CN107057294A - A kind of PET composite material of highly crystalline speed and its preparation method and application - Google Patents
A kind of PET composite material of highly crystalline speed and its preparation method and application Download PDFInfo
- Publication number
- CN107057294A CN107057294A CN201611235049.0A CN201611235049A CN107057294A CN 107057294 A CN107057294 A CN 107057294A CN 201611235049 A CN201611235049 A CN 201611235049A CN 107057294 A CN107057294 A CN 107057294A
- Authority
- CN
- China
- Prior art keywords
- composite material
- pet
- pet composite
- highly crystalline
- speed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a kind of PET composite material of highly crystalline speed and its preparation method and application, the PET composite material is formed by polyethylene terephthalate (PET) and the dicarboxylic acid disodium of two rings [2.2.1] heptane 2,3 through melt blending；Its preparation method comprises the following steps：(1) polyethylene terephthalate and the dicarboxylic acid disodium of two rings [2.2.1] heptane 2,3 are put into vacuum drying chamber and 5~6h is dried in vacuo at 150 DEG C；(2) predrying good PET pellets and HPN 68L are put into high-speed stirring mixer, 4~6min is sufficiently mixed under high speed shear effect；(3) obtained mixture is put into double screw extruder, is extruded after 4~6min of melt blending under the conditions of 260~280 DEG C, produce the PET composite material of highly crystalline speed.The PET composite material of highly crystalline speed prepared by the present invention can not only increase substantially PET crystalline rate, and the cost of PET composite material can be reduced again；Its preparation method technique is simple, and condition is easily-controllable, and production cost is low.
Description
Technical field：
The invention belongs to PET composite material and its preparing technical field, and in particular to one kind promotes PET knots using nucleator
The method of brilliant speed and corresponding PET composite material.
Background technology：
PET (PET) is as a kind of general engineering plastic, with cheap, good physical properties
The advantages of, so its usage amount increases year by year.PET is a kind of symmetrical regular linear polymer of strand, the conjugation of its molecule
The symmetry of rigid structure and molecule determines that it has good physical property, but simultaneously, rigid structure hinders PET points again
The motion of subchain so that crystallization becomes difficult, and then causes its injection mould temperature height, injection cycle length, the easy warpage of product, makes it
It is restricted in engineering plastics field.
In order to solve Mo Wengaos of the PET in injection moulding process, the problems such as molding cycle is long, domestic and foreign scholars, which have been done, largely grinds
Study carefully, such as, for the crystalline rate for improving PET, researcher have developed relatively effective organic nucleating agent, but be generally fragrance
The monocarboxylic acid sodium salt of race, such as United States Patent (USP) US.Pat.No.4451606 report the organic nucleating agent polyalkylene of PET a kind of
The copolymer of terephthalate and aromatic sulphonate, although its nucleating effect of this organic nucleating agent is preferable, but make half hitch
The brilliant time shortens 50%, but this organic nucleating agent can lose nucleation capability, Er Qiecheng in PET process because of degraded
This is also higher.In order to improve problem above, applicant is added in PET using a kind of new organic nucleating agent, in process
Nucleation capability will not be lost because of degraded, PET composite material cost is advantageously reduced, accelerates manufacturer's processing PET composite material
Speed, widen the market of PET composite material.
The content of the invention：
In view of the deficienciess of the prior art, the purpose of the present invention aims to provide a kind of PET composite woods of highly crystalline speed
Material, the PET composite material can increase substantially PET crystalline rate, the cost of PET composite material can be reduced again.
Simple it is a further object to provide a kind of technique, condition is easily-controllable, the low highly crystalline speed of production cost
PET composite material and its preparation method and application.
For achieving the above object, the present invention takes following technical scheme：
A kind of PET composite material of highly crystalline speed, it is by polyethylene terephthalate (PET) and two rings
[2.2.1] heptane -2,3- dicarboxylic acid disodium is formed through melt blending, wherein：The raw material composition is by mass percentage：Poly- pair
PET be 99.4~99.8wt%, two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium be 0.2~
0.6wt%.
