained mixture is then added to step
(1) it is mixed in high-speed mixer described in；
(3) mixture that step (2) mixes is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder, which is added, carries out melting extrusion, is granulated, technological parameter is as follows: area's temperature is 300
DEG C, two area's temperature: 310 DEG C, three area's temperature be 310 DEG C, four Qu Wendu: 310 DEG C, five area's temperature be 310 DEG C, six Qu Wendu: 310
DEG C, die head temperature: 310 DEG C, driving screw revolving speed are as follows: 350rpm.
The screw configuration of the parallel double-screw extruder is double thread, and the ratio between spiro rod length L and diameter D L/D are 45,
The screw rod is equipped with 1 gear block area, no left-hand thread area.
Comparative example 4:
A kind of polymer blend of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned polycarbonate compositions, comprising the following steps:
(1) the PCT resin is placed in 110 DEG C, it is cooling after 6 hours dry, by PCT resin after cooling and described
Toughener is added in high-speed mixer and is pre-mixed；
(2) by the white pigment, nucleating agent A, nucleating agent B, Hinered phenols antioxidant, phosphite ester antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another high-speed mixer and are mixed, and obtained mixture is then added to step
(1) it is mixed in high-speed mixer described in；
(3) mixture that step (2) mixes is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder, which is added, carries out melting extrusion, is granulated, technological parameter is as follows: area's temperature is 300
DEG C, two area's temperature: 310 DEG C, three area's temperature be 310 DEG C, four Qu Wendu: 310 DEG C, five area's temperature be 310 DEG C, six Qu Wendu: 310
DEG C, die head temperature: 310 DEG C, driving screw revolving speed are as follows: 350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is equipped with 2 gear block areas and 2 left-hand thread areas.
Comparative example 5:
A kind of polymer blend of the present embodiment, is prepared from the following raw materials:
The preparation method of above-mentioned polycarbonate compositions, comprising the following steps:
(1) the PCT resin is placed in 110 DEG C, it is cooling after 6 hours dry, by PCT resin after cooling and described
Toughener is added in high-speed mixer and is pre-mixed；
(2) by the white pigment, nucleating agent A, nucleating agent B, Hinered phenols antioxidant, phosphite ester antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another high-speed mixer and are mixed, and obtained mixture is then added to step
(1) it is mixed in high-speed mixer described in；
(3) mixture that step (2) mixes is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder, which is added, carries out melting extrusion, is granulated, technological parameter is as follows: area's temperature is 300
DEG C, two area's temperature: 310 DEG C, three area's temperature be 315 DEG C, four Qu Wendu: 315 DEG C, five area's temperature be 315 DEG C, six Qu Wendu: 315
DEG C, die head temperature: 310 DEG C, driving screw revolving speed are as follows: 350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 55,
The screw rod is equipped with 2 gear block areas and 2 left-hand thread areas.
The following are comparative examples and embodiment list:
1 comparative example of table and embodiment raw material form parts by weight list
Above-mentioned comparative example and the made sample of embodiment are subjected to following performance test:
Tensile property: ASTM D-638 standard testing, rate of extension 50mm/min are pressed；
Notched impact properties: pressing ASTM D-256 standard testing, and batten is band notch；
HDT: ASTM D648 (1.82MPa) standard testing, thickness of test piece 6.0mm are pressed；
Degree of supercooling (Δ T): it is tested using DSC, is tested according to GB/T 19466-2004 standard.Degree of supercooling (Δ T) is
Melting temperature (Tm) and thermal crystalline peak temperature (Tp) difference, meaning be degree of supercooling it is smaller, the crystalline rate of polymer is got over
Fastly.