The invention provides the preparation method of the PET composite material of above-mentioned highly crystalline speed, this method comprises the following steps：
S1：Polyethylene terephthalate and two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium are put into vacuum drying
Case carries out being dried in vacuo 5~6h under the conditions of 150 DEG C；
S2：By predrying good polyethylene terephthalate and two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium in
In high-speed stirring mixer, 4~6min is sufficiently mixed under high speed shear effect；
S3：By obtained mixture is in double screw extruder in step S1, the melt blending 4 under the conditions of 260~280 DEG C
Extrusion is produced above-mentioned (if added inventory is big, you can carry out melt blending using large-scale twin-screw extruder) after~6min
The PET composite material of highly crystalline speed.
Further, obtained mixture is in Minitype twin-screw extrusion machine in the step S1, in extruder head temperature
For 260 DEG C, remaining temperature is 270 DEG C, and screw speed is progress frit reaction extrusion under 20r/min, is produced described highly crystalline
The PET composite material of speed.
The addition of heptane -2, the 3- dicarboxylic acid disodium of two rings [2.2.1] described in above-mentioned preparation method is preferably 0.2~
0.6wt%, its fusing point is 400 DEG C, and bulk density is 0.28g/cc, and D95 particle diameters are less than 10 μm.
The intrinsic viscosity of polyethylene terephthalate described in above-mentioned preparation method is 0.80~0.85, and fusing point is
250~255 DEG C, crystallization temperature is 190~210 DEG C.
The crystallization temperature of the PET composite material of highly crystalline speed prepared by above-mentioned preparation method is 216.5~218.0
DEG C, crystallinity is 38.5~52.1%, and melting temperature is 246.7~247.5 DEG C, and cold crystallization temperature is 123~128 DEG C.
The structural formula of above-mentioned two ring [2.2.1] heptane -2,3- dicarboxylic acid disodium is：
It is added in the preparation method of the present invention using two rings [2.2.1] heptane -2,3- dicarboxylic acid disodiums as nucleator
In the higher PET of molecular weight, this organic nucleating agent is different from traditional nucleating agents, and its fusing point is up to 400 DEG C, in process not
Nucleation capability can be lost because of degraded, therefore, the PET composite material being prepared from can be used for engineering plastics field.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) two rings [2.2.1] heptane -2,3- dicarboxyl is used in the PET composite material of highly crystalline speed prepared by the present invention
With PET chemical nucleation reaction occurs for acid disodium nucleator, generates PET sodium salts, makes anionic end groups on PET molecular bands, this
Group has good nucleation, and because PET strands are broken, the enhancing of molecular chain movement ability, crystal growth
Speed is substantially accelerated, therefore the overall crystalline rate of PET composite material is greatly improved.
(2) because the PET composite material cold crystallization temperature of the highly crystalline speed of the present invention is greatly lowered, reduction is realized
The temperature of mould, it is ensured that product has higher crystallinity, can really shorten molding cycle, can reduce PET and be combined
The cost of material, accelerates the speed that manufacturer processes PET composite material, widens the market of PET composite material.
(3) two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium that the present invention is used is commercialized nucleator as one kind, into
This is relatively low, not only contributes to reduce the cost of PET composite material, and can improve PET crystal property, such as its crystallization temperature
218 DEG C can be brought up to by 203 DEG C, cold crystallization temperature is reduced to 123 DEG C by initial 148 DEG C.Meanwhile, two rings that the present invention is used
[2.2.1] heptane -2,3- dicarboxylic acid disodium fusing point is up to 400 DEG C, and the steady point property of heat is good, both can guarantee that organic nucleating agent nucleation efficiencies
It is higher, moreover it is possible to the problems such as being prevented effectively from the high temperature failure that organic nucleating agent is brought.
(4) the preparation method process that the present invention is provided is simple, and production technology is easily controlled.
Brief description of the drawings：
Fig. 1 is the nucleation efficiencies tendency chart of the PET composite material of highly crystalline speed in the embodiment of the present invention.
Embodiment：
The present invention is further illustrated below by embodiment, following examples are the present invention preferably embodiment party
Formula, but embodiments of the present invention are not limited by following embodiments.
Embodiment 1
By PET pellets 19.96g and 0.04g bis- ring [2.2.1] heptane -2,3- dicarboxylic acids two that intrinsic viscosity is 0.82
Sodium (HPN-68L) is put into vacuum drying chamber and 5~6h is dried in vacuo at 150 DEG C；By predrying good PET pellets 19.96g with
0.04g HPN-68L is put into high-speed stirring mixer, 4~6min is sufficiently mixed under high speed shear effect, then by PET
Mixture is with Minitype twin-screw extrusion machine (if added inventory is big, you can carry out melting altogether using large-scale twin-screw extruder
It is mixed) in extruder head temperature it is 260 DEG C, remaining temperature is 270 DEG C, and screw speed is to carry out frit reaction under 20r/min to squeeze
Go out, that is, obtain the PET/HPN-68L composites that HPN-68L contents are 0.2wt%.
Embodiment 2
PET pellets and two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium (HPN-68L) by intrinsic viscosity for 0.82
It is put into vacuum drying chamber and 5~6h is dried in vacuo at 150 DEG C；By predrying good PET pellets 19.92g and 0.08g HPN-
68L is put into high-speed stirring mixer, 4~6min is sufficiently mixed under high speed shear effect, then by PET mixtures with miniature
Double screw extruder (if added inventory is big, you can carry out melt blending using large-scale twin-screw extruder) is in extruder head
Temperature is 260 DEG C, and remaining temperature is 270 DEG C, and screw speed is progress frit reaction extrusion under 20r/min, that is, obtains HPN-
68L contents are 0.4wt% PET/HPN-68L composites.
Embodiment 3
PET pellets and two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium (HPN-68L) by intrinsic viscosity for 0.82
It is put into vacuum drying chamber and 5~6h is dried in vacuo at 150 DEG C；By predrying good PET pellets 19.88g and 0.12g HPN-
68L is put into high-speed stirring mixer, 4~6min is sufficiently mixed under high speed shear effect and then by PET mixtures with miniature
Double screw extruder (if added inventory is big, you can carry out melt blending using large-scale twin-screw extruder) is in extruder head
Temperature is 260 DEG C, and remaining temperature is 270 DEG C, and screw speed is progress frit reaction extrusion under 20r/min, that is, obtains HPN-
68L contents are 0.6wt% PET/HPN-68L composites.
Comparative example 1
The PET pellets that intrinsic viscosity is 0.82 are put into vacuum drying chamber 5~6h is dried in vacuo at 150 DEG C.Will be pre-
Dried PET pellets 20g is put into high-speed stirring mixer, and 4~6min is sufficiently mixed under high speed shear effect, then will
Pure PET is with Minitype twin-screw extrusion machine (if added inventory is big, you can carry out melting altogether using large-scale twin-screw extruder
It is mixed) in extruder head temperature it is 260 DEG C, remaining temperature is 270 DEG C, and screw speed is to carry out frit reaction under 20r/min to squeeze
Go out, that is, obtain pure PET composite material.
Above-described embodiment 1~3 and comparative example 1 are subjected to DSC tests, its specific method of testing is as follows：
Determined using differential scanning calorimeter DSC Q20, all tests are carried out under 50ml/min high pure nitrogen atmosphere.
Accurately weigh about 5mg samples to be sealed in aluminium crucible, be warming up to 280 DEG C with 20 DEG C/min speed and be incubated 3min
To eliminate thermal history, 35 DEG C then are cooled to 10 DEG C/min speed, the crystallization curve of sample, last 10 DEG C/min liters is recorded
Temperature records its melting curve to 280 DEG C.