2 comparative example of table and embodiment performance list
As shown in Table 1, comparative example 1 is the polymer blend of non-Added Nucleating Agents；Comparative example 4 is that small organic molecule nucleation is added
The polymer blend of agent.Have by the degree of supercooling that comparison can be seen that the polymer blend of addition small organic molecule nucleating agent bright
It is aobvious to reduce, show that its crystalline rate is improved, tensile strength, notch impact strength and HDT are better than non-Added Nucleating Agents
Polymer blend, this is because the raising of crystalline rate brings crystallinity also to correspondingly increase, to bring the above mechanics and heat-resisting
Performance improvement.Comparative example 5 is the polymer blend that ionomer sodium salt is added.Gathered by comparison as can be seen that ion is added
The degree of supercooling for closing the polymer blend of object sodium salt is obviously reduced, and shows that its crystalline rate is improved, tensile strength, notch
Impact strength and HDT are better than the polymer blend of non-Added Nucleating Agents, show that the ionomer sodium salt also contributes to raising group
Close the crystalline rate of object.
Comparative example 2 is the polymer blend for not adding toughener；Embodiment 3 is the polymer blend that toughener is added, the two
Remaining recipe ingredient is identical and all uses interworking nucleating agent.By comparison as can be seen that the polymer blend of toughener is added
Notch impact strength is bigger, remaining performance is suitable, and the addition of toughener helps to improve its toughness, and the nucleating agent is to remaining
Performance slightly influence but less.
Comparative example 3 is that screw configuration is double thread, and the ratio between spiro rod length L and diameter D L/D are 50, and screw rod is equipped with 1
Gear block area, the polymer blend that the double screw extruder in no left-hand thread area is prepared；Embodiment 3 is that screw configuration is single line
Screw thread, the ratio between spiro rod length L and diameter D L/D are 50, and screw rod is equipped with 2 gear block areas and the twin-screw in 2 left-hand thread areas squeezes
The polycarbonate compositions that machine is prepared out.The formula of the two is consistent.By comparison as can be seen that using screw rod of the invention
Shape is single thread, and the ratio between spiro rod length L and diameter D L/D are 50, and screw rod is equipped with 2 gear block areas and 2 left-hand thread areas
When, the degree of supercooling of polymer blend is lower, and tensile strength, notch impact strength and HDT are higher, which is more suitable for this
The processing of composition.
The nucleating agent (embodiment 1-5) of interworking is added than certain is used alone in comparative example 1-5 and comparative example 4-5, discovery
Kind nucleating agent better effect, degree of supercooling is lower than comparative example 4-5, and crystalline rate is further mentioned after showing its interworking
It is high.
The degree of supercooling of comparative example 1-5, embodiment 3 are minimum, and the performances such as tensile strength, notch impact strength and HDT are more
Good, the comprehensive performance of embodiment 3 is best；It is indicated above the nucleating agent ratio small organic molecule that interworking is added: ionomer sodium
Salt can obtain the highly crystalline rate polymer blend of optimal synthesis performance when being about 0.5:0.5.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of polymer blend, which is characterized in that be prepared by the raw material of following parts by weight:
The number-average molecular weight of the poly terephthalic acid 1,4 cyclohexane dimethanol ester resin is 25000~30000；
The nucleating agent A is carboxylic acid sodium salt organic micromolecule nucleating agent, and molecular weight is 100~200g/mol；
The nucleating agent B is ionomer salt nucleating agent；
In the preparation of the polymer blend, the screw configuration of used parallel double-screw extruder is single thread；Screw rod
The ratio between length L and diameter D L/D are 30~60；The screw rod is equipped with more than one gear block area and more than one anti-spiral shell
Line area.
2. polymer blend according to claim 1, which is characterized in that be prepared by the raw material of following parts by weight:
3. polymer blend according to claim 1, which is characterized in that the toughener is that EPDM is copolymerized rubber
Glue, Butadiene/Styrene block copolymer, polyolefin thermoelastic or ethylene-vinyl acetate copolymer.
4. polymer blend according to claim 1, which is characterized in that the antioxidant include Hinered phenols antioxidant and
The phosphite ester antioxidant.
5. polymer blend according to claim 4, which is characterized in that the Hinered phenols antioxidant is four (β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and/or β-(4- hydroxy phenyl -3,5- di-t-butyl) propionic acid positive 18
Carbon alcohol ester；The phosphite ester antioxidant is phosphorous acid three (2,4- di-tert-butyl-phenyl) ester.