Crystallinity can be calculated by following equations：
Wherein：ΔHmcFor crystallization enthalpy, θ is the percentage of other components,100% for PET crystallizes enthalpy
(117.6J/g2)。
Nucleation efficiencies can be calculated by following equations：
Wherein：Tc,NAFor the crystallization temperature of nucleated polymer, Tc1For the crystallization temperature of blank polymer, Tc2,maxFor from into
The crystallization temperature of nuclear polymer.
By above DSC method of testings, the crystallization temperature of embodiment 1~3 and comparative example 1, cold crystallization temperature are respectively obtained
Degree, crystallizes enthalpy, crystallinity, as a result such as table 1 below：
Under normal circumstances, the crystallization temperature of polymer is higher, and crystallinity is bigger and the lower explanation sample of cold crystallization temperature
Crystal property is better.The crystallization temperature of the PET/HPN-68L composites prepared from upper table 1,1~embodiment of embodiment 3,
Crystallization enthalpy, crystallinity its value are above comparative example 1, and cold crystallization temperature is significantly lower than comparative example 1, therefore, and the present invention is made
The PET composite material crystal property of standby highly crystalline speed is better than the crystal property of pure PET material.
As shown in Figure 1：, can by Fig. 1 for the nucleation efficiencies trend of the PET composite material of the highly crystalline speed of above-mentioned preparation
To find out, add after HPN-68L, the increase of PET nucleation efficiencies illustrates that HPN-68L has very effective nucleation, when with
When measuring as 0.6wt%, nucleation efficiencies are i.e. up to 68.4%, and the pure PET than not Added Nucleating Agents is significantly improved.When containing for HPN-68L
When amount is more than 0.6wt%, nucleation efficiencies decline on the contrary, illustrate that nucleator consumption has saturation value, if it exceeds saturation value, nucleator
It is possible that agglomeration.Therefore, HPN-68L optimum amount is 0.4~0.6wt%.
Claims (8)
1. a kind of PET composite material of highly crystalline speed, it is characterised in that：The PET composite material is by poly terephthalic acid
Glycol ester (PET) and two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium are through melt blending.
2. a kind of PET composite material of highly crystalline speed according to claim 1, it is characterised in that：The PET composite woods
The raw material composition of material is by mass percentage：Polyethylene terephthalate is 99.4~99.8wt%, two rings [2.2.1] heptan
Alkane -2,3- dicarboxylic acid disodium is 0.2~0.6wt%.
3. the preparation method of the PET composite material of highly crystalline speed according to claim 1 or 2, it is characterised in that：The party
Method comprises the following steps：
S1：Polyethylene terephthalate and two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium are put into vacuum drying chamber and existed
5~6h of vacuum drying is carried out under the conditions of 150 DEG C；
S2：By predrying good polyethylene terephthalate and two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium at a high speed
In stirring mixer, 4~6min is sufficiently mixed under high speed shear effect；
S3：Obtained mixture in step S2 is put into double screw extruder, under the conditions of 260~280 DEG C melt blending 4~
Extruded after 6min, produce the PET composite material of the highly crystalline speed.
4. the preparation method of the PET composite material of highly crystalline speed according to claim 3, it is characterised in that：This method
Described in two rings [2.2.1] heptane -2,3- dicarboxylic acid disodium addition be 0.2~0.6wt%, its fusing point be 400 DEG C, volume
Density is 0.28g/cc, and particle diameter is less than 10 μm.
5. the preparation method of the PET composite material of highly crystalline speed according to claim 3, it is characterised in that：This method
Described in the intrinsic viscosity of polyethylene terephthalate that uses for 0.80~0.85, fusing point is 250~255 DEG C, crystallization
Temperature is 190~210 DEG C.
6. the preparation method of the PET composite material of highly crystalline speed according to claim 3, it is characterised in that：The step
Obtained mixture is 260 DEG C in extruder head temperature, remaining temperature is 270 in Minitype twin-screw extrusion machine in rapid S1
DEG C, screw speed is progress frit reaction extrusion under 20r/min, produces the PET composite material of the highly crystalline speed.
7. the preparation method of the PET composite material of highly crystalline speed according to claim 3, it is characterised in that：This method
The crystallization temperature of the PET composite material of prepared highly crystalline speed be 216.5~218.0 DEG C, crystallinity be 38.5~
52.1%, melting temperature is 246.7~247.5 DEG C, and cold crystallization temperature is 123~128 DEG C.
8. the PET composite material of the highly crystalline speed as described in any one of claim 1~7 answering in engineering plastics field
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611235049.0A CN107057294A (en) | 2016-12-28 | 2016-12-28 | A kind of PET composite material of highly crystalline speed and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611235049.0A CN107057294A (en) | 2016-12-28 | 2016-12-28 | A kind of PET composite material of highly crystalline speed and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107057294A true CN107057294A (en) | 2017-08-18 |
Family
ID=59623973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611235049.0A Pending CN107057294A (en) | 2016-12-28 | 2016-12-28 | A kind of PET composite material of highly crystalline speed and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107057294A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102575089A (en) * | 2009-09-30 | 2012-07-11 | 株式会社Adeka | Polyester resin composition, polyester fiber, polyester resin molded article, and process for production of nucleating agent for polyester resin |
-
2016
- 2016-12-28 CN CN201611235049.0A patent/CN107057294A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102575089A (en) * | 2009-09-30 | 2012-07-11 | 株式会社Adeka | Polyester resin composition, polyester fiber, polyester resin molded article, and process for production of nucleating agent for polyester resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102532837B (en) | Preparation method for high molecular weight polylactic acid steric composite | |
| CN102086299A (en) | Transparent crystallization polylactic acid plastic and preparation method thereof | |
| CN106543622A (en) | Polyester is as flow improver additive in the purposes for improving enhancing ASA composition glossiness | |
| CN105001122A (en) | Polylactic acid organic nucleating agent as well as preparation method therefor and application thereof | |
| CN106566176A (en) | Application of polyester as a flow promoter in improving glossiness of reinforced ABS composition | |
| CN113583407B (en) | Polylactic acid composition containing carboxylate nucleating agent and preparation method thereof | |
| CN104927322A (en) | Method for rapidly forming polylactic acid stereocomplex | |
| CN112552624A (en) | Method for improving processability of polychlorotrifluoroethylene resin and mechanical toughness of product thereof | |
| CN103102646A (en) | Low-melting point and high-crystallization temperature PET copolyester, its preparation method and application | |
| CN113429768B (en) | Polylactic acid composition containing amide nucleating agent and preparation method thereof | |
| CN103450605B (en) | Preparation method of modified polytrifluorochloroethylene material | |
| CN101153111A (en) | Polyethylene terephthalate composite material and method of producing the same | |
| CN104194293B (en) | Biological poly ester composition of a kind of rapid crystallization and preparation method thereof | |
| CN104592723A (en) | Rapid-crystallization polylactic acid plastic and preparation method thereof | |
| CN108384173B (en) | A kind of high molecular weight height founds the preparation method of structure lactic acid composite material | |
| CN107057294A (en) | A kind of PET composite material of highly crystalline speed and its preparation method and application | |
| CN102190813B (en) | Nucleating agent, its preparation method and application | |
| CN111410807A (en) | Low-temperature water-soluble PVA composition capable of being melt and cast into film, particles and preparation method thereof | |
| WO2024060636A1 (en) | Polyhydroxyalkanoate composition containing ester nucleating agent, polyhydroxyalkanoate molded body, and preparation method therefor | |
| CN113429767B (en) | Polylactic acid composition containing imidazole type nucleating agent and preparation method thereof | |
| CN102875987B (en) | A kind of organic nucleating agent and its preparation and application | |
| CN111253723B (en) | Transparent heat-resistant polylactic acid composition and preparation method thereof | |
| CN101880424A (en) | Preparation method of beta crystal polypropylene/PET (Polyester) alloy | |
| CN104530662A (en) | Special biodegradable plastic material and preparing method thereof | |
| CN109134293A (en) | A kind of polylactic acid efficient nucleation agent and the preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170818 |