6. polymer blend according to claim 1, which is characterized in that the glass fibre is alkali-free glass fibre, should
Alkali-free glass fibre is continuous fiber and/or chopped strand.
7. polymer blend preparation method described in any one of claims 1-6, and be characterized in that, include the following steps:
(1) the poly terephthalic acid 1,4-CHDM ester resin is placed in 100~120 DEG C, drying 4~12 hours
Afterwards, cooling, poly terephthalic acid 1,4-CHDM ester resin after cooling and the toughener are added to high speed
It is pre-mixed in blender；
(2) by the nucleating agent A, nucleating agent B, antioxidant, lubricant and additive be added in another high-speed mixer into
Obtained mixture, is then added in step (1) described high-speed mixer and mixes by row mixing；
(3) mixture that step (2) mixes is placed in parallel double-screw extruder, and the glass fibre is put down from described
The lateral feeding of row double screw extruder, which is added, carries out melting extrusion, is granulated, technological parameter is as follows: area's temperature is 260~310
DEG C, two area's temperature: 280~330 DEG C, three area's temperature are 280~330 DEG C, and four Qu Wendu: 280~330 DEG C, five area's temperature are 280
~330 DEG C, six Qu Wendu: 280~330 DEG C, die head temperature: 280~325 DEG C, driving screw revolving speed are as follows: 100~450rpm.
8. polymer blend preparation method according to claim 7, which is characterized in that, will be described poly- in the step (1)
Terephthalic acid (TPA) 1,4-CHDM ester resin is placed in 110 DEG C, drying 4~6 hours；In the step (3), the technique
Parameter are as follows: area's temperature is 270~300 DEG C, two area's temperature: 290~325 DEG C, three area's temperature are 290~325 DEG C, four Qu Wen
Degree: 290~325 DEG C, five area's temperature are 290~325 DEG C, six Qu Wendu: 290~325 DEG C, die head temperature: 290~325 DEG C, are led
Screw speed are as follows: 250~450rpm.
9. polymer blend preparation method according to claim 7 or 8, which is characterized in that the parallel double-screw squeezes out
The screw configuration of machine is single thread；The ratio between spiro rod length L and diameter D L/D are 30~60；The screw rod is equipped with more than one
Gear block area and more than one left-hand thread area.
10. polymer blend preparation method according to claim 9, which is characterized in that the spiro rod length L and diameter D
The ratio between L/D be 40~55；The screw rod is equipped with 2 gear block areas and 2 left-hand thread areas.
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| CN114940813B (en) * | 2022-06-30 | 2023-07-11 | 广东中塑新材料有限公司 | PBT-based luminous composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787184A (en) * | 2009-12-30 | 2010-07-28 | 中国石油化工股份有限公司 | Quickly crystallized polyester engineering plastic and preparation method thereof |
| CN102040811A (en) * | 2010-12-29 | 2011-05-04 | 深圳市科聚新材料有限公司 | Polycaprolactam (PCT) engineering plastics and preparation method thereof |
| CN103589121A (en) * | 2012-08-14 | 2014-02-19 | 苏州汉扬精密电子有限公司 | Glass fiber reinforced PCT resin and preparation method thereof |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787184A (en) * | 2009-12-30 | 2010-07-28 | 中国石油化工股份有限公司 | Quickly crystallized polyester engineering plastic and preparation method thereof |
| CN102040811A (en) * | 2010-12-29 | 2011-05-04 | 深圳市科聚新材料有限公司 | Polycaprolactam (PCT) engineering plastics and preparation method thereof |
| CN103589121A (en) * | 2012-08-14 | 2014-02-19 | 苏州汉扬精密电子有限公司 | Glass fiber reinforced PCT resin and preparation method thereof |
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Address after: 523850 Baibugao Avenue, Wushajiang, Chang'an Town, Dongguan City, Guangdong Province, 355 Patentee after: Guangdong Sinoplast New Materials Co.,Ltd. Address before: 523850 Baibugao Avenue, Wushajiang, Chang'an Town, Dongguan City, Guangdong Province, 355 Patentee before: GUANGDONG SINOPLAST ADVANCED MATERIAL CO.,LTD. |